JP2011052253A - Highly corrosion resistant surface-treated steel sheet - Google Patents
Highly corrosion resistant surface-treated steel sheet Download PDFInfo
- Publication number
- JP2011052253A JP2011052253A JP2009201105A JP2009201105A JP2011052253A JP 2011052253 A JP2011052253 A JP 2011052253A JP 2009201105 A JP2009201105 A JP 2009201105A JP 2009201105 A JP2009201105 A JP 2009201105A JP 2011052253 A JP2011052253 A JP 2011052253A
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- JP
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- Prior art keywords
- titanium
- resin
- steel sheet
- film
- mass
- 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
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- 239000010959 steel Substances 0.000 title claims abstract description 83
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- 230000007797 corrosion Effects 0.000 title claims abstract description 75
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- 239000011347 resin Substances 0.000 claims abstract description 81
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- 229910052719 titanium Inorganic materials 0.000 claims abstract description 77
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 76
- -1 phosphoric acid compound Chemical class 0.000 claims abstract description 69
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- 239000011701 zinc Substances 0.000 claims description 15
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- 229910052791 calcium Inorganic materials 0.000 description 8
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- 238000011156 evaluation Methods 0.000 description 8
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
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- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 6
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- 150000003754 zirconium Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、自動車、家電、建材などの用途に最適な高耐食性表面処理鋼板であって、特に、皮膜中に6価クロムを含まない環境調和型表面処理鋼板に関するものである。 The present invention relates to a highly corrosion-resistant surface-treated steel sheet that is optimal for applications such as automobiles, home appliances, and building materials, and particularly relates to an environment-friendly surface-treated steel sheet that does not contain hexavalent chromium in a coating film.
従来、自動車用鋼板、家電製品用鋼板、建材用鋼板には、亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に、耐食性(耐白錆性、耐赤錆性)を向上させる目的で、6価クロムを主要成分とした処理液によるクロメート処理が施された鋼板が幅広く用いられてきた。しかし、クロメート処理は公害規制物質である6価クロムを使用するため、最近ではその使用を規制する動きが広まっており、一方において、クロメート処理に代わる、6価クロムを全く用いない表面処理技術の開発が盛んに行われている。このうち、有機系化合物や有機樹脂を利用した技術が幾つか提案されており、例えば、以下のようなものを挙げることができる。 Conventionally, for steel sheets for automobiles, steel sheets for household appliances, and steel sheets for building materials, hexavalent chromium is used for the purpose of improving corrosion resistance (white rust resistance, red rust resistance) on the surface of zinc-plated steel sheets or aluminum-based plated steel sheets. Steel plates that have been subjected to chromate treatment with a treatment liquid containing as a main component have been widely used. However, since chromate treatment uses hexavalent chromium, which is a pollution-controlling substance, recently there has been widespread movement to regulate its use. Development is actively underway. Among these, several techniques using an organic compound or an organic resin have been proposed, and examples include the following.
(1)エポキシ樹脂に活性水素を有するヒドラジン誘導体を反応させた水性樹脂組成物とシランカップリング剤とリン酸などを含む表面処理組成物により皮膜を形成する技術(例えば、特許文献1など)
(2)下層として酸化物微粒子とリン酸と特定の金属を含有する複合酸化物皮膜を形成し、その上層に、エポキシ樹脂などの有機樹脂に活性水素を有するヒドラジン誘導体を反応させた樹脂組成物と特定の防錆添加剤を含む塗料組成物により有機皮膜を形成する技術(例えば、特許文献2など)
(3)チタン化合物、有機リン酸化合物、水溶性樹脂、バナジン酸塩およびジルコニウム塩からなる下層皮膜を形成し、その上層に耐指紋性皮膜を形成する技術(例えば、特許文献3など)
(4)チタン化合物、有機リン酸化合物、無機リン酸からなる塗布剤により金属基材表面に皮膜を形成する技術(特許文献4)
(1) Technology for forming a film from an aqueous resin composition obtained by reacting an epoxy resin with a hydrazine derivative having active hydrogen, a surface treatment composition containing a silane coupling agent, phosphoric acid, and the like (for example, Patent Document 1)
(2) A resin composition in which a composite oxide film containing fine oxide particles, phosphoric acid and a specific metal is formed as a lower layer, and an hydrazine derivative having active hydrogen is reacted with an organic resin such as an epoxy resin on the upper layer. Of forming an organic film with a coating composition containing a rust preventive additive and a specific anticorrosive additive (for example, Patent Document 2)
(3) Technology for forming a lower layer film composed of a titanium compound, an organic phosphate compound, a water-soluble resin, a vanadate and a zirconium salt, and forming a fingerprint-resistant film on the upper layer (for example, Patent Document 3)
(4) Technology for forming a film on the surface of a metal substrate with a coating agent comprising a titanium compound, an organic phosphoric acid compound, and inorganic phosphoric acid (Patent Document 4)
しかしながら、これらの従来技術には以下に述べるような問題点がある。
まず、上記(1)、(2)の技術は、エポキシ樹脂にヒドラジン誘導体を付与することによって緻密な有機高分子皮膜(バリアー層)を形成させて耐食性を付与している。さらに、ポリイソシアネートなどの硬化剤を用いて架橋することで、皮膜のバリアー性を強化している。しかしながら、このような有機高分子皮膜では、長期にわたってバリアー性を確保し、腐食を抑制することは困難である。
また、上記(3)の技術は、下層皮膜によりある程度の耐食性を得ることができるが、接着接合性が大きく劣るという問題があり、その剥離界面はめっき面と下層皮膜間であることが判った。
また、上記(4)の技術は、チタン含有水溶液と有機酸をベースとし、耐食性向上のために無機リン酸の添加を可能としたものであるが、特許文献4に開示されている添加量の範囲では接着接合性が大きく劣ることが判った。
However, these conventional techniques have the following problems.
First, the techniques (1) and (2) provide corrosion resistance by forming a dense organic polymer film (barrier layer) by applying a hydrazine derivative to an epoxy resin. Furthermore, the barrier property of the film is enhanced by crosslinking using a curing agent such as polyisocyanate. However, with such an organic polymer film, it is difficult to ensure barrier properties over a long period of time and suppress corrosion.
Moreover, although the technique of said (3) can obtain a certain amount of corrosion resistance by a lower layer film | membrane, there exists a problem that adhesive bondability is greatly inferior, and it turned out that the peeling interface is between a plating surface and a lower layer film | membrane. .
Further, the technique (4) is based on a titanium-containing aqueous solution and an organic acid, and enables the addition of inorganic phosphoric acid to improve the corrosion resistance. It was found that the adhesive bondability was greatly inferior in the range.
したがって本発明の目的は、このような従来技術の課題を解決し、皮膜中に6価クロムを含まない表面処理鋼板であって、ユーザーでアルカリ脱脂され或いは長期間にわたり腐食環境に曝された場合でも優れた平板および加工後の耐食性を有し、さらに接着接合性にも優れた表面処理鋼板を提供することにある。 Accordingly, an object of the present invention is to solve such a problem of the prior art, and is a surface-treated steel sheet that does not contain hexavalent chromium in the film, and is subjected to alkaline degreasing by a user or exposed to a corrosive environment for a long period of time. However, the object is to provide a surface-treated steel sheet having excellent flat plate and post-processing corrosion resistance, and also excellent adhesive bondability.
上記課題を解決するために本発明者らが鋭意検討を行った結果、亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に、特定のチタン系水性液に対して有機リン酸化合物と無機リン酸化合物を所定の割合で複合添加した表面処理組成物による皮膜を形成し、さらにその上層に、溶剤系有機樹脂に非クロム系防錆添加剤を配合した塗料組成物による上層皮膜を形成することにより、上記課題を解決できる非常に優れた耐食性と接着接合性が得られることを見出した。 As a result of intensive studies by the present inventors in order to solve the above problems, an organic phosphate compound and an inorganic phosphate compound with respect to a specific titanium-based aqueous liquid on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet By forming a film with a surface treatment composition that is added in a composite at a predetermined ratio, and further forming an upper film with a coating composition in which a non-chromium rust preventive additive is blended with a solvent-based organic resin, It has been found that very excellent corrosion resistance and adhesive bondability that can solve the above problems can be obtained.
本発明はこのような知見に基づきなされたもので、下記を要旨とするものである。
[1]亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に、加水分解性チタン化合物、加水分解性チタン化合物の低縮合物、水酸化チタン、水酸化チタンの低縮合物の中から選ばれる少なくとも1種のチタン化合物を過酸化水素水と混合して得られるチタン含有水性液(A)の固形分100質量部に対して、有機リン酸化合物(B)を1〜400質量部、無機リン酸化合物(C)を50〜150質量部含有する表面処理組成物(X)を塗布し、乾燥させることにより形成された皮膜厚が0.01〜1.0μmの表面処理皮膜を有し、その上層に、溶剤系有機樹脂(E)と非クロム系防錆添加剤(F)を含有する塗料組成物(Y)を塗布し、乾燥することにより形成された皮膜厚が0.1〜3.0μmの上層皮膜を有することを特徴とする高耐食性表面処理鋼板。
The present invention has been made on the basis of such knowledge and has the following gist.
[1] At least one selected from a hydrolyzable titanium compound, a hydrolyzable titanium compound low-condensate, titanium hydroxide, and a titanium hydroxide low-condensate on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet 1 to 400 parts by mass of an organic phosphoric acid compound (B) with respect to 100 parts by mass of a solid content of a titanium-containing aqueous liquid (A) obtained by mixing a seed titanium compound with hydrogen peroxide water, an inorganic phosphoric acid compound The surface treatment composition (X) containing 50 to 150 parts by mass of (C) is applied and dried to have a surface treatment film with a film thickness of 0.01 to 1.0 μm, and in the upper layer The coating thickness (Y) containing the solvent-based organic resin (E) and the non-chromium-based anticorrosive additive (F) is applied and dried, and the film thickness is 0.1 to 3.0 μm. It has an upper layer film. Corrosion-resistant surface-treated steel sheet.
[2]上記[1]の表面処理鋼板において、表面処理組成物(X)が、さらに、水溶性有機樹脂または/および水分散性有機樹脂(D)をチタン含有水性液(A)の固形分100質量部に対して固形分の割合で2000質量部以下含有することを特徴とする高耐食性表面処理鋼板。
[3]上記[1]または[2]の表面処理鋼板において、塗料組成物(Y)に含まれる溶剤系有機樹脂(G)が、エポキシ樹脂、変性エポキシ樹脂、ポリヒドロキシポリエーテル樹脂、ポリアルキレングリコール変性エポキシ樹脂、ウレタン変性エポキシ樹脂、これらのエポキシ樹脂をさらに変性させた樹脂、ポリエステル樹脂、ウレタン樹脂、シリコン樹脂、アクリル樹脂の中から選ばれる1種以上であることを特徴とする高耐食性表面処理鋼板。
[2] In the surface-treated steel sheet according to [1], the surface treatment composition (X) further contains a water-soluble organic resin and / or a water-dispersible organic resin (D) in a solid content of the titanium-containing aqueous liquid (A). A highly corrosion-resistant surface-treated steel sheet containing not more than 2,000 parts by mass of solids with respect to 100 parts by mass.
[3] In the surface-treated steel sheet according to [1] or [2], the solvent-based organic resin (G) contained in the coating composition (Y) is an epoxy resin, a modified epoxy resin, a polyhydroxy polyether resin, or a polyalkylene. A highly corrosion-resistant surface characterized by being one or more selected from glycol-modified epoxy resins, urethane-modified epoxy resins, resins obtained by further modifying these epoxy resins, polyester resins, urethane resins, silicone resins, and acrylic resins Treated steel sheet.
[4]上記[1]〜[3]のいずれかの表面処理鋼板において、塗料組成物(Y)が、下記(a)〜(e)の中から選ばれる1種以上の非クロム系防錆添加剤(F)を、塗料組成物中の樹脂固形分100質量部に対して1〜100質量部含有することを特徴とする高耐食性表面処理鋼板。
(a)酸化ケイ素
(b)カルシウム化合物
(c)リン酸化合物
(d)モリブデン酸化合物
(e)トリアゾール類、チオール類、チアジアゾール類、チアゾール類、チウラム類の中から選ばれる1種以上の有機化合物
[4] In the surface-treated steel sheet according to any one of [1] to [3], the coating composition (Y) is one or more non-chromium rust preventives selected from the following (a) to (e): A highly corrosion-resistant surface-treated steel sheet containing 1 to 100 parts by mass of the additive (F) with respect to 100 parts by mass of the resin solid content in the coating composition.
(A) silicon oxide (b) calcium compound (c) phosphoric acid compound (d) molybdate compound (e) one or more organic compounds selected from triazoles, thiols, thiadiazoles, thiazoles, thiurams
本発明の表面処理鋼板は、皮膜中に6価クロムを含有しないにもかかわらず、非常に優れた平板および加工後の耐食性を有し、しかも接着接合性に優れ、さらに溶接性、塗装性にも優れている。このため本発明の表面処理鋼板は、自動車用途に特に有用である。 Although the surface-treated steel sheet of the present invention does not contain hexavalent chromium in the film, it has a very excellent flat plate and corrosion resistance after processing, is excellent in adhesive bondability, and further has excellent weldability and paintability. Is also excellent. For this reason, the surface-treated steel sheet of the present invention is particularly useful for automobile applications.
以下、本発明の詳細とその限定理由を説明する。
本発明の表面処理鋼板のベースとなる亜鉛系めっき鋼板としては、例えば、亜鉛めっき鋼板、Zn−Ni合金めっき鋼板、Zn−Fe合金めっき鋼板(電気めっき鋼板、合金化溶融亜鉛めっき鋼板)、Zn−Cr合金めっき鋼板、Zn−Mn合金めっき鋼板、Zn−Co合金めっき鋼板、Zn−Co−Cr合金めっき鋼板、Zn−Cr−Ni合金めっき鋼板、Zn−Cr−Fe合金めっき鋼板、Zn−Al合金めっき鋼板(例えば、Zn−5%Al合金めっき鋼板、Zn−55%Al合金めっき鋼板)、Zn−Mg合金めっき鋼板、Zn−Al−Mg合金めっき鋼板(例えば、Zn−6%Al−3%Mg合金めっき鋼板、Zn−11%Al−3%Mg合金めっき鋼板)、さらには、これらのめっき鋼板のめっき皮膜中に金属酸化物、ポリマーなどを分散した亜鉛系複合めっき鋼板(例えば、Zn−SiO2分散めっき鋼板)などを用いることができる。
The details of the present invention and the reasons for limitation will be described below.
Examples of the galvanized steel sheet used as the base of the surface-treated steel sheet of the present invention include a galvanized steel sheet, a Zn—Ni alloy plated steel sheet, a Zn—Fe alloy plated steel sheet (electroplated steel sheet, galvannealed steel sheet), Zn -Cr alloy plated steel sheet, Zn-Mn alloy plated steel sheet, Zn-Co alloy plated steel sheet, Zn-Co-Cr alloy plated steel sheet, Zn-Cr-Ni alloy plated steel sheet, Zn-Cr-Fe alloy plated steel sheet, Zn-Al Alloy-plated steel sheet (for example, Zn-5% Al alloy-plated steel sheet, Zn-55% Al alloy-plated steel sheet), Zn-Mg alloy-plated steel sheet, Zn-Al-Mg alloy-plated steel sheet (for example, Zn-6% Al-3) % Mg alloy-plated steel sheet, Zn-11% Al-3% Mg alloy-plated steel sheet), and metal oxides and polymers in the plating film of these plated steel sheets Etc. can be used as dispersed zinc composite-plated steel sheet (for example, Zn-SiO 2 dispersion plating steel plate).
また、上記のようなめっきのうち、同種または異種のものを2層以上めっきした複層めっき鋼板を用いることもできる。
また、本発明の表面処理鋼板のベースとなるアルミニウム系めっき鋼板としては、アルミニウムめっき鋼板、Al−Si合金めっき鋼板などを用いることができる。
また、めっき鋼板としては、鋼板面に予めNiなどの薄目付のめっきを施し、その上に上記のような各種めっきを施したものであってもよい。
めっき方法としては、電解法(水溶液中での電解または非水溶媒中での電解)、溶融法、気相法等、実施可能ないずれの方法も採用することができる。
さらに、めっきの黒変を防止する目的で、めっき皮膜中にNi、Co、Feの1種以上の微量元素を1〜2000ppm程度析出させたり、或いはめっき皮膜表面にNi、Co、Feの1種以上を含むアルカリ性水溶液または酸性水溶液による表面調整処理を施し、これら元素を析出させるようにしてもよい。
Moreover, the multilayer plating steel plate which plated two or more layers of the same kind or different kind among the above plating can also be used.
Moreover, as an aluminum system plated steel plate used as the base of the surface treatment steel plate of this invention, an aluminum plating steel plate, an Al-Si alloy plating steel plate, etc. can be used.
Moreover, as a plated steel plate, the steel plate surface may be plated in advance with thinning such as Ni, and the above-described various plating may be performed thereon.
As a plating method, any feasible method such as an electrolytic method (electrolysis in an aqueous solution or electrolysis in a nonaqueous solvent), a melting method, a gas phase method, or the like can be employed.
Furthermore, in order to prevent blackening of the plating, about 1 to 2000 ppm of one or more trace elements of Ni, Co, and Fe are deposited in the plating film, or one of Ni, Co, and Fe is deposited on the surface of the plating film. You may make it precipitate these elements by performing the surface adjustment process by the alkaline aqueous solution or acidic aqueous solution containing the above.
次に、上記亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に、第一層皮膜として形成される表面処理皮膜およびこの皮膜形成用の表面処理組成物について説明する。
本発明の表面処理鋼板において、亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に形成される表面処理皮膜は、特定のチタン含有水性液(A)、有機リン酸化合物(B)および無機リン酸化合物(C)を必須成分として含有する表面処理組成物(X)を塗布し、乾燥させることにより形成されるものである。この表面処理皮膜はクロム(但し、不可避不純物としてのクロムを除く)を含まない。
Next, the surface treatment film formed as the first layer film and the surface treatment composition for forming this film on the surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet will be described.
