JP2005264276A - Inorganic and organic composite treatment zinc-based plated steel sheet for blade supporting member - Google Patents
Inorganic and organic composite treatment zinc-based plated steel sheet for blade supporting member Download PDFInfo
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
Abstract
Description
本発明は、ブレード支持部材用無機有機複合処理亜鉛系メッキ鋼板に関する。 The present invention relates to an inorganic / organic composite-treated galvanized steel sheet for blade support members.
ブレードはこれを構成するブレード支持部材およびブレード部材や接着剤を介しての密着性に加え、ブレード支持部材の耐食性が求められている。後者については鋼板からブレード支持部材へのプレス成形後からブレード作製までの保管や搬送中に支持部材表面が錆びることを避ける必要があるためであり、トナーブレードメーカーでは支持部材用材料の採用に際しては厳しめの評価として塩水噴霧試験等の腐食試験を実施している。 The blade is required to have corrosion resistance of the blade support member in addition to the blade support member constituting the blade and the adhesion through the blade member and the adhesive. For the latter, it is necessary to avoid the surface of the support member from being rusted during storage and transportation from press forming from the steel plate to the blade support member until blade production. Corrosion tests such as a salt spray test are conducted as a strict evaluation.
その一方で、トナーブレードを製造するメーカーではブレード部材とブレード支持部材との接着性を向上させるべく鋼板メーカーから供給されたブレード支持部材用鋼板を打ち抜きし、プレス成形して脱脂した後に、シランカップリング剤によるプライマー処理を行っている。
近年、トナーブレードを製造するメーカーから、製造工程でのプライマー処理省略を要望されており、プライマー処理省略タイプのブレード支持部材への要求が高まっている。上記の例として以下の技術が提案されている。
On the other hand, a manufacturer that manufactures toner blades punches a steel sheet for blade support member supplied from a steel sheet manufacturer to improve the adhesion between the blade member and the blade support member, presses and degreases, Primer treatment with ring agent.
In recent years, manufacturers that manufacture toner blades are requested to omit the primer treatment in the production process, and there is an increasing demand for a blade support member of the primer treatment omitted type. The following techniques have been proposed as the above example.
複写装置やプリンターなどの電子写真方式の画像形成装置に用いられ、プライマーを塗布することなしに弾性体ブレードを接着して支持するための金属製ホルダーを、電気亜鉛メッキ鋼板の上にクロメート皮膜と有機潤滑皮膜層を有する鋼板で形成したことを特徴とするブレードが開示されている（例えば、特許文献１参照。）。
支持部材と接着剤層と前記支持部材に前記接着剤層を介して接着されたブレード部材とからなる電子写真装置用ブレード体において、前記支持部材が有機潤滑皮膜鋼板からなるものであることが開示されている。（例えば、特許文献２参照。）。
Used in electrophotographic image forming devices such as copying machines and printers, a metal holder for adhering and supporting an elastic blade without applying a primer, and a chromate film on an electrogalvanized steel sheet A blade characterized by being formed of a steel plate having an organic lubricating film layer is disclosed (for example, see Patent Document 1).
In a blade body for an electrophotographic apparatus comprising a support member, an adhesive layer, and a blade member bonded to the support member via the adhesive layer, it is disclosed that the support member is made of an organic lubricating film steel plate. Has been. (For example, refer to Patent Document 2).
熱硬化性ウレタンエラストマーからなるブレード部材と、支持部材と接着剤層とからなり、前記熱硬化性ウレタンエラストマーが吸水性を有するエラストマーであり、前記接着剤層が加水分解性有機シラン化合物を含有する湿気硬化型接着剤からなるものであることを特徴とする電子写真装置用クリーニングブレードが開示されている（例えば、特許文献３参照。）。
ウレタンエラストマーからなるブレード部材が接着剤で支持部材に接着された電子写真装置用クリーニングブレードであって、上記接着剤として、溶剤に溶解したホットメルト接着剤の溶液を用い、前記ホットメルト接着剤にはシランカップリング剤が添加されていることを特徴とする電子写真装置用クリーニングブレードが開示されている（例えば、特許文献４参照。）。
It consists of a blade member made of a thermosetting urethane elastomer, a support member and an adhesive layer, and the thermosetting urethane elastomer is an elastomer having water absorption, and the adhesive layer contains a hydrolyzable organosilane compound. There has been disclosed a cleaning blade for an electrophotographic apparatus characterized by comprising a moisture-curing adhesive (see, for example, Patent Document 3).
A cleaning blade for an electrophotographic apparatus in which a blade member made of a urethane elastomer is bonded to a support member with an adhesive, and a solution of a hot melt adhesive dissolved in a solvent is used as the adhesive, and the hot melt adhesive Discloses a cleaning blade for an electrophotographic apparatus in which a silane coupling agent is added (see, for example, Patent Document 4).
