JP2015196878A - Surface-treated steel sheet and composite member - Google Patents
Surface-treated steel sheet and composite member Download PDFInfo
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- JP2015196878A JP2015196878A JP2014075250A JP2014075250A JP2015196878A JP 2015196878 A JP2015196878 A JP 2015196878A JP 2014075250 A JP2014075250 A JP 2014075250A JP 2014075250 A JP2014075250 A JP 2014075250A JP 2015196878 A JP2015196878 A JP 2015196878A
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本発明は、樹脂（プラスチック）との接着性に優れた皮膜を有する表面処理鋼板、およびこの表面処理鋼板を用いて得られる複合部材に関するものである。 The present invention relates to a surface-treated steel sheet having a film excellent in adhesiveness with a resin (plastic), and a composite member obtained using the surface-treated steel sheet.
自動車、家電製品、ＯＡ機器等には、鋼板を始めとする多くの金属部品が使用されている。このような金属部品は、多くの場合、金属板がプレス加工されて所定の形状を付与された後、他の金属部品やプラスチック部品と溶接やネジ留め等により接合されて使用されている。 Many metal parts such as steel plates are used in automobiles, home appliances, OA equipment, and the like. In many cases, such metal parts are used after being pressed to give a predetermined shape to a metal plate and then joined to other metal parts or plastic parts by welding or screwing.
一方、金属板の表面にプラスチックとの接着性を付与できれば、その金属板をプレス加工した後、プラスチックの成形金型にセットして、溶融プラスチックを注入して冷却固化するだけで、金属部品とプラスチック部品とが接着した金属板複合樹脂成形品を形成することができ、部材製造工程の効率化や部材の軽量化に繋がる。そして、例えば、金属板の表面にプラスチックとの接着性を付与する方法としては、金属板やプラスチックとの親和性が高い樹脂材料が用いられ、例えば、特許文献１や２ではこのような技術が提案されている。 On the other hand, if the adhesion of the plastic to the surface of the metal plate can be imparted, after the metal plate is pressed, it is set in a plastic mold, poured into the molten plastic, and cooled and solidified. A metal plate composite resin molded product bonded to a plastic part can be formed, which leads to the efficiency of the member manufacturing process and the weight reduction of the member. For example, as a method of imparting adhesiveness to plastic on the surface of a metal plate, a resin material having high affinity with the metal plate or plastic is used. For example, Patent Documents 1 and 2 disclose such a technique. Proposed.
特許文献１には、ガラス繊維強化樹脂からなる成形体と接合するために、金属板表面に極性基含有熱可塑性樹脂層を形成しておく技術が開示されている。具体的には、無水マレイン変性ポリプロピレン系樹脂をプレス等で金属板表面に積層し、その後、金型内に装入して、ガラス繊維を含むポリプロピレン樹脂を射出成形して一体化するというものである。しかし、極性基含有熱可塑性樹脂層と金属板との接着強度が不充分と考えられ、後から接合するプラスチックとの親和性が高い樹脂材料を接着剤として使用するだけでは、金属板複合樹脂成形品全体としての接着強度は不充分である。 Patent Document 1 discloses a technique in which a polar group-containing thermoplastic resin layer is formed on the surface of a metal plate for joining with a molded body made of glass fiber reinforced resin. Specifically, an anhydrous maleic modified polypropylene resin is laminated on the surface of a metal plate with a press or the like, and then inserted into a mold, and a polypropylene resin containing glass fibers is injection molded and integrated. is there. However, it is thought that the adhesive strength between the polar group-containing thermoplastic resin layer and the metal plate is insufficient, and simply using a resin material that has a high affinity for the plastic to be joined later as an adhesive, metal plate composite resin molding The adhesive strength of the product as a whole is insufficient.
一方、特許文献２には、クロメート処理を施していない金属板に、感熱型架橋剤を含有する樹脂皮膜を付与した樹脂被覆金属板が開示されている。この技術は、感熱型架橋剤と所定のフィルム強度を有する樹脂皮膜によって、素地金属板と樹脂皮膜との接着強度を高めるものであるが、固体の被着材（例えば、ベニヤ板、プラスチック板、ゴム板、布等）に対し、焼付け時の高温加熱を利用して接着させるため、例えば、射出成形時に、金属板と溶融プラスチックとを接合させる場合には適さない。射出成形において、金属板と溶融プラスチックが高温で接触している時間は非常に短時間であり、感熱型架橋剤が反応・架橋するには不充分だからである。感熱型架橋剤の反応を促進するために、射出成形での溶融プラスチックの温度をさらに高めると、プラスチックの冷却固化に時間がかかり、射出成形の短時間・高効率で成形できるというメリットがなくなってしまう。 On the other hand, Patent Document 2 discloses a resin-coated metal plate obtained by applying a resin film containing a heat-sensitive crosslinking agent to a metal plate not subjected to chromate treatment. This technique increases the adhesive strength between a base metal plate and a resin film by using a heat-sensitive crosslinking agent and a resin film having a predetermined film strength. However, the solid adherend (eg, veneer plate, plastic plate, rubber) For example, it is not suitable for bonding a metal plate and a molten plastic at the time of injection molding. In the injection molding, the metal plate and the molten plastic are in contact with each other at a high temperature for a very short time, and the heat-sensitive crosslinking agent is insufficient for reaction and crosslinking. If the temperature of the molten plastic in the injection molding is further increased in order to accelerate the reaction of the heat-sensitive crosslinking agent, it takes time to cool and solidify the plastic, and there is no merit that it can be molded in a short time and with high efficiency of the injection molding. End up.
