JP4891211B2 - Method for producing coated steel sheet having inorganic coating film - Google Patents
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- JP4891211B2 JP4891211B2 JP2007321171A JP2007321171A JP4891211B2 JP 4891211 B2 JP4891211 B2 JP 4891211B2 JP 2007321171 A JP2007321171 A JP 2007321171A JP 2007321171 A JP2007321171 A JP 2007321171A JP 4891211 B2 JP4891211 B2 JP 4891211B2
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- 239000011248 coating agent Substances 0.000 title claims description 145
- 238000000576 coating method Methods 0.000 title claims description 145
- 229910000831 Steel Inorganic materials 0.000 title claims description 107
- 239000010959 steel Substances 0.000 title claims description 107
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000049 pigment Substances 0.000 claims description 60
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 46
- 229920001225 polyester resin Polymers 0.000 claims description 35
- 239000004645 polyester resin Substances 0.000 claims description 35
- 229920001296 polysiloxane Polymers 0.000 claims description 35
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010304 firing Methods 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 229910052782 aluminium Inorganic materials 0.000 description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 25
- 238000005266 casting Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- 239000003973 paint Substances 0.000 description 21
- 238000005192 partition Methods 0.000 description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229920002050 silicone resin Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- -1 Acrylic ester Chemical class 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
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- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Mold Materials And Core Materials (AREA)
Description
本発明は、無機塗膜を有する塗装鋼板に関する。 The present invention relates to a coated steel sheet having an inorganic coating film.
アルミニウム鋳物は、ダイカスト法や低圧鋳造法により製造される。これらの方法を用いて板状のアルミニウム鋳物を、同時に多数製造する場合、鋳造金型には仕切り板がセットされる。仕切り板により、金型内部は仕切られ、所定サイズのキャビティが形成される。当該仕切り板には、鋳造後にアルミニウム鋳物から容易に分離できることが必要とされる。 Aluminum castings are manufactured by die casting or low pressure casting. When a large number of plate-like aluminum castings are manufactured simultaneously using these methods, a partition plate is set in the casting mold. The inside of the mold is partitioned by the partition plate, and a cavity of a predetermined size is formed. The partition plate needs to be easily separable from the aluminum casting after casting.
アルミニウム鋳物と仕切り板との分離を容易にするため、離型剤を仕切り板に塗布する方法が提案されている。離型剤として黒鉛粉末、雲母やタルク等を主成分とするものが提案されている（特許文献１など）。
In order to facilitate separation of the aluminum casting and the partition plate, a method of applying a release agent to the partition plate has been proposed. As a release agent, a material mainly composed of graphite powder, mica, talc or the like has been proposed (
しかし、従来の仕切り板は、離型剤が仕切り板からアルミニウム鋳物に移行しやすく、アルミニウム鋳物表面を汚染するという問題があった。このような問題をふまえ、仕切り板の表面に離型剤を塗布する代わりに、アクリルシリコーン樹脂の塗膜を形成する方法が提案されている（特許文献２、３）。しかし、アクリルシリコーン樹脂は、耐熱性に劣るため、アルミニウムの鋳造時に有機物が分解しやすい。分解した有機物は気泡となって塗膜に巣穴を形成したり、塗膜を剥離・脱落させたりする。その結果アルミニウム鋳物に、鋳巣や肌荒れ等の不良が発生することがあった。あるいは、塗膜が脱落した部分では、鋳物と仕切り板に焼付きが生じるという問題があった。
However, the conventional partition plate has a problem that the mold release agent easily shifts from the partition plate to the aluminum casting and contaminates the surface of the aluminum casting. In view of such a problem, a method of forming an acrylic silicone resin coating instead of applying a release agent to the surface of the partition plate has been proposed (
このようなアクリルシリコーン樹脂の問題点を改善するため、特許文献４には、アクリルシリコーン樹脂とシリカ系バインダー（コロイダルシリカ分散液にオルガノアルコキシシランを添加して加水分解させて得たもの等）を含む塗料から形成された塗膜を有する塗装金属板が提案されている。当該塗装金属板は、シリカ系バインダーがアクリルシリコーン樹脂を巻き込む形で塗膜が形成され、６５０℃前後の高温雰囲気下でも塗膜自体が結合力の高い三次元の網目構造を維持し、シリコーン由来のＳｉ−Ｏ−Ｓｉ構造が離型性を向上さすため仕切り板として好適であるとされている。
特許文献４に記載の塗装金属板は、シリカ系バインダーが必須である。しかし、シリカ系バインダーの調製等は煩雑であることと、切断加工において切り口の塗膜が細長く剥離するため、本文献に記載の方法とは異なる、新規な、無機塗膜を有する塗装鋼板が望まれていた。
発明者らは、特許文献４に記載の塗装金属板において、シリカ系バインダーが必須である原因について詳細に検討した結果、６５０℃前後の高温雰囲気下ではアクリルシリコーン樹脂が分解するため、耐熱性を向上させて健全な塗膜を維持するために、シリカ系バインダーが必要であることを見出した。一方で、シリカ系バインダーは塗膜を硬くし、金属との密着性を低下させることも明らかにした。
このような事情に鑑み、本発明は、無機塗膜を有する塗装鋼板であって、無機塗膜と鋼板の密着性に優れ、アルミニウム鋳物との離型性に優れる塗装鋼板を提供することを目的とする。
In the coated metal plate described in Patent Document 4, a silica-based binder is essential. However, since the preparation of the silica-based binder is complicated and the coating film at the cut end is peeled long and thin in the cutting process, a new coated steel sheet having an inorganic coating film, which is different from the method described in this document, is desired. It was rare.
The inventors have studied in detail the cause of the necessity of the silica-based binder in the coated metal plate described in Patent Document 4, and as a result, the acrylic silicone resin decomposes in a high temperature atmosphere around 650 ° C. It has been found that a silica-based binder is necessary to improve and maintain a healthy coating film. On the other hand, it was also clarified that the silica-based binder hardens the coating film and lowers the adhesion with the metal.
In view of such circumstances, an object of the present invention is to provide a coated steel sheet having an inorganic coating film, which is excellent in adhesion between the inorganic coating film and the steel sheet and excellent in releasability from an aluminum casting. And
発明者らは、鋭意検討した結果、シリコーンポリエステル樹脂と特定の顔料を用いることにより、上記課題が解決できることを見出した。すなわち上記課題は以下の本発明により解決される。 As a result of intensive studies, the inventors have found that the above problems can be solved by using a silicone polyester resin and a specific pigment. That is, the said subject is solved by the following this invention.