熱硬化性タイプのウレタンエラストマーからなるブレード部材が接着剤で支持部材に接着された電子写真装置用クリーニングブレードであって、上記接着剤として、ポリビニルアセタール樹脂のホルムアルデヒド縮合型熱硬化性樹脂による変成物を用いたことを特徴とする電子写真装置用クリーニングブレードの内、支持部材は、シランカップリング剤で表面処理されていることを特徴とすることが開示されている（例えば、特許文献５参照。）。
前記特許文献のようにブレード支持部材としてクロメート処理した亜鉛系メッキ鋼板が一般に使用されてきた。しかしながら、近年、環境問題の高まりを背景に、毒性の大きいクロメートを用いない各種表面処理技術の開発が待望され、ブレード支持部材としても６価クロム等の環境負荷物質を含まないタイプのものの開発が必須となっている。他方、前記特許文献で示されたように、トナーブレード製造メーカーでのプライマー処理省略のためにブレード部材とブレード支持部材とを繋ぐ接着剤の中にシランカップリング剤や有機シラン化合物を添加することの提案がなされている。 As in the above-mentioned patent document, a zinc-based plated steel sheet that has been chromated as a blade support member has been generally used. However, in recent years, against the background of growing environmental problems, the development of various surface treatment techniques that do not use highly toxic chromate is awaited, and the development of types that do not contain environmentally hazardous substances such as hexavalent chromium as blade support members It is essential. On the other hand, as shown in the above patent document, a silane coupling agent or an organosilane compound is added to the adhesive connecting the blade member and the blade support member in order to omit the primer treatment at the toner blade manufacturer. Proposals have been made.
前記提案の内、ブレード支持部材としてクロメート処理した亜鉛系メッキ鋼板を使用した場合には充分な耐食性の担保がなされているが、クロメートフリーの処理を用いた鋼板の場合にはクロメート処理したものに比べ耐食性に劣るため改善の必要性がある。
また、上記提案のブレードはブレード部材とブレード支持部材とを繋ぐ接着剤の間での密着力は充分とはいえず、実用上は更なる密着力の向上が望まれる。
Among the above proposals, sufficient corrosion resistance is secured when using a chromate-treated galvanized steel sheet as a blade support member, but in the case of a steel sheet using a chromate-free process, There is a need for improvement because it is inferior in corrosion resistance.
In addition, the above-mentioned proposed blade does not have sufficient adhesion between the adhesive connecting the blade member and the blade support member, and further improvement in adhesion is desired in practice.
そもそも接着力や密着力は異材間の界面の局所的な結合力の不均一により強度にばらつきが生じ易く、不安定である場合が多い。ブレードの具備すべき主たる性能要件はブレード部材とブレード支持部材の高強度な密着力の確保であり、上記ブレードでは充分な性能を満足しているとは言えない。
更なるブレード部材とブレード支持部材との間の密着力の向上を図るためには、接着剤そのものの架橋構造の強化ではブレード支持部材と接着剤との間の密着力は不充分であるため、各界面での密着性の向上を図るべくブレード支持部材表面の皮膜の密着性および接着性の向上を目指し、最適な皮膜設計が必須と考えられる。
In the first place, the adhesive strength and the adhesive strength tend to vary in strength due to uneven local bonding force at the interface between different materials, and are often unstable. The main performance requirement of the blade is to secure a high strength adhesion between the blade member and the blade support member, and it cannot be said that the blade satisfies the sufficient performance.
In order to further improve the adhesion between the blade member and the blade support member, since the adhesion force between the blade support member and the adhesive is insufficient in strengthening the cross-linking structure of the adhesive itself, In order to improve the adhesion at each interface, it is considered that an optimum coating design is essential to improve the adhesion and adhesion of the coating on the blade support member surface.
本発明は、上記現状に鑑み、プライマー処理省略が可能で、処理された皮膜中に有害なクロメートを含有せず、充分な耐食性を担保しながら、且つブレード部材との密着性にも優れたブレード支持部材用無機有機複合処理亜鉛系メッキ鋼板を提供することを目的とするものである。 In view of the above situation, the present invention can omit the primer treatment, does not contain harmful chromate in the treated film, ensures sufficient corrosion resistance, and has excellent adhesion to the blade member. An object of the present invention is to provide an inorganic / organic composite-treated zinc-based plated steel sheet for a support member.
本発明は、亜鉛系メッキ鋼板の表面に、第１層としてリン酸亜鉛処理皮膜を形成し、その上に第２層として有機樹脂系皮膜を形成し、更に第３層として有機系後処理皮膜を有するブレード支持部材用無機有機複合処理亜鉛系メッキ鋼板であって、上記リン酸亜鉛処理皮膜量が０．３〜５ｇ／ｍ２、有機樹脂系皮膜が０．０１〜１ｇ／ｍ２、有機系後処理皮膜量が０．０１〜１ｇ／ｍ２であり、上記有機系後処理皮膜が、アミノ基含有シランカップリング剤１０〜１００質量％、その他のシランカップリング剤及び、または有機アルコキシシラン化合物０〜９０質量％からなることを特徴とするブレード支持部材用無機有機複合処理亜鉛系メッキ鋼板である。 In the present invention, a zinc phosphate treatment film is formed as a first layer on the surface of a zinc-based plated steel sheet, an organic resin film is formed as a second layer thereon, and an organic post-treatment film is formed as a third layer. An inorganic-organic composite-treated zinc-based plated steel sheet for blade support members having a zinc phosphate-treated film amount of 0.3-5 g / m 2 , an organic resin-based film of 0.01-1 g / m 2 , organic The amount of the system post-treatment film is 0.01 to 1 g / m 2 , and the organic post-treatment film is an amino group-containing silane coupling agent of 10 to 100% by mass, other silane coupling agents and / or organic alkoxysilanes. It is an inorganic-organic composite-treated zinc-based plated steel sheet for blade support members, comprising 0 to 90% by mass of a compound.