他方、接着剤が積層される前の表面処理金属板そのもの、あるいは接着剤積層後の接着剤層含有表面処理金属板において、高度な耐食性が求められるようになっている。特許文献３では、接着剤との接着性に優れた樹脂被覆鋼板として、α，β−エチレン性不飽和カルボン酸に由来する構成単位（Ａ）、α，β−エチレン性不飽和カルボン酸エステルに由来する構成単位（Ｂ）、およびダイアセトンアクリルアミドに由来する構成単位（Ｃ）を含有する重合体からなる樹脂膜を有する樹脂被覆鋼板が開示されており、比較例に相当する樹脂膜の構成成分として、スチレン−マレイン酸共重合体水溶液が用いられている（Ｎｏ．１１）が、この文献では、接着性、脱膜性、潤滑性が評価されるにとどまり、耐食性については何ら考慮されていない。 On the other hand, high corrosion resistance is required in the surface-treated metal plate itself before the adhesive is laminated or in the adhesive layer-containing surface-treated metal plate after the adhesive is laminated. In Patent Document 3, as a resin-coated steel sheet excellent in adhesiveness with an adhesive, a structural unit (A) derived from an α, β-ethylenically unsaturated carboxylic acid, an α, β-ethylenically unsaturated carboxylic acid ester is used. A resin-coated steel sheet having a resin film made of a polymer containing a structural unit (B) derived from and a structural unit (C) derived from diacetone acrylamide is disclosed, and a structural component of a resin film corresponding to a comparative example As an example, an aqueous solution of styrene-maleic acid copolymer is used (No. 11). However, in this document, only adhesiveness, film-removing property, and lubricity are evaluated, and no consideration is given to corrosion resistance. .
本発明は上記諸事情を考慮して、例えば、射出成形でプラスチック（樹脂）成形品と鋼板とを一体化させるときに有用で、かつ耐食性にも優れた表面処理鋼板を提供すると共に、この表面処理鋼板と樹脂層とが一体化された複合部材を提供することを課題として掲げた。 In consideration of the above circumstances, the present invention provides a surface-treated steel sheet that is useful when, for example, a plastic (resin) molded product and a steel sheet are integrated by injection molding and has excellent corrosion resistance. An object was to provide a composite member in which a treated steel plate and a resin layer were integrated.
本発明は、化成処理された合金化溶融亜鉛めっき鋼板の化成処理皮膜表面の一部または全面に接着剤層が積層された表面処理鋼板であって、化成処理皮膜が、水溶性樹脂とコロイダルシリカとを含むことを特徴とする。 The present invention relates to a surface-treated steel sheet in which an adhesive layer is laminated on part or all of the surface of a chemical conversion-treated hot-dip galvanized steel sheet, wherein the chemical conversion-treated film comprises a water-soluble resin and colloidal silica. It is characterized by including.
水溶性樹脂が、水溶性ウレタン樹脂または水溶性アクリル樹脂であることが好ましい。また、化成処理皮膜がさらに水性樹脂を含む態様も好ましい。本発明には、本発明の表面処理鋼板の接着剤層の上に樹脂層が積層された複合部材も含まれ、樹脂層としては、ナイロン樹脂で構成されていることが好ましい。 The water-soluble resin is preferably a water-soluble urethane resin or a water-soluble acrylic resin. Moreover, the aspect in which a chemical conversion treatment film further contains aqueous resin is also preferable. The present invention also includes a composite member in which a resin layer is laminated on the adhesive layer of the surface-treated steel sheet of the present invention, and the resin layer is preferably made of a nylon resin.
本発明により、耐食性に優れ、合金化溶融亜鉛めっき鋼板や樹脂層に対する接着性にも優れた樹脂複合用の表面処理鋼板、ならびに、この表面処理鋼板を用いて複合一体化された複合部材を提供することができた。 According to the present invention, a surface-treated steel sheet for resin composites having excellent corrosion resistance and excellent adhesion to an alloyed hot-dip galvanized steel sheet or resin layer, and a composite member composite-integrated using the surface-treated steel sheet are provided. We were able to.
従って、本発明の複合部材は、自動車部品、家電製品、建築材料、ＯＡ機器等、各種用途に有用である。 Therefore, the composite member of the present invention is useful for various applications such as automobile parts, home appliances, building materials, and OA equipment.
本発明の表面処理鋼板は、合金化溶融亜鉛めっき鋼板の上に化成処理皮膜が積層され、化成処理皮膜表面の一部または全面に接着剤層が積層された構造を有し、化成処理皮膜が水溶性樹脂とコロイダルシリカを含むところに特徴を有する。 The surface-treated steel sheet of the present invention has a structure in which a chemical conversion treatment film is laminated on an alloyed hot-dip galvanized steel sheet, and an adhesive layer is laminated on a part or the whole surface of the chemical conversion treatment film. It is characterized by including a water-soluble resin and colloidal silica.
