JP7414997B2 - Coating composition for electrogalvanized steel sheets with excellent heat resistance and tape adhesion, steel sheets surface-treated using the same, and manufacturing method thereof - Google Patents

Coating composition for electrogalvanized steel sheets with excellent heat resistance and tape adhesion, steel sheets surface-treated using the same, and manufacturing method thereof Download PDF

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JP7414997B2
JP7414997B2 JP2022534308A JP2022534308A JP7414997B2 JP 7414997 B2 JP7414997 B2 JP 7414997B2 JP 2022534308 A JP2022534308 A JP 2022534308A JP 2022534308 A JP2022534308 A JP 2022534308A JP 7414997 B2 JP7414997 B2 JP 7414997B2
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electrogalvanized steel
steel sheet
coating composition
silane
weight
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JP2023504882A (en
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デュ－フワン ジョ、
チャン－ソク バン、
ガ－ビョン キム、
ウク－ヒュン ソン、
キュン－ソ カン、
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Posco Holdings Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/5403—Silicon-containing compounds containing no other elements than carbon or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Electrochemistry (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)

Description

本発明は、耐熱性及びテープ付着性に優れた電気亜鉛めっき鋼板用コーティング組成物、これを用いて表面処理された鋼板及びその製造方法に関するものである。 The present invention relates to a coating composition for electrogalvanized steel sheets having excellent heat resistance and tape adhesion, a steel sheet surface-treated using the same, and a method for manufacturing the same.

電気亜鉛めっき鋼板は、映像家電のシャシ（ｃｈａｓｓｉｓ）及び家電製品の外板材として多く用いられている。従来には、映像家電シャシのプレス加工後、電線及びその他の付属品の固定のために、ボルトを用いて部品をシャシに固定する方式が行われてきたが、最近では、工程の単純化及び効率化のために、シャシに部品を固定する方式が両面テープを用いる方式にほとんど切り替えられている実情である。 Electrogalvanized steel sheets are often used as the chassis of video home appliances and the outer panel material of home appliances. Conventionally, after pressing the chassis of video home appliances, bolts were used to fix the parts to the chassis in order to fix the electric wires and other accessories, but recently, methods have been used to simplify the process and In order to improve efficiency, the method of fixing parts to the chassis has almost always been switched to using double-sided tape.

一方、現在まで電気亜鉛めっき鋼板の表面処理は、酸（ａｃｉｄ）値が高いポリオレフィン樹脂または水分散型ウレタン樹脂とともにシリカを用いており、このような方式の表面処理剤は、製造上及び使用上の利便性よって広く用いられてきた。 On the other hand, to date, the surface treatment of electrogalvanized steel sheets has used silica together with polyolefin resins or water-dispersed urethane resins with high acid values. It has been widely used due to its convenience.

しかし、酸値が高いポリオレフィン樹脂または水分散型ウレタン樹脂は、シャシ固定に用いられる両面テープとの付着性が良好でないという欠点があり、電気亜鉛めっき鋼板の上塗り塗装後の乾燥のために２５０℃以上の熱処理を行う過程において、塗装されていない部分の耐熱性が低くて、黄変が発生するという問題点がある。 However, polyolefin resins or water-dispersed urethane resins with high acid values have the disadvantage that they do not adhere well to the double-sided tape used for fixing the chassis, and they must be heated to 250°C for drying after topcoating electrogalvanized steel sheets. In the process of performing the above heat treatment, there is a problem in that the heat resistance of the unpainted part is low and yellowing occurs.

例えば、韓国公開特許第２０１０－００２６１２５号のように、接着テープを用いて鋼板を接着する技術が研究されているが、鋼板のコーティング層自体のテープ付着性を向上させた技術については研究が不十分な実情にある。 For example, as in Korean Patent Publication No. 2010-0026125, research has been conducted on technology for bonding steel plates using adhesive tape, but there has been little research into technology that improves the tape adhesion of the coating layer itself on steel plates. There are enough facts.

本発明は、優れた耐熱性、耐腐食性、耐化学性はもちろん、シャシ（ｃｈａｓｓｉｓ）に用いられるテープ付着性に優れた電気亜鉛めっき鋼板用コーティング組成物を提供するものである。 The present invention provides a coating composition for electrogalvanized steel sheets that not only has excellent heat resistance, corrosion resistance, and chemical resistance, but also has excellent tape adhesion for use in chassis.

本発明の一態様によると、本発明はシラン；シリカゾル；ポリウレタン樹脂、アクリル系エマルション樹脂またはこれらの混合物；腐食防止用添加剤；及び水を含み、上記シランは、４官能シラン及び３官能シランを含む、電気亜鉛めっき鋼板用コーティング組成物を提供する。 According to one aspect of the present invention, the present invention comprises a silane; a silica sol; a polyurethane resin, an acrylic emulsion resin, or a mixture thereof; a corrosion inhibitor additive; and water, wherein the silane comprises a tetrafunctional silane and a trifunctional silane. Provided is a coating composition for electrogalvanized steel sheet, comprising:

本発明の他の一態様によると、本発明は電気亜鉛めっき鋼板；及び上記鋼板上に、本発明の電気亜鉛めっき鋼板用コーティング組成物がコーティング及び硬化して形成されたコーティング層を含む電気亜鉛めっき鋼板を提供する。 According to another aspect of the present invention, the present invention provides an electrogalvanized steel sheet comprising: an electrogalvanized steel sheet; Provides plated steel sheets.

本発明のまた他の一態様によると、本発明は、電気亜鉛めっき鋼板の一面に本発明の電気亜鉛めっき鋼板用コーティング組成物をコーティングする段階を含む、電気亜鉛めっき鋼板の製造方法を提供する。 According to yet another aspect of the present invention, the present invention provides a method for producing an electrogalvanized steel sheet, comprising the step of coating one side of the electrogalvanized steel sheet with the coating composition for electrogalvanized steel sheet of the present invention. .

本発明の電気亜鉛めっき鋼板用コーティング組成物は、鋼板の表面に形成されためっき層との密着性に優れ、さらに耐熱性、耐腐食性及び耐化学性はもちろん、シャシ（ｃｈａｓｓｉｓ）に用いられるテープ付着性に優れ、また数回のコーティング層形成及び乾燥工程なしに１回のコーティング層形成及び乾燥によって上記のような特性が与えられる。 The coating composition for electrogalvanized steel sheets of the present invention has excellent adhesion with the plating layer formed on the surface of the steel sheet, and further has heat resistance, corrosion resistance, and chemical resistance, and can be used for chassis. It has excellent tape adhesion, and the above characteristics can be provided by forming and drying a coating layer in one time, without having to form and dry the coating layer several times.