［１］鋼板の上にケイ素を主成分とする無機塗膜を有する塗装鋼板であって、
前記無機塗膜は、金属元素を含む顔料を含有し、
前記塗装鋼板は、鋼板の上にシリコーンポリエステル樹脂と前記顔料を含む塗膜が形成された積層体を、５００℃以上で加熱して得られる、塗装鋼板。
［２］前記顔料は、金属酸化物を含む、［１］に記載の塗装鋼板。
［３］前記［１］または［２］に記載の塗装鋼板を用いた、アルミニウム鋳造用仕切り板。
［４］（Ａ）鋼板の上にシリコーンポリエステル樹脂および前記顔料を含む塗膜が形成された積層体を準備する工程と、
（Ｂ）前記積層体を５００℃以上で加熱する工程を含む、
鋼板の上にケイ素を主成分とする無機塗膜を有する塗装鋼板であって、
前記無機塗膜は、金属元素を含む顔料を含有する、塗装鋼板の製造方法。
［５］前記積層体に形成された塗膜中の前記顔料の含有量は、前記塗膜に対して２〜５０質量％である、［４］に記載の製造方法。
[1] A coated steel sheet having an inorganic coating film mainly composed of silicon on a steel sheet,
The inorganic coating film contains a pigment containing a metal element,
The coated steel sheet is a coated steel sheet obtained by heating a laminated body in which a coating film containing a silicone polyester resin and the pigment is formed on a steel sheet at 500 ° C. or higher.
[2] The coated steel sheet according to [1], wherein the pigment includes a metal oxide.
[3] A partition plate for aluminum casting using the coated steel plate according to [1] or [2].
[4] (A) preparing a laminate in which a coating film containing a silicone polyester resin and the pigment is formed on a steel plate;
(B) including a step of heating the laminate at 500 ° C. or higher.
A coated steel sheet having an inorganic coating film mainly composed of silicon on the steel sheet,
The said inorganic coating film is a manufacturing method of the coated steel plate containing the pigment containing a metallic element.
[5] The production method according to [4], wherein the content of the pigment in the coating film formed on the laminate is 2 to 50% by mass with respect to the coating film.
本発明により、無機塗膜を有する塗装鋼板であって、無機塗膜と鋼板の密着性に優れ、アルミニウム鋳物との離型性に優れる塗装鋼板が提供できる。 According to the present invention, a coated steel sheet having an inorganic coating film, which is excellent in adhesion between the inorganic coating film and the steel sheet and excellent in releasability from an aluminum casting, can be provided.
１．塗装鋼板
本発明の塗装鋼板は、鋼板の上にケイ素を主成分とする無機塗膜を有する塗装鋼板であって、前記無機塗膜は、金属元素を含む顔料を含有し、かつ鋼板の上にシリコーンポリエステル樹脂と前記顔料を含む塗膜が形成された積層体を、５００℃以上で加熱して得られる、ことを特徴とする。
1. Coated steel sheet The coated steel sheet of the present invention is a coated steel sheet having an inorganic coating film composed mainly of silicon on the steel sheet, the inorganic coating film containing a pigment containing a metal element, and on the steel sheet. It is characterized by being obtained by heating a laminate on which a coating film containing a silicone polyester resin and the pigment is formed at 500 ° C. or higher.
（１）鋼板
塗装鋼板とは鋼板表面に塗膜を有する鋼板である。塗膜は鋼板表面に塗料を塗布して（塗装して）得られるが、本発明においては、特定の塗料を鋼板表面に塗装した積層体を５００℃以上で加熱して得られる。これにより、塗膜に含まれる炭素・水素を主成分とする有機物が分解・除去され、ケイ素を主成分とする無機塗膜が鋼板の上に形成される。
(1) Steel plate A coated steel plate is a steel plate having a coating film on the surface of the steel plate. The coating film is obtained by applying (coating) a paint to the surface of the steel sheet, but in the present invention, it is obtained by heating a laminate having a specific paint applied to the surface of the steel sheet at 500 ° C. or higher. As a result, the organic substance mainly composed of carbon and hydrogen contained in the coating film is decomposed and removed, and an inorganic coating film mainly composed of silicon is formed on the steel sheet.
鋼板とは板状の鋼である。鋼板は、塗装鋼板の分野においては「塗装原板」とも呼ばれる。鋼板の例には冷圧延鋼板、ステンレス鋼板が含まれる。ステンレス鋼板の例には、オーステナイト系、フェライト系およびマルテンサイトが含まれる。 A steel plate is a plate-shaped steel. The steel sheet is also referred to as a “paint base sheet” in the field of coated steel sheets. Examples of the steel plate include a cold rolled steel plate and a stainless steel plate. Examples of the stainless steel sheet include austenitic, ferritic and martensite.
鋼板は、塗装される前に、必要に応じて酸洗浄、あるいはアルカリ脱脂処理等により、表面に洗浄処理が施されていてもよい。また、鋼板は、リン酸処理、表面調整、塗布型ノンクロメート等により、化成処理がなされていてもよい。
鋼板の厚みは、特に限定されないが、アルミニウム鋳造用仕切り板としたときの加工しやすさ、熱歪み等から、０．５〜２ｍｍであることが好ましく、経済的理由を加味すると、０．８ｍｍ程度であることがより好ましい。
Before the steel sheet is coated, the surface may be subjected to a cleaning process by acid cleaning or alkaline degreasing as required. Further, the steel sheet may be subjected to chemical conversion treatment by phosphoric acid treatment, surface conditioning, coating type non-chromate, or the like.
Although the thickness of the steel plate is not particularly limited, it is preferably 0.5 to 2 mm from the viewpoint of ease of processing when it is used as a partition plate for casting aluminum, thermal strain, and the like. More preferably, it is about.
（２）無機塗膜
無機塗膜とは、ケイ素等の無機元素が、単独あるいは酸素原子を介して結合して形成された塗膜をいう。本発明の無機塗膜は、ケイ素を主成分とし、かつ「金属元素を含む顔料」（以下「金属元素含有顔料」ともいう）を含む。本発明の無機塗膜は、シリコーンポリエステル樹脂、金属元素含有顔料を含む塗膜を、５００℃以上で加熱する（「焼成する」ともいう）ことにより、鋼板表面に形成される。
便宜上、焼成前の塗膜を「焼成前塗膜」と、焼成後の塗膜を「焼成後塗膜」または「無機塗膜」という。
(2) Inorganic coating The inorganic coating refers to a coating formed by combining inorganic elements such as silicon alone or through oxygen atoms. The inorganic coating film of the present invention contains silicon as a main component and includes a “pigment containing a metal element” (hereinafter also referred to as “metal element-containing pigment”). The inorganic coating film of the present invention is formed on the steel sheet surface by heating (also referred to as “calcining”) a coating film containing a silicone polyester resin and a metal element-containing pigment at 500 ° C. or higher.