［基板］
本発明の表面処理鋼板は、合金化溶融Ｚｎ−Ｆｅめっき鋼板（ＧＡ）、合金化溶融Ｚｎ−５％Ａｌめっき鋼板（ＧＦ）等である。クロメート処理は行われていないノンクロメートのものが好ましい。鋼板の厚みは特に限定されないが、最終製品の軽量化のためには、０．３〜３．２ｍｍ程度が好ましい。
[substrate]
The surface-treated steel sheet of the present invention is an alloyed hot-dip Zn—Fe plated steel sheet (GA), an alloyed hot-dip Zn-5% Al-plated steel sheet (GF), or the like. Non-chromate that has not been chromated is preferred. Although the thickness of a steel plate is not specifically limited, About 0.3-3.2 mm is preferable for weight reduction of a final product.
［化成処理皮膜］
［コロイダルシリカ］
本発明の化成処理皮膜には、コロイダルシリカが含まれる。耐食性を高める効果を有するからである。コロイダルシリカとしては、「スノーテックス（登録商標）」シリーズ（日産化学工業社製のコロイダルシリカ）の「ＸＳ」、「ＳＳ」、「４０」、「Ｎ」、「ＵＰ」等が好適に用いられる。特に、表面積平均粒子径が１０〜２０ｎｍ程度の「スノーテックス−４０」が好適に用いられる。コロイダルシリカの量は、水溶性樹脂１０質量部に対し、１０〜１００質量部程度が好ましく、１２〜７５質量部がより好ましい。
[Chemical conversion coating]
[Colloidal silica]
The chemical conversion film of the present invention contains colloidal silica. This is because it has the effect of increasing the corrosion resistance. As the colloidal silica, “XS”, “SS”, “40”, “N”, “UP”, etc. of “Snowtex (registered trademark)” series (colloidal silica manufactured by Nissan Chemical Industries, Ltd.) are preferably used. . In particular, “Snowtex-40” having a surface area average particle diameter of about 10 to 20 nm is preferably used. About 10-100 mass parts is preferable with respect to 10 mass parts of water-soluble resin, and, as for the quantity of colloidal silica, 12-75 mass parts is more preferable.
［水溶性樹脂］
本発明では、化成処理皮膜は水溶性樹脂を必須的に含有する。水溶性樹脂は、後に積層される樹脂層（プラスチック）との接着性に優れている上に、高い耐食性を実現することができる。この理由の一つに、水溶性樹脂は水に溶解しているため、鋼板表面を均一な連続皮膜で覆うことができるためである。なお、本発明でいう水溶性樹脂とは、２５℃の水に、１質量％以上溶解するもの、より好ましくは５質量％以上溶解するものを指す。また、ｐＨを５〜９にアルカリ等で調製することで、目視で均一な透明溶液になるようなものも、水溶性樹脂に含まれるものとする。
[Water-soluble resin]
In the present invention, the chemical conversion film essentially contains a water-soluble resin. The water-soluble resin is excellent in adhesiveness with a resin layer (plastic) to be laminated later, and can realize high corrosion resistance. One reason for this is that the water-soluble resin is dissolved in water, so that the surface of the steel sheet can be covered with a uniform continuous film. In addition, the water-soluble resin as used in the field of this invention refers to what melt | dissolves 1 mass% or more in 25 degreeC water, More preferably, it melt | dissolves 5 mass% or more. Moreover, the thing which becomes a transparent solution uniform visually by adjusting pH to 5-9 with an alkali etc. shall be contained in water-soluble resin.
水溶性樹脂としては、水溶性のウレタン樹脂が好ましく、ブロックイソシアネート基を有する自己架橋型の水溶性ウレタン樹脂が好ましい。このような水溶性ウレタン樹脂としては、第一工業製薬社製の「エラストロン（登録商標）」シリーズを挙げることができ、中でも、「エラストロンＭＦ−２５Ｋ」が特に好ましい。 As the water-soluble resin, a water-soluble urethane resin is preferable, and a self-crosslinking water-soluble urethane resin having a blocked isocyanate group is preferable. Examples of such a water-soluble urethane resin include “Elastolon (registered trademark)” series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., among which “Elastoron MF-25K” is particularly preferable.
また、水溶性樹脂として水溶性のアクリル樹脂を用いてもよい。アクリル樹脂も、プラスチックとの接着性に優れている上に、高い耐食性を実現することができる。このような水溶性アクリル樹脂としては、住友精化社製の「ＡＱＵＰＥＣ（登録商標）」シリーズが挙げられ、中でも、「ＡＱＵＰＥＣ ＨＶ−５０１」が特に好ましい。 A water-soluble acrylic resin may be used as the water-soluble resin. Acrylic resin is also excellent in adhesiveness with plastic and can realize high corrosion resistance. Examples of such a water-soluble acrylic resin include “AQUPEC (registered trademark)” series manufactured by Sumitomo Seika Co., Ltd., and among them, “AQUPEC HV-501” is particularly preferable.