本発明によれば、無機有機複合処理亜鉛系メッキ鋼板の第１層のリン酸亜鉛処理皮膜は、鋼板表面への強固な密着と表面凹凸による表面積の拡大に寄与し、且つ亜鉛メッキ表面の腐食因子からの保護皮膜の役目を担い、第２層の有機樹脂系皮膜は第１層のリン酸亜鉛処理皮膜との密着性に寄与し、腐食因子の透過抑制能に因って第１層のリン酸亜鉛処理皮膜の耐食性を補足し向上させる機能を有し、第３層の有機系後処理皮膜は、第２層の有機樹脂系皮膜及びその上に接着されるブレード部材または接着剤に対する密着に寄与するため、結果として、処理された皮膜中に有害なクロメートを含有せず、耐食性に優れ、ブレード製造工程でのプライマー処理が不要な、ブレード部材との密着性に優れたブレード支持部材用無機有機複合処理亜鉛系メッキ鋼板を得ることができる。 According to the present invention, the zinc phosphate-treated film of the first layer of the inorganic-organic composite-treated zinc-based plated steel sheet contributes to strong adhesion to the steel sheet surface and an increase in surface area due to surface irregularities, and corrosion of the galvanized surface. The organic resin film of the second layer contributes to adhesion with the zinc phosphate-treated film of the first layer, and the first layer of the first layer due to the ability of inhibiting the permeation of corrosion factors. It has the function of supplementing and improving the corrosion resistance of the zinc phosphate-treated film, and the third-layer organic post-treated film is adhered to the second-layer organic resin-based film and the blade member or adhesive adhered thereon. As a result, it does not contain harmful chromate in the treated film, has excellent corrosion resistance, does not require primer treatment in the blade manufacturing process, and has excellent adhesion to the blade member. Inorganic organic composite-treated zinc It is possible to obtain a plated steel sheet.
以下に、本発明を詳細に説明する。
本発明の無機有機複合処理亜鉛系メッキ鋼板は、亜鉛系メッキ鋼板の表面に、第１層としてリン酸亜鉛処理皮膜を有し、その上に第２層として有機樹脂系皮膜、第３層として有機系後処理皮膜を有するもので、上記リン酸亜鉛処理皮膜量が０．３〜５ｇ／ｍ２、有機樹脂系皮膜が０．０１〜１ｇ／ｍ２、有機系後処理皮膜量が０．０１〜１ｇ／ｍ２であり、上記有機系後処理皮膜が、アミノ基含有シランカップリング剤１０〜１００質量％、その他のシランカップリング剤及び、または有機アルコキシシラン化合物０〜９０質量％からなるものであり、これら三種類の皮膜を有することにより、耐食性とブレード部材乃至接着剤を介してのブレード部材との密着性を格段に向上させたものである。
The present invention is described in detail below.
The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention has a zinc phosphate-treated film as the first layer on the surface of the zinc-based plated steel sheet, and an organic resin-based film as the second layer and a third layer thereon. It has an organic post-treatment film, the zinc phosphate treatment film amount is 0.3 to 5 g / m 2 , the organic resin film is 0.01 to 1 g / m 2 , and the organic post-treatment film amount is 0.00. a 01~1g / m 2, the organic post-treatment coating is an amino group-containing silane coupling agent 10 to 100% by weight, other silane coupling agents and or made of an organic alkoxysilane compounds 0-90 wt% By having these three types of coatings, the corrosion resistance and the adhesion between the blade member and the blade member through the adhesive are remarkably improved.
本発明の無機有機複合処理亜鉛系メッキ鋼板は、亜鉛系メッキ鋼板の表面に、第１層皮膜としてリン酸亜鉛処理皮膜が形成されたものである。リン酸亜鉛処理皮膜層が、亜鉛系メッキ鋼板のメッキ表層に針状乃至葉状乃至粒状の粒が食い込むように形成されるため、高い密着力が発現され、且つ亜鉛メッキ表面の腐食因子からの保護皮膜効果が享受できる。 The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention is obtained by forming a zinc phosphate-treated film as a first layer film on the surface of a zinc-based plated steel sheet. The zinc phosphate treatment coating layer is formed so that needle-like, leaf-like or granular grains bite into the plating surface layer of the zinc-based plated steel sheet, so that high adhesion is expressed and protection from corrosion factors on the galvanized surface The film effect can be enjoyed.
上記リン酸亜鉛処理皮膜は、下限０．３ｇ／ｍ２、上限５ｇ／ｍ２の皮膜量で形成されたものである。０．３ｇ／ｍ２未満であると、緻密なリン酸亜鉛処理皮膜が形成されない部位が多くなるため、メッキとの密着力が不十分であるおそれがあり、同時に亜鉛メッキ表面の腐食因子からの保護皮膜効果が享受できない。また、５ｇ／ｍ２を超えると、皮膜粒径の粗大化のためにメッキ表面との食い込みの粒密度が低下するため、メッキとリン酸亜鉛処理皮膜の界面の密着力も低下する。更に、この皮膜量領域では二次核成長に起因してリン酸亜鉛処理皮膜内の下層と二次核の間で剥離が起こりやすくなるため、やはり密着力は低下する。上記下限は、０．５ｇ／ｍ２であることがより好ましく、上記上限は、２．５ｇ／ｍ２であることがより好ましい。特に、リン酸亜鉛処理皮膜中にＭｇを含有させると耐食性は更に向上する。 The zinc phosphate-treated film is formed with a film amount having a lower limit of 0.3 g / m 2 and an upper limit of 5 g / m 2 . If it is less than 0.3 g / m 2 , there will be more sites where a dense zinc phosphate treatment film will not be formed, so there is a risk of insufficient adhesion with the plating, and at the same time from corrosion factors on the galvanized surface. The protective film effect cannot be enjoyed. On the other hand, if it exceeds 5 g / m 2 , the particle density of the bite with the plating surface decreases due to the coarsening of the film particle diameter, and the adhesion between the plating and the zinc phosphate-treated film also decreases. Further, in this coating amount region, peeling is likely to occur between the lower layer and the secondary nuclei in the zinc phosphate-treated coating due to the secondary nucleus growth, so that the adhesion strength is also lowered. The lower limit is more preferably 0.5 g / m 2 , and the upper limit is more preferably 2.5 g / m 2 . In particular, when Mg is contained in the zinc phosphate-treated film, the corrosion resistance is further improved.