実施例及び比較例の耐熱性の評価結果に対するグラフである。It is a graph of heat resistance evaluation results of Examples and Comparative Examples. 実施例及び比較例のテープ付着性の評価結果に対するグラフである。It is a graph of the evaluation results of tape adhesion of Examples and Comparative Examples.

以下、添付された図面を参照して本発明の好ましい実施形態を説明する。しかしながら、本発明の実施形態は、様々な形態に変更することができ、本発明の範囲が以下に説明する実施形態に限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified in various forms, and the scope of the present invention is not limited to the embodiments described below.

本発明は、優れた耐熱性、耐腐食性、耐化学性はもちろん、シャシ（ｃｈａｓｓｉｓ）に用いられるテープに対する付着性に優れた電気亜鉛めっき鋼板用コーティング組成物を提供するものである。 The present invention provides a coating composition for electrogalvanized steel sheets that not only has excellent heat resistance, corrosion resistance, and chemical resistance, but also has excellent adhesion to tapes used for chassis.

詳細には、本発明はシラン；シリカゾル；ポリウレタン樹脂、アクリル系エマルション樹脂またはこれらの混合物；腐食防止用添加剤；及び水を含み、上記シランは、４官能シラン及び３官能シランを含む、電気亜鉛めっき鋼板用コーティング組成物を提供するものである。 In particular, the present invention comprises a silane; a silica sol; a polyurethane resin, an acrylic emulsion resin, or a mixture thereof; an additive for corrosion protection; A coating composition for plated steel sheets is provided.

より詳細には、本発明は、電気亜鉛めっき鋼板用コーティング組成物の総重量を基準に、シラン５～２０重量％；シリカゾル２～１０重量％；ポリウレタン樹脂、アクリル系エマルション樹脂またはこれらの混合物１０～５０重量％；腐食防止用添加剤０．１～２．０重量％；及び残部の水を含む、電気亜鉛めっき鋼板用コーティング組成物を提供する。 More specifically, the present invention provides, based on the total weight of the coating composition for electrogalvanized steel sheets, 5 to 20% by weight of silane; 2 to 10% by weight of silica sol; 10 to 10% by weight of polyurethane resin, acrylic emulsion resin, or a mixture thereof. A coating composition for electrogalvanized steel sheet is provided, comprising: ~50% by weight; 0.1-2.0% by weight of a corrosion-inhibiting additive; and the balance water.

上記シランは、鋼板とシリカ、またはシリカ間を結合させる役割を果たし、鋼板上に形成されたコーティング層のテープ付着性を高める役割を果たす。上記シランは、電気亜鉛めっき鋼板用コーティング組成物の総重量を基準に５～２０重量％含まれ、５重量％未満の場合には、コーティング層の耐熱性、耐溶剤性、耐化学性及びテープ付着性などの全体物性が低下し、２０重量％以上添加すると、コーティング層の硬度が上昇してコーティング層の表面にクラックが発生するため、耐食性及び加工部耐食性などが脆弱になる。 The silane serves to bond the steel plate and silica or between silica, and serves to enhance tape adhesion of the coating layer formed on the steel plate. The above-mentioned silane is contained in an amount of 5 to 20% by weight based on the total weight of the coating composition for electrogalvanized steel sheets, and if it is less than 5% by weight, it may improve the heat resistance, solvent resistance, chemical resistance of the coating layer and the tape. Overall physical properties such as adhesion deteriorate, and if it is added in an amount of 20% by weight or more, the hardness of the coating layer increases and cracks occur on the surface of the coating layer, resulting in weakening of corrosion resistance and corrosion resistance of processed parts.

さらに、上記シランは、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、デシ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、２－（３，４エポキシシクロヘキシル）－エチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、及び３－アミノプロピルトリエトキシシラン、３－ウルレイドプロピルアルコキシシラン（３－Ｕｒｅｉｄｏｐｒｏｐｙｌｔｒｉａｌｋｏｘｙｓｉｌａｎｅ）、３－イソシアネートプロピルトリエトキシシラン（３－Ｉｓｏｃｙｎａｔｅｐｒｏｐｙｌｔｒｉｅｔｈｏｘｙ ｓｉｌａｎｅ）、及びトリス－（トリメトキシシリルプロピル）イソシアヌレート（Ｔｒｉｓ－（ｔｒｉｍｅｔｈｏｘｙｓｉｌｙｌｐｒｏｐｙｌ）ｉｓｏｃｙａｎｕｒａｔｅ）からなる群から選択される１つ以上を用いることができるが、これに制限されるものではなく、２つ以上を用いる場合には、２つ以上のシランが加水分解縮合物であることができる。 Furthermore, the above silanes include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, decyltrimethoxysilane, and vinyltrimethoxysilane. Silane, vinyltriethoxysilane, 2-(3,4epoxycyclohexyl)-ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane Ethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, N-(2-aminoethyl)-3 -aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-Aminopropyltriethoxysilane, 3-Ureidopropyltrialkoxysilane, 3-Isocyanatepropyltriethoxysilane, and Tris-(trimethoxysilylpropyl)isocyanine Rate (Tris-( One or more silanes selected from the group consisting of (trimethoxysilylpropyl)isocyanurate) can be used, but the invention is not limited thereto, and when two or more silanes are used, the two or more silanes are hydrolyzed condensates. Something can happen.

好ましくは、上記テープ付着性の向上のためには、エポキシ基、アミノ基、イソシアネート基、ウレイド基のシランを１つまたは２つ以上混合して用いることが好ましく、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、及び３－アミノプロピルトリエトキシシラン、３－ウルレイドプロピルアルコキシシラン（３－Ｕｒｅｉｄｏｐｒｏｐｙｌｔｒｉａｌｋｏｘｙｓｉｌａｎｅ）、３－イソシアネートプロピルトリエトキシシラン（３－Ｉｓｏｃｙｎａｔｅｐｒｏｐｙｌｔｒｉｅｔｈｏｘｙ ｓｉｌａｎｅ）、及びトリス－（トリメトキシシリルプロピル）イソシアヌレート（Ｔｒｉｓ－（ｔｒｉｍｅｔｈｏｘｙｓｉｌｙｌｐｒｏｐｙｌ）ｉｓｏｃｙａｎｕｒａｔｅ）からなる群から２つ以上のシランを用いてテープ付着性を向上させることができる。 Preferably, in order to improve the tape adhesion, it is preferable to use one or a mixture of two or more silanes having an epoxy group, an amino group, an isocyanate group, or a ureido group. For example, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl) -3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane, 3-ulureidopropylalkoxysilane (3-Ureidopropyltrialkoxysilane), 3-Isocyanatepropyltriethoxysilane (3-Isocyanatepropyltriethoxysilane), and Tris-(trimethoxysilylpropyl)isocyanurate (Tris-(trimethoxysilylpropyl) using two or more silanes from the group consisting of can improve tape adhesion.