For convenience, the coating before firing is referred to as “coating before firing”, and the coating after firing is referred to as “coating after firing” or “inorganic coating”.
１）シリコーンポリエステル樹脂
シリコーンポリエステル樹脂とは、水酸基を有する有機ケイ素化合物等の水酸基含有化合物と酸をエステル化反応させて得られる樹脂をいう。水酸基含有化合物は、通常のポリエステル樹脂に用いられるアルコールを含んでいてもよい。本発明においては、後述するとおり、シリコーンポリエステル樹脂をマトリックスとし、金属元素含有顔料を含む塗膜を鋼板の上に形成して積層体を調製し、その後、当該積層体を５００℃以上で焼成することにより無機塗膜が形成される。
1) Silicone polyester resin Silicone polyester resin refers to a resin obtained by esterifying a hydroxyl group-containing compound such as an organic silicon compound having a hydroxyl group with an acid. The hydroxyl group-containing compound may contain an alcohol used for a normal polyester resin. In the present invention, as will be described later, a silicone polyester resin is used as a matrix and a coating film containing a metal element-containing pigment is formed on a steel sheet to prepare a laminate, and then the laminate is fired at 500 ° C. or higher. Thus, an inorganic coating film is formed.
このとき、シリコーンポリエステル樹脂と鋼板との密着性が十分でないと、焼成時に塗膜が剥離してしまうため、無機塗膜と鋼板の接着性が低下する。また、焼成時に塗膜が剥離して鋼板から脱落し、無機塗膜が得られない場合がある。従って、本発明においては、シリコーンポリエステル樹脂と鋼板の密着性が十分である必要がある。シリコーンポリエステル樹脂の柔軟性が低いと、塗膜と鋼板の密着性は低下する傾向にあるため、シリコーンポリエステル樹脂は柔軟性が高いことが好ましい。 At this time, if the adhesiveness between the silicone polyester resin and the steel plate is not sufficient, the coating film is peeled off at the time of firing, so that the adhesion between the inorganic coating film and the steel plate is lowered. Moreover, a coating film peels off at the time of baking, and it may fall off from a steel plate, and an inorganic coating film may not be obtained. Therefore, in the present invention, the adhesion between the silicone polyester resin and the steel plate needs to be sufficient. If the flexibility of the silicone polyester resin is low, the adhesion between the coating film and the steel sheet tends to decrease. Therefore, the silicone polyester resin preferably has a high flexibility.
このようなことから、本発明で用いるシリコーンポリエステル樹脂は、水酸基を有する有機ケイ素化合物、アルコール、酸をエステル化反応させて得られる樹脂であって、水酸基を有する有機ケイ素化合物成分の含有量が、全モノマー中、２０〜６０質量％であることが好ましい。前記有機ケイ素化合物成分の含有量が、この範囲にあると、焼成前塗膜と鋼板の密着性に優れる。 Therefore, the silicone polyester resin used in the present invention is a resin obtained by esterification reaction of an organic silicon compound having a hydroxyl group, an alcohol, and an acid, and the content of the organic silicon compound component having a hydroxyl group is It is preferable that it is 20-60 mass% in all the monomers. When the content of the organosilicon compound component is within this range, the adhesion between the coating film before firing and the steel sheet is excellent.
シリコーンポリエステル樹脂の原料である水酸基を有する有機ケイ素化合物としては、公知のものを用いてよいが、本発明においては、一分子内に水酸基を３つ有する「三官能タイプ」や、一分子内に水酸基を４つ有する「四官能タイプ」の有機ケイ素化合物が好ましい。さらには、「三官能タイプ」と「四官能タイプ」の有機ケイ素化合物を混合して用いることがより好ましい。 As the organosilicon compound having a hydroxyl group as a raw material for the silicone polyester resin, a known compound may be used. However, in the present invention, a “trifunctional type” having three hydroxyl groups in one molecule, “Tetrafunctional type” organosilicon compounds having four hydroxyl groups are preferred. Furthermore, it is more preferable to use a mixture of “trifunctional type” and “tetrafunctional type” organosilicon compounds.
シリコーンポリエステル樹脂の原料である酸としては、公知のものを用いてよい。しかしながら、本発明においてはイソフタル酸が好ましい。 As the acid that is a raw material of the silicone polyester resin, a known acid may be used. However, isophthalic acid is preferred in the present invention.
本発明のシリコーンポリエステル樹脂の分子量は数平均分子量（Ｍｎ）が２０００〜３０００であり、重量数平均分子量（Ｍｗ）は３００００〜６００００であることが好ましい。分子量がこの範囲にあると、焼成前塗膜と鋼板との密着性に優れる。本発明において記号「〜」はその両端の数値を含む。分子量はＧＰＣを用いて、ポリスチレン換算して求めることが好ましい。 The molecular weight of the silicone polyester resin of the present invention is preferably a number average molecular weight (Mn) of 2000 to 3000 and a weight number average molecular weight (Mw) of 30000 to 60000. When the molecular weight is within this range, the adhesion between the coating film before firing and the steel sheet is excellent. In the present invention, the symbol “˜” includes numerical values at both ends thereof. The molecular weight is preferably determined in terms of polystyrene using GPC.
ポリエステルはその末端に水酸基またはカルボキシル基を有する。本発明のシリコーンポリエステル樹脂の酸価は１２〜１６ｍｇＫＯＨ／ｇであることが好ましい。 Polyester has a hydroxyl group or a carboxyl group at its terminal. The acid value of the silicone polyester resin of the present invention is preferably 12 to 16 mg KOH / g.
本発明のシリコーンポリエステル樹脂は、硬化剤を含んでいてもよい。硬化剤の例には、メラミン硬化剤が含まれる。メラミン硬化剤は、シリコーンポリエステル樹脂１００質量部に対して、１０〜６０質量％であることが好ましく、４０質量％程度であることがより好ましい。 The silicone polyester resin of the present invention may contain a curing agent. Examples of the curing agent include a melamine curing agent. The melamine curing agent is preferably 10 to 60% by mass and more preferably about 40% by mass with respect to 100 parts by mass of the silicone polyester resin.