上記リン酸亜鉛処理皮膜は、リン酸イオン及び亜鉛イオンを含有する従来公知のリン酸亜鉛処理剤によって形成することができ、亜鉛イオン、リン酸イオンの供給源としては、亜鉛、リン酸を含有する化合物であれば特に限定されることはなく、また、リン酸亜鉛処理剤に使用されうる他の成分を適宜含有してもよい。
上記リン酸亜鉛処理皮膜を形成する処理液としては、リン酸イオン、亜鉛イオンを主成分として、さらに亜鉛以外の金属イオン、硝酸イオン、フッ化物イオン等も必要に応じて添加された市販の処理液が使用できる。
The zinc phosphate-treated film can be formed by a conventionally known zinc phosphate treatment agent containing phosphate ions and zinc ions. As a source of zinc ions and phosphate ions, zinc and phosphate are contained. If it is a compound to be used, there is no particular limitation, and other components that can be used in the zinc phosphate treating agent may be appropriately contained.
The treatment liquid for forming the zinc phosphate treatment film is a commercially available treatment mainly containing phosphate ions and zinc ions, and further containing metal ions other than zinc, nitrate ions, fluoride ions and the like as necessary. Liquid can be used.
上記リン酸亜鉛処理剤による亜鉛系メッキ鋼板のリン酸亜鉛処理方法としては、反応型処理、塗布型処理のいずれの方法によってもリン酸亜鉛処理皮膜を形成させることが可能である。反応型処理としては、たとえば、亜鉛系メッキ鋼板に脱脂、水洗、表面調整を行った後に、上記リン酸亜鉛処理液と接触させ、水洗、乾燥を行うことによりリン酸亜鉛処理皮膜を形成することができる。リン酸亜鉛処理皮膜の皮膜量は、たとえば処理時間や処理剤濃度を変化させることにより調整できる。 As the zinc phosphate treatment method for the zinc-based plated steel sheet with the zinc phosphate treatment agent, the zinc phosphate treatment film can be formed by any of the reactive treatment and the coating treatment. As a reactive type treatment, for example, after degreasing, rinsing and surface adjustment of a zinc-based plated steel sheet, contact with the zinc phosphating solution, washing and drying to form a zinc phosphate-treated film Can do. The coating amount of the zinc phosphate-treated film can be adjusted, for example, by changing the treatment time or the treatment agent concentration.
塗布型処理としては、たとえば、亜鉛系メッキ鋼板に、必要な皮膜量に応じた量の上記リン酸亜鉛処理液をロールコート法により塗布するほか、浸漬法やスプレー法により塗布した後にロール絞り法により必要な塗布量に調整する方法もある。リン酸亜鉛処理剤を亜鉛系メッキ鋼板に塗布した後、乾燥炉等を用いて乾燥させることにより、リン酸亜鉛処理皮膜を形成させる。 As the coating type treatment, for example, the zinc phosphate-treated liquid in an amount corresponding to the required coating amount is applied to a zinc-based plated steel sheet by a roll coating method, and after being applied by a dipping method or a spray method, a roll squeezing method There is also a method of adjusting to a necessary coating amount. After applying the zinc phosphate treatment agent to the zinc-based plated steel sheet, the zinc phosphate treatment film is formed by drying using a drying furnace or the like.
本発明の無機有機複合処理亜鉛系メッキ鋼板は、上記リン酸亜鉛処理皮膜上に、第二の皮膜として有機樹脂系皮膜が形成されたものである。上記リン酸亜鉛処理皮膜上に、有機樹脂系皮膜が形成されることにより、リン酸亜鉛処理皮膜と有機樹脂系皮膜の界面の密着性を向上させ、且つ腐食因子のリン酸亜鉛処理皮膜による遮蔽と有機樹脂系皮膜による透過抑制効果によって耐食性も向上することができる。 The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention is obtained by forming an organic resin-based film as a second film on the zinc phosphate-treated film. By forming an organic resin-based film on the zinc phosphate-treated film, the adhesion at the interface between the zinc phosphate-treated film and the organic resin-based film is improved and the corrosion factor is shielded by the zinc phosphate-treated film. And the corrosion resistance can be improved by the permeation suppressing effect of the organic resin film.