In the surface-treated steel sheet of the present invention, the surface-treated film formed on the surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet is composed of a specific titanium-containing aqueous liquid (A), an organic phosphate compound (B), and an inorganic phosphate compound. The surface treatment composition (X) containing (C) as an essential component is applied and dried. This surface treatment film does not contain chromium (except for chromium as an inevitable impurity).
このような表面処理皮膜は、高度のバリアー性と下地金属との高い密着性を有する。その理由は必ずしも明らかではないが、特定のチタン系水性液に所定量の有機リン酸化合物および無機リン酸化合物を組合わせて複合添加した処理液の塗布・乾燥によってめっき表面に皮膜が形成される過程で、無機リン酸化合物によりめっき表面のエッチングがなされ、これにより溶出した金属イオンと処理液に含まれる金属イオンとリン酸による複合塩の形成と酸化チタン系の緻密な皮膜成分の析出により、接着接合性に優れるとともに、バリアー性が高く、腐食抑制能の良好な皮膜が形成されるためであると考えられる。 Such a surface treatment film has high barrier properties and high adhesion to the base metal. The reason for this is not necessarily clear, but a film is formed on the plating surface by applying and drying a treatment solution in which a specific amount of an organic phosphate compound and an inorganic phosphate compound are combined and added to a specific aqueous titanium solution. In the process, the plating surface is etched with an inorganic phosphate compound, and by this formation of a complex salt of metal ions eluted and metal ions contained in the treatment liquid and phosphoric acid and precipitation of a dense titanium oxide-based film component, This is presumably because a film having excellent adhesion and bonding properties, high barrier properties, and good corrosion-inhibiting ability is formed.
上記チタン含有水性液(A)は、加水分解性チタン化合物、加水分解性チタン化合物の低縮合物、水酸化チタン、水酸化チタンの低縮合物の中から選ばれる少なくとも1種のチタン化合物と過酸化水素水とを混合して得られるチタンを含む水性液である。
上記加水分解性チタン化合物は、チタンに直接結合する加水分解性基を有するチタン化合物であって、水、水蒸気などの水分と反応することにより水酸化チタンを生成するものである。また、加水分解性チタン化合物は、チタンに結合する基の全てが加水分解性基であるものでもよいし、チタンに結合する基の一部が加水分解性基であるものでもよい。
上記加水分解性基としては、上記したように水分と反応することにより水酸化チタンを生成させるものであれば特に制限はないが、例えば、低級アルコキシル基やチタンと塩を形成する基(例えば、塩素などのハロゲン原子、水素原子、硫酸イオンなど)などが挙げられる。
The titanium-containing aqueous liquid (A) contains at least one titanium compound selected from hydrolyzable titanium compounds, hydrolyzable titanium compound low condensates, titanium hydroxide, and titanium hydroxide low condensates. It is an aqueous liquid containing titanium obtained by mixing with hydrogen oxide water.
The hydrolyzable titanium compound is a titanium compound having a hydrolyzable group directly bonded to titanium, and generates titanium hydroxide by reacting with water such as water or water vapor. The hydrolyzable titanium compound may be one in which all of the groups bonded to titanium are hydrolyzable groups, or a part of the groups bonded to titanium may be hydrolyzable groups.
The hydrolyzable group is not particularly limited as long as it generates titanium hydroxide by reacting with moisture as described above. For example, a lower alkoxyl group or a group that forms a salt with titanium (for example, Halogen atoms such as chlorine, hydrogen atoms, sulfate ions, etc.).
加水分解性基として低級アルコキシル基を含有する加水分解性チタン化合物としては、特に、一般式Ti(OR)4(式中、Rは同一若しくは異なる炭素数1〜5のアルキル基を示す)で示されるテトラアルコキシチタンが好ましい。炭素数1〜5のアルキル基としては、例えば、メチル基、エチル基、n−プロピル基、iso−プロピル基、n−ブチル基、iso−ブチル基、sec−ブチル基、tert−ブチル基などが挙げられる。
加水分解性基として、チタンと塩を形成する基を有する加水分解性チタン化合物としては、塩化チタン、硫酸チタンなどが代表的なものとして挙げられる。
The hydrolyzable titanium compound containing a lower alkoxyl group as the hydrolyzable group is particularly represented by the general formula Ti (OR) 4 (wherein R represents the same or different alkyl groups having 1 to 5 carbon atoms). Tetraalkoxy titanium is preferred. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Can be mentioned.
Typical examples of the hydrolyzable titanium compound having a group capable of forming a salt with titanium as a hydrolyzable group include titanium chloride and titanium sulfate.
また、加水分解性チタン化合物の低縮合物は、上記した加水分解性チタン化合物どうしの低縮合物である。この低縮合物は、チタンに結合する基の全てが加水分解性基であるものでもよいし、チタンに結合する基の一部が加水分解性であるものでもよい。
加水分解性基がチタンと塩を形成する基である加水分解性チタン化合物(例えば、塩化チタン、硫酸チタンなど)については、その加水分解性チタン化合物の水溶液とアンモニアや苛性ソーダなどのアルカリ溶液との反応により得られるオルトチタン酸(水酸化チタンゲル)も低縮合物として使用できる。
Moreover, the low condensate of a hydrolysable titanium compound is a low condensate of the above-mentioned hydrolysable titanium compounds. This low condensate may be one in which all of the groups bonded to titanium are hydrolyzable groups, or a part of the groups bonded to titanium may be hydrolysable.
For hydrolyzable titanium compounds whose hydrolyzable group forms a salt with titanium (for example, titanium chloride, titanium sulfate, etc.), an aqueous solution of the hydrolyzable titanium compound and an alkaline solution such as ammonia or caustic soda Orthotitanic acid (titanium hydroxide gel) obtained by the reaction can also be used as a low condensate.
加水分解性チタン化合物の低縮合物及び水酸化チタンの低縮合物としては、縮合度が2〜30の化合物が使用可能であり、特に縮合度が2〜10の化合物を使用することが好ましい。縮合度が30を超えると、過酸化水素と混合した際に白色沈殿を生じ、安定なチタン含有水性液が得られない。
以上挙げた加水分解性チタン化合物、加水分解性チタン化合物の低縮合物、水酸化チタン、水酸化チタンの低縮合物は、1種または2種以上を使用できるが、そのなかでも、上述した一般式で示される加水分解性チタン化合物であるテトラアルコキシチタンが特に好ましい。
As the low condensate of the hydrolyzable titanium compound and the low condensate of titanium hydroxide, a compound having a condensation degree of 2 to 30 can be used, and a compound having a condensation degree of 2 to 10 is particularly preferable. When the condensation degree exceeds 30, a white precipitate is formed when mixed with hydrogen peroxide, and a stable titanium-containing aqueous liquid cannot be obtained.
The hydrolyzable titanium compounds listed above, low-condensates of hydrolyzable titanium compounds, titanium hydroxide, and low-condensates of titanium hydroxide can be used alone or in combination of two or more thereof. Tetraalkoxy titanium which is a hydrolyzable titanium compound represented by the formula is particularly preferable.
チタン含有水性液(A)としては、上記したチタン化合物と過酸化水素水を混合することにより得られるチタンを含む水性液であれば、従来公知のものを特に制限なしに使用することができる。具体的には、下記のものを挙げることができる。
(i)含水酸化チタンのゲルまたはゾルに過酸化水素水を添加して得られるチタニルイオン過酸化水素錯体またはチタン酸(ペルオキソチタン水和物)水溶液(特開昭63−35419号公報、特開平1−224220号公報参照)。
As the titanium-containing aqueous liquid (A), any conventionally known liquid can be used without particular limitation as long as it is an aqueous liquid containing titanium obtained by mixing the above-described titanium compound and hydrogen peroxide solution. Specifically, the following can be mentioned.
(I) A titanyl ion hydrogen peroxide complex or titanic acid (peroxotitanium hydrate) aqueous solution obtained by adding hydrogen peroxide to a hydrous titanium oxide gel or sol (JP-A 63-35419, JP 1-2224220 gazette).
(ii)塩化チタンや硫酸チタンの水溶液と塩基性溶液から製造した水酸化チタンゲルに過酸化水素水を作用させ、合成することで得られるチタニア膜形成用液体(特開平9−71418号公報、特開平10−67516号公報参照)。
このチタニア膜形成用液体を得る場合、チタンと塩を形成する基を有する塩化チタンや硫酸チタンの水溶液とアンモニアや苛性ソーダなどのアルカリ溶液とを反応させることによりオルトチタン酸と呼ばれる水酸化チタンゲルを沈殿させる。次いで、水を用いたデカンテーションによって水酸化チタンゲルを分離し、良く水洗し、さらに過酸化水素水を加え、余分な過酸化水素を分解除去することにより、黄色透明粘性液体を得ることができる。
(Ii) A liquid for forming a titania film obtained by synthesizing a titanium hydroxide gel produced from an aqueous solution of titanium chloride or titanium sulfate and a basic solution with a hydrogen peroxide solution (Japanese Patent Laid-Open No. 9-71418, (See Kaihei 10-67516).
When this titania film forming liquid is obtained, titanium hydroxide gel called ortho titanic acid is precipitated by reacting an aqueous solution of titanium chloride or titanium sulfate having a salt forming group with titanium and an alkaline solution such as ammonia or caustic soda. Let Subsequently, the titanium hydroxide gel is separated by decantation using water, washed well with water, further added with hydrogen peroxide water, and excess hydrogen peroxide is decomposed and removed, whereby a yellow transparent viscous liquid can be obtained.
沈殿した上記オルトチタン酸は、OHどうしの重合や水素結合によって高分子化したゲル状態にあり、そのままではチタンを含む水性液としては使用できない。このゲルに過酸化水素水を添加するとOHの一部が過酸化状態になり、ペルオキソチタン酸イオンとして溶解或いは高分子鎖が低分子に分断された一種のゾル状態になり、余分な過酸化水素は水と酸素になって分解し、無機膜形成用のチタンを含む水性液として使用できるようになる。
このゾルはチタン原子以外に酸素原子と水素原子しか含まないので、乾燥や焼成によって酸化チタンに変化する場合、水と酸素しか発生しないため、ゾルゲル法や硫酸塩などの熱分解に必要な炭素成分やハロゲン成分の除去が必要でなく、低温でも比較的密度の高い酸化チタン膜を形成することができる。
The precipitated orthotitanic acid is in a gel state polymerized by polymerization of OH or hydrogen bonds, and cannot be used as an aqueous liquid containing titanium as it is. When hydrogen peroxide solution is added to this gel, a part of OH is in a peroxidized state, dissolved as a peroxotitanate ion or in a kind of sol state in which the polymer chain is divided into low molecules, and excess hydrogen peroxide Is decomposed into water and oxygen, and can be used as an aqueous liquid containing titanium for forming an inorganic film.
Since this sol contains only oxygen and hydrogen atoms in addition to titanium atoms, when it is changed to titanium oxide by drying or firing, only water and oxygen are generated, so carbon components necessary for thermal decomposition such as sol-gel method and sulfate Further, it is not necessary to remove the halogen component, and a titanium oxide film having a relatively high density can be formed even at a low temperature.
(iii)塩化チタンや硫酸チタンの無機チタン化合物水溶液に過酸化水素を加えてぺルオキソチタン水和物を生成させた後に、塩基性物質を添加して得られた溶液を放置または加熱することによってペルオキソチタン水和物重合体の沈殿物を生成させ、次いで、少なくともチタン含有原料溶液に由来する水以外の溶解成分を除去した後に過酸化水素を作用させて得られるチタン酸化物形成用溶液(特開2000−247638号公報、特開2000−247639号公報参照)。 (Iii) Hydrogen peroxide is added to an aqueous solution of an inorganic titanium compound such as titanium chloride or titanium sulfate to form peroxotitanium hydrate, and then the resulting solution obtained by adding a basic substance is allowed to stand or be heated. A titanium oxide forming solution obtained by forming a precipitate of a titanium hydrate polymer, and then removing hydrogen and other dissolved components derived from at least a titanium-containing raw material solution (Japanese Patent Application Laid-Open 2000-247638, JP-A-2000-247639).
チタン化合物として加水分解性チタン化合物および/またはその低縮合物(以下、説明の便宜上「加水分解性チタン化合物a」という)を用いるチタン含有水性液(A)は、加水分解性チタン化合物aを過酸化水素水と反応温度1〜70℃で10分間〜20時間程度反応させることにより得ることができる。
この加水分解性チタン化合物aを用いたチタン含有水性液(A)は、加水分解性チタン化合物aと過酸化水素水とを反応させることにより、加水分解性チタン化合物aが水で加水分解されて水酸基含有チタン化合物を生成し、次いで、この水酸基含有チタン化合物に過酸化水素が配位するものと考えられ、この加水分解反応及び過酸化水素による配位が同時近くに起こることにより得られたものであり、室温域での安定性が極めて高く、長期の保存に耐えるキレート液を生成する。従来の製法で用いられる水酸化チタンゲルは、Ti−O−Ti結合により部分的に三次元化しており、このゲルと過酸化水素水を反応させたチタン含有水性液(A)とは組成及び安定性が本質的に異なる。
The titanium-containing aqueous liquid (A) using a hydrolyzable titanium compound and / or a low condensate thereof as a titanium compound (hereinafter referred to as “hydrolyzable titanium compound a” for convenience of explanation) contains hydrolyzable titanium compound a. It can be obtained by reacting with hydrogen oxide water at a reaction temperature of 1 to 70 ° C. for about 10 minutes to 20 hours.
In the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a, the hydrolyzable titanium compound a is hydrolyzed with water by reacting the hydrolyzable titanium compound a with hydrogen peroxide. A product obtained by producing a hydroxyl group-containing titanium compound and then coordinating hydrogen peroxide to this hydroxyl group-containing titanium compound, and this hydrolysis reaction and coordination by hydrogen peroxide occur simultaneously. It produces a chelate solution that is extremely stable at room temperature and can withstand long-term storage. The titanium hydroxide gel used in the conventional manufacturing method is partially three-dimensionalized by Ti—O—Ti bonds, and the titanium-containing aqueous liquid (A) obtained by reacting this gel with hydrogen peroxide is composition and stable. Sex is essentially different.
また、加水分解性チタン化合物aを用いたチタン含有水性液(A)を80℃以上で加熱処理またはオートクレーブ処理すると、結晶化した酸化チタンの超微粒子を含む酸化チタン分散液が得られる。前記加熱処理またはオートクレーブ処理が80℃未満では、酸化チタンの結晶化が十分に進まない。このようにして製造された酸化チタン分散液は、酸化チタン超微粒子の平均粒子径が10nm以下、好ましくは1〜6nm程度が望ましい。酸化チタン超微粒子の平均粒子径が10nmより大きくなると造膜性が低下する(塗布後乾燥して皮膜とした場合、膜厚1μm以上でワレを生じる)ので好ましくない。この酸化チタン分散液の外観は半透明状のものである。このような酸化チタン分散液も、チタン含有水性液(A)として使用することができる。 Further, when the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a is heated or autoclaved at 80 ° C. or higher, a titanium oxide dispersion liquid containing ultrafine particles of crystallized titanium oxide is obtained. When the heat treatment or autoclave treatment is less than 80 ° C., crystallization of titanium oxide does not proceed sufficiently. The titanium oxide dispersion thus produced has an average particle diameter of titanium oxide ultrafine particles of 10 nm or less, preferably about 1 to 6 nm. When the average particle diameter of the titanium oxide ultrafine particles is larger than 10 nm, the film forming property is deteriorated (when the film is dried after coating to form a film, cracking occurs at a film thickness of 1 μm or more), which is not preferable. The appearance of this titanium oxide dispersion is translucent. Such a titanium oxide dispersion can also be used as the titanium-containing aqueous liquid (A).
加水分解性チタン化合物aを用いたチタン含有水性液(A)を含む表面処理組成物(X0)を、めっき鋼板表面に塗布・乾燥(例えば、低温で加熱乾燥)することにより、それ自体で付着性に優れた緻密な酸化チタン含有皮膜(表面処理皮膜)を形成することができる。
表面処理組成物(X0)を塗布した後の加熱温度としては、例えば200℃以下、特に150℃以下が好ましく、このような温度で加熱乾燥することにより、水酸基を若干含む非晶質(アモルファス)の酸化チタン含有皮膜が形成できる。
また、上記したような80℃以上の加熱処理またはオートクレーブ処理を経て得られた酸化チタン分散液をチタン含有水性液(A)として用いた場合、表面処理組成物(X0)を塗布するだけで結晶性の酸化チタン含有皮膜が形成できるため、加熱処理できない材料のコーティング材として有用である。
The surface treatment composition (X 0 ) containing the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a is applied to the surface of the plated steel sheet and dried (for example, heat-dried at a low temperature), so that A dense titanium oxide-containing film (surface treatment film) having excellent adhesion can be formed.
The heating temperature after applying the surface treatment composition (X 0 ) is, for example, preferably 200 ° C. or lower, particularly preferably 150 ° C. or lower. ) Of titanium oxide-containing film can be formed.
Moreover, when the titanium oxide dispersion obtained through the heat treatment or autoclave treatment as described above at 80 ° C. or more is used as the titanium-containing aqueous liquid (A), only the surface treatment composition (X 0 ) is applied. Since a crystalline titanium oxide-containing film can be formed, it is useful as a coating material for materials that cannot be heat-treated.
また、チタン含有水性液(A)としては、酸化チタンゾルの存在下で、加水分解性チタン化合物aと過酸化水素水とを反応させて得られるチタン含有水性液(A1)を使用することもできる。
前記酸化チタンゾルは、無定型チタニア微粒子または/およびアナタース型チタニア微粒子が水(必要に応じて、例えばアルコール系、アルコールエーテル系などの水性有機溶剤を添加してもよい)に分散したゾルである。この酸化チタンゾルとしては、従来公知のものを使用することができ、例えば、(i)硫酸チタンや硫酸チタニルなどの含チタン溶液を加水分解して得られる酸化チタン凝集物、(ii)チタンアルコキシドなどの有機チタン化合物を加水分解して得られる酸化チタン凝集物、(iii)四塩化チタンなどのハロゲン化チタン溶液を加水分解または中和して得られる酸化チタン凝集物、などの酸化チタン凝集物を水に分散した無定型チタニアゾル、或いは前記酸化チタン凝集物を焼成してアナタース型チタン微粒子とし、このものを水に分散したゾルを使用することができる。
In addition, as the titanium-containing aqueous liquid (A), a titanium-containing aqueous liquid (A1) obtained by reacting the hydrolyzable titanium compound a with hydrogen peroxide in the presence of a titanium oxide sol can also be used. .