［水性樹脂］
化成処理皮膜には、さらに、水性樹脂を含めてもよい。水性樹脂としては、性能の点で水性ウレタン樹脂が好ましく、ウレタン樹脂の水分散体（エマルション）が上記水溶性樹脂との混合が容易であり、好適である。ウレタン樹脂の水分散体としては、第一工業製薬社製の「スーパーフレックス（登録商標）」シリーズが挙げられ、中でも、「スーパーフレックス１７０」が好ましいものとして挙げられる。ウレタン樹脂の水分散体は水溶性ウレタン樹脂と組み合わせて使用することが好ましく、水性樹脂を水溶性樹脂１０質量部に対し１０〜５０質量部用いることが好ましい。この際、架橋剤として後述するカルボジイミド化合物を併用することが好ましい。
[Aqueous resin]
The chemical conversion film may further contain an aqueous resin. As the aqueous resin, an aqueous urethane resin is preferable from the viewpoint of performance, and an aqueous dispersion (emulsion) of the urethane resin is preferable because it can be easily mixed with the water-soluble resin. Examples of the aqueous dispersion of the urethane resin include “Superflex (registered trademark)” series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Among them, “Superflex 170” is preferable. The aqueous dispersion of the urethane resin is preferably used in combination with the water-soluble urethane resin, and the aqueous resin is preferably used in an amount of 10 to 50 parts by mass with respect to 10 parts by mass of the water-soluble resin. In this case, it is preferable to use a carbodiimide compound described later as a crosslinking agent in combination.
また、水性樹脂として、水溶性アクリル樹脂である東亞合成社製の「ジュリマー（登録商標）」シリーズも好ましいものとして挙げられる。前記「ＡＱＵＰＥＣ」と合わせて用いるとよい。「ＡＱＵＰＥＣ」と「ジュリマー」とを併用する場合は、「ＡＱＵＰＥＣ」１０質量部に対し、「ジュリマー」を１０〜５０質量部とすることが好ましい。この際、架橋剤として後述するカルボジイミド化合物を併用することが好ましい。
なお、「ＡＱＵＰＥＣ」を用いずに、「ジュリマー」だけ、またはジュリマーとカルボジイミド化合物を用いると、耐食性が劣るため、水溶性アクリル樹脂としては、必ず「ＡＱＵＰＥＣ」を用いることが重要である。
Moreover, as a water-based resin, “Jurimer (registered trademark)” series manufactured by Toagosei Co., Ltd., which is a water-soluble acrylic resin, is also preferable. It may be used in combination with the “AQUPEC”. When “AQUPEC” and “Jurimer” are used in combination, it is preferable that “Jurimer” is 10 to 50 parts by mass with respect to 10 parts by mass of “AQUPEC”. In this case, it is preferable to use a carbodiimide compound described later as a crosslinking agent in combination.
Note that it is important to always use “AQUPEC” as the water-soluble acrylic resin, because “AQUPEC” is not used but only “Durimer” or a durimer and a carbodiimide compound has poor corrosion resistance.
［架橋剤］
化成処理皮膜を形成するに当たっては、架橋剤を用いてもよい。架橋剤としては、カルボジイミド化合物が好ましい。カルボジイミド化合物は、イソシアネート類をカルボジイミド化触媒の存在下で加熱することにより製造することができ、また変性により水性（水溶性、水乳化性または水分散性）にすることができる。本発明では、化成処理皮膜形成用の塗工液は水性が好ましいため、水性のカルボジイミド化合物が好ましい。また１分子中に複数のカルボジイミド基を含有する化合物が好ましい。１分子中に複数のカルボジイミド基があると、樹脂成分中のカルボキシル基との架橋反応により、耐食性等をさらに向上させることができる。
[Crosslinking agent]
In forming the chemical conversion film, a crosslinking agent may be used. As a crosslinking agent, a carbodiimide compound is preferable. The carbodiimide compound can be produced by heating isocyanates in the presence of a carbodiimidization catalyst, and can be made aqueous (water-soluble, water-emulsifiable or water-dispersible) by modification. In the present invention, since the coating liquid for forming the chemical conversion film is preferably aqueous, an aqueous carbodiimide compound is preferable. A compound containing a plurality of carbodiimide groups in one molecule is preferable. When there are a plurality of carbodiimide groups in one molecule, corrosion resistance and the like can be further improved by a crosslinking reaction with a carboxyl group in the resin component.
市販されているポリカルボジイミド化合物として、例えば日清紡社製のポリカルボジイミド（１分子中に複数のカルボジイミド基を有する重合体）である「カルボジライト（登録商標）」シリーズを挙げることができる。「カルボジライト（登録商標）」のグレードとしては、水溶性の「ＳＶ−０２」、「Ｖ−０２」、「Ｖ−０２−Ｌ２」、「Ｖ−０４」やエマルジョンタイプの「Ｅ−０１」、「Ｅ−０２」等が好適である。これらのカルボジイミド化合物は、樹脂成分（水溶性樹脂と水性樹脂）の合計量１００質量部に対し、５〜２０質量部が好ましい。 Examples of commercially available polycarbodiimide compounds include the “Carbodilite (registered trademark)” series, which is a polycarbodiimide (polymer having a plurality of carbodiimide groups in one molecule) manufactured by Nisshinbo. As the grade of “Carbodilite (registered trademark)”, water-soluble “SV-02”, “V-02”, “V-02-L2”, “V-04” and emulsion type “E-01”, “E-02” and the like are preferable. As for these carbodiimide compounds, 5-20 mass parts is preferable with respect to 100 mass parts of total amounts of a resin component (water-soluble resin and aqueous resin).