２）金属元素含有顔料
本発明の無機塗膜は、金属元素含有顔料を含む。当該顔料は、後述するようにシリコーンポリエステル樹脂が焼成されて生成されるケイ素を主成分とする強固な無機塗膜の中に分散して存在する。また、当該顔料は金属元素を含むため、同じ金属元素であるケイ素との親和性も高く、無機塗膜との密着性も良好である。そのため、塗膜から当該顔料が脱落しにくい。よって本発明の塗装鋼板は、アルミニウム鋳物との離型性（以下単に「離型性」という）に優れる。
鋳型に注入されたアルミニウムと鋼板は、原子が互いに拡散し合って接合する、いわゆる拡散接合を生じやすい。しかし、本発明の塗装鋼板は、無機塗膜中に強固に固定された金属元素含有顔料が存在するため、アルミニウム原子と鉄原子の拡散を防止できる。このようなメカニズムによって、顔料による離型性が発現していると推察される。
2) Metal element-containing pigment The inorganic coating film of the present invention contains a metal element-containing pigment. As will be described later, the pigment is dispersed in a strong inorganic coating film mainly composed of silicon produced by baking a silicone polyester resin. In addition, since the pigment contains a metal element, the pigment has high affinity with silicon, which is the same metal element, and good adhesion with an inorganic coating film. Therefore, it is difficult for the pigment to fall off from the coating film. Therefore, the coated steel sheet of the present invention is excellent in releasability from an aluminum casting (hereinafter simply referred to as “releasing property”).
The aluminum and the steel plate injected into the mold are likely to cause so-called diffusion bonding in which atoms are diffused and bonded to each other. However, since the coated steel sheet of the present invention has a metal element-containing pigment firmly fixed in the inorganic coating film, it can prevent diffusion of aluminum atoms and iron atoms. It is presumed that the releasability by the pigment is expressed by such a mechanism.
本発明で好ましく用いられる金属元素含有顔料の例には、金属酸化物、金属塩や、表面を金属酸化物で被覆した有機顔料が含まれる。金属酸化物の例には、四酸化三鉄（Ｆｅ３Ｏ４）、酸化第二鉄（Ｆｅ２Ｏ３）、水酸化鉄（ＦｅＯ・ＯＨ）、シリカ（ＳｉＯ２）、酸化チタン（ＴｉＯ２）が含まれる。金属塩の例には、硫酸バリウム（ＢａＳＯ４）が含まれる。表面を金属酸化物で被覆した有機顔料の例には、キナクリドン、フタロシアニンブルー、イソインドリノンを、アルミナやシリカで表面被覆したものが含まれる。 Examples of the metal element-containing pigments preferably used in the present invention include metal oxides, metal salts, and organic pigments whose surfaces are coated with metal oxides. Examples of metal oxides include triiron tetroxide (Fe 3 O 4 ), ferric oxide (Fe 2 O 3 ), iron hydroxide (FeO.OH), silica (SiO 2 ), titanium oxide (TiO 2 ). ) Is included. Examples of the metal salt include barium sulfate (BaSO 4 ). Examples of the organic pigment whose surface is coated with a metal oxide include quinacridone, phthalocyanine blue, and isoindolinone whose surface is coated with alumina or silica.
本発明に用いられる金属元素含有顔料の粒径は、通常顔料として用いられる粒径であれば限定されない。 The particle size of the metal element-containing pigment used in the present invention is not limited as long as it is a particle size usually used as a pigment.
本発明に用いられる金属元素含有顔料の添加量は、焼成前塗膜中、２〜５０質量％であることが好ましく、２〜４６質量％であることがより好ましい。ここでの「焼成前塗膜」とは、焼成前の塗膜であって、溶剤等の揮発分を含まない塗膜を意味する。金属元素含有顔料の添加量が２質量％未満では、離型性が十分でないことがある。また、金属元素含有顔料の添加量が４６質量％を超えると、当該顔料が無機塗膜から脱落しやすくなり、その結果、アルミニウム鋳物に付着することがある。 The addition amount of the metal element-containing pigment used in the present invention is preferably 2 to 50% by mass, more preferably 2 to 46% by mass in the coating film before firing. Here, the “coating film before firing” means a coating film before firing, which does not contain a volatile component such as a solvent. If the addition amount of the metal element-containing pigment is less than 2% by mass, the releasability may not be sufficient. Moreover, when the addition amount of a metal element containing pigment exceeds 46 mass%, the said pigment will be easy to drop | omit from an inorganic coating film, As a result, it may adhere to an aluminum casting.
３）無機塗膜
本発明の無機塗膜は、焼成前塗膜を５００℃以上で焼成して得られる。この際に、有機物は分解して除去され、シリコーンポリエステル樹脂由来のケイ素を主成分とする無機塗膜が鋼板の上に形成される。このときケイ素は酸素と交互に結合して三次元状の構造体、すなわち、ケイ素酸化物を形成していると考えられる。本発明においては、焼成前塗膜と鋼板が良好な密着を保ったまま焼成され、ケイ素を主成分とする塗膜が形成される。従って、ケイ素を主成分とする塗膜は、鋼板と強固に密着している。そして、この塗膜中に、離型剤である前記顔料が分散している。このような構造をとることにより、本発明の塗装鋼板は、離型性に優れるのである。
3) Inorganic coating film The inorganic coating film of this invention is obtained by baking the coating film before baking at 500 degreeC or more. At this time, the organic matter is decomposed and removed, and an inorganic coating film mainly composed of silicon derived from the silicone polyester resin is formed on the steel plate. At this time, it is considered that silicon is alternately bonded to oxygen to form a three-dimensional structure, that is, a silicon oxide. In the present invention, the pre-firing coating film and the steel plate are baked while maintaining good adhesion to form a coating film mainly composed of silicon. Therefore, the coating film containing silicon as a main component is firmly adhered to the steel plate. And the said pigment which is a mold release agent is disperse | distributing in this coating film. By taking such a structure, the coated steel sheet of the present invention is excellent in releasability.
無機塗膜の厚みは、焼成前塗膜を焼成して得られるため、焼成前塗膜の厚みよりも薄くなる。また、無機塗膜に含まれる金属元素含有顔料の濃度も、焼成前塗膜に含まれる金属元素含有顔料の濃度よりも高くなる。
無機塗膜の厚さは、離型性を発現できる厚さであれば特に限定されないが、１〜５μｍであることが好ましい。また、無機塗膜中に含まれる金属元素含有顔料の量も離型性を発現できる厚さであれば特に限定されないが、無機塗膜に対して１０〜８０質量％であることが好ましい。
Since the thickness of an inorganic coating film is obtained by baking the coating film before baking, it becomes thinner than the thickness of the coating film before baking. Moreover, the density | concentration of the metal element containing pigment contained in an inorganic coating film also becomes higher than the density | concentration of the metal element containing pigment contained in the coating film before baking.