The titanium oxide sol is a sol in which amorphous titania fine particles and / or anatase type titania fine particles are dispersed in water (for example, an aqueous organic solvent such as an alcohol or alcohol ether may be added if necessary). As this titanium oxide sol, conventionally known ones can be used. For example, (i) titanium oxide aggregates obtained by hydrolyzing a titanium-containing solution such as titanium sulfate or titanyl sulfate, (ii) titanium alkoxide, etc. Titanium oxide aggregates obtained by hydrolyzing organic titanium compounds of (ii), titanium oxide aggregates obtained by hydrolyzing or neutralizing titanium halide solutions such as titanium tetrachloride, etc. An amorphous titania sol dispersed in water, or a sol in which the titanium oxide aggregates are calcined to form anatase-type titanium fine particles and this is dispersed in water can be used.
前記無定形チタニアの焼成では、少なくともアナタースの結晶化温度以上の温度、例えば、400℃〜500℃以上の温度で焼成すれば、無定形チタニアをアナタース型チタニアに変換させることができる。この酸化チタンの水性ゾルとしては、例えば、TKS−201(商品名,テイカ社製,アナタース型結晶形,平均粒子径6nm)、TA−15(商品名,日産化学社製,アナタース型結晶形)、STS−11(商品名,石原産業社製,アナタース型結晶形)などが挙げられる。
チタン含有水性液(A1)において、上記酸化チタンゾルxとチタン過酸化水素反応物y(加水分解性チタン化合物aと過酸化水素水との反応生成物)との質量比率x/yは、1/99〜99/1、好ましくは約10/90〜90/10の範囲が適当である。質量比率x/yが1/99未満では、安定性、光反応性などの点において酸化チタンゾルを添加した効果が十分に得られず、一方、99/1を超えると造膜性が劣るので好ましくない。
In the firing of the amorphous titania, the amorphous titania can be converted into anatase titania by firing at a temperature at least higher than the crystallization temperature of anatase, for example, 400 ° C. to 500 ° C. or more. Examples of the aqueous sol of titanium oxide include, for example, TKS-201 (trade name, manufactured by Teika, anatase crystal form, average particle diameter 6 nm), TA-15 (trade name, manufactured by Nissan Chemical Co., anatase crystal form). STS-11 (trade name, manufactured by Ishihara Sangyo Co., Ltd., anatase crystal form).
In the titanium-containing aqueous liquid (A1), the mass ratio x / y between the titanium oxide sol x and the titanium hydrogen peroxide reactant y (reaction product of the hydrolyzable titanium compound a and hydrogen peroxide solution) is 1 / A range of 99 to 99/1, preferably about 10/90 to 90/10 is suitable. If the mass ratio x / y is less than 1/99, the effect of adding the titanium oxide sol cannot be sufficiently obtained in terms of stability, photoreactivity, etc. On the other hand, if it exceeds 99/1, the film forming property is inferior. Absent.
チタン含有水性液(A1)は、酸化チタンゾルの存在下で加水分解性チタン化合物aを過酸化水素水と反応温度1〜70℃で10分間〜20時間程度反応させることにより得ることができる。
チタン含有水性液(A1)の生成形態やその特性は、さきに述べた加水分解性チタン化合物aを用いたチタン含有水性液(A)と同様であるが、特に、酸化チタンゾルを使用することにより、合成時に一部縮合反応が起きて増粘するのが抑えられる。その理由は、縮合反応物が酸化チタンゾルの表面に吸着され、溶液状態での高分子化が抑えられるためであると考えられる。
また、チタン含有水性液(A1)を80℃以上で加熱処理またはオートクレーブ処理すると、結晶化した酸化チタンの超微粒子を含む酸化チタン分散液が得られる。この酸化チタン分散液を得るための温度条件、結晶化した酸化チタン超微粒子の粒子径、分散液の外観なども、さきに述べた加水分解性チタン化合物aを用いたチタン含有水性液(A)と同様である。このような酸化チタン分散液も、チタン含有水性液(A1)として使用することができる。
The titanium-containing aqueous liquid (A1) can be obtained by reacting the hydrolyzable titanium compound a with hydrogen peroxide at a reaction temperature of 1 to 70 ° C. for about 10 minutes to 20 hours in the presence of a titanium oxide sol.
The production form and characteristics of the titanium-containing aqueous liquid (A1) are the same as those of the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a described above, but in particular, by using a titanium oxide sol. , It is possible to suppress a partial condensation reaction during the synthesis to increase the viscosity. The reason is considered to be that the condensation reaction product is adsorbed on the surface of the titanium oxide sol, and polymerization in a solution state is suppressed.
Further, when the titanium-containing aqueous liquid (A1) is subjected to a heat treatment or autoclave treatment at 80 ° C. or higher, a titanium oxide dispersion containing ultrafine particles of crystallized titanium oxide is obtained. The titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a described above also describes the temperature conditions for obtaining this titanium oxide dispersion, the particle diameter of the crystallized titanium oxide ultrafine particles, the appearance of the dispersion, etc. It is the same. Such a titanium oxide dispersion can also be used as the titanium-containing aqueous liquid (A1).
さきに述べた加水分解性チタン化合物aを用いたチタン含有水性液(A)と同様、チタン含有水性液(A1)を含む表面処理組成物(X0)を、めっき鋼板表面に塗布・乾燥(例えば、低温で加熱乾燥)することにより、それ自体で付着性に優れた緻密な酸化チタン含有皮膜(表面処理皮膜)を形成することができる。
表面処理組成物(X0)を塗布した後の加熱温度としては、例えば200℃以下、特に150℃以下が好ましく、このような温度で加熱乾燥することにより、水酸基を若干含むアナタース型の酸化チタン含有皮膜が形成できる。
以上述べたように、チタン含有水性液(A)の中でも、加水分解性チタン化合物aを用いたチタン含有水性液(A)やチタン含有水性液(A1)は、貯蔵安定性、耐食性などに優れた性能を有するので、本発明ではこれらを使用することが特に好ましい。
Like the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a described above, the surface treatment composition (X 0 ) containing the titanium-containing aqueous liquid (A1) is applied to the surface of the plated steel sheet and dried ( For example, by performing heat drying at a low temperature, a dense titanium oxide-containing film (surface treatment film) having excellent adhesion can be formed.
The heating temperature after applying the surface treatment composition (X 0 ) is, for example, preferably 200 ° C. or less, particularly preferably 150 ° C. or less. By heating and drying at such a temperature, anatase-type titanium oxide containing some hydroxyl groups. A contained film can be formed.
As described above, of the titanium-containing aqueous liquid (A), the titanium-containing aqueous liquid (A) and the titanium-containing aqueous liquid (A1) using the hydrolyzable titanium compound a are excellent in storage stability, corrosion resistance, and the like. It is particularly preferable to use these in the present invention.
加水分解性チタン化合物、加水分解性チタン化合物の低縮合物、水酸化チタン、水酸化チタンの低縮合物の中から選ばれる少なくとも1種のチタン化合物に対する過酸化水素水の配合割合は、チタン化合物10質量部に対して過酸化水素換算で0.1〜100質量部、望ましく1〜20質量部とすることが好ましい。過酸化水素水の配合割合が過酸化水素換算で0.1質量部未満では、キレート形成が十分でないため白濁沈殿が生じてしまう。一方、100質量部を超えると未反応の過酸化水素が残存し易く、貯蔵中に危険な活性酸素を放出するので好ましくない。 The compounding ratio of hydrogen peroxide water to at least one titanium compound selected from hydrolyzable titanium compounds, hydrolyzable titanium compound low condensates, titanium hydroxide, titanium hydroxide low condensates is titanium compounds It is preferably 0.1 to 100 parts by mass, preferably 1 to 20 parts by mass in terms of hydrogen peroxide with respect to 10 parts by mass. If the blending ratio of the hydrogen peroxide solution is less than 0.1 parts by mass in terms of hydrogen peroxide, chelate formation is not sufficient and white turbid precipitation occurs. On the other hand, if it exceeds 100 parts by mass, unreacted hydrogen peroxide tends to remain, and dangerous active oxygen is released during storage, which is not preferable.
過酸化水素水の過酸化水素濃度は特に限定されないが、3〜30質量%程度であることが、取り扱いやすさ、塗装作業性に関係する生成液の固形分の点で好ましい。
チタン含有水性液(A)には、必要に応じて、他のゾルや顔料を添加分散させることもできる。例えば、添加物としては、市販の酸化チタンゾルや酸化チタン粉末、マイカ、タルク、シリカ、バリタ、クレーなどが挙げられ、これらの1種以上を添加することができる。
表面処理組成物(X)中でのチタン含有水性液(A)の含有量は、固形分で1〜100g/L、好ましくは5〜50g/Lとすることが、処理液の安定性などの点から好ましい。
The hydrogen peroxide concentration of the hydrogen peroxide solution is not particularly limited, but it is preferably about 3 to 30% by mass from the viewpoint of ease of handling and the solid content of the product liquid related to coating workability.
Other sols and pigments can be added and dispersed in the titanium-containing aqueous liquid (A) as necessary. Examples of the additive include commercially available titanium oxide sol, titanium oxide powder, mica, talc, silica, barita, clay, and the like, and one or more of these can be added.
The content of the titanium-containing aqueous liquid (A) in the surface treatment composition (X) is 1 to 100 g / L, preferably 5 to 50 g / L in terms of solid content. It is preferable from the point.
上記有機リン酸化合物(B)としては、例えば、1−ヒドロキシメタン−1,1−ジホスホン酸、1−ヒドロキシエタン−1,1−ジホスホン酸、1−ヒドロキシプロパン−1,1−ジホスホン酸などのヒドロキシル基含有有機亜リン酸;2−ヒドロキシホスホノ酢酸、2−ホスホノブタン−1,2,4−トリカルボン酸などのカルボキシル基含有有機亜リン酸、及びこれらの塩などが好適なものとして挙げられ、これらの1種または2種以上を用いることができる。 Examples of the organic phosphate compound (B) include 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid, and the like. Suitable examples include hydroxyl group-containing organic phosphorous acid; carboxyl group-containing organic phosphorous acid such as 2-hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and salts thereof. These 1 type (s) or 2 or more types can be used.
有機リン酸化合物(B)は、チタン含有水性液(A)の貯蔵安定性を向上させる効果が大きいが、なかでも、1−ヒドロキシエタン−1,1−ジホスホン酸はその効果が特に大きいことから、これを使用するのが特に好ましい。
有機リン酸化合物(B)の配合量は、チタン含有水性液(A)の固形分100質量部に対して固形分の割合で1〜400質量部、特に20〜300質量部とすることが、耐水付着性などの点から好ましい。有機リン酸化合物(B)の配合量が、チタン含有水性液(A)の固形分100質量部に対して1質量部未満では貯蔵安定性が劣り、一方、400質量部を超えると造膜性が低下し、耐水付着性や耐食性などが劣るため好ましくない。
The organic phosphoric acid compound (B) has a large effect of improving the storage stability of the titanium-containing aqueous liquid (A). Among them, 1-hydroxyethane-1,1-diphosphonic acid has a particularly large effect. It is particularly preferred to use this.
The compounding amount of the organic phosphoric acid compound (B) is 1 to 400 parts by mass, particularly 20 to 300 parts by mass in terms of the solid content with respect to 100 mass parts of the solid content of the titanium-containing aqueous liquid (A). This is preferable from the viewpoint of water resistance adhesion. If the amount of the organic phosphoric acid compound (B) is less than 1 part by mass relative to 100 parts by mass of the solid content of the titanium-containing aqueous liquid (A), the storage stability is inferior. This is not preferable because water resistance and corrosion resistance are poor.
上記無機リン酸化合物(C)は、めっき皮膜表面をエッチング(反応)することで密着性を向上させるものであり、さらに溶出した金属イオンとリン酸やチタン化合物等との複合化した皮膜を形成することで、緻密なバリアー皮膜を形成するものである。
無機リン酸化合物(C)としては、例えば、亜リン酸、強リン酸、三リン酸、次亜リン酸、次リン酸、トリメタリン酸、二亜リン酸、二リン酸、ピロ亜リン酸、ピロリン酸、メタ亜リン酸、メタリン酸、オルトリン酸などのモノリン酸類、モノリン酸類の誘導体および塩類、トリポリリン酸、テトラリン酸、ヘキサリン酸などの縮合リン酸類、これら縮合リン酸類の誘導体および塩類等を挙げることができ、これらの1種または2種以上を用いることができる。但し、めっき表面との反応性の点からは、上記リン酸類の誘導体および塩類よりも、上記リン酸類の方が好ましい。また、無機リン酸化合物としては、水に溶解性のあるものが好ましい。特に、オルトリン酸、ピロリン酸、トリポリリン酸、テトラリン酸、メタリン酸、ヘキサメタリン酸などを使用することが、処理液の貯蔵安定性、耐食性および接着接合性の観点から好ましい。
無機リン酸化合物(C)の配合量は、チタン含有水性液(A)の固形分100質量部に対して固形分の割合で50〜150質量部、特に70〜120質量部とすることが、接着接合性の点から好ましい。無機リン酸化合物(C)の配合量が、チタン含有水性液(A)の固形分100質量部に対して50質量部未満では接着接合性が劣り、一方、150質量部を超えると接着接合性が劣り、さらには耐食性,塗装性も劣化するため好ましくない。
The inorganic phosphate compound (C) improves adhesion by etching (reacting) the surface of the plating film, and forms a composite film of the eluted metal ions and phosphoric acid, titanium compounds, etc. By doing so, a dense barrier film is formed.
Examples of the inorganic phosphoric acid compound (C) include phosphorous acid, strong phosphoric acid, triphosphoric acid, hypophosphorous acid, hypophosphoric acid, trimetaphosphoric acid, diphosphorous acid, diphosphoric acid, pyrophosphorous acid, Examples include monophosphoric acids such as pyrophosphoric acid, metaphosphorous acid, metaphosphoric acid and orthophosphoric acid, derivatives and salts of monophosphoric acids, condensed phosphoric acids such as tripolyphosphoric acid, tetraphosphoric acid and hexaphosphoric acid, derivatives and salts of these condensed phosphoric acids, etc. 1 type, or 2 or more types of these can be used. However, from the viewpoint of reactivity with the plating surface, the above phosphoric acids are preferable to the derivatives and salts of the above phosphoric acids. Moreover, as an inorganic phosphoric acid compound, what is soluble in water is preferable. In particular, it is preferable to use orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, metaphosphoric acid, hexametaphosphoric acid and the like from the viewpoints of storage stability, corrosion resistance, and adhesive bondability of the treatment liquid.
The compounding amount of the inorganic phosphoric acid compound (C) is 50 to 150 parts by mass, particularly 70 to 120 parts by mass, based on 100 parts by mass of the solid content of the titanium-containing aqueous liquid (A). It is preferable from the viewpoint of adhesive bondability. If the blending amount of the inorganic phosphate compound (C) is less than 50 parts by mass with respect to 100 parts by mass of the solid content of the titanium-containing aqueous liquid (A), the adhesive bondability is inferior. Inferior, and further, corrosion resistance and paintability are also deteriorated.
表面処理組成物(X)は、さらに必要に応じて、水溶性有機樹脂または/および水分散性有機樹脂(D)を含有することができ、これにより塗装性が向上する。
この水溶性有機樹脂または/および水分散性有機樹脂(D)は、水に溶解または分散することのできる有機樹脂であり、有機樹脂を水に水溶化または分散化させる方法としては、従来公知の方法を適用することができる。具体的には、有機樹脂として、単独で水溶化や水分散化できる官能基(例えば、水酸基、ポリオキシアルキレン基、カルボキシル基、アミノ(イミノ)基、スルフィド基、ホスフィン基など)を含有するもの、および必要に応じてそれらの官能基の一部または全部を、酸性樹脂(カルボキシル基含有樹脂など)であればエタノールアミン、トリエチルアミンなどのアミン化合物;アンモニア水;水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物で中和したもの、また、塩基性樹脂(アミノ基含有樹脂など)であれば、酢酸、乳酸などの脂肪酸;リン酸などの鉱酸で中和したものなどを使用することができる。
The surface treatment composition (X) can further contain a water-soluble organic resin and / or a water-dispersible organic resin (D) as necessary, thereby improving paintability.
This water-soluble organic resin and / or water-dispersible organic resin (D) is an organic resin that can be dissolved or dispersed in water, and a conventionally known method for water-solubilizing or dispersing an organic resin in water is known. The method can be applied. Specifically, the organic resin contains a functional group (for example, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, an amino (imino) group, a sulfide group, a phosphine group, etc.) that can be water-soluble or water-dispersed independently. And, if necessary, part or all of these functional groups may be converted to acidic compounds (such as carboxyl group-containing resins) with amine compounds such as ethanolamine and triethylamine; ammonia water; lithium hydroxide, sodium hydroxide, water Neutralized with alkali metal hydroxides such as potassium oxide, and basic resins (amino group-containing resins, etc.), fatty acids such as acetic acid and lactic acid; neutralized with mineral acids such as phosphoric acid, etc. Can be used.
水溶性または水分散性有機樹脂としては、例えば、エポキシ系樹脂、フェノール系樹脂、アクリル系樹脂、ウレタン系樹脂、オレフィン−カルボン酸系樹脂、ナイロン系樹脂、ポリオキシアルキレン鎖を有する樹脂、ポリビニルアルコール、ポリグリセリン、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロースなどが挙げられる。上記有機樹脂は1種または2種以上を用いることができる。
これらのなかでも特に、水溶性または水分散性のアクリル系樹脂、ウレタン系樹脂およびエポキシ系樹脂の中から選ばれる少なくとも1種の有機樹脂を用いることが表面処理組成物(X)の貯蔵安定性の面から好ましく、また特に、水溶性または水分散性のアクリル系樹脂を主成分として用いることが、表面処理組成物(X)の貯蔵安定性と塗膜性能とのバランスの面から好ましい。
Examples of water-soluble or water-dispersible organic resins include epoxy resins, phenol resins, acrylic resins, urethane resins, olefin-carboxylic acid resins, nylon resins, resins having a polyoxyalkylene chain, and polyvinyl alcohol. , Polyglycerin, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose and the like. The said organic resin can use 1 type (s) or 2 or more types.