［シランカップリング剤］
化成処理皮膜を形成する際の塗工液にはシランカップリング剤を配合しておくことが好ましい。合金化溶融亜鉛めっき鋼板に対する化成処理皮膜の密着性を向上させることができる。シランカップリング剤としては、具体的には、例えば、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、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などのアミノ基含有シランカップリング剤；γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシメチルジメトキシシランなどのグリシドキシ基含有シランカップリング剤；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シランなどのビニル基含有シランカップリング剤；γ−メタクリロキシプロピルトリメトキシシランなどのメタクリロキシ基含有シランカップリング剤；γ−メルカプトプロピ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などのメルカプト基含有シランカップリング剤；γ−クロロプロピルメトキシシラン、γ−クロロプロピルトリメトキシシランなどのハロゲン基含有シランカップリング剤などが挙げられる。これらのシランカップリング剤は、単独で用いも良いし、２種以上を併用してもよい。これらの中では、最終的に得られる複合部材における、表面処理鋼板と樹脂層との接合強度が良好になる点で、アミノ基含有シランカップリング剤やグリシドキシ基含有シランカップリング剤が好ましく、アミノ基含有シランカップリング剤が特に好ましい。シランカップリング剤の量は、化成処理皮膜形成用塗工液の固形分１００質量部中、５〜３０質量部程度が好ましい。
[Silane coupling agent]
It is preferable to add a silane coupling agent to the coating solution for forming the chemical conversion film. The adhesion of the chemical conversion film to the galvannealed steel sheet can be improved. Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- ( amino group-containing silane coupling agents such as β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltri Glycidoxy group-containing silane coupling agents such as ethoxysilane and γ-glycidoxymethyldimethoxysilane; Vinyl group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy) silane; γ -Methacryloxypropi Methacryloxy group-containing silane coupling agents such as trimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane and other mercapto group-containing silane coupling agents; γ-chloropropylmethoxysilane, γ-chloropropyltri Examples include halogen group-containing silane coupling agents such as methoxysilane. These silane coupling agents may be used alone or in combination of two or more. Among these, an amino group-containing silane coupling agent and a glycidoxy group-containing silane coupling agent are preferable in terms of improving the bonding strength between the surface-treated steel sheet and the resin layer in the finally obtained composite member. A group-containing silane coupling agent is particularly preferred. As for the quantity of a silane coupling agent, about 5-30 mass parts is preferable in 100 mass parts of solid content of the coating liquid for chemical conversion treatment film formation.
［酸］
化成処理皮膜を形成するための塗工液には、金属表面を活性化させるために、酸またはその塩を加えてもよい。用い得る酸としては、オルトりん酸、メタりん酸等のりん酸類、りん酸水素二アンモニウム等のアンモニウム塩等のりん酸化合物；ヘキサフルオロりん酸やそのナトリウム塩等のヘキサフルオロ金属酸；が挙げられる。これらを使用する場合は、化成処理皮膜中、０．１〜５０質量％程度となるようにすることが好ましい。０．１質量％より少ないと、耐食性向上効果が得られない場合がある。５０質量％を超えると、化成処理皮膜が脆くなるおそれがある。
[acid]
An acid or a salt thereof may be added to the coating solution for forming the chemical conversion film in order to activate the metal surface. Examples of acids that can be used include phosphoric acid compounds such as orthophosphoric acid and metaphosphoric acid, and phosphoric acid compounds such as ammonium salts such as diammonium hydrogen phosphate; hexafluorometallic acids such as hexafluorophosphoric acid and sodium salts thereof. It is done. When using these, it is preferable to make it become about 0.1-50 mass% in a chemical conversion treatment film. If it is less than 0.1% by mass, the effect of improving corrosion resistance may not be obtained. When it exceeds 50 mass%, there exists a possibility that a chemical conversion treatment film may become weak.
［化成処理皮膜の形成方法］
化成処理皮膜形成時には、塗工液中にその他の公知の添加剤を加えてもよい。合金化溶融亜鉛めっき鋼板上に化成処理皮膜を形成する方法は特に限定されず、従来公知の塗布方法が採用でき、例えば、化成処理皮膜用塗工液を、ロールコーター法、スプレー法、カーテンフローコーター法等を用いて、合金化溶融亜鉛めっき鋼板表面の片面もしくは両面に塗布して、加熱乾燥すればよい。加熱乾燥温度は特に限定されるものではないが、自己架橋型のポリウレタンの自己架橋反応や、架橋剤であるカルボジイミドと樹脂成分との反応が完全に終了してしまわない程度の温度で加熱乾燥することが好ましい。化成処理皮膜形成時に架橋反応が終了してしまうと、後に積層される接着剤層との接合強度が低下するためである。化成処理皮膜形成用の塗工液は水性なため、水が蒸発する１００℃前後で数十秒〜数分程度加熱するとよい。
[Formation method of chemical conversion coating]
At the time of forming the chemical conversion film, other known additives may be added to the coating solution. The method for forming the chemical conversion coating on the galvannealed steel sheet is not particularly limited, and a conventionally known coating method can be employed. For example, a coating liquid for chemical conversion coating can be applied to the roll coater method, spray method, curtain flow. What is necessary is just to apply | coat to the single side | surface or both surfaces of the alloyed hot-dip galvanized steel plate surface using a coater method etc., and to heat-dry. The heat drying temperature is not particularly limited, but the heat drying is performed at a temperature that does not completely complete the self-crosslinking reaction of the self-crosslinking polyurethane or the reaction between the carbodiimide as a crosslinking agent and the resin component. It is preferable. This is because if the crosslinking reaction is completed when the chemical conversion film is formed, the bonding strength with the adhesive layer to be laminated later is lowered. Since the coating solution for forming the chemical conversion film is water-based, it may be heated at around 100 ° C. where water evaporates for several tens of seconds to several minutes.