即ち、上記リン酸亜鉛処理皮膜がメッキ表面に緻密な粒の集合体として形成されているため、その上の有機樹脂系皮膜はリン酸亜鉛処理皮膜の隙間に充填されると共にリン酸亜鉛処理皮膜の凹凸表面に沿って形成されるため、優れた有機樹脂系皮膜とリン酸亜鉛処理皮膜の界面の密着性が得られる。また、密着性が良好であるがゆえに、腐食因子の侵入も抑制され、リン酸亜鉛処理皮膜による遮蔽と有機樹脂系皮膜による透過抑制効果との相乗効果により耐食性も格段に向上する。更に、有機樹脂系皮膜が被覆されても、リン酸亜鉛処理皮膜の凹凸表面によるアンカー効果（投錨効果）が発揮されるため、ブレード部材乃至接着樹脂層を介して接着されるゴム等のブレード部材、または接着剤層との密着性が得られる。 That is, since the zinc phosphate-treated film is formed as a dense aggregate of particles on the plating surface, the organic resin-based film thereon is filled in the gaps of the zinc phosphate-treated film and the zinc phosphate-treated film. Therefore, excellent adhesion between the organic resin film and the zinc phosphate-treated film can be obtained. Further, since the adhesion is good, the invasion of the corrosion factor is also suppressed, and the corrosion resistance is remarkably improved by the synergistic effect of the shielding by the zinc phosphate treatment film and the permeation suppressing effect by the organic resin film. Furthermore, even when an organic resin film is coated, the anchor effect (throwing effect) due to the uneven surface of the zinc phosphate-treated film is exerted, so a blade member such as a rubber member bonded via a blade member or an adhesive resin layer Or adhesion with the adhesive layer is obtained.
上記有機樹脂系皮膜は、有機樹脂（Ａ）を含む皮膜であるが、更に、この中に有機防錆剤、無機防錆剤、顔料、染料、界面活性剤、潤滑剤等の他の添加剤の単独乃至二種以上が配合されていてもよい。
上記有機樹脂（Ａ）の役割は有機樹脂系皮膜中に含有させることによって、リン酸亜鉛処理皮膜上に欠陥のない均一な有機樹脂系皮膜を形成させ、腐食因子の透過抑制能を付与させるためである。また、添加剤を皮膜中で固定するのに好適であり、優れた有機樹脂系皮膜とリン酸亜鉛処理皮膜の界面の密着性発現に寄与するものである。
The organic resin-based film is a film containing an organic resin (A), and further, other additives such as an organic rust inhibitor, an inorganic rust inhibitor, a pigment, a dye, a surfactant, and a lubricant. These may be blended alone or in combination.
The role of the organic resin (A) is to form a uniform organic resin-based film having no defects on the zinc phosphate-treated film by adding it to the organic resin-based film, and to impart the ability of inhibiting the permeation of corrosion factors. It is. Moreover, it is suitable for fixing an additive in a film | membrane, and contributes to adhesiveness expression of the interface of the outstanding organic resin-type film | membrane and a zinc-phosphate process film | membrane.
上記有機樹脂（Ａ）としては耐食性の観点から特に限定されないが、ポリエステル樹脂、ポリウレタン樹脂、ポリオレフィン樹脂、アクリル樹脂、ビニル樹脂、エポキシ樹脂、シリコン樹脂等の単独乃至二種以上の混合物乃至複数樹脂の変性体を使用することが添加剤の皮膜中での固定および有機樹脂系皮膜とリン酸亜鉛処理皮膜の密着性の向上に好適である。 The organic resin (A) is not particularly limited from the viewpoint of corrosion resistance, but may be a single resin or a mixture of two or more resins or a plurality of resins such as polyester resin, polyurethane resin, polyolefin resin, acrylic resin, vinyl resin, epoxy resin, and silicon resin. Use of the modified body is suitable for fixing the additive in the film and improving the adhesion between the organic resin film and the zinc phosphate-treated film.
上記有機樹脂系皮膜は、下限０．０１ｇ／ｍ２、上限１ｇ／ｍ２の皮膜量で形成されたものである。０．０１ｇ／ｍ２未満であると、有機樹脂系皮膜はリン酸亜鉛処理皮膜の隙間に充分に満たされず、且つリン酸亜鉛処理皮膜の凹凸表面を不均一に被覆するため、リン酸亜鉛処理皮膜と有機樹脂系皮膜の界面の密着性の向上が見られず、且つ耐食性に乏しいおそれがあり、１ｇ／ｍ２を超えると、有機樹脂系皮膜がリン酸亜鉛処理皮膜の凹凸を隠蔽してしまい、アンカー効果が低下し、ブレード部材乃至接着樹脂層を介して接着されるゴム等のブレード部材、または接着剤層との密着性が低下するおそれがある。上記下限は、０．０３ｇ／ｍ２であることがより好ましく、上記上限は、０．７ｇ／ｍ２であることがより好ましい。 The organic resin film is formed with a film amount having a lower limit of 0.01 g / m 2 and an upper limit of 1 g / m 2 . If it is less than 0.01 g / m 2 , the organic resin film is not sufficiently filled in the gaps of the zinc phosphate-treated film, and the uneven surface of the zinc phosphate-treated film is unevenly coated. There is a possibility that the adhesion of the interface between the film and the organic resin film is not improved, and the corrosion resistance may be poor, and if it exceeds 1 g / m 2 , the organic resin film hides the unevenness of the zinc phosphate-treated film. As a result, the anchor effect is lowered, and there is a possibility that the adhesiveness with the blade member such as rubber or the adhesive layer bonded through the blade member or the adhesive resin layer may be lowered. The lower limit is more preferably 0.03 g / m 2 , and the upper limit is more preferably 0.7 g / m 2 .