Among these, in particular, the storage stability of the surface treatment composition (X) is obtained by using at least one organic resin selected from water-soluble or water-dispersible acrylic resins, urethane resins and epoxy resins. In view of the above, it is particularly preferable to use a water-soluble or water-dispersible acrylic resin as a main component from the viewpoint of the balance between the storage stability of the surface treatment composition (X) and the coating film performance.
水溶性または水分散性アクリル樹脂は、従来公知の方法、例えば、乳化重合法、懸濁重合法、親水性の基を有する重合体を溶液重合により合成し、必要に応じて中和、水性化する方法などにより得ることができる。
前記親水性の基を有する重合体は、例えば、カルボキシル基、アミノ基、水酸基、ポリオキシアルキレン基などの親水性の基を有する不飽和単量体、必要に応じて、さらにその他の不飽和単量体を重合させることにより得ることができる。
水溶性または水分散性アクリル樹脂は、耐食性などの点からスチレンを共重合してなるものが好ましく、全不飽和単量体中のスチレンの量は10〜60質量%、特に15〜50質量%であることが好ましい。また、共重合して得られるアクリル樹脂のTg(ガラス転移点)は30〜80℃、特に40〜70℃であることが、得られる皮膜の強靭性などの点から好ましい。
A water-soluble or water-dispersible acrylic resin is synthesized by a conventionally known method, for example, an emulsion polymerization method, a suspension polymerization method, or a polymer having a hydrophilic group by solution polymerization. Or the like.
The polymer having a hydrophilic group includes, for example, an unsaturated monomer having a hydrophilic group such as a carboxyl group, an amino group, a hydroxyl group, and a polyoxyalkylene group, and, if necessary, other unsaturated monomers. It can be obtained by polymerizing the monomer.
The water-soluble or water-dispersible acrylic resin is preferably obtained by copolymerizing styrene from the viewpoint of corrosion resistance and the like. The amount of styrene in the total unsaturated monomer is 10 to 60% by mass, particularly 15 to 50% by mass. It is preferable that Moreover, it is preferable from points, such as toughness of the film obtained, that Tg (glass transition point) of the acrylic resin obtained by copolymerization is 30-80 degreeC, especially 40-70 degreeC.
上記カルボキシル基含有不飽和単量体としては、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、クロトン酸、イタコン酸などが挙げられる。
上記アミノ基含有不飽和単量体などのような含窒素不飽和単量体としては、N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレート、N−t−ブチルアミノエチル(メタ)アクリレートなどの含窒素アルキル(メタ)アクリレート;アクリルアミド、メタクリルアミド、N−メチル(メタ)アクリルアミド、N−エチル(メタ)アクリルアミド、N−メチロール(メタ)アクリルアミド、N−メトキシメチル(メタ)アクリルアミド、N−ブトキシメチル(メタ)アクリルアミド、N,N−ジメチル(メタ)アクリルアミド、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、N,N−ジメチルアミノエチル(メタ)アクリルアミドなどの重合性アミド類;2−ビニルピリジン、1−ビニル−2−ピロリドン、4−ビニルピリジンなどの芳香族含窒素モノマー;アリルアミンなどが挙げられる。
Examples of the carboxyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, crotonic acid, and itaconic acid.
Examples of the nitrogen-containing unsaturated monomer such as the amino group-containing unsaturated monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt- Nitrogen-containing alkyl (meth) acrylates such as butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl Polymerization of (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, etc. Amides; 2-vinylpyridine, - vinyl-2-pyrrolidone, aromatic nitrogen-containing monomers such as 4-vinylpyridine; and allylamine and the like.
上記水酸基含有不飽和単量体としては、2−ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、2,3−ジヒドロキシブチル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレートなどの多価アルコールとアクリル酸またはメタクリル酸とのモノエステル化物;上記多価アルコールとアクリル酸またはメタクリル酸とのモノエステル化物にε−カプロラクトンを開環重合した化合物などが挙げられる。 Examples of the hydroxyl group-containing unsaturated monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono Monoesterified product of polyhydric alcohol such as (meth) acrylate and polypropylene glycol mono (meth) acrylate and acrylic acid or methacrylic acid; ε-caprolactone is opened to monoesterified product of polyhydric alcohol and acrylic acid or methacrylic acid. Examples include a ring-polymerized compound.
その他の不飽和単量体としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert−ブチル(メタ)アクリレート、2−エチルヘキシルアクリレート、n−オクチル(メタ)アクリレート、ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート、オクタデシル(メタ)アクリレート、イソステアリル(メタ)アクリレートなどの炭素数1〜24のアルキル(メタ)アクリレート;酢酸ビニルなどが挙げられる。
以上挙げた不飽和単量体は、1種または2種以上を用いることができる。なお、本願の記載において、「(メタ)アクリレート」とは「アクリレート又はメタアクリレート」を意味する。
Other unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 1 carbon number such as tert-butyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate -24 alkyl (meth) acrylates; vinyl acetate and the like.
The unsaturated monomer mentioned above can use 1 type (s) or 2 or more types. In the description of the present application, “(meth) acrylate” means “acrylate or methacrylate”.
上記ウレタン系樹脂としては、ポリエステルポリオール、ポリエーテルポリオールなどのポリオールとジイソシアネートからなるポリウレタンを必要に応じてジオール、ジアミンなどのような2個以上の活性水素を持つ低分子量化合物である鎖伸長剤の存在下で鎖伸長し、水中に安定に分散または溶解させたものを好適に使用でき、従来公知のものを広く使用できる(例えば、特公昭42−24192号公報、特公昭42−24194号公報、特公昭42−5118号公報、特公昭49−986号公報、特公昭49−33104号公報、特公昭50−15027号公報、特公昭53−29175号公報参照)。 Examples of the urethane resin include a chain extender that is a low molecular weight compound having two or more active hydrogens such as a diol and a diamine, if necessary, and a polyurethane comprising a polyol and a diisocyanate such as a polyester polyol and a polyether polyol. Those which are chain-extended in the presence and stably dispersed or dissolved in water can be suitably used, and conventionally known ones can be widely used (for example, Japanese Patent Publication No. 42-24192, Japanese Patent Publication No. 42-24194, (See JP-B-42-5118, JP-B-49-986, JP-B-49-33104, JP-B-50-15027, JP-B-53-29175).
ポリウレタン樹脂を水中に安定に分散または溶解させる方法としては、例えば下記の方法が利用できる。
(1)ポリウレタンポリマーの側鎖または末端に水酸基、アミノ基、カルボキシル基などのイオン性基を導入することにより親水性を付与し、自己乳化により水中に分散または溶解する方法。
(2)反応の完結したポリウレタンポリマーまたは末端イソシアネート基をオキシム、アルコール、フェノール、メルカプタン、アミン、重亜硫酸ソーダなどのブロック剤でブロックしたポリウレタンポリマーを乳化剤と機械的剪断力を用いて強制的に水中に分散する方法。さらに、末端イソシアネート基を持つウレタンポリマーを水、乳化剤および鎖伸長剤と混合し、機械的剪断力を用いて分散化と高分子量化を同時に行う方法。
(3)ポリウレタン主原料のポリオールとしてポリエチレングリコールのごとき水溶性ポリオールを使用し、水に可溶なポリウレタンとして水中に分散または溶解する方法。
なお、ポリウレタン系樹脂は、上述した分散または溶解方法のうち異なる方法で得られたものを混合して用いることもできる。
As a method for stably dispersing or dissolving the polyurethane resin in water, for example, the following method can be used.
(1) A method of imparting hydrophilicity by introducing an ionic group such as a hydroxyl group, an amino group or a carboxyl group into the side chain or terminal of a polyurethane polymer, and dispersing or dissolving in water by self-emulsification.
(2) A polyurethane polymer whose reaction has been completed or a polyurethane polymer whose terminal isocyanate group is blocked with a blocking agent such as oxime, alcohol, phenol, mercaptan, amine or sodium bisulfite is forcibly submerged in water using an emulsifier and mechanical shearing force. How to disperse. Further, a method in which a urethane polymer having a terminal isocyanate group is mixed with water, an emulsifier and a chain extender, and dispersion and high molecular weight are simultaneously performed using mechanical shearing force.
(3) A method in which a water-soluble polyol such as polyethylene glycol is used as a polyol as a main polyurethane material and is dispersed or dissolved in water as a water-soluble polyurethane.
In addition, as the polyurethane resin, those obtained by different methods among the above-described dispersion or dissolution methods can be mixed and used.
上記ポリウレタン系樹脂の合成に使用できるジイソシアネートとしては、芳香族、脂環族または脂肪族のジイソシアネートが挙げられ、具体的には、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、3,3′−ジメトキシ−4,4′−ビフェニレンジイソシアネート、p−キシリレンジイソシアネート、m−キシリレンジイソシアネート、1,3−(ジイソシアナトメチル)シクロヘキサノン、1,4−(ジイソシアナトメチル)シクロヘキサノン、4,4′−ジイソシアナトシクロヘキサノン、4,4′−メチレンビス(シクロヘキシルイソシアネート)、イソホロンジイソシアネート、2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、p−フェニレンジイソシアネート、ジフェニルメタンジイソシアネート、m−フェニレンジイソシアネート、2,4−ナフタレンジイソシアネート、3,3′−ジメチル−4,4′−ビフェニレンジイソシアネート、4,4′−ビフェニレンジイソシアネートなどが挙げられる。これらなかでも、2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネートが特に好ましい。
ポリウレタン系樹脂の市販品としては、ハイドランHW−330、同HW−340、同HW−350(いずれも商品名,大日本インキ化学工業社製)、スーパーフレックス100、同150、同E−2500、同F−3438D(いずれも商品名,第一工業製薬社製)などを挙げることができる。
Examples of the diisocyanate that can be used for the synthesis of the polyurethane resin include aromatic, alicyclic or aliphatic diisocyanates. Specifically, hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3′-dimethoxy-4, 4'-biphenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1,3- (diisocyanatomethyl) cyclohexanone, 1,4- (diisocyanatomethyl) cyclohexanone, 4,4'-diisocyanato Cyclohexanone, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane Isocyanate, m- phenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate and the like. Among these, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable.
Examples of commercially available polyurethane resins include Hydran HW-330, HW-340, HW-350 (both trade names, manufactured by Dainippon Ink and Chemicals), Superflex 100, 150, E-2500, F-3438D (all are trade names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
上記エポキシ系樹脂としては、エポキシ樹脂にアミンを付加してなるカチオン系エポキシ樹脂;アクリル変性、ウレタン変性などの変性エポキシ樹脂などが好適に使用できる。カチオン系エポキシ樹脂としては、例えば、エポキシ化合物と、1級モノ−またはポリアミン、2級モノ−またはポリアミン、1,2級混合ポリアミンなどとの付加物(例えば、米国特許第3984299号明細書参照);エポキシ化合物とケチミン化された1級アミノ基を有する2級モノ−またはポリアミンとの付加物(例えば、米国特許第4017438号明細書参照);エポキシ化合物とケチミン化された1級アミノ基を有するヒドロキシル化合物とのエーテル化反応生成物(例えば、特開昭59−43013号公報参照)などが挙げられる。 As the epoxy resin, a cationic epoxy resin obtained by adding an amine to an epoxy resin; a modified epoxy resin such as an acrylic modification or a urethane modification can be suitably used. Examples of cationic epoxy resins include adducts of epoxy compounds with primary mono- or polyamines, secondary mono- or polyamines, and primary and secondary mixed polyamines (see, for example, US Pat. No. 3,984,299). An adduct of an epoxy compound with a secondary mono- or polyamine having a ketiminated primary amino group (see, for example, US Pat. No. 4,017,438); having an epoxy compound and a primary amino group ketiminated Examples include etherification reaction products with hydroxyl compounds (see, for example, JP-A-59-43013).
上記エポキシ系樹脂としては、数平均分子量が400〜4000、特に800〜2000、エポキシ当量が190〜2000、特に400〜1000であるものが好ましい。そのようなエポキシ系樹脂は、例えば、ポリフェノール化合物とエピクロルヒドリンとの反応によって得ることができ、ポリフェノール化合物としては、例えば、ビス(4−ヒドロキシフェニル)−2,2−プロパン、4,4−ジヒドロキシベンゾフェノン、ビス(4−ヒドロキシフェニル)−1,1−エタン、ビス(4−ヒドロキシフェニル)−1,1−イソブタン、ビス(4−ヒドロキシ−tert−ブチルフェニル)−2,2−プロパン、ビス(2−ヒドロキシナフチル)メタン、1,5−ジヒドロキシナフタレン、ビス(2,4−ジヒドロキシフェニル)メタン、テトラ(4−ヒドロキシフェニル)−1,1,2,2−エタン、4,4−ジヒドロキシジフェニルスルホン、フェノールノボラック、クレゾールノボラックなどが挙げられる。 The epoxy resin preferably has a number average molecular weight of 400 to 4000, particularly 800 to 2000, and an epoxy equivalent of 190 to 2000, particularly 400 to 1000. Such an epoxy resin can be obtained, for example, by a reaction between a polyphenol compound and epichlorohydrin. Examples of the polyphenol compound include bis (4-hydroxyphenyl) -2,2-propane and 4,4-dihydroxybenzophenone. Bis (4-hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-tert-butylphenyl) -2,2-propane, bis (2 -Hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) methane, tetra (4-hydroxyphenyl) -1,1,2,2-ethane, 4,4-dihydroxydiphenylsulfone, Phenol novolak, cresol novolak, etc. That.
水溶性有機樹脂または/および水分散性有機樹脂(D)の配合量は、チタン含有水性液(A)の固形分100質量部に対して固形分の割合で2000質量部以下、特に5〜1500質量部とすることが、アルカリ脱脂後の耐食性などの点から好ましい。水溶性有機樹脂または/および水分散性有機樹脂(D)の配合量が、チタン含有水性液(A)の固形分100質量部に対して2000質量部を超えると、アルカリ脱脂した後の耐食性が劣るため好ましくない。 The blending amount of the water-soluble organic resin and / or the water-dispersible organic resin (D) is 2000 parts by mass or less, particularly 5 to 1500 in terms of the solid content with respect to 100 mass parts of the solid content of the titanium-containing aqueous liquid (A). It is preferable to set it as a mass part from points, such as corrosion resistance after alkali degreasing. When the blending amount of the water-soluble organic resin and / or water-dispersible organic resin (D) exceeds 2000 parts by mass with respect to 100 parts by mass of the solid content of the titanium-containing aqueous liquid (A), the corrosion resistance after alkali degreasing is reduced. Since it is inferior, it is not preferable.
表面処理組成物(X)には、さらに必要に応じて、シランカップリング剤を添加することができる。シランカップリング剤としては、例えば、N−β(アミノエチル)γ−アミノプロピルトリメトキシシラン、N−β(アミノエチル)γ−アミノプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、N−β(N−ビニルベンジルアミノエチル)γ−アミノプロピルトリメトキシシラン−塩酸塩、γ−グリシドキシプロピルトリメトキシシラン、γ−メルカプトピロプルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、メチルトリメトキシシラン、ビニリトリアセトキシシラン、γ−クロロプロピルトリメトキシシラン、ヘキサメチルジシラザン、γ−アニリノプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、オクタデシルジメチル[3−(トリメトキシシリル)プロピル]アンモニウムクロライド、トリメチルクロロシランなどが挙げられ、これらの1種または2種以上を用いることができる。
シランカップリング剤の配合量は、チタン含有水性液(A)の固形分100質量部に対して1〜400質量部、特に10〜400質量部であることが、皮膜をアルカリ脱脂した後の耐食性などの点から好ましい。
A silane coupling agent can be further added to the surface treatment composition (X) as necessary. Examples of the silane coupling agent include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- β (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopyrrolotrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrimethoxy Silane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, octadecyldimethyl [3- (trimethoxysilane Yl) propyl] ammonium chloride, trimethylchlorosilane, and the like, and one or more of these may be used.
The compounding amount of the silane coupling agent is 1 to 400 parts by weight, particularly 10 to 400 parts by weight, based on 100 parts by weight of the solid content of the titanium-containing aqueous liquid (A). From the point of view, it is preferable.
表面処理組成物(X)には、さらに必要に応じて、有機微粒子および/または無機微粒子を添加することができる。このような微粒子を添加することにより塗膜の透明性が下がり、薄膜において発生しやすいニジムラ(干渉色)を抑えることができ、外観を重視する用途に特に適したものとなる。上記微粒子は、平均粒子径が3〜1000nm、特に3〜500nmのものが、粒子の沈降安定性および耐食性の点から好ましい。
上記有機微粒子としては、例えば、アクリル、ポリウレタン、ナイロン、ポリエチレングリコールなどの樹脂微粒子が挙げられる。また、無機微粒子としては、例えば、シリカ、二酸化チタン、硫酸バリウム、炭酸カルシウムなどを挙げることができる。コストなどの点から、シリカ、二酸化チタン、硫酸バリウムなどが特に好ましい。
有機微粒子および/または無機微粒子の配合量は、表面処理組成物(X)の固形分中で1〜30質量%、特に1〜20質量%とすることが、耐食性などの点から好ましい。
If necessary, organic fine particles and / or inorganic fine particles can be further added to the surface treatment composition (X). By adding such fine particles, the transparency of the coating film is lowered, and nitrite (interference color) that tends to occur in the thin film can be suppressed, which makes it particularly suitable for applications in which appearance is important. The fine particles preferably have an average particle size of 3 to 1000 nm, particularly 3 to 500 nm, from the viewpoint of sedimentation stability and corrosion resistance of the particles.
Examples of the organic fine particles include resin fine particles such as acrylic, polyurethane, nylon, and polyethylene glycol. Examples of the inorganic fine particles include silica, titanium dioxide, barium sulfate, and calcium carbonate. From the viewpoint of cost, silica, titanium dioxide, barium sulfate and the like are particularly preferable.