化成処理皮膜の付着量は、特に限定されないが、０．０１〜１ｇ／ｍ2が好ましく、０．０５〜０．５ｇ／ｍ2がより好ましい。０．０１ｇ／ｍ2より少ないと、化成処理皮膜による接着強度向上の効果が不充分となるおそれがあり、また、１ｇ／ｍ2を超えても接着強度向上効果が飽和するため、コスト的に無駄である。 Deposition amount of the chemical conversion film is not particularly limited, but is preferably 0.01~1g / m 2, 0.05~0.5g / m 2 is more preferable. If it is less than 0.01 g / m 2, the effect of improving the adhesive strength by the chemical conversion coating film may be insufficient, and even if it exceeds 1 g / m 2 , the effect of improving the adhesive strength is saturated. It is useless.
［接着剤層］
化成処理皮膜形成後は、接着剤層を設ける。接着剤としては、後に複合される樹脂との接着性に優れたものが好ましい。例えば、ナイロンと複合するのなら、ナイロン用の接着剤が好ましく、ポリプロピレンと複合するのなら、ポリプロピレン用の接着剤が好ましい。具体的には、ホットメルト型ウレタン系接着剤、ホットメルト型ナイロン系接着剤、ウレタン変性ナイロン系接着剤、ウレタン変性オレフィン系接着剤、酸変性ポリプロピレン系接着剤、塩素化ポリプロピレン系接着剤、ポリエステル系接着剤等が好適である。
[Adhesive layer]
After the chemical conversion treatment film is formed, an adhesive layer is provided. As the adhesive, those having excellent adhesiveness with a resin to be combined later are preferable. For example, if it is combined with nylon, an adhesive for nylon is preferable, and if it is combined with polypropylene, an adhesive for polypropylene is preferable. Specifically, hot-melt urethane adhesive, hot-melt nylon adhesive, urethane-modified nylon adhesive, urethane-modified olefin adhesive, acid-modified polypropylene adhesive, chlorinated polypropylene adhesive, polyester A system adhesive or the like is preferable.
ホットメルト型接着剤は粉末の状態で化成処理鋼板に塗布することができる。例えば、ダイセル・エボニック社製のホットメルト型ナイロン系接着剤「ベスタメルト（登録商標）」シリーズが使用できる。また、接着剤を有機溶剤に溶解させた溶液や、水に分散させた水分散液を、化成処理鋼板に塗布してもよい。接着剤塗布後は、接着剤の種類に適した温度（例えば、１８０〜２３０℃程度）で、１〜３分程度加熱する。このとき、化成処理皮膜中の自己架橋型ポリウレタンの自己架橋反応や樹脂成分と架橋剤との架橋反応が進行する。なお、接着剤層は、化成処理皮膜表面の全面に設けてもよいし、樹脂との複合化のために必要な場所だけに設けてもよいし、例えば何本かのライン状や、ドット状に設けてもよい。 The hot melt adhesive can be applied to the chemical conversion treated steel sheet in a powder state. For example, a hot melt type nylon adhesive “Vestamelt (registered trademark)” series manufactured by Daicel-Evonik can be used. Moreover, you may apply | coat to the chemical conversion treatment steel plate the solution which melt | dissolved the adhesive agent in the organic solvent, or the water dispersion liquid disperse | distributed to water. After application of the adhesive, it is heated for about 1 to 3 minutes at a temperature suitable for the type of adhesive (for example, about 180 to 230 ° C.). At this time, the self-crosslinking reaction of the self-crosslinking polyurethane in the chemical conversion film or the crosslinking reaction between the resin component and the crosslinking agent proceeds. The adhesive layer may be provided on the entire surface of the chemical conversion treatment film, or may be provided only in a place necessary for compounding with the resin. For example, some lines or dots May be provided.
接着剤層の厚さは特に限定されないが、乾燥後の厚さで５〜４０μｍ程度が好ましく、１０〜３０μｍがより好ましい。接着剤層が５μｍより薄いと、樹脂成形品との接着強度が低くなるおそれがあり、４０μｍを超えても接着強度が向上することは特には認められず、却ってコスト高となり好ましくない。接着剤層を積層することで、本発明の表面処理鋼板が完成する。 Although the thickness of an adhesive bond layer is not specifically limited, About 5-40 micrometers is preferable at the thickness after drying, and 10-30 micrometers is more preferable. If the adhesive layer is thinner than 5 μm, the adhesive strength with the resin molded product may be lowered, and it is not particularly recognized that the adhesive strength is improved even if it exceeds 40 μm. By laminating the adhesive layer, the surface-treated steel sheet of the present invention is completed.