Although the thickness of an inorganic coating film will not be specifically limited if it is the thickness which can express mold release property, It is preferable that it is 1-5 micrometers. Moreover, the amount of the metal element-containing pigment contained in the inorganic coating film is not particularly limited as long as it is a thickness that can exhibit releasability, but it is preferably 10 to 80% by mass with respect to the inorganic coating film.
図１は、本発明の塗装鋼板の一態様を示す図である。図中、１は鋼板であり、２は化成処理層であり、３は無機塗膜である。 FIG. 1 is a view showing an embodiment of the coated steel sheet of the present invention. In the figure, 1 is a steel plate, 2 is a chemical conversion treatment layer , and 3 is an inorganic coating film .
２．本発明の塗装鋼板の製造方法
本発明の塗装鋼板は、
（Ａ）鋼板の上にシリコーンポリエステル樹脂、金属元素含有顔料を含む塗膜が形成された積層体を準備する工程と、
（Ｂ）前記積層体を５００℃以上で加熱する工程、
を含む方法により製造される。
2. Manufacturing method of coated steel sheet of the present invention The coated steel sheet of the present invention is
(A) preparing a laminate in which a coating film containing a silicone polyester resin and a metal element-containing pigment is formed on a steel sheet;
(B) a step of heating the laminate at 500 ° C. or higher;
It is manufactured by the method containing.
（１） Ａ工程について
本工程では、鋼板の上にシリコーンポリエステル樹脂、金属元素含有顔料を含む塗膜、すなわち焼成前塗膜を有する鋼板（「積層体」という）を準備する。「積層体」は、シリコーンポリエステル樹脂、顔料を含む塗料を調整し、これを鋼板の表面に塗装して得ることができる。
(1) About Step A In this step, a steel sheet having a coating film containing a silicone polyester resin and a metal element-containing pigment on the steel sheet, that is, a coating film before firing (referred to as “laminated body”) is prepared. The “laminate” can be obtained by preparing a coating material containing a silicone polyester resin and a pigment and coating the surface of the steel sheet.
１）塗料の調整
シリコーンポリエステル樹脂、金属元素含有顔料を含む塗料は、公知の方法で製造されうる。例えばシリコーンポリエステル樹脂に金属元素含有顔料、必要に応じて各種添加剤（メラミン硬化剤等）を混合して得られる。混合する手段は特に限定されないが、三本ロール、ビーズミル等を用いることが好ましい。金属元素含有顔料の配合量は、シリコーンポリエステル樹脂と金属元素含有顔料の合計量（「焼成前塗膜」または「乾燥塗膜」ともいう）に対して２〜５０質量％とすることが好ましい。
また、塗料は溶媒を含んでいてもよく、シリコーンポリエステル樹脂と金属元素含有顔料の合計量が塗料中４５〜５５質量％となるように加えられることが好ましい。
1) Preparation of paint A paint containing a silicone polyester resin and a metal element-containing pigment can be produced by a known method. For example, it can be obtained by mixing a silicone element resin with a metal element-containing pigment and optionally various additives (such as a melamine curing agent). The means for mixing is not particularly limited, but it is preferable to use a triple roll, a bead mill or the like. The blending amount of the metal element-containing pigment is preferably 2 to 50% by mass with respect to the total amount of the silicone polyester resin and the metal element-containing pigment (also referred to as “coating film before firing” or “dry coating film”).
Moreover, the coating material may contain the solvent and it is preferable to add so that the total amount of a silicone polyester resin and a metal element containing pigment may be 45-55 mass% in a coating material.
２）塗装
上記のようにして得た塗料を鋼板に塗布し（「塗布工程」ともいう）、当該塗膜を加熱して乾燥させる（「焼付工程」ともいう）ことにより積層体が製造される。
塗料を鋼板に塗布する方法の例には、ロールコート、カーテンコート、ダイコート、ナイフコートが含まれる。塗料の塗布量は、無機塗膜としたときに所望の膜厚となるように調整される。焼付処理は最高到達板温度が２００〜２８０℃となるような条件で２０〜９０秒加熱して行うことが好ましい。
2) Coating A laminate is produced by applying the paint obtained as described above to a steel sheet (also referred to as “application process”) and heating and drying the coating film (also referred to as “baking process”). .
Examples of the method for applying the paint to the steel sheet include roll coating, curtain coating, die coating, and knife coating. The coating amount of the paint is adjusted so as to obtain a desired film thickness when an inorganic coating film is used. The baking treatment is preferably performed by heating for 20 to 90 seconds under conditions such that the maximum plate temperature is 200 to 280 ° C.
本（Ａ）工程において得られる積層体は、焼成前塗膜と鋼板の密着性に優れるため、切断や折り曲げ加工を行うことができる。次工程で焼成して得た塗装鋼板を、後から加工することも可能ではあるが、無機塗膜は焼成前塗膜ほど柔軟ではないため、加工の仕方によっては、塗膜が割れることがある。従って、焼成後の塗装鋼板は、加工性が制限されることがある。しかし、折り曲げ加工後を施した積層体を次工程で焼成すれば、無機塗膜を有する塗装鋼板であって、任意の形状を有する塗装鋼板が得られる。従って、本発明の製造方法は、無機塗膜を有する塗装鋼板の形状の自由度を向上させられる利点がある。 Since the laminate obtained in this step (A) is excellent in the adhesion between the pre-firing coating film and the steel sheet, it can be cut or bent. Although it is possible to process the coated steel sheet obtained by firing in the next step later, the inorganic coating film is not as flexible as the coating film before firing, so the coating film may be cracked depending on the processing method. . Therefore, the workability of the fired coated steel sheet may be limited. However, if the laminated body after the bending process is fired in the next step, a coated steel sheet having an inorganic coating film and having an arbitrary shape can be obtained. Therefore, the production method of the present invention has an advantage that the degree of freedom of the shape of the coated steel sheet having the inorganic coating film can be improved.
また、積層体は、焼成前塗膜と鋼板の密着性に優れているため、切断された際に塗膜が細い線状に剥離する、いわゆるエナメルヘアーの発生を低減させることができる。エナメルヘアーが発生すると、連続加工性すなわち生産性が極めて悪くなることがある。従って、本製造方法は、生産性に優れるという利点も有する。 Moreover, since the laminate is excellent in the adhesion between the coating film before firing and the steel plate, it is possible to reduce the occurrence of so-called enamel hair in which the coating film peels into a thin line when cut. When enamel hair is generated, continuous processability, that is, productivity may be extremely deteriorated. Therefore, this manufacturing method also has the advantage that it is excellent in productivity.