上記有機樹脂系皮膜は、上記リン酸亜鉛処理皮膜が形成された亜鉛系メッキ鋼板に、上記有機樹脂系処理剤を塗布することによって形成することができる。上記塗布方法としては特に限定されず、例えば、浸漬法、スプレー法、エアレススプレー法、ロールコーター法等を挙げることができる。ただし、有機樹脂にはそれぞれ最適成膜温度が存在するため、塗布直後の焼き付け温度（到達板温度）は有機樹脂系処理剤に含まれる有機樹脂により選択がなされる。 The organic resin-based film can be formed by applying the organic resin-based processing agent to a zinc-based plated steel sheet on which the zinc phosphate-treated film is formed. The application method is not particularly limited, and examples thereof include an immersion method, a spray method, an airless spray method, and a roll coater method. However, since there is an optimum film forming temperature for each organic resin, the baking temperature (reach plate temperature) immediately after coating is selected depending on the organic resin contained in the organic resin processing agent.
更に、本発明の無機有機複合処理亜鉛系メッキ鋼板は、上記有機樹脂系皮膜上に、第三の皮膜として有機系後処理皮膜が形成されたものである。上記有機樹脂系皮膜上に、有機系後処理皮膜が形成されることにより、有機樹脂系皮膜と有機系後処理皮膜の界面の密着性を向上させることができる。 Furthermore, the inorganic-organic composite-treated zinc-based plated steel sheet of the present invention is obtained by forming an organic post-treatment film as a third film on the organic resin-based film. By forming an organic post-treatment film on the organic resin-based film, the adhesion at the interface between the organic resin-based film and the organic post-treatment film can be improved.
即ち、上記メッキ表面に緻密な粒の集合体として形成されているリン酸亜鉛処理皮膜の隙間と凹凸表面に沿って形成された有機樹脂系皮膜の表面形状を反映するように有機系後処理皮膜が形成されるために、有機樹脂系皮膜と有機系後処理皮膜の間で水素結合力や強いファンデルワールス力等の作用により密な架橋構造が界面に形成され、優れた有機系後処理皮膜と有機樹脂系皮膜の界面の密着性が得られる。更に、有機系後処理皮膜が被覆されても、リン酸亜鉛処理皮膜形状を反映した有機系後処理皮膜の凹凸表面によるアンカー効果（投錨効果）が保持されることと、有機系後処理皮膜と接着剤またはブレード部材の含有官能基による相互作用や化学結合等よる化学的な作用により、ブレード部材乃至接着樹脂層を介して接着されるゴム等のブレード部材、または接着剤層との高い密着性が得られる。 That is, the organic post-treatment film reflects the gap between the zinc phosphate treatment film formed as an aggregate of dense grains on the plating surface and the surface shape of the organic resin film formed along the uneven surface. As a result, a dense cross-linked structure is formed at the interface between the organic resin film and the organic post-treatment film by the action of hydrogen bonding force, strong van der Waals force, etc. Adhesiveness at the interface of the organic resin film can be obtained. Furthermore, even if the organic post-treatment film is coated, the anchor effect (throwing effect) due to the uneven surface of the organic post-treatment film reflecting the shape of the zinc phosphate treatment film is retained, and the organic post-treatment film High adhesion to blade member such as rubber or adhesive layer bonded via blade member or adhesive resin layer due to chemical action such as interaction or chemical bonding by adhesive or functional group contained in blade member Is obtained.
上記有機系後処理皮膜は、アミノ基含有シランカップリング剤１０〜１００質量％、その他のシランカップリング剤及び、または有機アルコキシシラン化合物０〜９０質量％からなることを特徴とする有機成分で構成される。アミノ基含有シランカップリング剤、その他のシランカップリング剤、有機アルコキシシラン化合物は、それらの使用にあたり、いずれも単独であっても二種以上の混合物であってもそれらの誘導体であってもよい。 The organic post-treatment film is composed of 10 to 100% by mass of an amino group-containing silane coupling agent, another silane coupling agent, and / or an organic component characterized by comprising 0 to 90% by mass of an organic alkoxysilane compound. Is done. The amino group-containing silane coupling agent, the other silane coupling agent, and the organic alkoxysilane compound may be used alone, in a mixture of two or more, or a derivative thereof. .
上記アミノ基含有シランカップリング剤としては、３−アミノプロピルトリメトキシシラン、３−アミノ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、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−フェニル−３アミノプロピルトリメトキシシラン、ビス（トリメトキシシリルプロピル）アミン、Ｎ、Ｎ’−ビス［３−（トリメトキシシリル）プロピル］エチレンジアミン等、及びそれらのオリゴマーが挙げられる。 Examples of the amino group-containing silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3aminopropyltrimethoxysilane, and N- (2-aminoethyl). 3aminopropyltriethoxysilane, N- (2-aminoethyl) 3aminopropylmethyldimethoxysilane, N-phenyl-3aminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, N, N′-bis [3 -(Trimethoxysilyl) propyl] ethylenediamine and the like and oligomers thereof.
その他のシランカップリング剤としては、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−エポキシシクロへキシル）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トリエトキシシラン、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、３−アクリロキシプロピルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３−イソシアネートプロピルトリエトキシシラン等、及びそれらのオリゴマーが挙げられる。 Other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc., and oligomers thereof.
有機アルコキシシラン化合物としては、テトラメトキシシラン、テトラエトキシシラン、ビス（トリエトキシシリル）メタン、ビス（トリメトキシシリル）エタン、ビス（トリエトキシシリル）エタン等、及びそれらのオリゴマーが挙げられる。 Examples of the organic alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, bis (triethoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, and oligomers thereof.