［複合部材］
本発明の表面処理鋼板は、樹脂成形品と複合して用いることが好ましい。このとき、加工が必要な場合は、予め、表面処理鋼板を目的とする形状に加工しておく。そして、加工後の表面処理鋼板を、射出成形機の金型の中に装入し、型締めして、溶融樹脂を型内に射出し、樹脂が冷却固化すれば、金属板複合樹脂成形品が得られる。もちろん、本発明の表面処理鋼板は、プレス成形法で樹脂と複合してもよいが、射出成形の短時間・高効率というメリットを生かすには、射出成形法を採用することが好ましい。
[Composite material]
The surface-treated steel sheet of the present invention is preferably used in combination with a resin molded product. At this time, if processing is necessary, the surface-treated steel sheet is processed into a target shape in advance. Then, the processed surface-treated steel sheet is inserted into a mold of an injection molding machine, clamped, and the molten resin is injected into the mold. When the resin cools and solidifies, the metal plate composite resin molded product Is obtained. Of course, the surface-treated steel sheet of the present invention may be combined with a resin by a press molding method, but in order to take advantage of the short time and high efficiency of injection molding, it is preferable to adopt the injection molding method.
射出成形の条件は、成形品を構成する樹脂の種類に応じて適宜変更すればよく、成形品用樹脂がナイロン６の場合の一例を挙げれば、シリンダー温度を２４０〜２５０℃、金型温度を７０〜８０℃、射出保持時間を５〜８秒、冷却時間を２０〜３０秒程度とすることができ、成形品用樹脂がポリプロピレンの場合の一例を挙げれば、シリンダー温度を２３０〜２５０℃、金型温度を４５〜５５℃、射出保持時間を５〜８秒、冷却時間を２０〜３０秒程度とすることができる。この条件で射出成形を行うと、接着剤と表面処理鋼板とが強固に接着した本発明の複合部材が得られる。 The injection molding conditions may be changed as appropriate according to the type of resin constituting the molded product. For example, when the molded product resin is nylon 6, the cylinder temperature is 240 to 250 ° C. and the mold temperature is 70 to 80 ° C., injection holding time can be set to 5 to 8 seconds, cooling time can be set to about 20 to 30 seconds, and the cylinder temperature is set to 230 to 250 ° C. The mold temperature can be 45 to 55 ° C., the injection holding time can be 5 to 8 seconds, and the cooling time can be about 20 to 30 seconds. When injection molding is performed under these conditions, the composite member of the present invention in which the adhesive and the surface-treated steel sheet are firmly bonded is obtained.
成形品用樹脂としては公知の成形品用樹脂であればいずれも使用でき、特に限定されないが、各種ナイロンやポリプロピレン等が好ましい樹脂として挙げられる。成形品としての強度を高めるために、ガラス繊維や炭素繊維等の強化繊維を５〜６０質量％程度添加してもよい。また、各種顔料や染料、難燃剤、抗菌剤、酸化防止剤、可塑剤、滑剤等の公知の添加剤を加えてもよい。 Any resin for molded products can be used as long as it is a known resin for molded products, and is not particularly limited, but various types of nylon, polypropylene, and the like are preferable resins. In order to increase the strength as a molded product, about 5 to 60% by mass of reinforcing fibers such as glass fibers and carbon fibers may be added. Moreover, you may add well-known additives, such as various pigments and dyes, a flame retardant, an antibacterial agent, antioxidant, a plasticizer, and a lubricant.
以下実施例によって本発明をさらに詳述するが、下記実施例は本発明を制限するものではなく、本発明の趣旨を逸脱しない範囲で変更実施することは全て本発明に包含される。なお、特に断らない限り、部は質量部を、％は質量％を意味する。 The present invention will be described in further detail with reference to the following examples. However, the following examples are not intended to limit the present invention, and all modifications and implementations without departing from the spirit of the present invention are included in the present invention. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
［化成処理鋼板の製造］
厚さ０．８ｍｍの合金化溶融亜鉛めっき鋼板の表面に、化成処理皮膜形成用塗工液をバーコーターで付着量が０．５ｇ／ｍ2となるように塗布し、１００℃で１分間加熱し、化成処理鋼板を得た。樹脂、架橋剤の内容を表１に、塗工液の組成（添加量は固形分である）を表２に示す。なお、表１、２中、「エラストロン」、「ＡＱＵＰＥＣ」、「スーパーフレックス」、「ジュリマー」は、それぞれ各メーカーの有する登録商標である。また、架橋剤として、ポリカルボジイミド化合物である「カルボジライト（登録商標）ＳＶ−０２」を用いた。コロイダルシリカの欄の「ＳＴ−４０」は「スノーテックス（登録商標）４０」（日産化学工業社製;表面積平均粒径１０〜２０ｎｍ）であり、シランカップリング剤の欄の「ＫＢＭ９０３」は、信越化学工業社製のγ−アミノプロピルトリメトキシシランである。
[Manufacture of chemical conversion treated steel sheet]
The thickness 0.8mm surface of the galvannealed steel sheet, coated with a chemical conversion coating forming coating solution so that the amount deposited in a bar coater is 0.5 g / m 2, heated for 1 minute at 100 ° C. And the chemical conversion treatment steel plate was obtained. The contents of the resin and the crosslinking agent are shown in Table 1, and the composition of the coating liquid (added amount is solid content) is shown in Table 2. In Tables 1 and 2, “Elastoron”, “AQUPEC”, “Superflex”, and “Jurimer” are registered trademarks of the respective manufacturers. Further, “carbodilite (registered trademark) SV-02” which is a polycarbodiimide compound was used as a crosslinking agent. “ST-40” in the column of colloidal silica is “Snowtex (registered trademark) 40” (manufactured by Nissan Chemical Industries, Ltd .; surface area average particle size of 10 to 20 nm), and “KBM903” in the column of silane coupling agent is This is γ-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.