さらに、本発明のシランは、４官能シラン及び３官能シランを混合して用いることが好ましい。４官能シランのみを用いてコーティング層を形成する場合、シランの有機官能基が存在せず、テープ付着性が不良となり、さらにコーティング層の硬度が上昇して最終コーティング層が割れやすい。また、溶液の分子量が極大化して溶液の安定性が劣るという問題が生じることがある。一方、３官能シランのみを用いると、乾燥速度及び後硬化速度が顕著に劣り、これによってロールコーティング時にロールに組成物が付着する現象が発生する。その結果、スタッキング（Ｓｔａｃｋｉｎｇ）時にブロッキング現象が発生しやすい。 Furthermore, the silane of the present invention is preferably a mixture of a tetrafunctional silane and a trifunctional silane. When a coating layer is formed using only a tetrafunctional silane, the organic functional groups of the silane are absent, resulting in poor tape adhesion, and furthermore, the hardness of the coating layer increases, making the final coating layer prone to cracking. Further, there may arise a problem that the molecular weight of the solution is maximized and the stability of the solution is poor. On the other hand, when only trifunctional silane is used, the drying rate and post-curing rate are significantly inferior, which causes the composition to adhere to the roll during roll coating. As a result, a blocking phenomenon is likely to occur during stacking.

但し、上記４官能シランと３官能シランを混合して用いる場合、３官能シランの含有量が４官能シランの含有量より多いことが好ましい。４官能シランの含有量が３官能シランより多い場合、有機官能基が少なくなってテープ付着性が不良しやすくなるためである。 However, when using a mixture of the above-mentioned tetrafunctional silane and trifunctional silane, it is preferable that the content of the trifunctional silane is greater than the content of the tetrafunctional silane. This is because when the content of tetrafunctional silane is higher than that of trifunctional silane, the number of organic functional groups decreases and tape adhesion tends to be poor.

上記３官能シランは、Ｘ－Ｓｉ－（ＯＲ）３の構造式を有することができ（ここで、Ｘはビニル基（Ｖｉｎｙｌ）、エポキシ基（Ｅｐｏｘｙ）、アミノ基（Ａｍｉｎｏ）、メタクリロキシ基（Ｍｅｔｈａｃｒｙｌｏｘｙ）、またはメルカプト基（Ｍｅｒｃａｐｔｏ）のいずれか一つであることができ、Ｒは水素、メチル（Ｍｅｔｈｙｌ）、エチル（Ｅｔｈｙｌ）、またはプロピル（Ｐｒｏｐｙｌ）のいずれか一つであることができる）、上記構造式において、Ｘ基はコーティング層の樹脂と有機成分との化学結合を誘導してコーティング層の付着性及びテープ付着性を向上させる役割を果たすことができ、Ｒ基は無機成分との結合を促進させる役割を果たすことができる。 The trifunctional silane may have a structural formula of X-Si-(OR) 3 (where X is a vinyl group, an epoxy group, an amino group, or a methacryloxy group). ), or a mercapto group, and R can be any one of hydrogen, methyl, ethyl, or propyl), In the above structural formula, the X group can play the role of inducing a chemical bond between the resin of the coating layer and the organic component to improve the adhesion of the coating layer and the tape adhesion, and the R group can play the role of improving the adhesion of the coating layer and the tape adhesion. can play a role in promoting

一方、上記シリカゾルは、鋼板の耐食性及び上記コーティング組成物の安定性を強化させるために用いられる。上記シリカゾルは、電気亜鉛めっき鋼板用コーティング組成物の総重量を基準に２～１０重量％用いることができ、２重量％未満の場合には、上記組成物の耐食性及びコーティング組成物の安定性が低下し、１０重量％を超えると、上記組成物によって形成されるコーティング層の耐化学性及び加工性が低下して、素材加工時の脱脂工程でコーティング層の脱膜などの問題が発生しやすく、鋼板の加工時にコーティング層が割れるという問題が発生する可能性がある。 Meanwhile, the silica sol is used to enhance the corrosion resistance of the steel sheet and the stability of the coating composition. The silica sol can be used in an amount of 2 to 10% by weight based on the total weight of the coating composition for electrogalvanized steel sheets, and if it is less than 2% by weight, the corrosion resistance of the composition and the stability of the coating composition may deteriorate. If it exceeds 10% by weight, the chemical resistance and processability of the coating layer formed by the above composition will decrease, and problems such as peeling of the coating layer will easily occur during the degreasing process during material processing. , there is a possibility that the coating layer may crack during processing of the steel plate.

このとき、上記シリカゾルは、ナノサイズシリカが水分散したシリカゾルであることができ、ナノサイズのシリカを用いると、溶液の安定性、最終形成されたコーティング層の耐食性及びコーティング層の耐スクラッチ性が向上することができ、例えば、平均粒径が５～２０ｎｍであるナノシリカを用いることができる。 At this time, the silica sol may be a silica sol in which nano-sized silica is dispersed in water, and the use of nano-sized silica improves the stability of the solution, the corrosion resistance of the finally formed coating layer, and the scratch resistance of the coating layer. For example, nanosilica having an average particle size of 5 to 20 nm can be used.

さらに、上記シリカゾルは酸性のシリカゾルであることができ、上記シリカゾルが塩基性である場合には、シランの加水分解縮合反応によるゾル－ゲル反応が進行しにくいという問題が発生するおそれがある。 Further, the silica sol may be an acidic silica sol, and if the silica sol is basic, a problem may arise in that the sol-gel reaction due to the hydrolytic condensation reaction of silane is difficult to proceed.

このとき、シランは低温の酸性状態で次のように結晶化及び縮合反応が進行される。
At this time, the silane undergoes crystallization and condensation reactions in an acidic state at a low temperature as follows.

詳細には、上記（１）のように酸性雰囲気（ｐＨ＜２．５）でアルコキシ基の酸素がカチオンに帯電した粒子［Ｈ３Ｏ］＋を攻撃する。
Specifically, as described in (1) above, the oxygen of the alkoxy group attacks the cationically charged particles [H 3 O] + in an acidic atmosphere (pH<2.5).

これは、上記（２）のような反応式で表すことができ、その後には、下記（３）のように縮合反応が起こる。
This can be expressed by the reaction formula as shown in (2) above, and then a condensation reaction occurs as shown in (3) below.