The blending amount of the organic fine particles and / or inorganic fine particles is preferably 1 to 30% by mass, particularly 1 to 20% by mass in the solid content of the surface treatment composition (X) from the viewpoint of corrosion resistance and the like.
表面処理組成物(X)には、さらに必要に応じて、フッ化水素酸などのエッチング剤、本発明が規定する成分以外の重金属化合物、水性有機高分子化合物、増粘剤、界面活性剤、防錆剤(タンニン酸、フィチン酸、ベンゾトリアゾールなど)、着色顔料、体質顔料、シリカ、防錆顔料などを添加することができる。
また、表面処理組成物(X)は、通常水で希釈して使用されるが、必要に応じて、例えば、メタノール、エタノール、イソプロピルアルコール、エチレングリコール系溶剤、プロピレングリコール系溶剤などの親水性溶剤で希釈してもよい。
In the surface treatment composition (X), if necessary, an etching agent such as hydrofluoric acid, a heavy metal compound other than the components specified by the present invention, an aqueous organic polymer compound, a thickener, a surfactant, Rust preventives (tannic acid, phytic acid, benzotriazole, etc.), colored pigments, extender pigments, silica, rust preventive pigments and the like can be added.
The surface treatment composition (X) is usually diluted with water and used. If necessary, for example, a hydrophilic solvent such as methanol, ethanol, isopropyl alcohol, an ethylene glycol solvent, or a propylene glycol solvent. It may be diluted with.
表面処理組成物(X)は、中性または酸性領域で安定な液体となるので、特にpH1〜7、特に1〜5の範囲が好ましい。
表面処理組成物(X)により形成される表面処理皮膜の皮膜厚は、経済性と塗膜性能、特に耐食性、付着性および溶接性の観点から0.01〜1.0μm、好ましくは0.05〜0.7μmとする。皮膜厚が0.01μm未満では十分な耐食性が得られず、一方、1.0μmを超えると溶接性が劣り、また、加工後耐食性や電着塗装性、接着接合性も低下する。
Since the surface treatment composition (X) becomes a stable liquid in a neutral or acidic region, pH 1 to 7, particularly 1 to 5 is particularly preferable.
The film thickness of the surface treatment film formed by the surface treatment composition (X) is 0.01 to 1.0 μm, preferably 0.05 from the viewpoints of economy and film performance, particularly corrosion resistance, adhesion and weldability. ˜0.7 μm. If the film thickness is less than 0.01 μm, sufficient corrosion resistance cannot be obtained. On the other hand, if it exceeds 1.0 μm, the weldability is inferior, and the post-processing corrosion resistance, electrodeposition coating property, and adhesive bondability also deteriorate.
次に、本発明の表面処理鋼板において、上述した表面処理皮膜の上に形成される上層皮膜(有機皮膜)について説明する。
この上層皮膜は、溶剤系有機樹脂(E)と非クロム系防錆添加剤(F)を含有する、好ましくはこれらを主成分とする塗料組成物(Y)を塗布し、乾燥することにより形成された皮膜である。この上層皮膜もクロム(但し、不可避不純物としてのクロムを除く)を含まない。このような上層皮膜を上記特定の表面処理皮膜(下層皮膜)の上層に形成することにより、両皮膜の複合作用によって特に高度な加工部耐食性やアルカリ脱脂後耐食性が得られる。これは、バリアー性に優れた下層皮膜と加工性に優れた上層皮膜との組み合わせにより、加工後においても下層皮膜の受ける損傷が少なく、バリアー性が保持されるためであると考えられる。
Next, in the surface-treated steel sheet of the present invention, an upper layer film (organic film) formed on the surface-treated film described above will be described.
This upper layer film is formed by applying and drying a coating composition (Y) containing a solvent-based organic resin (E) and a non-chromium-based anticorrosive additive (F), preferably containing these as a main component. It is a coated film. This upper layer film also does not contain chromium (except for chromium as an inevitable impurity). By forming such an upper layer film on the upper layer of the specific surface treatment film (lower layer film), particularly high processed part corrosion resistance and corrosion resistance after alkaline degreasing can be obtained by the combined action of both films. This is presumably because the combination of the lower layer film having excellent barrier properties and the upper layer film having excellent processability causes little damage to the lower layer film even after processing and maintains the barrier properties.
上記溶剤系有機樹脂(E)は水分散性樹脂や水溶性樹脂などに比べて腐食因子である水に対するバリアー性が高く、より優れた耐食性が得られることから、本発明で用いる有機樹脂として好ましい。さらには、アルカリ脱脂などの耐薬品性についても、溶剤系有機樹脂の方が水分散性樹脂や水溶性樹脂などに比べて優れていることから、ユーザーで塗油した後にプレス加工が施され、さらに油を除去するためのアルカリ脱脂が行われた後でも、初期の耐食性と変わらない耐食性を実現することができる。 The solvent-based organic resin (E) is preferable as the organic resin used in the present invention because it has a higher barrier property against water, which is a corrosive factor, and better corrosion resistance than water-dispersible resins and water-soluble resins. . Furthermore, with regard to chemical resistance such as alkaline degreasing, solvent-based organic resins are superior to water-dispersible resins and water-soluble resins. Furthermore, even after alkaline degreasing to remove the oil is performed, corrosion resistance that is the same as the initial corrosion resistance can be realized.
溶剤系有機樹脂(E)の種類に特別な制限はないが、特に、エポキシ樹脂、変性エポキシ樹脂、ポリヒドロキシポリエーテル樹脂、ポリアルキレングリコール変性エポキシ樹脂、ウレタン変性エポキシ樹脂、これらの樹脂をさらに変性させた有機樹脂、ポリエステル樹脂、ウレタン樹脂、シリコン樹脂、アクリル樹脂などが好ましく、これらの1種または2種以上を用いることが好ましい。特に、耐食性および下地との密着性の観点からはエポキシ系樹脂をベースとして、これに加工性を向上させることを狙いとして分子量を適宜最適化したものや樹脂の一部にウレタンやポリエステル、アミンなどの変性を加えたものが望ましい。このようなエポキシ樹脂としては、ビスフェノールA、ビスフェノールF、ノボラック型フェノールなどのポリフェノール類とエピクロルヒドリンなどのエピハロヒドリンとを反応させてグリシジル基を導入してなるか、若しくはグリシジル基導入反応生成物に更にポリフェノール類を反応させて分子量を増大させてなる芳香族エポキシ樹脂、さらには脂肪族エポキシ樹脂、脂環族エポキシ樹脂などが挙げられ、これらの1種を単独でまたは2種以上を混合して使用することができる。これらのエポキシ樹脂は、特に低温での皮膜形成性および加工後の耐食性を必要とする場合には、数平均分子量を1500以上とすることが好ましい。変性エポキシ樹脂としては、エポキシ樹脂骨格中のエポキシ基またはヒドロキシル基に各種変性剤を反応させたものが挙げられる。例えば、乾性油脂肪酸中のカルボキシル基を反応させたエポキシエステル樹脂、アクリル酸、メタクリル酸などで変性したエポキシアクリレート樹脂、イソシアネート化合物を反応させたウレタン変性エポキシ樹脂などが挙げられる。 There are no particular restrictions on the type of solvent-based organic resin (E), but in particular, epoxy resins, modified epoxy resins, polyhydroxy polyether resins, polyalkylene glycol-modified epoxy resins, urethane-modified epoxy resins, and these resins are further modified. Preferred are organic resins, polyester resins, urethane resins, silicone resins, acrylic resins, and the like, and it is preferable to use one or more of these. In particular, from the viewpoint of corrosion resistance and adhesion to the base, an epoxy resin is used as a base, and the molecular weight is appropriately optimized for the purpose of improving processability, and urethane, polyester, amine, etc. are used as part of the resin. Those with the modification of are desirable. As such an epoxy resin, a polyphenol such as bisphenol A, bisphenol F, or novolak type phenol is reacted with an epihalohydrin such as epichlorohydrin to introduce a glycidyl group, or a polyphenol is further added to a glycidyl group introduction reaction product. Aromatic epoxy resins obtained by reacting a polymer to increase the molecular weight, and aliphatic epoxy resins, alicyclic epoxy resins, etc., are used alone or in combination of two or more. be able to. These epoxy resins preferably have a number average molecular weight of 1500 or more, particularly when film formation at low temperatures and corrosion resistance after processing are required. Examples of the modified epoxy resin include those obtained by reacting various modifiers with epoxy groups or hydroxyl groups in the epoxy resin skeleton. For example, an epoxy ester resin obtained by reacting a carboxyl group in a dry oil fatty acid, an epoxy acrylate resin modified with acrylic acid, methacrylic acid, or the like, a urethane-modified epoxy resin reacted with an isocyanate compound, and the like.
また、上層皮膜の耐食性や加工性の向上を狙いとして、特に有機樹脂として熱硬化性樹脂を用いることが好ましい。この場合、尿素樹脂(ブチル化尿素樹脂など)、メラミン樹脂(ブチル化メラミン樹脂など)、ベンゾグアナミン樹脂などのアミノ樹脂、ブロックイソシアネート、フェノール樹脂などの硬化剤を配合することができる。
以上のことから耐食性、加工性を考慮すると、溶剤系熱硬化性のエポキシ系樹脂が最も好ましい。
In order to improve the corrosion resistance and workability of the upper layer film, it is particularly preferable to use a thermosetting resin as the organic resin. In this case, a curing agent such as urea resin (such as butylated urea resin), melamine resin (such as butylated melamine resin), amino resin such as benzoguanamine resin, blocked isocyanate, and phenol resin can be blended.
In view of the above, in view of corrosion resistance and workability, a solvent-based thermosetting epoxy resin is most preferable.
有機樹脂を溶解させる有機溶媒の種類は特に限定されない。例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジブチルケトン、シクロヘキサノンなどのケトン類、エタノール、ブタノール、2−エチルヘキシルアルコール、ベンジルアルコール、エチレングリコール、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノエチルエーテルなどの水酸基を含有するアルコール類やエーテル類、酢酸エチル、酢酸ブチル、エチレングリコールモノブチルエーテルアセテートなどのエステル類、トルエン、キシレンなどの芳香族炭化水素などを例示でき、これらの1種または2種以上を使用することができる。また、有機樹脂としてエポキシ系樹脂を使用する場合は、溶解性、塗膜形成性などの面から、ケトン系またはエーテル系の溶剤が好ましい。 The kind of the organic solvent in which the organic resin is dissolved is not particularly limited. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dibutyl ketone, cyclohexanone, ethanol, butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether , Propylene glycol, propylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoethyl ether and other alcohols and ethers containing hydroxyl groups, ethyl acetate, butyl acetate, ethylene glycol monobutyl ether acetate and other esters, toluene, xylene and other aromatics Hydrocarbons and the like, and one or more of these It is possible to use. Further, when an epoxy resin is used as the organic resin, a ketone-based or ether-based solvent is preferable from the viewpoints of solubility, coating film formation, and the like.
上記非クロム系防錆添加剤(F)の種類に特別な制限はないが、特に、下記(a)〜(e)の中から選ばれる1種以上の非クロム系防錆添加剤を配合することが好ましい。
(a)酸化ケイ素
(b)カルシウム化合物
(c)リン酸化合物
(d)モリブデン酸化合物
(e)トリアゾール類、チオール類、チアジアゾール類、チアゾール類、チウラム類の中から選ばれる1種以上の有機化合物
Although there is no special restriction | limiting in the kind of the said non-chromium-type antirust additive (F), In particular, the 1 or more types of non-chromium-type antirust additive selected from the following (a)-(e) is mix | blended. It is preferable.
(A) silicon oxide (b) calcium compound (c) phosphoric acid compound (d) molybdate compound (e) one or more organic compounds selected from triazoles, thiols, thiadiazoles, thiazoles, thiurams
これら(a)〜(e)の非クロム系防錆添加剤の詳細及び防食機構は以下の通りである。
上記成分(a)である酸化ケイ素は、コロイダルシリカ、乾式シリカのいずれでもよい。コロイダルシリカとしては、水系皮膜形成樹脂をベースとする場合には、例えば、日産化学工業(株)製のスノーテックスO、スノーテックスN、スノーテックス20、スノーテックス30、スノーテックス40、スノーテックスC、スノーテックスS(以上、いずれも商品名)、触媒化成工業(株)製のカタロイドS、カタロイドSI−350、カタロイドSI−40、カタロイドSA、カタロイドSN(以上、いずれも商品名)、旭電化工業(株)製のアデライトAT−20〜50、アデライトAT−20N、アデライトAT−300、アデライトAT−300S、アデライトAT20Q(以上、いずれも商品名)などを用いることができる。
The details and anticorrosion mechanism of these non-chromium rust preventive additives (a) to (e) are as follows.
The silicon oxide as the component (a) may be either colloidal silica or dry silica. When colloidal silica is based on a water-based film-forming resin, for example, Snowtex O, Snowtex N, Snowtex 20, Snowtex 30, Snowtex 40, Snowtex C manufactured by Nissan Chemical Industries, Ltd. , Snowtex S (above, all are trade names), Cataloid S, Cataloid SI-350, Cataloid SI-40, Cataloid SA, Cataloid SN (above, all are trade names) manufactured by Catalytic Kasei Kogyo Co., Ltd., Asahi Denka Adelite AT-20-50 manufactured by Kogyo Co., Ltd., Adelite AT-20N, Adelite AT-300, Adelite AT-300S, Adelite AT20Q (all are trade names) and the like can be used.
また、溶剤系皮膜形成樹脂をベースとする場合には、例えば、日産化学工業(株)製のオルガノシリカゾルMA−ST−M、オルガノシリカゾルIPA−ST、オルガノシリカゾルEG−ST、オルガノシリカゾルE−ST−ZL、オルガノシリカゾルNPC−ST、オルガノシリカゾルDMAC−ST、オルガノシリカゾルDMAC−ST−ZL、オルガノシリカゾルXBA−ST、オルガノシリカゾルMIBK−ST(以上、いずれも商品名)、触媒化成工業(株)製のOSCAL−1132、OSCAL−1232、OSCAL−1332、OSCAL−1432、OSCAL−1532、OSCAL−1632、OSCAL−1722(以上、いずれも商品名)などを用いることができる。
特に、有機溶剤分散型シリカゾルは、分散性に優れ、ヒュームドシリカよりも耐食性に優れている。
In addition, when the solvent-based film forming resin is used as a base, for example, organosilica sol MA-ST-M, organosilica sol IPA-ST, organosilica sol EG-ST, organosilica sol E-ST manufactured by Nissan Chemical Industries, Ltd. -ZL, organosilica sol NPC-ST, organosilica sol DMAC-ST, organosilica sol DMAC-ST-ZL, organosilica sol XBA-ST, organosilica sol MIBK-ST (all are trade names), manufactured by Catalyst Kasei Kogyo Co., Ltd. OSCAL-1132, OSCAL-1232, OSCAL-1332, OSCAL-1432, OSCAL-1532, OSCAL-1632, OSCAL-1722 (all of which are trade names) can be used.
In particular, the organic solvent-dispersed silica sol is excellent in dispersibility and superior in corrosion resistance than fumed silica.
また、ヒュームドシリカとしては、例えば、日本アエロジル(株)製のAEROSIL R971、AEROSIL R812、AEROSIL R811、AEROSIL R974、AEROSIL R202、AEROSIL R805、AEROSIL 130、AEROSIL 200、AEROSIL 300、AEROSIL 300CF(以上、いずれも商品名)などを用いることができる。
酸化ケイ素は、腐食環境下において緻密で安定な亜鉛の腐食生成物の生成に寄与し、この腐食生成物がめっき表面に緻密に形成されることによって、腐食の促進を抑制することができると考えられている。
耐食性の観点からは、酸化ケイ素は粒子径が2〜50nm、望ましくは2〜20nm、さらに好ましくは2〜15nmのものを用いるのが好ましい。
Examples of the fumed silica include AEROSIL R971, AEROSIL R812, AEROSIL R811, AEROSIL R974, AEROSIL R202, AEROSIL R805, AEROSIL 130, AEROSIL 200, AEROSIL 300, and more from AEROSIL 300CF manufactured by Nippon Aerosil Co., Ltd. Can also be used.
Silicon oxide contributes to the formation of a dense and stable zinc corrosion product in a corrosive environment, and it is believed that this corrosion product can be formed densely on the plating surface to suppress the promotion of corrosion. It has been.
From the viewpoint of corrosion resistance, it is preferable to use silicon oxide having a particle size of 2 to 50 nm, desirably 2 to 20 nm, more preferably 2 to 15 nm.
また、上記成分(a)である酸化ケイ素としては、カルシウムイオンを多孔質シリカゲル粉末の表面に固定したCaイオン交換シリカが、耐食性の観点から特に好ましい。このCaイオン交換シリカは、腐食環境下でCaイオンが放出されて沈殿膜を形成する。
Caイオン交換シリカ中のCa濃度は1mass%以上、望ましくは2〜8mass%であることが好ましい。Ca濃度が1mass%未満ではCa放出による防錆効果が十分に得られない。なお、Caイオン交換シリカの表面積、pH、吸油量については特に限定されない。
以上のようなCaイオン交換シリカとしては、例えば、W.R.Grace&Co.製のSHIELDEX C303(平均粒子径2.5〜3.5μm、Ca濃度3mass%)、SHIELDEX AC3(平均粒子径2.3〜3.1μm、Ca濃度6mass%)、SHIELDEX AC5(平均粒子径3.8〜5.2μm、Ca濃度6mass%)(以上、いずれも商品名)、富士シリシア化学(株)製のSHIELDEX(平均粒子径3μm、Ca濃度6〜8mass%)、SHIELDEX SY710(平均粒子径2.2〜2.5μm、Ca濃度6.6〜7.5mass%)(以上、いずれも商品名)などを用いることができる。
Moreover, as a silicon oxide which is the said component (a), the Ca ion exchange silica which fixed the calcium ion to the surface of the porous silica gel powder is especially preferable from a corrosion-resistant viewpoint. The Ca ion exchange silica forms a precipitated film by releasing Ca ions in a corrosive environment.