上記アミノ基含有シランカップリング剤、その他のシランカップリング剤、有機アルコキシシラン化合物はいずれも加水分解によりアルコキシシリル基がシラノール基に変換される。シラノール基は直下の有機樹脂系皮膜表面とは強い水素結合等の化学結合を形成する一方、自己縮合することにより高分子化して強固な後処理皮膜を形成する。このため有機系後処理皮膜は有機樹脂系皮膜に対してきわめて高い密着性を発現する。 In the amino group-containing silane coupling agent, other silane coupling agents, and organic alkoxysilane compounds, the alkoxysilyl group is converted to a silanol group by hydrolysis. The silanol group forms a chemical bond such as a strong hydrogen bond with the surface of the organic resin film directly underneath, while forming a strong post-treatment film by polymerizing by self-condensation. For this reason, the organic post-treatment film exhibits extremely high adhesion to the organic resin film.
上記シランカップリング剤はその官能基と接着剤又はブレード部材の含有官能基との間の相互作用や化学結合により密着性の向上に有効であるが、特にシランカップリング剤がアミノ基を含有する場合にその効果が著しい。アミノ基は極性が高く、多様な反応性を有するため、接着剤またはブレード部材の含有官能基との相互作用や化学結合の形成に特に好適であるためと考えられる。
アミノ基以外の官能基を有するシランカップリング剤及び、または有機アルコキシシラン化合物は、有機系後処理皮膜が最適な接着強度を発現するように、前記皮膜のアミノ基濃度の調節や架橋度の調整に利用される。
The silane coupling agent is effective for improving adhesion by interaction or chemical bond between the functional group and the functional group contained in the adhesive or blade member, but the silane coupling agent particularly contains an amino group. The effect is remarkable in some cases. It is considered that the amino group is highly polar and has various reactivity, so that it is particularly suitable for the interaction with the functional group contained in the adhesive or the blade member and the formation of a chemical bond.
A silane coupling agent having a functional group other than an amino group and / or an organoalkoxysilane compound is used to adjust the concentration of amino groups and the degree of crosslinking so that the organic post-treatment film exhibits optimum adhesive strength. Used for
上記アミノ基含有シランカップリング剤の有機後処理皮膜中の含有量は、１０〜１００質量％で、好ましくは３０〜９０質量％である。この含有量が１０質量％未満では、ブレード部材乃至接着樹脂層を介して接着されるゴム等のブレード部材、または接着剤層との密着性が低下する場合がある。 Content in the organic post-processing film | membrane of the said amino group containing silane coupling agent is 10-100 mass%, Preferably it is 30-90 mass%. When the content is less than 10% by mass, the adhesion with a blade member such as rubber or an adhesive layer bonded via a blade member or an adhesive resin layer may be lowered.
上記有機系後処理皮膜は、下限０．０１ｇ／ｍ２、上限１ｇ／ｍ２の皮膜量で形成されたものである。０．０１ｇ／ｍ２未満であると、有機系後処理皮膜は有機樹脂系皮膜表面を不均一に被覆するため、充分な水素結合力やファンデルワールス力が確保されないため、有機樹脂系皮膜と有機系後処理皮膜の界面の密着性の向上が見られないおそれがあり、１ｇ／ｍ２を超えると、有機系後処理皮膜が有機樹脂系皮膜表面の凹凸を完全に隠蔽してしまい、アンカー効果が低下し、ブレード部材乃至接着樹脂層を介して接着されるゴム等のブレード部材、または接着剤層との密着性が低下するおそれがある。上記下限は、０．０３ｇ／ｍ２であることがより好ましく、上記上限は、０．７ｇ／ｍ２であることがより好ましい。 The organic post-treatment film is formed with a film amount having a lower limit of 0.01 g / m 2 and an upper limit of 1 g / m 2 . If it is less than 0.01 g / m 2 , the organic post-treatment film coats the surface of the organic resin film non-uniformly, so that sufficient hydrogen bonding force or van der Waals force cannot be secured. There is a risk that the adhesion of the interface of the organic post-treatment film may not be improved, and if it exceeds 1 g / m 2 , the organic post-treatment film completely hides the irregularities on the surface of the organic resin film, and the anchor The effect is reduced, and there is a possibility that the adhesion to a blade member such as rubber or an adhesive layer bonded via a blade member or an adhesive resin layer, or an adhesive layer may be reduced. The lower limit is more preferably 0.03 g / m 2 , and the upper limit is more preferably 0.7 g / m 2 .
上記有機系後処理皮膜は、上記有機樹脂系皮膜が形成された亜鉛系メッキ鋼板に、上記アミノ基含有シランカップリング剤に、あるいはアミノ基含有シランカップリング剤とその他のシランカップリング剤及び、または有機アルコキシシラン化合物に、水、アルコール等の希釈剤を加えて希釈して得られる有機系後処理剤を塗布し、乾燥させることによって形成することができる。上記塗布方法としては特に限定されず、例えば、浸漬法、スプレー法、エアレススプレー法、ロール法等を挙げることができる。上記乾燥は、例えば熱風炉、直火炉、ＩＨ炉等を用いて、到達板温として４０〜１８０℃、好ましくは６０〜１５０℃で実施する。 The organic post-treatment film is formed on the zinc-based plated steel sheet on which the organic resin film is formed, on the amino group-containing silane coupling agent, or on the amino group-containing silane coupling agent and other silane coupling agents, Or it can form by apply | coating and drying the organic type | system | group post-processing agent obtained by adding diluents, such as water and alcohol, to an organic alkoxysilane compound. The application method is not particularly limited, and examples thereof include an immersion method, a spray method, an airless spray method, and a roll method. The said drying is implemented at 40-180 degreeC as an ultimate board temperature, for example using a hot air furnace, a direct-fired furnace, an IH furnace etc., Preferably it is 60-150 degreeC.