上記（２）及び（３）の反応のようにシランの縮合反応は、２段階のＳｎ２反応に進行され、加水分解反応が縮合反応より速く起きて順に反応が行われる。したがって、本発明では、シランの加水分解及び縮合反応のために、酸性シリカゾルを用いることが好ましい。 As in the reactions (2) and (3) above, the silane condensation reaction proceeds as a two-step Sn2 reaction, in which the hydrolysis reaction occurs faster than the condensation reaction, and the reactions are performed in order. Therefore, in the present invention, it is preferable to use acidic silica sol for the hydrolysis and condensation reaction of silane.

一方、本発明のポリウレタン樹脂、アクリル系エマルション樹脂またはこれらの混合物は水分散したものであることができ、これにより鋼板の耐化学性、耐腐食性及び表面再コーティング性を付与することができ、水溶液の貯蔵安定性及び機械的特性のために、カチオン系またはノニオン系を用いることができる。このとき、上記ポリウレタン樹脂、アクリル系エマルション樹脂またはこれらの混合物は、電気亜鉛めっき鋼板用コーティング組成物の総重量を基準に１０～５０重量％、好ましくは１０～３０重量％用いることが好ましい。上記含有量が１０重量％未満の場合には、コーティング層の加工性が劣ってプレス作業時にパウダリング及び素材破断が生じることがあり、加工部の耐食性が脆弱になることがあり、５０重量％を超える場合には、耐熱性、テープ付着性及び耐溶剤性などの物性が脆弱になることがある。 On the other hand, the polyurethane resin, acrylic emulsion resin, or a mixture thereof of the present invention can be water-dispersed, thereby imparting chemical resistance, corrosion resistance, and surface recoatability to the steel plate. Cationic or nonionic systems can be used for storage stability and mechanical properties of aqueous solutions. At this time, the polyurethane resin, acrylic emulsion resin, or a mixture thereof is preferably used in an amount of 10 to 50% by weight, preferably 10 to 30% by weight, based on the total weight of the electrogalvanized steel sheet coating composition. If the above content is less than 10% by weight, the workability of the coating layer may be poor and powdering and material breakage may occur during pressing work, and the corrosion resistance of the processed part may become weak. If it exceeds 20%, physical properties such as heat resistance, tape adhesion, and solvent resistance may become weak.

さらに、上記ポリウレタン樹脂は、アクリルポリオール、ポリエチレンポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリカプロラクトンポリオールなどと、ジイソシアネート（Ｄｉｉｓｏｃｙａｎａｔｅ）、鎖（Ｃｈａｉｎ）延長剤、及び第３級アミンなどの親水性官能基を用いて水分散して用いることができ、上記ジイソシアネートは、ｐ－フェニレンジイソシアネート（ｐ－ｐｈｅｎｙｌｅｎｅ ｄｉｉｓｏｃｙａｎａｔｅ）、１，６－ヘキサメチレンジイソシアネート（１，６－Ｈｅｘａｍｅｔｈｙｌｅｎｅ ｄｉｉｓｏｃｙａｎａｔｅ）、トルエンジイソシアネート（Ｔｏｌｕｅｎｅ ｄｉｉｓｏｃｙａｎａｔｅ）、１，５－ナフタレンジイソシアネート（１，５Ｎａｐｈｔｈａｌｅｎｅ ｄｉｉｓｏｃｙａｎａｔｅ）、イソホロンジイソシアネート（Ｉｓｏｐｈｏｒｏｎｅ ｄｉｉｓｏｃｙａｎａｔｅ）、４，４－ジフェニルメタンジイソシアネート（４，４－Ｄｉｐｈｅｎｙｌｍｅｔｈａｎｅ ｄｉｉｓｏｃｙａｎａｔｅ）、及びシクロヘキシルメタンジイソシアネート（Ｃｙｃｌｏｈｅｘｙｌｍｅｔｈａｎｅ ｄｉｉｓｏｃｙａｎａｔｅ）からなる群から選択される少なくとも一つのジイソシアネートであり、好ましくは上記ジイソシアネートは、鋼板に耐熱性及び耐紫外線性を付与するために、脂環族ジイソシアネートを用いることができる。 Furthermore, the polyurethane resin contains acrylic polyol, polyethylene polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, etc., and hydrophilic functional groups such as diisocyanate, chain extender, and tertiary amine. The above diisocyanates include p-phenylene diisocyanate, 1,6-hexamethylene diisocyanate, and toluene diisocyanate. nate), 1 , 5-Naphthalene diisocyanate, Isophorone diisocyanate, 4,4-Diphenylmethane diisocyanate , and Cyclohexylmethane diisocyanate. One diisocyanate, preferably an alicyclic diisocyanate, can be used as the diisocyanate to impart heat resistance and ultraviolet resistance to the steel sheet.

また、上記ポリウレタン樹脂は、２５０℃×１時間の耐熱性を付与するために、水分散性ウレタン樹脂の合成時のプレポリマーの遊離ＮＣＯ％を１～５％、好ましくは２～３％とすることができる。遊離ＮＣＯ％が５％を超えると、最終水分散性ポリウレタン樹脂のウレア（Ｕｒｅａ）基が多くなって耐熱性が脆弱になり、１％以下であると、水分散性ポリウレタンの分子量が小さくなって耐食性、耐化学性などの物性が脆弱になる可能性がある。 Furthermore, in order to impart heat resistance to 250°C for 1 hour, the above polyurethane resin has a free NCO% of 1 to 5%, preferably 2 to 3%, in the prepolymer during synthesis of the water-dispersible urethane resin. be able to. If the free NCO% exceeds 5%, the number of urea groups in the final water-dispersible polyurethane resin increases and the heat resistance becomes weak, and if it is less than 1%, the molecular weight of the water-dispersible polyurethane becomes small. Physical properties such as corrosion resistance and chemical resistance may become fragile.

さらに、本発明は、鋼板の腐食防止のための腐食防止用添加剤を含むことができる。上記腐食防止用添加剤は、金属の有機酸塩、無機酸塩または水酸化物であることができ、例えば、上記腐食防止用添加剤は、Ａｌ、Ｔｉ、Ｍｏ、Ｖ、Ｍｎ、Ｍｇ、Ｐ及びＺｒからなる群から選択される１つ以上の金属の塩を用いることができる。また、例えば、上記塩はリン酸塩、硝酸塩、炭酸塩、酢酸塩または水酸化物であることができるが、これに制限されるものではなく、好ましくはＴｉ、Ｚｒ、Ｖ、Ｐ、Ｍｏの無機酸塩とリン酸変性物を組み合わせて用いることができる。 Furthermore, the present invention can include corrosion inhibitor additives for corrosion prevention of steel sheets. The corrosion-inhibiting additive may be an organic acid salt, an inorganic acid salt, or a hydroxide of a metal. For example, the corrosion-inhibiting additive may include Al, Ti, Mo, V, Mn, Mg, P Salts of one or more metals selected from the group consisting of Zr and Zr can be used. Further, for example, the above-mentioned salt can be a phosphate, a nitrate, a carbonate, an acetate, or a hydroxide, but is not limited thereto, and is preferably a salt of Ti, Zr, V, P, or Mo. An inorganic acid salt and a phosphoric acid modified product can be used in combination.