The Ca concentration in the Ca ion exchange silica is preferably 1 mass% or more, and preferably 2 to 8 mass%. If the Ca concentration is less than 1 mass%, the rust prevention effect due to Ca release cannot be sufficiently obtained. The surface area, pH, and oil absorption amount of the Ca ion exchange silica are not particularly limited.
Examples of the Ca ion exchange silica as described above include WR Grace & Co. SHIELDEX C303 (average particle size 2.5 to 3.5 μm, Ca concentration 3 mass%), SHIELDEX AC3 (average particle size 2.3 to 3.1 μm, Ca concentration 6 mass%), SHIELDEX AC5 (average particle size 3. 8 to 5.2 μm, Ca concentration 6 mass% (all are trade names), SHIELDEX (average particle diameter 3 μm, Ca concentration 6 to 8 mass%) manufactured by Fuji Silysia Chemical Ltd., SHIELDEX SY710 (average particle diameter 2) 0.2 to 2.5 μm, Ca concentration of 6.6 to 7.5 mass%) (all are trade names) and the like can be used.
また、上記(b)、(c)の成分は沈殿作用によって特に優れた防食性能(自己補修性)を発現する。
上記(b)の成分であるカルシウム化合物は、カルシウム酸化物、カルシウム水酸化物、カルシウム塩のいずれでもよく、これらの1種または2種以上を使用できる。また、カルシウム塩の種類にも特に制限はなく、ケイ酸カルシウム、炭酸カルシウム、リン酸カルシウムなどのようなカチオンとしてカルシウムのみを含む単塩のほか、リン酸カルシウム・亜鉛、リン酸カルシウム・マグネシウムなどのようなカルシウムとカルシウム以外のカチオンを含む複塩を使用してもよい。この(b)の成分は、腐食環境下においてめっき金属である亜鉛やアルミニウムよりも卑なカルシウムが優先溶解し、これがカソード反応により生成したOH−と緻密で難溶性の生成物として欠陥部を封鎖し、腐食反応を抑制する。また、上記のようなシリカとともに配合された場合には、表面にカルシウムイオンが吸着し、表面電荷を電気的に中和して凝集する。その結果、緻密で且つ難溶性の保護皮膜が生成して腐食が封鎖し、腐食反応を抑制する。
In addition, the above components (b) and (c) exhibit particularly excellent anticorrosion performance (self-repairing property) due to precipitation.
The calcium compound as the component (b) may be any of calcium oxide, calcium hydroxide, and calcium salt, and one or more of these can be used. In addition, there are no particular restrictions on the type of calcium salt. In addition to simple salts containing only calcium as a cation such as calcium silicate, calcium carbonate, and calcium phosphate, calcium and calcium such as calcium phosphate / zinc, calcium phosphate / magnesium, etc. Double salts containing other cations may be used. The components (b) is baser calcium than zinc and aluminum as the plating metal in a corrosive environment is preferentially dissolved, this OH produced by the cathode reaction - sequestering defective portion as a product of dense and poorly soluble And suppress the corrosion reaction. Moreover, when it mix | blends with the above silicas, a calcium ion adsorb | sucks to the surface and neutralizes a surface charge electrically and aggregates. As a result, a dense and sparingly soluble protective film is generated to block the corrosion and suppress the corrosion reaction.
また、上記(c)の成分であるリン酸化合物としては、リン酸塩を用いることができる。このリン酸塩は単塩、複塩など全ての種類の塩を含む。また、それを構成する金属カチオンに限定はなく、リン酸亜鉛、リン酸マグネシウム、リン酸カルシウム、リン酸アルミニウムなどのいずれの金属カチオンでもよい。また、リン酸イオンの骨格や縮合度などにも限定はなく、正塩、二水素塩、一水素塩または亜リン酸塩のいずれでもよく、さらに、正塩はオルトリン酸塩の他、ポリリン酸塩などの全ての縮合リン酸塩を含む。このリン酸化合物は、腐食によって溶出しためっき金属の亜鉛やアルミニウムが、加水分解により解離したリン酸イオンと錯形成反応により緻密で且つ難溶性の保護皮膜を生成して腐食起点を封鎖し、腐食反応を抑制する。 Moreover, a phosphate can be used as a phosphoric acid compound which is a component of said (c). This phosphate includes all kinds of salts such as simple salts and double salts. Moreover, there is no limitation in the metal cation which comprises it, and any metal cation, such as zinc phosphate, magnesium phosphate, calcium phosphate, and aluminum phosphate, may be used. Further, there is no limitation on the skeleton or the degree of condensation of phosphate ions, and any of normal salt, dihydrogen salt, monohydrogen salt or phosphite may be used. In addition, orthophosphate may be polyphosphate other than orthophosphate. Includes all condensed phosphates such as salts. In this phosphate compound, zinc or aluminum of the plating metal eluted by corrosion forms a dense and sparingly soluble protective film by complex formation reaction with phosphate ions dissociated by hydrolysis, thereby blocking the corrosion starting point. Suppresses the reaction.
また、上記成分(c)であるリン酸化合物とともに、上記(b)の成分であるカルシウム化合物を複合添加することにより、耐食性をさらに向上させることができる。カルシウム化合物は、カルシウム酸化物、カルシウム水酸化物、カルシウム塩のいずれでもよく、これらの1種または2種以上を使用できる。また、カルシウム塩の種類にも特に制限はなく、ケイ酸カルシウム、炭酸カルシウム、リン酸カルシウムなどのようなカチオンとしてカルシウムのみを含む単塩のほか、リン酸カルシウム・亜鉛、リン酸カルシウム・マグネシウムなどのようなカルシウムとカルシウム以外のカチオンを含む複塩を使用してもよい。 Moreover, corrosion resistance can be further improved by adding together the calcium compound which is the said component (b) with the phosphoric acid compound which is the said component (c). The calcium compound may be any of calcium oxide, calcium hydroxide, and calcium salt, and one or more of these can be used. In addition, there are no particular restrictions on the type of calcium salt. In addition to simple salts containing only calcium as a cation such as calcium silicate, calcium carbonate, and calcium phosphate, calcium and calcium such as calcium phosphate / zinc, calcium phosphate / magnesium, etc. Double salts containing other cations may be used.
また、上記(d)の成分であるモリブデン酸化合物としては、例えば、モリブデン酸塩を用いることができる。このモリブデン酸塩は、その骨格、縮合度に限定はなく、例えばオルトモリブデン酸塩、パラモリブデン酸塩、メタモリブデン酸塩などが挙げられる。また、単塩、複塩などの全ての塩を含み、複塩としてはリンモリブデン酸塩などが挙げられる。モリブデン酸化合物は不動態化効果によって自己補修性を発現する。すなわち、腐食環境下で溶存酸素と共にめっき皮膜表面に緻密な酸化物を形成することで腐食起点を封鎖し、腐食反応を抑制する。 In addition, as the molybdate compound as the component (d), for example, molybdate can be used. The molybdate is not limited in its skeleton and degree of condensation, and examples thereof include orthomolybdate, paramolybdate, and metamolybdate. Moreover, all salts, such as a single salt and a double salt, are included, and a phosphomolybdate etc. are mentioned as a double salt. Molybdate compounds exhibit self-repairing properties due to the passivating effect. That is, by forming a dense oxide on the plating film surface together with dissolved oxygen in a corrosive environment, the corrosion starting point is blocked and the corrosion reaction is suppressed.
また、上記(e)の成分である有機化合物としては、例えば、以下のようなものを挙げることができる。すなわち、トリアゾール類としては、1,2,4−トリアゾール、3−アミノ−1,2,4−トリアゾール、3−メルカプト−1,2,4−トリアゾール、5−アミノ−3−メルカプト−1,2,4−トリアゾール、1H−ベンゾトリアゾールなどが、またチオール類としては、1,3,5−トリアジン−2,4,6−トリチオール、2−メルカプトベンツイミダゾールなどが、またチアジアゾール類としては、5−アミノ−2−メルカプト−1,3,4−チアジアゾール、2,5−ジメルカプト−1,3,4−チアジアゾールなどが、またチアゾール類としては、2−N,N−ジエチルチオベンゾチアゾール、2−メルカプトベンゾチアゾール類などが、またチウラム類としては、テトラエチルチウラムジスルフィドなどが、それぞれ挙げられる。これらの有機化合物は吸着効果によって自己補修性を発現する。すなわち、腐食によって溶出した亜鉛やアルミニウムがこれらの有機化合物が有する硫黄を含む極性基に吸着して不活性皮膜を形成することで腐食起点を封鎖し、腐食反応を抑制する。 Moreover, as an organic compound which is a component of said (e), the following can be mentioned, for example. That is, as triazoles, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino-3-mercapto-1,2 1,4-triazole, 1H-benzotriazole, etc., and as thiols, 1,3,5-triazine-2,4,6-trithiol, 2-mercaptobenzimidazole, etc., and as thiadiazoles, 5- Amino-2-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole and the like, and as thiazoles, 2-N, N-diethylthiobenzothiazole, 2-mercapto Examples include benzothiazoles, and examples of thiurams include tetraethylthiuram disulfide. It is. These organic compounds exhibit self-repairing properties due to the adsorption effect. That is, zinc and aluminum eluted by corrosion are adsorbed on polar groups containing sulfur contained in these organic compounds to form an inert film, thereby blocking the corrosion starting point and suppressing the corrosion reaction.
非クロム系防錆添加剤(F)の配合量は、塗料組成物(Y)中の樹脂固形分100質量部に対して、固形分の割合で好ましくは1〜100質量部、より好ましくは5〜80質量部、さらに好ましくは10〜50質量部とすることが適当である。非クロム系防錆添加剤(F)の配合量が1質量部未満では耐食性向上効果が小さく、一方、配合量が100質量部を超えても、却って耐食性が低下するので好ましくない。
なお、上記(a)〜(e)の防錆添加剤を2種以上複合添加してもよく、この場合にはそれぞれ固有の防食作用が複合化されるため、より高度の耐食性が得られる。特に、上記(a)の成分としてカルシウムイオン交換シリカを用い、且つこれに(c)、(d)、(e)の成分の1種以上、特に好ましくは(c)〜(e)の成分の全部を複合添加した場合に特に優れた耐食性が得られる。
The blending amount of the non-chromium rust preventive additive (F) is preferably 1 to 100 parts by mass, more preferably 5 in terms of the solid content with respect to 100 parts by mass of the resin solid content in the coating composition (Y). It is appropriate to set it to -80 mass parts, More preferably, it is 10-50 mass parts. If the blending amount of the non-chromium rust preventive additive (F) is less than 1 part by mass, the effect of improving the corrosion resistance is small. On the other hand, even if the blending amount exceeds 100 parts by mass, the corrosion resistance is lowered, which is not preferable.
In addition, two or more kinds of the rust preventive additives (a) to (e) may be added in combination. In this case, since the inherent anticorrosive action is combined, higher corrosion resistance can be obtained. In particular, calcium ion-exchanged silica is used as the component (a), and one or more of the components (c), (d), and (e), particularly preferably the components (c) to (e). When all are added in combination, particularly excellent corrosion resistance is obtained.
また、塗料組成物(Y)(上層皮膜)中には上記の防錆添加成分に加えて、腐食抑制剤として、他の酸化物微粒子(例えば、酸化アルミニウム、酸化ジルコニウム、酸化チタン、酸化セリウム、酸化アンチモンなど)、リンモリブデン酸塩(例えば、リンモリブデン酸アルミニウムなど)、有機リン酸及びその塩(例えば、フィチン酸、フィチン酸塩、ホスホン酸、ホスホン酸塩、およびこれらの金属塩、アルカリ金属塩、アルカリ土類金属塩など)、有機インヒビター(例えば、ヒドラジン誘導体、チオール化合物、ジチオカルバミン酸塩など)などの1種または2種以上を添加することができる。 Further, in the coating composition (Y) (upper layer film), other oxide fine particles (for example, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, Antimony oxide, etc.), phosphomolybdate (eg, aluminum phosphomolybdate), organic phosphoric acid and its salts (eg, phytic acid, phytate, phosphonic acid, phosphonate, and metal salts thereof, alkali metals) 1 type, or 2 or more types, such as a salt, alkaline-earth metal salt, etc.), an organic inhibitor (For example, a hydrazine derivative, a thiol compound, a dithiocarbamate etc.) can be added.
塗料組成物(Y)(上層皮膜)中には、さらに必要に応じて、皮膜の加工性を向上させる目的で固形潤滑剤を配合することができる。
本発明に適用できる固形潤滑剤としては、例えば、以下のようなものが挙げられ、これらの1種または2種以上を用いることができる。
(1)ポリオレフィンワックス、パラフィンワックス:例えば、ポリエチレンワックス、合成パラフィン、天然パラフィン、マイクロワックス、塩素化炭化水素など
(2)フッ素樹脂微粒子:例えば、ポリフルオロエチレン樹脂(ポリ4フッ化エチレン樹脂など)、ポリフッ化ビニル樹脂、ポリフッ化ビニリデン樹脂など
In the coating composition (Y) (upper layer film), a solid lubricant can be further blended for the purpose of improving the processability of the film, if necessary.
Examples of the solid lubricant applicable to the present invention include the following, and one or more of these can be used.
(1) Polyolefin wax, paraffin wax: For example, polyethylene wax, synthetic paraffin, natural paraffin, micro wax, chlorinated hydrocarbon, etc. (2) Fluororesin fine particles: For example, polyfluoroethylene resin (polytetrafluoroethylene resin, etc.) , Polyvinyl fluoride resin, polyvinylidene fluoride resin, etc.
また、この他にも、脂肪酸アミド系化合物(例えば、ステアリン酸アミド、パルミチン酸アミド、メチレンビスステアロアミド、エチレンビスステアロアミド、オレイン酸アミド、エシル酸アミド、アルキレンビス脂肪酸アミドなど)、金属石けん類(例えば、ステアリン酸カルシウム、ステアリン酸鉛、ラウリン酸カルシウム、パルミチン酸カルシウムなど)、金属硫化物(例えば、二硫化モリブデン、二硫化タングステンなど)、グラファイト、フッ化黒鉛、窒化ホウ素、ポリアルキレングリコール、アルカリ金属硫酸塩などの1種または2種以上を用いてもよい。 In addition, fatty acid amide compounds (eg, stearic acid amide, palmitic acid amide, methylene bis stearoamide, ethylene bis stearoamide, oleic acid amide, esylic acid amide, alkylene bis fatty acid amide), metal Soaps (eg, calcium stearate, lead stearate, calcium laurate, calcium palmitate, etc.), metal sulfides (eg, molybdenum disulfide, tungsten disulfide, etc.), graphite, graphite fluoride, boron nitride, polyalkylene glycol, You may use 1 type, or 2 or more types, such as an alkali metal sulfate.
以上の固形潤滑剤の中でも、特に、ポリエチレンワックス、フッ素樹脂微粒子(なかでも、ポリ4フッ化エチレン樹脂微粒子)が好適である。
ポリエチレンワックスとしては、例えば、クラリアントジャパン(株)製のセリダスト9615A、セリダスト3715、セリダスト3620、セリダスト3910、三洋化成(株)製のサンワックス131−P、サンワックス161−P、三井化学(株)製のケミパールW−100、ケミパールW−200、ケミパールW−500、ケミパールW−800、ケミパールW−950などを用いることができる(以上、いずれも商品名)。
Among the above solid lubricants, polyethylene wax and fluororesin fine particles (in particular, polytetrafluoroethylene resin fine particles) are preferable.
Examples of the polyethylene wax include Clariant Japan Co., Ltd., Selidust 9615A, Selidust 3715, Selidust 3620, Selidust 3910, Sanyo Chemical Co., Ltd. Sun Wax 131-P, Sun Wax 161-P, Mitsui Chemicals, Inc. Chemipearl W-100, Chemipearl W-200, Chemipearl W-500, Chemipearl W-800, Chemipearl W-950, etc. can be used (all are trade names).
また、フッ素樹脂微粒子としては、テトラフルオロエチレン微粒子が最も好ましく、例えば、ダイキン工業(株)製のルブロンL−2、ルブロンL−5、三井・デュポンフロロケミカル(株)製のMP1100、MP1200、旭硝子(株)製のフルオンディスパージョンAD1、フルオンディスパージョンAD2、フルオンL141J、フルオンL150J、フルオンL155Jなどが好適である(以上、いずれも商品名)。
また、これらのなかで、ポリオレフィンワックスとテトラフルオロエチレン微粒子の併用により特に優れた潤滑効果が期待できる。
固形潤滑剤(G)の配合量は、塗料組成物の樹脂固形分100質量部に対して、固形分の割合で1〜30質量部、好ましくは1〜10質量部とすることが適当である。固形潤滑剤(G)の配合量が1質量部未満では潤滑効果が乏しく、一方、配合量が30質量部を超えると塗装性が低下するので好ましくない。
The fluororesin fine particles are most preferably tetrafluoroethylene fine particles. For example, Lubron L-2 and Lubron L-5 manufactured by Daikin Industries, Ltd., MP1100 and MP1200 manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Asahi Glass. A full-on dispersion AD1, a full-on dispersion AD2, a full-on L141J, a full-on L150J, a full-on L155J, etc. manufactured by Co., Ltd. are suitable (all are trade names).
Among these, a particularly excellent lubricating effect can be expected by the combined use of polyolefin wax and tetrafluoroethylene fine particles.
The blending amount of the solid lubricant (G) is suitably 1 to 30 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the resin solid content of the coating composition. . If the blending amount of the solid lubricant (G) is less than 1 part by mass, the lubricating effect is poor. On the other hand, if the blending amount exceeds 30 parts by mass, the paintability is lowered, which is not preferable.