焼付工程により形成された焼成前塗膜の厚みは、１〜２０μｍであることが好ましく、５〜１０μｍであることがより好ましい。焼成前塗膜の厚みがこの範囲にあると、後述する（Ｂ）工程での焼成により、無機塗膜厚みを好ましい範囲である１〜５μｍとすることができ、かつ積層体の加工性にも優れるからである。 The thickness of the pre-firing coating film formed by the baking step is preferably 1 to 20 μm, and more preferably 5 to 10 μm. When the thickness of the coating film before firing is in this range, the inorganic coating thickness can be set to 1 to 5 μm, which is a preferred range, by firing in the step (B) described later, and also for the workability of the laminate. Because it is excellent.
ただし、焼付工程は、本工程の後の（Ｂ）工程の中で行ってもよい。この場合は、本発明の塗装鋼板をより簡易な工程で製造できるという利点がある。 However, you may perform a baking process in the (B) process after this process. In this case, there exists an advantage that the coated steel plate of this invention can be manufactured by a simpler process.
（２） Ｂ工程について
本工程では、前工程で得た積層体を５００℃以上で加熱して、塗膜の焼成を行う。本工程においては、シリコーンポリエステル樹脂中の、炭素、水素等の成分が分解されて、除去される。ほとんどの有機物は二酸化炭素となって塗膜から除去されると考えられる。そのため、焼成の雰囲気には酸素が存在することが好ましい。すなわち、焼成は大気中で行われることが好ましい。焼成において、ケイ素は塗膜にもともと存在していた酸素または空気中の酸素と反応し、ケイ素酸化物になると考えられる。つまり、ケイ素を主成分とする無機塗膜が鋼板の上に形成される。本発明においては、焼成前塗膜が鋼板と良好な密着性を保ったままケイ素酸化物が生成されるので、無機塗膜と鋼板の密着性も非常に良好となる。
(2) About B process In this process, the laminated body obtained at the previous process is heated at 500 degreeC or more, and a coating film is baked. In this step, components such as carbon and hydrogen in the silicone polyester resin are decomposed and removed. Most organic substances are thought to be removed from the coating film as carbon dioxide. Therefore, oxygen is preferably present in the firing atmosphere. That is, the firing is preferably performed in the air. In firing, silicon is considered to react with oxygen originally present in the coating film or with oxygen in the air to form silicon oxide. That is, an inorganic coating film mainly composed of silicon is formed on the steel plate. In the present invention, since the silicon oxide is produced while the coating film before firing maintains good adhesion to the steel sheet, the adhesion between the inorganic coating film and the steel sheet is very good.
金属元素含有顔料として金属酸化物や金属塩を用いた場合は、焼成においてその形状、化学的構造はほとんど変化しないと考えられる。また顔料として金属酸化物で被覆された有機顔料を用いた場合も、金属酸化物被覆層には変化が生じないため、顔料全体の形状、化学的構造も大きく変化しないと考えられる。金属元素含有顔料は、無機塗膜中に分散して存在し、かつ無機塗膜との密着性も、金属元素を含んでいるため良好と考えられる。以上から、優れた離型性を有する無機塗膜が形成される。 When a metal oxide or metal salt is used as the metal element-containing pigment, it is considered that the shape and chemical structure hardly change during firing. Also, when an organic pigment coated with a metal oxide is used as the pigment, the metal oxide coating layer does not change, so the shape and chemical structure of the entire pigment are considered not to change significantly. The metal element-containing pigment is present in a dispersed state in the inorganic coating film, and the adhesion to the inorganic coating film is considered to be good because it contains the metal element. From the above, an inorganic coating film having excellent releasability is formed.
また、前記積層体は、焼成前塗膜と鋼板の密着性が良好であるため、本（Ｂ）工程の前に、積層体に切削加工、折り曲げ加工を施されていても、本工程において焼成前塗膜が鋼板から剥離・脱落しにくい。そのため、所望の形状に成形された、無機塗膜含有塗装鋼板を得ることができる。特に、積層体が、垂直方向に延びる部分を有するように加工されたり、焼成前塗膜が鋼板の下（鉛直方向）に存在する部分を有するように加工されたりした場合、焼成前塗膜と鋼板の密着性が良好でないと、本工程での加熱時に焼成前塗膜が剥離し、重力により塗膜が脱落・落下することがある。また、焼成前塗膜が鋼板の下（鉛直方向）に存在するように積層体を静置して本工程を行う際にも、焼成前塗膜と鋼板の密着性が良好でないと塗膜が脱落・落下することがある。しかし本発明においては、焼成前塗膜と鋼板の密着性が良好であるため、このような問題が生じにくい。 Further, since the laminate has good adhesion between the coating film before firing and the steel sheet, even if the laminate is subjected to cutting and bending before the step (B), firing is performed in this step. The pre-coating film is difficult to peel off from the steel sheet. Therefore, a coated steel sheet containing an inorganic coating film formed into a desired shape can be obtained. In particular, when the laminate is processed so as to have a portion extending in the vertical direction, or when the pre-fired coating film is processed so as to have a portion existing under the steel sheet (vertical direction), If the adhesion of the steel sheet is not good, the pre-firing coating film may be peeled off during heating in this step, and the coating film may fall off or drop due to gravity. In addition, when this process is performed by allowing the laminate to stand so that the pre-firing coating film exists under the steel sheet (in the vertical direction), the coating film is not good unless the adhesion between the pre-firing coating film and the steel sheet is good. It may fall off or fall. However, in the present invention, since the adhesion between the pre-fired coating film and the steel sheet is good, such a problem hardly occurs.
焼成の時間は特に限定されないが、０．５〜３時間程度とすることが好ましい。焼成の温度も、５００℃以上であれば特に限定されないが、６００〜７００℃であることが好ましい。 The firing time is not particularly limited, but is preferably about 0.5 to 3 hours. The firing temperature is not particularly limited as long as it is 500 ° C. or higher, but is preferably 600 to 700 ° C.
３．本発明の塗装鋼板の用途
本発明の塗装鋼板は、アルミニウム鋳造用仕切り板（以下単に「仕切り板」ということがある）として好適である。仕切り板とは、板状のアルミニウム鋳物を、同時に多数製造する場合に、鋳造金型にセットされる板である。仕切り板は、本発明の塗装鋼板をそのまま用いてもよいが、前記の積層体を鋳型の中にセットし、鋳型を加熱して、当該積層体を焼成して、鋳型内で仕切り板を製造してもよい。
3. Use of the coated steel plate of the present invention The coated steel plate of the present invention is suitable as a partition plate for aluminum casting (hereinafter sometimes simply referred to as “partition plate”). A partition plate is a plate set in a casting mold when a large number of plate-like aluminum castings are manufactured simultaneously. As the partition plate, the coated steel plate of the present invention may be used as it is. However, the laminate is set in a mold, the mold is heated, the laminate is fired, and the partition plate is manufactured in the mold. May be.