上記腐食防止用添加剤は、電気亜鉛めっき鋼板用コーティング組成物の総重量を基準に０．１～２重量％含まれることができ、好ましくは０．１～１重量％であることができる。上記腐食防止用添加剤の含有量が０．１重量％未満の場合には、鋼板の耐食性向上の効果が僅かであり、２重量％を超える場合には、コーティング組成物のゲル化が進行して溶液安定性が減少することがある。 The corrosion-inhibiting additive may be included in an amount of 0.1 to 2% by weight, preferably 0.1 to 1% by weight, based on the total weight of the coating composition for electrogalvanized steel sheets. If the content of the corrosion-inhibiting additive is less than 0.1% by weight, the effect of improving the corrosion resistance of steel sheets is slight, and if it exceeds 2% by weight, gelation of the coating composition progresses. may reduce solution stability.

さらに、本発明の電気亜鉛めっき鋼板用コーティング組成物は、有機溶媒、表面形成用添加剤及び水などをさらに含むことができる。 Furthermore, the coating composition for electrogalvanized steel sheets of the present invention may further contain an organic solvent, a surface forming additive, water, and the like.

上記有機溶媒は、コーティング組成物の溶液の安定性、作業性などのために用いられることができ、例えば、メタノール、エタノール、イソプロパノール、Ｎ－ブタノールなどのアルコール類またはエチレングリコール、プロピレングリコール、ブチルセロソルブ、エチルセロソルブ、ジアセトンアルコール、アセチルアセトンなどの親水性有機溶媒を用いることができるが、これに制限されるものではない。上記有機溶媒は、総組成物を基準に５～１５重量％含まれることができ、好ましくは５～１０重量％含まれることができる。有機溶媒が５重量％未満含まれると、コーティング組成物の溶液の安定性が劣り、溶液の乾燥速度が遅くなる。また、有機溶媒が１５重量％を超えて含まれると、ロール作業時に溶剤の揮発により作業性に多くの問題を発生させ、硬化過程で揮発される溶剤による有害蒸気問題などの発生の原因となる。 The above organic solvent can be used for stability, workability, etc. of the solution of the coating composition, and includes, for example, alcohols such as methanol, ethanol, isopropanol, and N-butanol, or ethylene glycol, propylene glycol, butyl cellosolve, Hydrophilic organic solvents such as ethyl cellosolve, diacetone alcohol, and acetylacetone can be used, but are not limited thereto. The organic solvent may be included in an amount of 5 to 15% by weight, preferably 5 to 10% by weight, based on the total composition. If the organic solvent is contained in an amount less than 5% by weight, the stability of the solution of the coating composition will be poor and the drying rate of the solution will be slow. In addition, if the organic solvent is contained in an amount exceeding 15% by weight, many problems will occur in workability due to the volatilization of the solvent during rolling operation, and the problem of harmful vapors caused by the solvent volatilized during the curing process may occur. .

さらに、上記表面形成用添加剤としては、消泡剤、レベリング剤などを添加することができ、電気亜鉛めっき鋼板用コーティング組成物の総重量を基準に１～６重量％、好ましくは１～５重量％、さらに好ましくは１～２重量％含まれることができ、水は上記電気亜鉛めっき鋼板用コーティング組成物の固形分が５～３０重量％となるように添加することができる。上記固形分が５重量％未満の場合には、粘度が高くて作業性が良好でない問題が生じることがあり、３０重量％を超える場合には、逆に粘度が低すぎて目標の塗膜厚さを得ることができない問題が生じることがある。 Furthermore, as the above-mentioned surface forming additives, antifoaming agents, leveling agents, etc. can be added, and 1 to 6% by weight, preferably 1 to 5% by weight, preferably 1 to 5% by weight, based on the total weight of the coating composition for electrogalvanized steel sheets. Water may be added in an amount of 5 to 30% by weight, more preferably 1 to 2% by weight, and water may be added so that the solid content of the electrogalvanized steel sheet coating composition is 5 to 30% by weight. If the solid content is less than 5% by weight, the viscosity may be high and workability may be poor, while if it exceeds 30% by weight, the viscosity is too low to achieve the desired coating film thickness. Problems may arise where it is not possible to obtain

一方、本発明は、電気亜鉛めっき鋼板用コーティング組成物によって、コーティング層が形成された電気亜鉛めっき鋼板を提供する。 On the other hand, the present invention provides an electrogalvanized steel sheet in which a coating layer is formed using a coating composition for electrogalvanized steel sheet.

詳細には、本発明は電気亜鉛めっき鋼板；及び上記鋼板上に本発明の電気亜鉛めっき鋼板用コーティング組成物がコーティング及び硬化して形成されたコーティング層を含む電気亜鉛めっき鋼板を提供することができ、上記組成物の塗布による１コーティングによってプライマーなしにコーティング層を形成するとともに、優れた耐熱性、耐腐食性、耐化学性及びテープ付着性を有する鋼板が得られる。 Specifically, the present invention provides an electrogalvanized steel sheet; and an electrogalvanized steel sheet comprising a coating layer formed by coating and curing the electrogalvanized steel sheet coating composition of the present invention on the steel sheet. A coating layer can be formed without a primer by one coating of the above composition, and a steel plate having excellent heat resistance, corrosion resistance, chemical resistance, and tape adhesion can be obtained.

一方、上記コーティング層は０．１～２．０μｍの厚さで形成されることができ、厚さが０．１μｍ未満の場合には、十分な物性を示すことができないという問題が生じることがあり、２．０μｍを超える場合には、耐指紋鋼板に求められる表面電気導電性が良好でないという問題が生じることがある。したがって、映像家電用パネルとして用いるために、最も好ましくは０．５～１．５μｍが適切である。 On the other hand, the coating layer may be formed with a thickness of 0.1 to 2.0 μm, and if the thickness is less than 0.1 μm, a problem may occur that it cannot exhibit sufficient physical properties. If the thickness exceeds 2.0 μm, a problem may arise that the surface electrical conductivity required for a fingerprint-resistant steel plate is not good. Therefore, for use as a panel for video home appliances, the most suitable thickness is 0.5 to 1.5 μm.

さらに、本発明は、上記電気亜鉛めっき鋼板を製造する方法を提供する。 Furthermore, the present invention provides a method for manufacturing the electrogalvanized steel sheet.