塗料組成物(Y)(上層皮膜)中には、さらに必要に応じて、添加剤として、有機着色顔料(例えば、縮合多環系有機顔料、フタロシアニン系有機顔料など)、着色染料(例えば、有機溶剤可溶性アゾ系染料、水溶性アゾ系金属染料など)、無機顔料(例えば、酸化チタンなど)、キレート剤(例えば、チオールなど)、導電性顔料(例えば、亜鉛、アルミニウム、ニッケルなどの金属粉末、リン化鉄、アンチモンドープ型酸化錫など)、カップリング剤(例えば、シランカップリング剤、チタンカップリング剤など)、メラミン・シアヌル酸付加物などの1種または2種以上を添加することができる。
上層皮膜の膜厚は0.1〜3.0μm、好ましくは0.4〜1.5μmとする。上層皮膜の膜厚が0.1μm未満では十分な耐食性が得られず、一方、3.0μmを超えると溶接性や電着塗装性が低下する。
また、溶接性や電着塗装性の観点からは、第一層の表面処理皮膜と第二層の上層皮膜の合計膜厚は2.0μm以下とすることが好ましい。
In the coating composition (Y) (upper layer film), an organic coloring pigment (for example, a condensed polycyclic organic pigment, a phthalocyanine organic pigment, etc.) or a coloring dye (for example, an organic coating) is further added as necessary. Solvent-soluble azo dyes, water-soluble azo metal dyes, etc.), inorganic pigments (eg, titanium oxide), chelating agents (eg, thiols), conductive pigments (eg, metal powders such as zinc, aluminum, nickel, etc.) 1 type, or 2 or more types, such as an iron phosphide and an antimony dope type tin oxide), a coupling agent (for example, a silane coupling agent, a titanium coupling agent, etc.), a melamine cyanuric acid adduct, etc. can be added. .
The film thickness of the upper film is 0.1 to 3.0 μm, preferably 0.4 to 1.5 μm. If the film thickness of the upper layer film is less than 0.1 μm, sufficient corrosion resistance cannot be obtained. On the other hand, if it exceeds 3.0 μm, the weldability and the electrodeposition coating property are deteriorated.
Further, from the viewpoint of weldability and electrodeposition coating properties, the total film thickness of the surface treatment film of the first layer and the upper film of the second layer is preferably 2.0 μm or less.
以上のような表面処理鋼板を製造するには、亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に、上述したような成分が配合された表面処理組成物(X)(処理液)を塗布して乾燥させ、次いで、上述したような成分が配合された上層皮膜形成用の塗料組成物(Y)を塗布し、乾燥させる。
表面処理組成物(X)をめっき鋼板表面にコーティングする方法としては、塗布法、浸漬法、スプレー法などの任意の方法を採用できる。塗布法としては、ロールコーター(3ロール方式、2ロール方式など)、スクイズコーター、ダイコーターなどのいずれの方法を用いてもよい。また、スクイズコーターなどによる塗布処理、浸漬処理またはスプレー処理の後に、エアナイフ法やロール絞り法により塗布量の調整、外観の均一化、膜厚の均一化を行うことも可能である。
In order to produce the surface-treated steel sheet as described above, the surface treatment composition (X) (treatment liquid) in which the components as described above are blended is applied to the surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet. Then, a coating composition (Y) for forming an upper layer film containing the above-described components is applied and dried.
As a method for coating the surface treatment composition (X) on the surface of the plated steel sheet, any method such as a coating method, a dipping method, a spray method, or the like can be adopted. As a coating method, any method such as a roll coater (3-roll method, 2-roll method, etc.), a squeeze coater, or a die coater may be used. In addition, after the coating process, dipping process or spraying process using a squeeze coater or the like, the coating amount can be adjusted, the appearance can be made uniform, and the film thickness can be made uniform by an air knife method or a roll drawing method.
表面処理組成物(X)をコーティングした後は、通常は水洗することなく加熱乾燥を行う。加熱乾燥処理には、ドライヤー、熱風炉、高周波誘導加熱炉、赤外線炉などを用いることができる。加熱乾燥は、到達板温で30〜200℃、好ましくは40℃〜140℃の範囲で行うことが望ましい。加熱乾燥温度が30℃未満では皮膜中の水分が多量に残り、耐食性が不十分となる。また、加熱乾燥温度が200℃を超えると非経済的であるばかりでなく、皮膜に欠陥が生じて耐食性が低下するおそれがある。
上層皮膜形成用の塗料組成物(Y)をコーティングする方法としても、塗布法、浸漬法、スプレー法などの任意の方法を採用できる。塗布法としては、ロールコーター(3ロール方式、2ロール方式など)、スクイズコーター、ダイコーターなどのいずれの方法を用いてもよい。また、スクイズコーターなどによる塗布処理、浸漬処理またはスプレー処理の後に、エアナイフ法やロール絞り法により塗布量の調整、外観の均一化、膜厚の均一化を行うことも可能である。
After coating the surface treatment composition (X), it is usually heated and dried without washing with water. For the heat drying treatment, a dryer, a hot air furnace, a high-frequency induction heating furnace, an infrared furnace, or the like can be used. The heat drying is desirably performed in the range of 30 to 200 ° C., preferably 40 ° C. to 140 ° C., at the ultimate plate temperature. If the heating and drying temperature is less than 30 ° C., a large amount of moisture remains in the film, resulting in insufficient corrosion resistance. In addition, when the heating and drying temperature exceeds 200 ° C., not only is it uneconomical, but there is a possibility that defects occur in the film and the corrosion resistance decreases.
As a method for coating the coating composition (Y) for forming the upper layer film, any method such as a coating method, a dipping method, a spray method and the like can be adopted. As a coating method, any method such as a roll coater (3-roll method, 2-roll method, etc.), a squeeze coater, or a die coater may be used. In addition, after the coating process, dipping process or spraying process using a squeeze coater or the like, the coating amount can be adjusted, the appearance can be made uniform, and the film thickness can be made uniform by an air knife method or a roll drawing method.
塗料組成物(Y)の塗布後、通常は水洗することなく、加熱乾燥を行うが、塗料組成物の塗布後に水洗工程を実施してもよい。加熱乾燥処理には、ドライヤー、熱風炉、高周波誘導加熱炉、赤外線炉などを用いることができるが、耐食性の観点からは高周波誘導加熱炉が特に好ましい。加熱処理は、到達板温で50〜350℃、好ましくは80℃〜250℃の範囲で行うことが望ましい。加熱温度が50℃未満では皮膜中の溶媒が多量に残り、耐食性が不十分となる。また、加熱温度が350℃を超えると非経済的であるばかりでなく、皮膜に欠陥が生じて耐食性が低下するおそれがある。 After application of the coating composition (Y), heating drying is usually performed without washing with water, but a washing process may be performed after application of the coating composition. For the heat drying treatment, a dryer, a hot air furnace, a high frequency induction heating furnace, an infrared furnace, or the like can be used, but a high frequency induction heating furnace is particularly preferable from the viewpoint of corrosion resistance. The heat treatment is desirably performed in the range of 50 to 350 ° C., preferably 80 to 250 ° C., at the ultimate plate temperature. If the heating temperature is less than 50 ° C., a large amount of the solvent remains in the film, resulting in insufficient corrosion resistance. Further, when the heating temperature exceeds 350 ° C., not only is it uneconomical, but there is a possibility that defects occur in the film and the corrosion resistance is lowered.
本発明は、以上述べたような皮膜を両面または片面に有する鋼板を含むものである。したがって、本発明の表面処理鋼板の形態としては、例えば、以下のようなものがある。
(1)片面:めっき皮膜−表面処理皮膜−上層皮膜、片面:めっき皮膜
(2)片面:めっき皮膜−表面処理皮膜−上層皮膜、片面:めっき皮膜−公知のリン酸塩処理皮膜など
(3)両面:めっき皮膜−表面処理皮膜−上層皮膜
(4)片面:めっき皮膜−表面処理皮膜−上層皮膜、片面:めっき皮膜−表面処理皮膜(本発明の表面処理皮膜に相当する皮膜)
(5)片面:めっき皮膜−表面処理皮膜−上層皮膜、片面:めっき皮膜−有機皮膜(本発明の上層皮膜に相当する皮膜)
The present invention includes a steel plate having a coating as described above on both sides or one side. Accordingly, examples of the form of the surface-treated steel sheet according to the present invention include the following.
(1) One side: plating film-surface treatment film-upper layer film, one side: plating film (2) One side: plating film-surface treatment film-upper layer film, one side: plating film-known phosphate treatment film, etc. (3) Both sides: plating film-surface treatment film-upper layer film (4) Single side: plating film-surface treatment film-upper layer film, one side: plating film-surface treatment film (film corresponding to the surface treatment film of the present invention)
(5) One side: plating film-surface treatment film-upper layer film, one side: plating film-organic film (film corresponding to the upper layer film of the present invention)
[第一層(表面処理皮膜)用の表面処理組成物]
表面処理組成物に用いたチタン含有水性液A1〜A7、有機リン酸化合物B1〜B6、無機リン酸化合物C1〜C5、水性有機樹脂D1〜D7(水溶性又は水分散性有機樹脂)を以下に示す。これらの成分を表2および表3に示す割合で配合し、表面処理組成物P1〜P42を得た。
[Surface treatment composition for first layer (surface treatment film)]
Titanium-containing aqueous liquids A1 to A7, organic phosphoric acid compounds B1 to B6, inorganic phosphoric acid compounds C1 to C5, and aqueous organic resins D1 to D7 (water-soluble or water-dispersible organic resins) used for the surface treatment composition are as follows. Show. These components were blended in the proportions shown in Tables 2 and 3 to obtain surface treatment compositions P1 to P42.
(1)チタン含有水性液A1〜A7の製造
・製造例1
四塩化チタン60%溶液5ccを蒸留水で500ccとした溶液にアンモニア水(1:9)を滴下し、水酸化チタンを沈殿させた。蒸留水で洗浄後、過酸化水素水30%溶液を10cc加えてかき混ぜ、チタンを含む黄色半透明の粘性のあるチタン含有水性液A1を得た。
・製造例2
テトラiso−プロポキシチタン10質量部とiso−プロパノール10質量部の混合物を30%過酸化水素水10質量部と脱イオン水100質量部の混合物中に20℃で1時間かけて撹拌しながら滴下した。その後25℃で2時間熟成し、黄色透明の少し粘性のあるチタン含有水性液A2を得た。
(1) Production and production example 1 of titanium-containing aqueous liquids A1 to A7
Ammonia water (1: 9) was dropped into a solution in which 5 cc of a titanium tetrachloride 60% solution was made 500 cc with distilled water to precipitate titanium hydroxide. After washing with distilled water, 10 cc of a 30% hydrogen peroxide solution was added and mixed to obtain a yellow translucent viscous titanium-containing aqueous liquid A1 containing titanium.
・ Production example 2
A mixture of 10 parts by mass of tetraiso-propoxytitanium and 10 parts by mass of iso-propanol was dropped into a mixture of 10 parts by mass of 30% hydrogen peroxide and 100 parts by mass of deionized water while stirring at 20 ° C. over 1 hour. . Thereafter, aging was carried out at 25 ° C. for 2 hours to obtain a yellow transparent slightly viscous titanium-containing aqueous liquid A2.
・製造例3
製造例2で使用したテトラiso−プロポキシチタンの代わりにテトラn−ブトキシチタンを使用した以外は製造例2と同様の製造条件で、チタン含有水性液A3を得た。
・製造例4
製造例2で使用したテトラiso−プロポキシチタンの代わりにテトラiso−プロポキシチタンの3量体を使用した以外は製造例2と同様の製造条件で、チタン含有水性液A4を得た。
・製造例5
製造例2に対して過酸化水素水を3倍量用い、50℃で1時間かけて滴下し、さらに60℃で3時間熟成した以外は製造例2と同様の製造条件で、チタン含有水性液A5を得た。
・ Production Example 3
A titanium-containing aqueous liquid A3 was obtained under the same production conditions as in Production Example 2 except that tetra-n-butoxy titanium was used instead of tetraiso-propoxy titanium used in Production Example 2.
・ Production Example 4
A titanium-containing aqueous liquid A4 was obtained under the same production conditions as in Production Example 2, except that tetraiso-propoxytitanium trimer was used instead of tetraiso-propoxytitanium used in Production Example 2.
・ Production Example 5
A titanium-containing aqueous liquid was produced under the same production conditions as in Production Example 2, except that hydrogen peroxide water was used in 3 times the amount of Production Example 2, dropped at 50 ° C. over 1 hour, and further aged at 60 ° C. for 3 hours. A5 was obtained.
・製造例6
製造例3で製造したチタン含有水性液A3を、さらに95℃で6時間加熱処理することにより、白黄色の半透明なチタン含有水性液A6を得た。
・製造例7
テトラiso−プロポキシチタン10質量部とiso−プロパノール10質量部の混合物を、「TKS−203」(商品名,テイカ社製,酸化チタンゾル)5質量部(固形分)、30%過酸化水素水10質量部及び脱イオン水100質量部の混合物中に10℃で1時間かけて撹拌しながら滴下した。その後10℃で24時間熟成し、黄色透明の少し粘性のあるチタン含有水性液A7を得た。
・ Production Example 6
The titanium-containing aqueous liquid A3 produced in Production Example 3 was further heat-treated at 95 ° C. for 6 hours to obtain a white-yellow translucent titanium-containing aqueous liquid A6.
・ Production Example 7
A mixture of 10 parts by mass of tetraiso-propoxytitanium and 10 parts by mass of iso-propanol, 5 parts by mass (solid content) of “TKS-203” (trade name, manufactured by Teika Co., Ltd.), 30% hydrogen peroxide solution 10 The mixture was added dropwise to a mixture of parts by mass and 100 parts by mass of deionized water at 10 ° C. with stirring for 1 hour. Thereafter, the mixture was aged at 10 ° C. for 24 hours to obtain a yellow transparent slightly viscous titanium-containing aqueous liquid A7.
(2)有機リン酸化合物B1〜B6
B1:1−ヒドロキシメタン−1,1−ジホスホン酸
B2:1−ヒドロキシエタン−1,1−ジホスホン酸
B3:1−ヒドロキシプロパン−1,1−ジホスホン酸
B4:2−ヒドロキシホスホノ酢酸
B5:3−ホスホノブタン−1,2,4−トリカルボン酸
B6:2−ヒドロキシホスホノ酢酸カリウム
(3)無機リン酸化合物C1〜C5
C1:10%オルトリン酸
C2:10%メタリン酸
C3:トリポリリン酸
C4:ピロリン酸ナトリウム
C5:メタリン酸アンモニウム
(2) Organophosphate compounds B1 to B6
B1: 1-hydroxymethane-1,1-diphosphonic acid B2: 1-hydroxyethane-1,1-diphosphonic acid B3: 1-hydroxypropane-1,1-diphosphonic acid B4: 2-hydroxyphosphonoacetic acid B5: 3 -Phosphonobutane-1,2,4-tricarboxylic acid B6: Potassium 2-hydroxyphosphonoacetate (3) Inorganic phosphate compounds C1 to C5
C1: 10% orthophosphoric acid C2: 10% metaphosphoric acid C3: tripolyphosphoric acid C4: sodium pyrophosphate C5: ammonium metaphosphate
(4-1)水性有機樹脂D1〜D4の合成
・合成例1
窒素封入管、玉入りコンデンサー、滴下ロートおよびメカニカルスターラーを備えたフラスコに、プロピレングリコールモノメチルエーテル200質量部を入れ、90℃まで加熱した後、温度を90℃に保持した状態で、フラスコ内にスチレン10質量部、tert−ブチルアクリレート80質量部、2−ヒドロキシエチルアクリレート10質量部およびアゾビスイソブチロニトリル1質量部の混合物を3時間かけて滴下し、滴下終了後さらに90℃に2時間保持した後、室温まで冷却して水性有機樹脂(アクリル樹脂溶液)D1を得た。得られたアクリル樹脂のTg(ガラス転移点)は33℃である。
・合成例2
窒素封入管、玉入りコンデンサー、滴下ロートおよびメカニカルスターラーを備えたフラスコに、プロピレングリコールモノメチルエーテル200質量部を入れ、90℃まで加熱した後、温度を90℃に保持した状態で、フラスコ内にスチレン25質量部、メチルアクリレート60質量部、アクリルアミド15質量部およびアゾビスイソブチロニトリル1質量部の混合物を3時間かけて滴下し、滴下終了後さらに90℃に2時間保持した後、室温まで冷却して水性有機樹脂(アクリル樹脂溶液)D2を得た。得られたアクリル樹脂のTgは46℃である。
(4-1) Synthesis / Synthesis Example 1 of water-based organic resins D1 to D4
In a flask equipped with a nitrogen-filled tube, a ball condenser, a dropping funnel and a mechanical stirrer, 200 parts by mass of propylene glycol monomethyl ether was heated to 90 ° C., and then the temperature was maintained at 90 ° C., and styrene was added to the flask. A mixture of 10 parts by mass, 80 parts by mass of tert-butyl acrylate, 10 parts by mass of 2-hydroxyethyl acrylate, and 1 part by mass of azobisisobutyronitrile was added dropwise over 3 hours, and after completion of the addition, maintained at 90 ° C. for 2 hours. Then, it was cooled to room temperature to obtain an aqueous organic resin (acrylic resin solution) D1. The obtained acrylic resin has a Tg (glass transition point) of 33 ° C.
Synthesis example 2
In a flask equipped with a nitrogen-filled tube, a ball condenser, a dropping funnel and a mechanical stirrer, 200 parts by mass of propylene glycol monomethyl ether was heated to 90 ° C., and then the temperature was maintained at 90 ° C., and styrene was added to the flask. A mixture of 25 parts by mass, 60 parts by mass of methyl acrylate, 15 parts by mass of acrylamide and 1 part by mass of azobisisobutyronitrile was added dropwise over 3 hours. After completion of the addition, the mixture was further maintained at 90 ° C. for 2 hours and then cooled to room temperature. Thus, an aqueous organic resin (acrylic resin solution) D2 was obtained. The obtained acrylic resin has a Tg of 46 ° C.