［実施例１〜８］
１）塗料の調製
シリコーンポリエステル樹脂、金属元素含有顔料、溶媒を三本ロールで混練して、塗料を調製した。
金属元素含有顔料は、表１に示すものを用い、乾燥塗膜（シリコーンポリエステル樹脂および金属元素含有顔料の合計量）１００質量％に対して、７質量％となるようにした。溶媒にはシクロヘキサンを用い、溶媒の含有量は、金属元素含有顔料と樹脂の合計量が塗料の５０質量％となるようにした。表１に示す金属元素含有顔料は、総て市販のものを用いた。
[Examples 1 to 8]
1) Preparation of paint A paint was prepared by kneading a silicone polyester resin, a metal element-containing pigment, and a solvent with three rolls.
As the metal element-containing pigment, those shown in Table 1 were used, and the amount was 7% by mass with respect to 100% by mass of the dry coating film (total amount of the silicone polyester resin and the metal element-containing pigment). Cyclohexane was used as the solvent, and the content of the solvent was such that the total amount of the metal element-containing pigment and the resin was 50% by mass of the paint. All the metal element-containing pigments shown in Table 1 were commercially available.
２）塗装鋼板の調製
塗装原板として、板厚０．８ｍｍのＳＵＳ４３０ステンレス鋼板を準備した。当該鋼板に公知の方法により、アルカリ脱脂処理を施した。
続いて、前記のとおり調整した塗料を、ロールコーターを用いて塗布して塗布膜を形成した。塗布膜が形成された鋼板をオーブンに入れ、２３０℃で１分加熱して、鋼板の上に焼成前塗膜を形成し、積層体を得た。焼成前塗膜の厚みは、８μｍであった。
2) Preparation of coated steel plate A SUS430 stainless steel plate having a thickness of 0.8 mm was prepared as a coating original plate. The steel sheet was subjected to alkali degreasing treatment by a known method.
Subsequently, the coating material prepared as described above was applied using a roll coater to form a coating film. The steel plate on which the coating film was formed was placed in an oven and heated at 230 ° C. for 1 minute to form a pre-fired coating film on the steel plate to obtain a laminate. The thickness of the coating film before baking was 8 micrometers.
３）離型性試験
ｉ）このようにして得た積層体を、５０ｍｍ×５０ｍｍの大きさに切断したものを二枚準備した。このときの加工性は良好であった。これらを６００℃に加熱した炉に装入し、１５０分間加熱して、焼成し、無機塗膜を有する塗装鋼板を調製した。無機塗膜の厚みは２μｍであった。無機塗膜中の金属元素含有顔料の含有量は、３０質量％であった。
ii）一方の塗装鋼板の上に、８００℃のアルミニウム溶湯を流し込み、もう一方の塗装鋼板をその上に被せ、アルミニウム溶湯８〜１０ｇを本発明の塗装鋼板でサンドイッチした構造体を作成した。
iii）前記ii）工程の直後に、炉の温度を７００℃に昇温し、アルミニウム溶湯の流動性を保持しながら、３０分間放置した。
iv）構造体を炉から取り出して、室温まで冷却した。
ｖ）構造体から、凝固したアルミニウムを剥がし、容易に剥がすことができたかどうかで、離型性を評価した。具体的には、容易に剥がすことができたものを○、やや容易に剥がすことができたものを△、容易に剥がすことができなかったものを×として評価した。
3) Releasability test i) Two laminates obtained by cutting the laminate thus obtained into a size of 50 mm × 50 mm were prepared. The workability at this time was good. These were placed in a furnace heated to 600 ° C., heated for 150 minutes, fired, and a coated steel sheet having an inorganic coating film was prepared. The thickness of the inorganic coating film was 2 μm. The content of the metal element-containing pigment in the inorganic coating film was 30% by mass.
ii) A molten aluminum at 800 ° C. was poured onto one coated steel sheet, the other coated steel sheet was covered thereon, and a structure in which 8 to 10 g of molten aluminum was sandwiched with the coated steel sheet of the present invention was prepared.
iii) Immediately after the step ii), the temperature of the furnace was raised to 700 ° C. and left for 30 minutes while maintaining the fluidity of the molten aluminum.
iv) The structure was removed from the furnace and cooled to room temperature.
v) From the structure, the solidified aluminum was peeled off, and the releasability was evaluated based on whether or not it could be peeled off easily. Specifically, it was evaluated as “◯” for those that could be easily peeled, “Δ” for those that could be easily peeled, and “×” for those that could not be easily peeled off.
また、離型性試験において、離型されアルミニウム鋳物の表面を観察し、汚染されていないかどうかを評価した。当該評価を「非汚染性」評価とし、以下の基準で評価した。
汚染されていない場合 ○
やや汚染されていた場合 △
かなり汚染されていた場合 ×
これらの結果を表１に示す。
In the releasability test, the surface of the cast aluminum was released and evaluated for contamination. The said evaluation was made into "non-contamination" evaluation, and the following criteria evaluated.
If not contaminated ○
If slightly contaminated △
If heavily contaminated ×
These results are shown in Table 1.
［実施例９〜１２］
顔料として酸化チタンを用い、酸化チタンの添加量を乾燥塗膜１００質量％に対して２、２３、３０、４６質量％とした塗料を、実施例１〜８と同様にして調製した。これらの塗料を用いて、実施例１〜８と同様にして、本発明の塗装鋼板を調製し、離型性試験を行った。結果を表２に示す。
[Examples 9 to 12]
Titanium oxide was used as a pigment, and paints with the addition amount of titanium oxide being 2, 23, 30, 46 mass% with respect to 100 mass% of the dried coating film were prepared in the same manner as in Examples 1-8. Using these coating materials, the coated steel sheet of the present invention was prepared in the same manner as in Examples 1 to 8, and a releasability test was performed. The results are shown in Table 2.
実施例７に関しては、切断加工性についても評価を行った。切断時にエナメルヘアーが観察されたものは切断加工性が不良として×、エナメルヘアーが観察されなかったものは切断加工性が良好として○と評価した。結果を表４に示す。 Regarding Example 7, cutting workability was also evaluated. When the enamel hair was observed at the time of cutting, the cutting processability was evaluated as x, and when the enamel hair was not observed, the cutting processability was evaluated as good. The results are shown in Table 4.