詳細には、本発明は、電気亜鉛めっき鋼板の一面に本発明の電気亜鉛めっき鋼板用コーティング組成物をコーティングする段階を含む電気亜鉛めっき鋼板の製造方法を提供する。 Specifically, the present invention provides a method for producing an electrogalvanized steel sheet, which includes the step of coating one side of the electrogalvanized steel sheet with the coating composition for electrogalvanized steel sheet of the present invention.

上記コーティングは、ロールコーティング、バーコーティングなどのコーティング方法によって行われることができるが、これに制限されるものではなく、一定厚さでコーティング層を形成することができる方法であれば、どのような方法も用いられることができる。 The above-mentioned coating can be performed by a coating method such as roll coating or bar coating, but is not limited thereto. Any method can be used as long as it can form a coating layer with a constant thickness. Methods can also be used.

さらに、上記コーティング層は熱処理によって硬化されることができ、例えば、コーティングの段階後に１５０～１８０℃の温度で硬化させる段階をさらに行うことができる。このとき、上記硬化させる段階の温度が１５０℃未満の場合には、十分な乾燥が起こらず塗膜の形成が難しく、硬化温度が１８０℃を超える場合には、十分な硬化は起こるが、エネルギーが多くかかるという欠点が生じることがある。 Furthermore, the coating layer may be cured by heat treatment, for example, a curing step at a temperature of 150 to 180° C. may be further performed after the coating step. At this time, if the temperature in the curing step is less than 150°C, sufficient drying will not occur and it will be difficult to form a coating, and if the curing temperature exceeds 180°C, sufficient curing will occur, but the energy The disadvantage is that it takes a lot of time.

以下、具体的な実験例を挙げて本発明をより詳細に説明する。下記実施例は、本発明の理解を助けるための例示に過ぎず、本発明の範囲がこれに限定されるものではない。 Hereinafter, the present invention will be explained in more detail by giving specific experimental examples. The following examples are merely illustrative to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

（実施例）
攪拌機、還流冷却器、温度計、漏斗（Ｄｒｏｐｐｉｎｇ Ｆｕｎｎｅｌ）及び窒素注入器が付着した４つ口フラスコに組成物の総重量を基準にシランを添加し、上記シランに酢酸、シリカゾル（ｐＨ４、平均粒径１２ｎｍ、ＳｉＯ２２０重量％）及びイオン交換水の混合物を２時間常温でゆっくり滴下する。このとき、発熱に注意して上記フラスコの温度が３０℃を超えないように温度を調節しながら滴下する。 (Example)
Silane was added based on the total weight of the composition to a four-necked flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen injector, and to the silane was added acetic acid, silica sol (pH 4, average particle size). A mixture of 12 nm in diameter, 20% by weight of SiO 2 ) and ion-exchanged water was slowly added dropwise at room temperature for 2 hours. At this time, the mixture is added dropwise while controlling the temperature of the flask so that it does not exceed 30°C, being careful not to generate heat.

滴下が完了した後、常温で２４時間撹拌する。これから、シリカシランの透明な共重合体が含まれた溶液が得られた。 After the addition is complete, stir at room temperature for 24 hours. This resulted in a solution containing a transparent copolymer of silica silane.

上記溶液にイオン交換水、水分散ポリウレタン樹脂（固形分３０重量％）、エタノール、腐食防止剤としてバナジウム塩（アンモニウムメタバナデート）及びジルコニウム塩（ヘキサフルオロジルコン酸）とともに、リン酸、レベリング剤としてエタノール、及び消泡剤としてポリシロキサンジメチルポリシロキサンを加えて３０分間攪拌した後、３０ミクロンのろ過フィルターで包装した。製造された組成物の具体的な成分及び成分の含有量を組成物の総重量を基準として表１に示した。 The above solution contains ion-exchanged water, water-dispersed polyurethane resin (solid content 30% by weight), ethanol, vanadium salt (ammonium metavanadate) and zirconium salt (hexafluorozirconate) as corrosion inhibitors, and phosphoric acid as a leveling agent. After adding ethanol and polysiloxane dimethylpolysiloxane as an antifoaming agent and stirring for 30 minutes, the mixture was packaged with a 30 micron filter. Specific components and contents of the components of the prepared composition are shown in Table 1 based on the total weight of the composition.

Figure 0007414997000004
Figure 0007414997000004

＊残部には、イオン交換水が含まれる。
＊Ｓ１）テトラエトキシシラン；Ｓ２）ビニルトリエトキシシラン；Ｓ３）３－グリシドキシプロピルトリメトキシシラン；Ｓ４）３－グリシドキシプロピルトリエトキシシラン；Ｓ５）Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン；Ｓ６）３－アミノプロピルトリメトキシシラン；Ｓ７）３－アミノプロピルトリエトキシシラン；Ｓ８）３－ウルレイドプロピルアルコキシシラン（３－Ｕｒｅｉｄｏｐｒｏｐｙｌｔｒｉａｌｋｏｘｙｓｉｌａｎｅ）；Ｓ９）３－イソシアネートプロピルトリエトキシシラン（３－Ｉｓｏｃｙｎａｔｅｐｒｏｐｙｌｔｒｉｅｔｈｏｓｙ ｓｉｌａｎｅ）；Ｒ１）カチオン系水分散ポリウレタン樹脂（ポリカーボネートポリオール）；Ｒ２）カチオン系水分散ポリウレタン樹脂（ポリエステルポリオール）；Ｒ３）ノニオン系水分散ポリウレタン樹脂（ポリカーボネートポリオール）；Ｒ４）ノニオン系アクリルエマルション *The remainder includes ion exchange water.
*S1) Tetraethoxysilane; S2) Vinyltriethoxysilane; S3) 3-glycidoxypropyltrimethoxysilane; S4) 3-glycidoxypropyltriethoxysilane; S5) N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane; S6) 3-aminopropyltrimethoxysilane; S7) 3-aminopropyltriethoxysilane; S8) 3-Ureidopropyltrialkoxysilane; S9) 3-Isocyanatepropyltriethoxy Silane (3-Isocynatepropyltriethosy silane); R1) Cationic water-dispersed polyurethane resin (polycarbonate polyol); R2) Cationic water-dispersed polyurethane resin (polyester polyol); R3) Nonionic water-dispersed polyurethane resin (polycarbonate polyol); R4) Nonion Acrylic emulsion

（実験例）
厚さが０．５ｍｍの電気亜鉛めっき鋼板に、上記実施例１－６及び比較例１－４を２０±２ｇ／ｍ２になるようにバーコーターを用いてコーティングした。製造されたコーティング鋼板の耐熱性、耐腐食性、テープ付着性及び耐化学性を評価し、評価方法は以下のとおりであり、各評価結果を表２に示した。 (Experiment example)
An electrogalvanized steel sheet having a thickness of 0.5 mm was coated with the above Examples 1-6 and Comparative Example 1-4 to a coating weight of 20±2 g/m 2 using a bar coater. The heat resistance, corrosion resistance, tape adhesion, and chemical resistance of the manufactured coated steel sheet were evaluated, and the evaluation methods were as follows, and the evaluation results are shown in Table 2.