・合成例3
窒素封入管、玉入りコンデンサー、滴下ロートおよびメカニカルスターラーを備えたフラスコに、プロピレングリコールモノメチルエーテル200質量部を入れ、90℃まで加熱した後、温度を90℃に保持した状態で、フラスコ内にスチレン55質量部、n−ブチルアクリレート5質量部、2−ヒドロキシエチルメタクリレート20質量部、N−メチルアクリルアミド20質量部およびアゾビスイソブチロニトリル1質量部の混合物を3時間かけて滴下し、滴下終了後さらに90℃に2時間保持した後、室温まで冷却して水性有機樹脂(アクリル樹脂溶液)D3を得た。得られたアクリル樹脂のTgは78℃である。
・合成例4
窒素封入管、玉入りコンデンサー、滴下ロートおよびメカニカルスターラーを備えたフラスコに、プロピレングリコールモノメチルエーテル200質量部を入れ、90℃まで加熱した後、温度を90℃に保持した状態で、フラスコ内にメチルメタクリレート80質量部、n−ブチルアクリレート10質量部、2−ヒドロキシエチルアクリレート10質量部およびアゾビスイソブチロニトリル1質量部の混合物を3時間かけて滴下し、滴下終了後さらに90℃に2時間保持した後、室温まで冷却して水性有機樹脂(アクリル樹脂溶液)D4を得た。得られたアクリル樹脂のTgは56℃である。
Synthesis example 3
In a flask equipped with a nitrogen-filled tube, a ball condenser, a dropping funnel and a mechanical stirrer, 200 parts by mass of propylene glycol monomethyl ether was heated to 90 ° C., and then the temperature was maintained at 90 ° C., and styrene was added to the flask. A mixture of 55 parts by mass, 5 parts by mass of n-butyl acrylate, 20 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of N-methylacrylamide and 1 part by mass of azobisisobutyronitrile was added dropwise over 3 hours, and the addition was completed. Thereafter, the mixture was further maintained at 90 ° C. for 2 hours, and then cooled to room temperature to obtain an aqueous organic resin (acrylic resin solution) D3. The obtained acrylic resin has a Tg of 78 ° C.
Synthesis example 4
In a flask equipped with a nitrogen-filled tube, a ball condenser, a dropping funnel and a mechanical stirrer, 200 parts by mass of propylene glycol monomethyl ether was heated to 90 ° C., and the temperature was maintained at 90 ° C. A mixture of 80 parts by weight of methacrylate, 10 parts by weight of n-butyl acrylate, 10 parts by weight of 2-hydroxyethyl acrylate, and 1 part by weight of azobisisobutyronitrile is dropped over 3 hours. After being held, it was cooled to room temperature to obtain an aqueous organic resin (acrylic resin solution) D4. The obtained acrylic resin has a Tg of 56 ° C.
(4-2)水性有機樹脂D5〜D7
D5:「スーパーフレックスE−2500」(商品名,第一工業製薬社製,水性ポリウレタン樹脂)
D6:「バイロナールMD−1100」(商品名,東洋紡績社製,水性ポリエステル樹脂)
D7:「アデカレジンEM−0718」(商品名,(株)ADEKA社製,水性エポキシ樹脂)
(4-2) Water-based organic resins D5 to D7
D5: “Superflex E-2500” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin)
D6: “Vaironal MD-1100” (trade name, manufactured by Toyobo Co., Ltd., water-based polyester resin)
D7: “Adeka Resin EM-0718” (trade name, manufactured by ADEKA Corporation, water-based epoxy resin)
[第二層(上層皮膜)用の塗料組成物]
第二層形成用の塗料組成物は、有機樹脂(樹脂組成物)として表4に示すものを用い、これに非クロム系防錆添加剤(表5)を適宜配合し、塗料用分散機(サンドグラインダー)を用いて所定時間攪拌することで調製した。
[Coating composition for second layer (upper layer film)]
As the coating composition for forming the second layer, the organic resin (resin composition) shown in Table 4 is used, and a non-chromium rust preventive additive (Table 5) is appropriately blended therein, and a coating disperser ( It was prepared by stirring for a predetermined time using a sand grinder.
[表面処理鋼板の製造]
冷延鋼板をベースとした家電、建材、自動車部品用のめっき鋼板である、表1に示すめっき鋼板を処理原板として用いた。なお、鋼板の板厚は評価の目的に応じて所定の板厚のものを採用した。このめっき鋼板の表面をアルカリ脱脂処理、水洗乾燥した後、上記第一層形成用の表面処理組成物をロールコーターにより塗布し、各種温度で加熱乾燥した。皮膜の膜厚は、表面処理組成物の固形分(加熱残分)または塗布条件(ロールの圧下力、回転速度など)により調整した。
次いで、上記第二層形成用の塗料組成物をロールコーターにより塗布し、各種温度で加熱乾燥した。皮膜の膜厚は、塗料組成物の固形分(加熱残分)または塗布条件(ロールの圧下力、回転速度など)により調整した。
[Manufacture of surface-treated steel sheets]
The plated steel sheet shown in Table 1, which is a plated steel sheet for home appliances, building materials, and automobile parts based on cold-rolled steel sheets, was used as a processing original sheet. In addition, the thing of predetermined | prescribed board thickness was employ | adopted for the board thickness of the steel plate according to the objective of evaluation. After the surface of this plated steel sheet was subjected to alkali degreasing treatment, washed with water and dried, the surface treatment composition for forming the first layer was applied with a roll coater and dried by heating at various temperatures. The film thickness of the film was adjusted by the solid content (heating residue) of the surface treatment composition or coating conditions (rolling force of the roll, rotation speed, etc.).
Next, the coating composition for forming the second layer was applied by a roll coater and dried by heating at various temperatures. The film thickness of the film was adjusted by the solid content (heating residue) of the coating composition or application conditions (rolling force of roll, rotation speed, etc.).
[表面処理鋼板の性能評価]
得られた表面処理鋼板の品質性能(耐食性、アルカリ脱脂後耐食性、加工後耐食性、溶接性、電着塗装性、接着接合性)を評価した結果を、皮膜構成とともに表6〜表11に示す。なお、品質性能の評価は以下のようにして行った。
(1)耐食性
各サンプルについて、下記の複合サイクル試験(CCT)を施し、81サイクル経過後の白錆発生面積率および赤錆発生面積率で評価した。
塩水噴霧(JIS−Z−2371に基づく):2時間
↓
乾燥(60℃):4時間
↓
湿潤(50℃、≧95%RH):2時間
その評価基準は以下の通りである。
◎ :白錆発生面積率5%未満
○+:白錆発生面積率5%以上、10%未満
○ :白錆発生面積率10%以上、30%未満で、赤錆発生なし
△ :赤錆発生ありで、赤錆発生面積率10%未満
× :赤錆発生面積率10%以上
[Performance evaluation of surface-treated steel sheet]
Tables 6 to 11 show the results of evaluating the quality performance (corrosion resistance, corrosion resistance after alkaline degreasing, corrosion resistance after processing, weldability, electrodeposition paintability, adhesive bondability) of the obtained surface-treated steel sheets together with the coating composition. The quality performance was evaluated as follows.
(1) Corrosion resistance About each sample, the following combined cycle test (CCT) was given, and the white rust generation | occurrence | production area ratio and red rust generation | occurrence | production area ratio after 81 cycles passed were evaluated.
Salt spray (based on JIS-Z-2371): 2 hours ↓
Dry (60 ° C): 4 hours ↓
Wet (50 ° C., ≧ 95% RH): 2 hours The evaluation criteria are as follows.
◎: White rust generation area ratio less than 5% ○ +: White rust generation area ratio of 5% or more and less than 10% ○: White rust generation area ratio of 10% or more and less than 30%, no red rust generation △: Red rust generation , Red rust occurrence area ratio less than 10% ×: Red rust occurrence area ratio 10% or more
(2)アルカリ脱脂後耐食性
各サンプルについて、日本パーカラインジング(株)製「FC−4460」を用いて、60℃、2分間スプレー処理の条件で脱脂した後、下記の複合サイクル試験(CCT)を施し、81サイクル経過後の白錆発生面積率および赤錆発生面積率で評価した。
塩水噴霧(JIS−Z−2371に基づく):2時間
↓
乾燥(60℃):4時間
↓
湿潤(50℃、≧95%RH):2時間
その評価基準は以下のとおりである。
◎ :白錆発生面積率5%未満
○+:白錆発生面積率5%以上、10%未満
○ :白錆発生面積率10%以上、30%未満で、赤錆発生なし
△ :赤錆発生ありで、赤錆発生面積率10%未満
× :赤錆発生面積率10%以上
(2) Corrosion resistance after alkaline degreasing Each sample was degreased under the conditions of spray treatment at 60 ° C for 2 minutes using "FC-4460" manufactured by Nippon Parker Lines Co., Ltd. and then subjected to the following combined cycle test (CCT) And the white rust generation area ratio and red rust generation area ratio after 81 cycles were evaluated.
Salt spray (based on JIS-Z-2371): 2 hours ↓
Dry (60 ° C): 4 hours ↓
Wet (50 ° C., ≧ 95% RH): 2 hours The evaluation criteria are as follows.
◎: White rust generation area ratio less than 5% ○ +: White rust generation area ratio of 5% or more and less than 10% ○: White rust generation area ratio of 10% or more and less than 30%, no red rust generation △: Red rust generation , Red rust occurrence area ratio less than 10% ×: Red rust occurrence area ratio 10% or more
(3)加工後耐食性
各サンプルについて、下記の条件によるドロービードで変形と摺動を付加し、このサンプルを日本パーカライジング(株)製「FC−4460」を用いて、60℃、2分間スプレー処理の条件で脱脂した後、前記「(1)耐食性」で行ったCCTを施し、42サイクル経過後の白錆発生面積率および赤錆発生面積率で評価した。
押付荷重:800kgf
引抜速度:1000mm/min
ビード肩R:オス側2mmR、メス側3mmR
押し込み深さ:7mm
使用油:スギムラ化学工業(株)製「プレトンR−352L」
その評価基準は以下のとおりである。
◎ :白錆発生面積率5%未満
○+:白錆発生面積率5%以上、10%未満
○ :白錆発生面積率10%以上で、赤錆発生なし
△ :赤錆発生ありで、赤錆発生面積率10%未満
× :赤錆発生面積率10%以上
(3) Corrosion resistance after processing For each sample, deformation and sliding were added with a draw bead according to the following conditions, and this sample was subjected to spray treatment at 60 ° C. for 2 minutes using “FC-4460” manufactured by Nihon Parkerizing Co., Ltd. After degreasing under the conditions, the CCT performed in “(1) Corrosion resistance” was performed, and the white rust generation area ratio and the red rust generation area ratio after 42 cycles were evaluated.
Pressing load: 800kgf
Drawing speed: 1000mm / min
Bead shoulder R: male side 2mmR, female side 3mmR
Pushing depth: 7mm
Oil used: “Preton R-352L” manufactured by Sugimura Chemical Co., Ltd.
The evaluation criteria are as follows.
◎: White rust generation area ratio less than 5% ○ +: White rust generation area ratio of 5% or more and less than 10% ○: White rust generation area ratio of 10% or more, no red rust generation △: Red rust generation, red rust generation area Rate less than 10% ×: Red rust generation area rate of 10%
(4)溶接性
各サンプルについて、使用電極:CF型Cr−Cu電極、加圧力:200kgf、通電時間:10サイクル/50Hz、溶接電流:10kAの条件で連続打点性の溶接試験を行い、連続打点数で評価した。その評価基準は以下のとおりである。
◎ :2000点以上
○ :1000点以上、2000点未満
△ :500点以上、1000点未満
× :500点未満
(5)電着塗装性
各サンプルにカチオン系電着塗料(関西ペイント(株)製「GT−10」)を膜厚30μmとなるように塗装した後、170℃×20分の焼付を行った。塗装したサンプルを40℃温水中に240時間浸漬し、直ちに碁盤目(10×10個、1mm間隔)のカットを入れて接着テープによる貼着・剥離を行い、塗膜の剥離面積率を測定した。その評価基準は以下のとおりである。
◎:剥離なし
○:剥離面積率5%未満
△:剥離面積率5%以上、20%未満
×:剥離面積率20%以上
(4) Weldability For each sample, a welding test with continuous spotting was performed under the conditions of electrode used: CF type Cr—Cu electrode, applied pressure: 200 kgf, energization time: 10 cycles / 50 Hz, welding current: 10 kA The score was evaluated. The evaluation criteria are as follows.
◎: 2000 points or more ○: 1000 points or more, less than 2000 points △: 500 points or more, less than 1000 points ×: Less than 500 points (5) Electrodeposition coating property Cationic electrodeposition paint (manufactured by Kansai Paint Co., Ltd.) After coating “GT-10”) to a film thickness of 30 μm, baking was performed at 170 ° C. for 20 minutes. The coated sample was immersed in warm water at 40 ° C. for 240 hours, immediately cut into grids (10 × 10 pieces, 1 mm interval), attached and peeled with adhesive tape, and the peeled area ratio of the coating film was measured. . The evaluation criteria are as follows.
◎: No peeling ○: Peeling area ratio less than 5% △: Peeling area ratio of 5% or more and less than 20% ×: Peeling area ratio of 20% or more
(6)接着接合性
各サンプルを25mm×200mmのサイズに剪断し、その表面に洗浄油(スギムラ化学工業(株)製「プレトン303P」)を1g/m2塗布し、一日放置後、接着剤(セメダインヘンケル社製「マクロプラストPV5308」)をサンプルの25mm×150mmの範囲に塗布し、0.15mmのピアノ線を3本挟むようにして、もう一方のサンプルを重ね合わせ、クリップで固定した。焼付処理を170℃×20分行い、また一日放置してサンプルを作成した。接着剤を塗布していない25mm×50mmの部分を90度に折り曲げ、引張り試験機を用いて200mm/minの条件にてTピール剥離試験を行い、その時の剥離強度を測定した。その評価基準は以下の通りである。
◎:125N/25mm以上
○:118N/25mm以上、125N/25mm未満
△:50N/25mm以上、118N/25mm未満
×:50N/25mm未満
(6) Adhesive bondability Each sample was sheared to a size of 25 mm × 200 mm, and 1 g / m 2 of cleaning oil (“Preton 303P” manufactured by Sugimura Chemical Industry Co., Ltd.) was applied to the surface. An agent (“Macroplast PV5308” manufactured by Cemedine Henkel Co., Ltd.) was applied to a 25 mm × 150 mm range of the sample, and three other 0.15 mm piano wires were sandwiched, and the other sample was overlapped and fixed with a clip. A baking treatment was performed at 170 ° C. for 20 minutes, and the sample was left standing for one day to prepare a sample. A 25 mm × 50 mm portion to which no adhesive was applied was bent at 90 degrees, a T peel peel test was performed using a tensile tester at 200 mm / min, and the peel strength at that time was measured. The evaluation criteria are as follows.
◎: 125 N / 25 mm or more ○: 118 N / 25 mm or more, less than 125 N / 25 mm Δ: 50 N / 25 mm or more, less than 118 N / 25 mm ×: less than 50 N / 25 mm
表2および表3において、*1〜*5は以下の内容を示す。
*1 明細書本文に記載のチタン含有水性液A1〜A7
*2 明細書本文に記載の有機リン酸化合物B1〜B6
*3 明細書本文に記載の無機リン酸化合物C1〜C5
*4 明細書本文に記載の水溶性又は水分散性有機樹脂D1〜D7
*5 固形分の質量部
In Tables 2 and 3, * 1 to * 5 indicate the following contents.
* 1 Titanium-containing aqueous liquids A1 to A7 described in the main text of the specification
* 2 Organophosphate compounds B1 to B6 described in the specification text
* 3 Inorganic phosphate compounds C1 to C5 described in the specification text
* 4 Water-soluble or water-dispersible organic resins D1 to D7 described in the main text of the specification
* 5 Mass parts of solid content
表6〜表11において、*1〜*5は以下の内容を示す。
*1 表1に記載のめっき鋼板No.1〜No.9
*2 表2および表3に記載の表面処理組成物P1〜P42
*3 表4に記載の有機樹脂No.1〜No.5
*4 表5に記載の防錆添加剤No.1〜No.7
*5 固形分の質量部
In Tables 6 to 11, * 1 to * 5 indicate the following contents.
* 1 Plated steel plate No. 1-No. 9
* 2 Surface treatment compositions P1 to P42 described in Tables 2 and 3
* 3 Organic resin Nos. Listed in Table 4 1-No. 5
* 4 Rust prevention additive No. described in Table 5 1-No. 7
* 5 Mass parts of solid content
Claims (4)
(a)酸化ケイ素
(b)カルシウム化合物
(c)リン酸化合物
(d)モリブデン酸化合物
(e)トリアゾール類、チオール類、チアジアゾール類、チアゾール類、チウラム類の中から選ばれる1種以上の有機化合物 The coating composition (Y) contains at least one non-chromium rust preventive additive (F) selected from the following (a) to (e) with respect to 100 parts by mass of the resin solid content in the coating composition. The highly corrosion-resistant surface-treated steel sheet according to any one of claims 1 to 3, which is contained in an amount of 1 to 100 parts by mass.
(A) silicon oxide (b) calcium compound (c) phosphoric acid compound (d) molybdate compound (e) one or more organic compounds selected from triazoles, thiols, thiadiazoles, thiazoles, thiurams
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US10508203B2 (en) | 2014-09-26 | 2019-12-17 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
EP3456862A4 (en) * | 2016-05-10 | 2020-01-08 | Hoden Seimitsu Kako Kenkyusho Co., Ltd. | Aqueous anti-rust surface treatment composition and surface-coated metal member |
CN114703470A (en) * | 2022-03-10 | 2022-07-05 | 福建宏贯路桥防腐科技股份有限公司 | Environment-friendly passivation solution and passivation process for metal component |
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JP2003193088A (en) * | 2001-12-26 | 2003-07-09 | Kansai Paint Co Ltd | Surface-finishing composition for metallic material |
JP2006022370A (en) * | 2004-07-07 | 2006-01-26 | Kansai Paint Co Ltd | Surface-treated steel sheet |
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JP2003193088A (en) * | 2001-12-26 | 2003-07-09 | Kansai Paint Co Ltd | Surface-finishing composition for metallic material |
JP2006022370A (en) * | 2004-07-07 | 2006-01-26 | Kansai Paint Co Ltd | Surface-treated steel sheet |
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US10508203B2 (en) | 2014-09-26 | 2019-12-17 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
US11459466B2 (en) | 2014-09-26 | 2022-10-04 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
EP3456862A4 (en) * | 2016-05-10 | 2020-01-08 | Hoden Seimitsu Kako Kenkyusho Co., Ltd. | Aqueous anti-rust surface treatment composition and surface-coated metal member |
CN114703470A (en) * | 2022-03-10 | 2022-07-05 | 福建宏贯路桥防腐科技股份有限公司 | Environment-friendly passivation solution and passivation process for metal component |
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