実施例１〜４，比較例１，２
上記で得られた化成処理鋼板から試験片を切り出して、切り口（端面）をテープでシールし、ＪＩＳ Ｚ ２３７１に準拠した塩水噴霧試験（ＳＳＴ）を１２０時間行い、白錆発生率を求めた。結果を表３に示した。接着剤が塗布される前でも、本発明の化成処理鋼板は高い耐食性を示した。
Examples 1 to 4, Comparative Examples 1 and 2
A test piece was cut out from the chemical conversion treated steel plate obtained above, the cut end (end face) was sealed with tape, a salt spray test (SST) based on JIS Z 2371 was performed for 120 hours, and the white rust generation rate was determined. The results are shown in Table 3. Even before the adhesive was applied, the chemical conversion treated steel sheet of the present invention showed high corrosion resistance.
実施例５〜８，比較例３，４
上記各化成処理鋼板の化成処理皮膜上に、ダイセル・エボニック社製の粉末状ホットメルト型ナイロン系接着剤「ベスタメルト（登録商標）１３３３Ｐ１」を膜厚５０μｍとなるように部分的に静電塗装した後、１９０℃で２分間加熱乾燥して、接着剤層を備えた表面処理鋼板を得た。上記と同様にして、塩水噴霧試験を１２０時間行い、白錆発生率を求めた。結果を表４に示した。接着剤塗布後の本発明の表面処理鋼板はさらに高い耐食性を示した。
Examples 5 to 8, Comparative Examples 3 and 4
A powdered hot-melt nylon adhesive “Vestamelt (registered trademark) 1333P1” manufactured by Daicel-Evonik Co., Ltd. was partially electrostatically coated on the chemical conversion film of each of the chemical conversion steel sheets to a film thickness of 50 μm. Then, it heat-dried at 190 degreeC for 2 minute (s), and obtained the surface treatment steel plate provided with the adhesive bond layer. In the same manner as described above, a salt spray test was conducted for 120 hours to determine the white rust occurrence rate. The results are shown in Table 4. The surface-treated steel sheet of the present invention after applying the adhesive showed even higher corrosion resistance.
次に、射出成形機（日精樹脂工業社製；ＰＮＸ６０）を用いて射出成形を行った。上記表面処理鋼板を１００ｍｍ×２５ｍｍにカットし、金型に入れ、ガラス繊維が３０体積％含まれたナイロン６（東レ社製；アミラン（登録商標）ＣＭ１０１１Ｇ−３０）を溶融させて、１００ｍｍ×２５ｍｍ×３ｍｍ厚となるように射出した。樹脂と表面処理鋼板とは、１２．５ｍｍ長さ×２５ｍｍ幅で重なるように接着させた。 Next, injection molding was performed using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd .; PNX60). The surface-treated steel sheet is cut into a size of 100 mm × 25 mm, put into a mold, and nylon 6 (manufactured by Toray Industries, Inc .; Amilan (registered trademark) CM1011G-30) containing 30% by volume of glass fiber is melted to be 100 mm × 25 mm. The injection was performed so that the thickness was 3 mm. The resin and the surface-treated steel sheet were bonded so as to overlap each other at 12.5 mm length × 25 mm width.
得られた複合部材の長手方向端部を、２５℃の雰囲気下で、引張試験機のチャックで掴み、１０ｍｍ／分の引張速度で引張り、破断時の強度を接着強度とした。評価結果を表４に併せて示した。実施例はいずれも高い接着強度を示した。 The obtained longitudinal end of the composite member was grasped with a chuck of a tensile tester in an atmosphere at 25 ° C. and pulled at a tensile rate of 10 mm / min, and the strength at break was defined as the adhesive strength. The evaluation results are also shown in Table 4. All the examples showed high adhesive strength.
本発明の表面処理鋼板は、射出成形機の金型内で溶融樹脂と複合することで、鋼板と樹脂との複合部材を容易に高効率で製造することができ、鋼板と樹脂との接着強度も高い。本発明の複合部材は、自動車、家電製品、ＯＡ機器等の部品として、有用である。 The surface-treated steel sheet of the present invention can be easily combined with a molten resin in a mold of an injection molding machine so that a composite member of the steel sheet and the resin can be easily manufactured with high efficiency. Is also expensive. The composite member of this invention is useful as components, such as a motor vehicle, household appliances, and OA equipment.
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