［耐熱性］
耐熱性試験は、オーブン温度２５０℃で１時間測定した。
１＝試験前後の色差値（ΔＥ）５．０未満
２＝試験前後の色差値（ΔＥ）５．０以上、６．０未満
３＝試験前後の色差値（ΔＥ）６．０以上、７．０未満
４＝試験前後の色差値（ΔＥ）７．０以上、８．０未満
５＝試験前後の色差値（ΔＥ）８．０以上、９．０未満
６＝試験前後の色差値（ΔＥ）９．０以上 [Heat-resistant]
The heat resistance test was carried out at an oven temperature of 250° C. for 1 hour.
1 = Color difference value before and after the test (ΔE) less than 5.0 2 = Color difference value before and after the test (ΔE) 5.0 or more but less than 6.0 3 = Color difference value before and after the test (ΔE) 6.0 or more, 7. Less than 0 4 = Color difference value before and after the test (ΔE) 7.0 or more, less than 8.0 5 = Color difference value before and after the test (ΔE) 8.0 or more, less than 9.0 6 = Color difference value before and after the test (ΔE) 9.0 or higher

［耐腐食性］
（１）Ｓ．Ｓ．Ｔ平面部の試験
５％ＮａＣｌ、３５℃１２０時間試験して白錆発生を観察した。
１＝白錆発生面積が全面積の５％未満
２＝白錆発生面積が全面積の５％以上、１０％未満
３＝白錆発生面積が全面積の１０％以上、３０％未満
４＝白錆発生面積が全面積の３０％以上、６０％未満
５＝白錆発生面積が全面積の６０％以上
（２）Ｓ．Ｓ．Ｔ加工部の試験
エリクセン試験（６ｍｍ）を施行した後、５％ＮａＣｌ、３５℃、４８時間行って白錆発生を観察した。
１＝白錆発生面積が加工部面積の５％未満
２＝白錆発生面積が加工部面積の５％以上、１０％未満
３＝白錆発生面積が加工部面積の１０％以上、３０％未満
４＝白錆発生面積が加工部面積の３０％以上、６０％未満
５＝白錆発生面積が加工部面積の６０％以上 [Corrosion resistance]
(1) S. S. Test on T plane part Tested in 5% NaCl at 35°C for 120 hours to observe the occurrence of white rust.
1 = Area where white rust occurs is less than 5% of the total area 2 = Area where white rust occurs is 5% or more and less than 10% of the total area 3 = Area where white rust occurs is 10% or more and less than 30% of the total area 4 = White The area where rust occurs is 30% or more and less than 60% of the total area 5 = The area where white rust occurs is 60% or more of the total area (2) S. S. Test on T-processed part After conducting an Erichsen test (6 mm), the test was carried out in 5% NaCl at 35°C for 48 hours to observe the occurrence of white rust.
1 = Area where white rust occurs is less than 5% of the area of the machined part 2 = Area where white rust occurs is 5% or more but less than 10% of the area of the machined part 3 = Area where white rust occurs is 10% or more but less than 30% of the area of the machined part 4 = Area where white rust occurs is 30% or more and less than 60% of the area of the machined part 5 = Area where white rust occurs is 60% or more of the area of the machined part

［テープ付着性（接着性）］
テープ付着性は、３Ｍ社のテープを用い、試験テープの幅は２０ｍｍ、テープの長さは１００ｍｍサイズとした。試験片は、テープ付着前にアルコールで洗浄した後、テープを８０ｇ重りを吊り下げて常温及び６０℃で評価した。等級は、常温及び６０℃でテープを付着した後、１２日経過した時のテープ剥離長さの平均を測定して評価した。
１＝剥離長さ５ｍｍ未満
２＝剥離長さ５ｍｍ以上、６ｍｍ未満
３＝剥離長さ６ｍｍ以上、７ｍｍ未満
４＝剥離長さ７ｍｍ以上、８ｍｍ未満
５＝剥離長さ８ｍｍ以上、１０ｍｍ未満
６＝剥離長さ１０ｍｍ以上 [Tape adhesion (adhesion)]
For tape adhesion, a tape manufactured by 3M was used, the width of the test tape was 20 mm, and the length of the tape was 100 mm. The test piece was washed with alcohol before being attached with the tape, and then the tape was hung with an 80 g weight and evaluated at room temperature and 60°C. The grade was evaluated by measuring the average length of tape peeling 12 days after attaching the tape at room temperature and 60°C.
1=Peeling length less than 5mm 2=Peeling length 5mm or more and less than 6mm 3=Peeling length 6mm or more and less than 7mm 4=Peeling length 7mm or more and less than 8mm 5=Peeling length 8mm or more and less than 10mm 6=Peeling Length 10mm or more

［耐化学性］
耐化学性は、重アルカリ脱脂剤である日本パーカのＰＡＬＫＬＩＮ Ｎ３６４Ｓを用い、２％水溶液を製造して素地を沈積し、超音波機器に入れて５分間超音波脱脂を進行した。
１＝塗膜剥離面積０％
２＝塗膜剥離面積０％超過、１０％未満
３＝塗膜剥離面積１０％以上、２０％未満
４＝塗膜剥離面積２０％以上、３０％未満
５＝塗膜剥離面積３０％以上、４０％未満
６＝塗膜剥離面積４０％以上 [Chemical resistance]
For chemical resistance, a 2% aqueous solution was prepared using PALKLIN N364S from Nippon Parker, which is a heavy alkali degreaser, and the substrate was deposited, and then placed in an ultrasonic device and subjected to ultrasonic degreasing for 5 minutes.
1 = Paint film peeling area 0%
2 = Paint film peeling area more than 0%, less than 10% 3 = Paint film peeling area 10% or more, less than 20% 4 = Paint film peeling area 20% or more, less than 30% 5 = Paint film peeling area 30% or more, 40 Less than % 6 = Paint film peeling area 40% or more

その結果、表２に示したように、実施例１～６は耐熱性、耐腐食性、テープ付着性及び耐化学性がすべて優れたものと表れたのに対し、比較例１～４は耐熱性、耐腐食性、テープ付着性及び耐化学性の一つ以上の特性が劣化したものと示された。 As a result, as shown in Table 2, Examples 1 to 6 showed excellent heat resistance, corrosion resistance, tape adhesion, and chemical resistance, whereas Comparative Examples 1 to 4 showed excellent heat resistance. It was shown that one or more of the following properties were deteriorated: corrosion resistance, corrosion resistance, tape adhesion, and chemical resistance.