［比較例１〜５］
シリコーンポリエステル樹脂の代わりに、表３に示す樹脂を用いて、実施例と同様にして、比較用塗料を調製した。ただし、顔料は酸化チタンを、乾燥塗膜１００質量％に対して７質量％用いた。これらの塗料を用いて、実施例１〜８と同様にして、塗装鋼板を調製し、離型性試験を行った。結果を表３に示す。
表３に示す樹脂は総て市販のものを用いた。
[Comparative Examples 1-5]
A comparative paint was prepared in the same manner as in the Examples using the resins shown in Table 3 instead of the silicone polyester resin. However, the pigment used was 7% by mass of titanium oxide with respect to 100% by mass of the dried coating film. Using these paints, a coated steel plate was prepared in the same manner as in Examples 1 to 8, and a releasability test was performed. The results are shown in Table 3.
All the resins shown in Table 3 were commercially available.
［比較例６］
シリコーンポリエステル樹脂、溶媒を三本ロールで混練して、顔料を含まない塗料を調製した。溶媒の量は、顔料と樹脂の合計量の５０質量％となるようにした。この塗料を用いて、実施例１〜８と同様にして、塗装鋼板を調製し、離型性試験を行った。結果を表３に示す。
[Comparative Example 6]
A silicone polyester resin and a solvent were kneaded with three rolls to prepare a paint containing no pigment. The amount of the solvent was 50% by mass of the total amount of the pigment and the resin. Using this paint, a coated steel sheet was prepared in the same manner as in Examples 1 to 8, and a releasability test was performed. The results are shown in Table 3.
［比較例７］
シリコーンポリエステル樹脂、カーボンブラック、溶媒を三本ロールで混練して、塗料を調製した。カーボンブラックの量は焼成前の乾燥塗膜１００質量％に対して７質量％とした。溶媒の量は、顔料と樹脂の合計量の５０質量％となるようにした。この塗料を用いて、実施例１〜８と同様にして、塗装鋼板を調製し、離型性試験を行った。結果を表３に示す。
[Comparative Example 7]
Silicone polyester resin, carbon black, and solvent were kneaded with three rolls to prepare a paint. The amount of carbon black was 7% by mass relative to 100% by mass of the dried coating film before firing. The amount of the solvent was 50% by mass of the total amount of the pigment and the resin. Using this paint, a coated steel sheet was prepared in the same manner as in Examples 1 to 8, and a releasability test was performed. The results are shown in Table 3.
［比較例８］
１）アクリルシリコーン樹脂の調製
アクリル酸エステルおよびγ−メタクリロキシプロピルトリメトキシシランをエチレングリコールモノブチルエーテルで希釈し、窒素雰囲気中でアゾビスイソブチルニトリルを添加した。この混合物を８０℃で約６時間加熱して、重合させて、固形分３０％の樹脂溶液を調製した。
[Comparative Example 8]
1) Preparation of acrylic silicone resin Acrylic ester and γ-methacryloxypropyltrimethoxysilane were diluted with ethylene glycol monobutyl ether, and azobisisobutylnitrile was added in a nitrogen atmosphere. This mixture was heated at 80 ° C. for about 6 hours for polymerization to prepare a resin solution having a solid content of 30%.
２）シリカ系バインダーの調製
酸性の水性コロイド状シリカ分散液をと、メタノール性コロイド状シリカ分散液と混合した後、メチルトリエトキシシラン及び塩基性アルコキシランを添加した。この混合物を室温で５時間撹拌して、加水分解反応を完結させた。当該加水分解生成物をエチレングリコールモノブチルエーテルで希釈し、固形分３０％の溶液を調製した。
2) Preparation of silica-based binder After mixing the acidic aqueous colloidal silica dispersion with the methanolic colloidal silica dispersion, methyltriethoxysilane and basic alkoxysilane were added. The mixture was stirred at room temperature for 5 hours to complete the hydrolysis reaction. The hydrolysis product was diluted with ethylene glycol monobutyl ether to prepare a solution having a solid content of 30%.
３）比較塗料の調合
このようにして得たアクリルシリコーン樹脂、シリカ系バインダーを固形分で６：４（質量比）の割合で混合した。この混合物にさらに顔料として酸化チタンを、焼成前の乾燥塗膜１００質量％に対して７質量％となるように配合して、塗料を調製した。
3) Preparation of comparative paint The acrylic silicone resin and silica-based binder thus obtained were mixed at a solid content ratio of 6: 4 (mass ratio). Further, titanium oxide as a pigment was blended with this mixture so as to be 7% by mass with respect to 100% by mass of the dried coating film before firing to prepare a paint.
４）塗装鋼板の調製、評価
このようにして得た塗料を用いて、実施例７と同様にして塗装鋼板を調製し、評価した。結果を表４に示す。
4) Preparation and evaluation of coated steel plate A coated steel plate was prepared and evaluated in the same manner as in Example 7 using the coating material thus obtained. The results are shown in Table 4.
実施例と比較例から、本発明の塗装鋼板は離型性に優れることが明らかである。また、実施例１２から、金属元素含有顔料の添加量が多すぎると、アルミニウム鋳物の表面が汚染されやすくなる傾向が見られた。 From the examples and comparative examples, it is clear that the coated steel sheet of the present invention is excellent in releasability. Moreover, from Example 12, when the addition amount of the metal element-containing pigment was too large, there was a tendency that the surface of the aluminum casting was easily contaminated.
本発明の塗装鋼板は、アルミニウム鋳物との離型性に優れるため、アルミニウム鋳造用仕切り板として有用である。 Since the coated steel sheet of the present invention is excellent in releasability from an aluminum casting, it is useful as a partition plate for aluminum casting.
１ 鋼板
２ 化成処理層
３ 無機塗膜
1
Claims (2)
（Ａ）鋼板の上にシリコーンポリエステル樹脂および金属元素を含む顔料を含む塗膜が形成された積層体を準備する工程と、
（Ｂ）前記積層体を５００℃以上で加熱する工程を含む、
塗装鋼板の製造方法。 A method for producing a coated steel sheet having an inorganic coating film containing a pigment containing a metal element containing silicon as a main component on the steel sheet,
(A) preparing a laminate in which a coating film containing a pigment containing a silicone polyester resin and a metal element is formed on a steel sheet;
(B) including a step of heating the laminate at 500 ° C. or higher.
Manufacturing method of painted steel sheet.
Content of the said pigment in the coating film formed in the said laminated body is a manufacturing method of Claim 1 which is 2-50 mass% with respect to the said coating film.
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