特に、実施例１及び５と比較例１及び２の温度による耐熱性及びテープ接着性を図１及び２にそれぞれ示し、図１及び２に示したように、本発明の組成物は耐熱性に優れ、常温及び６０℃においてもテープ付着性が維持されることが確認できた。 In particular, the heat resistance and tape adhesion depending on the temperature of Examples 1 and 5 and Comparative Examples 1 and 2 are shown in FIGS. 1 and 2, respectively. As shown in FIGS. It was confirmed that the tape adhesion was excellent and maintained even at room temperature and 60°C.

以上、本発明の実施形態について詳細に説明したが、本発明の権利範囲はこれに限定されず、特許請求の範囲に記載された本発明の技術的思想から逸脱しない範囲内で多様な修正及び変形が可能であるということは、当技術分野の通常の知識を有する者には明らかである。 Although the embodiments of the present invention have been described in detail above, the scope of rights of the present invention is not limited thereto, and various modifications and changes may be made without departing from the technical idea of the present invention as described in the claims. It will be apparent to those of ordinary skill in the art that variations are possible.

Claims (10)

シラン；
シリカゾル；
ポリウレタン樹脂；
腐食防止用添加剤；及び
水を含み、
前記シランは、４官能シラン及び３官能シランを含み、
前記３官能シランの含有量は、４官能シランの含有量より多く、
前記ポリウレタン樹脂の総重量を基準に、前記ポリウレタン樹脂のＮＣＯ％は１～５％である、電気亜鉛めっき鋼板用コーティング組成物。 Silane;
Silica sol;
Polyurethane resin;
Corrosion inhibiting additive; and water;
The silane includes a tetrafunctional silane and a trifunctional silane,
The content of the trifunctional silane is greater than the content of the tetrafunctional silane,
A coating composition for electrogalvanized steel sheets, wherein the polyurethane resin has an NCO% of 1 to 5% based on the total weight of the polyurethane resin. 前記電気亜鉛めっき鋼板用コーティング組成物の総重量を基準に、
前記シラン５～２０重量％；
前記シリカゾル２～１０重量％；
前記ポリウレタン樹脂１０～５０重量％；
前記腐食防止用添加剤０．１～２．０重量％；及び
残部の水を含む、請求項１に記載の電気亜鉛めっき鋼板用コーティング組成物。 Based on the total weight of the coating composition for electrogalvanized steel sheet,
5 to 20% by weight of the silane;
2 to 10% by weight of the silica sol;
10 to 50% by weight of the polyurethane resin;
The coating composition for electrogalvanized steel sheet according to claim 1, comprising: 0.1 to 2.0% by weight of the corrosion-inhibiting additive; and the balance water. 前記シランは、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、デシ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、２－（３，４エポキシシクロヘキシル）－エチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、及び３－アミノプロピルトリエトキシシラン、３－ウルレイドプロピルアルコキシシラン（３－Ｕｒｅｉｄｏｐｒｏｐｙｌｔｒｉａｌｋｏｘｙｓｉｌａｎｅ）、３－イソシアネートプロピルトリエトキシシラン（３－Ｉｓｏｃｙｎａｔｅｐｒｏｐｙｌｔｒｉｅｔｈｏｘｙ ｓｉｌａｎｅ）、及びトリス－（トリメトキシシリルプロピル）イソシアヌレート（Ｔｒｉｓ－（ｔｒｉｍｅｔｈｏｘｙｓｉｌｙｌｐｒｏｐｙｌ）ｉｓｏｃｙａｎｕｒａｔｅ）からなる群から選択される一つ以上である、請求項１に記載の電気亜鉛めっき鋼板用コーティング組成物。 The silane includes tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, 2-(3,4epoxycyclohexyl)-ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane , 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Aminopropyltriethoxysilane, 3-Ureidopropyltrialkoxysilane, 3-Isocyanatepropyltriethoxysilane, and Tris-(trimethoxysilylpropyl)isocyanurate ( Tris-(trimethoxysilylpropyl) The coating composition for electrogalvanized steel sheets according to claim 1, wherein the coating composition is one or more selected from the group consisting of isocyanurate. 前記シリカゾルは、ナノサイズシリカが水分散されたシリカゾルである、請求項１に記載の電気亜鉛めっき鋼板用コーティング組成物。 The coating composition for an electrogalvanized steel sheet according to claim 1, wherein the silica sol is a silica sol in which nano-sized silica is dispersed in water. 前記シリカゾルは酸性シリカゾルである、請求項１に記載の電気亜鉛めっき鋼板用コーティング組成物。 The coating composition for an electrogalvanized steel sheet according to claim 1, wherein the silica sol is an acidic silica sol. 前記ポリウレタン樹脂は、カチオン系またはノニオン系である、請求項１に記載の電気亜鉛めっき鋼板用コーティング組成物。 The coating composition for electrogalvanized steel sheets according to claim 1, wherein the polyurethane resin is cationic or nonionic. 前記腐食防止用添加剤は、Ａｌ、Ｔｉ、Ｍｏ、Ｖ、Ｍｎ、Ｍｇ、Ｐ及びＺｒからなる群から選択される一つ以上の金属の塩である、請求項１に記載の電気亜鉛めっき鋼板用コーティング組成物。 The electrogalvanized steel sheet according to claim 1, wherein the corrosion-inhibiting additive is a salt of one or more metals selected from the group consisting of Al, Ti, Mo, V, Mn, Mg, P, and Zr. Coating composition for use. 電気亜鉛めっき鋼板；及び
前記鋼板上に請求項１から７のいずれか一項に記載の組成物がコーティング及び硬化して形成されたコーティング層を含む、電気亜鉛めっき鋼板。 An electrogalvanized steel sheet, comprising: an electrogalvanized steel sheet; and a coating layer formed by coating and curing the composition according to any one of claims 1 to 7 on the steel sheet. 電気亜鉛めっき鋼板の一面に請求項１から７のいずれか一項に記載の組成物をコーティングする段階を含む、電気亜鉛めっき鋼板の製造方法。 A method for producing an electrogalvanized steel sheet, comprising the step of coating one side of the electrogalvanized steel sheet with the composition according to any one of claims 1 to 7 . 前記コーティングする段階後に１５０～１８０℃の温度で硬化させる段階をさらに含む、請求項９に記載の電気亜鉛めっき鋼板の製造方法。 The method of manufacturing an electrogalvanized steel sheet according to claim 9 , further comprising the step of curing at a temperature of 150 to 180° C. after the coating step.
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