上記有機系後処理はトナーブレード製造現場におけるシーラー処理としても実施可能ではあるが、鋼板メーカーにおいてリン酸亜鉛処理から有機系後処理までを連続して実施する方が、より均一性の高い後処理皮膜が形成されうる点と、本発明の目的の一つである現場でのプライマー処理が省略できるという効果が得られる点でより好ましい。 The organic post-treatment can be performed as a sealer treatment at the toner blade manufacturing site, but it is more uniform post-treatment in the steel plate manufacturer from zinc phosphate treatment to organic post-treatment continuously. It is more preferable in that a film can be formed and an effect that the on-site primer treatment which is one of the objects of the present invention can be omitted is obtained.
本発明の無機有機複合処理亜鉛系メッキ鋼板に使用する亜鉛系メッキ鋼板としては特に限定されず、例えば、亜鉛メッキ鋼板、亜鉛−アルミニウムメッキ鋼板、亜鉛−マグネシウムメッキ鋼板、亜鉛−ニッケルメッキ鋼板、亜鉛−鉄メッキ鋼板、亜鉛−クロムメッキ鋼板、亜鉛−マンガンメッキ鋼板、等の亜鉛系の電気メッキ、溶融メッキ、蒸着メッキ鋼板等の亜鉛又は亜鉛系合金メッキ鋼板等を挙げることができる。 The zinc-based plated steel sheet used for the inorganic-organic composite-treated zinc-based plated steel sheet of the present invention is not particularly limited. -Zinc-based electroplating such as iron-plated steel plate, zinc-chromium-plated steel plate, zinc-manganese-plated steel plate, hot-dip plated, zinc-plated alloy-plated steel plate, etc.
本発明の無機有機複合処理亜鉛系メッキ鋼板は、亜鉛系メッキ鋼板の表面に、第１層としてリン酸亜鉛処理皮膜を０．３〜５ｇ／ｍ２の皮膜量で形成し、その上に、第２層として有機樹脂（Ａ）乃至この中に有機防錆剤、無機防錆剤、顔料、染料、界面活性剤、潤滑剤等の他の添加剤の単独乃至二種以上が配合されること、からなる有機樹脂系皮膜を０．０１〜１ｇ／ｍ２の皮膜量、更に第３層としてアミノ基含有シランカップリング剤、あるいはアミノ基含有シランカップリング剤と、その他のシランカップリング剤及び、または有機アルコキシシラン化合物、からなる有機系後処理皮膜を０．０１〜１ｇ／ｍ２の皮膜量で形成することにより得られるものであることから、鋼板の全面を均一、且つ表面凹凸のある皮膜で覆うことができる。これにより、亜鉛系メッキ鋼板のメッキ表面とリン酸亜鉛処理皮膜、リン酸亜鉛処理皮膜と有機樹脂系皮膜、有機樹脂系皮膜と有機系後処理皮膜、有機系後処理皮膜と接着剤乃至ブレード部材の各界面の密着力を向上することが可能となり、ブレードの具備すべき主たる性能要件であるブレード部材とブレード支持部材の高強度且つ安定な密着力が確保できる。従って、本発明の無機有機複合処理亜鉛系メッキ鋼板をブレード支持部材とすることで充分な密着性能を満足できる。 The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention is formed on the surface of the zinc-based plated steel sheet with a zinc phosphate-treated film having a film amount of 0.3 to 5 g / m 2 as the first layer, As the second layer, the organic resin (A) or an organic rust preventive agent, an inorganic rust preventive agent, a pigment, a dye, a surfactant, a lubricant, and other additives alone or in combination thereof may be blended therein. A coating amount of 0.01 to 1 g / m 2, and an amino group-containing silane coupling agent, or an amino group-containing silane coupling agent, and other silane coupling agents and Or an organic post-treatment film made of an organic alkoxysilane compound with a film amount of 0.01 to 1 g / m 2 , so that the entire surface of the steel sheet is uniform and has surface irregularities. Can be covered with a film . Accordingly, the plated surface of the zinc-based plated steel sheet and the zinc phosphate-treated film, the zinc phosphate-treated film and the organic resin-based film, the organic resin-based film and the organic post-treated film, the organic post-treated film and the adhesive or blade member It is possible to improve the adhesion of each interface of the blades, and it is possible to secure a high strength and stable adhesion between the blade member and the blade support member, which is the main performance requirement of the blade. Therefore, sufficient adhesion performance can be satisfied by using the inorganic-organic composite-treated zinc-based plated steel sheet of the present invention as a blade support member.
更に、本発明の無機有機複合処理亜鉛系メッキ鋼板は、亜鉛系メッキ鋼板の表面に、リン酸亜鉛処理皮膜を形成し、その上に有機樹脂系皮膜と有機系後処理皮膜を有する皮膜構成であるため腐食因子のメッキ表面への到達を抑制し、耐食性を有するため、長時間の耐久性を要する接着用途には好適である。 Furthermore, the inorganic-organic composite-treated zinc-based plated steel sheet of the present invention has a film configuration in which a zinc phosphate-treated film is formed on the surface of the zinc-based plated steel sheet, and an organic resin-based film and an organic post-treated film are formed thereon. Therefore, the corrosion factor is suppressed from reaching the plating surface and has corrosion resistance, so that it is suitable for adhesive applications that require long-term durability.
以下本発明について実施例を掲げて更に詳しく説明するが、本発明はこれらの実施例のみに限定されるものではない。
（亜鉛メッキ鋼板への処理方法）
使用したメッキ原板を表１に示す。アルカリ脱脂処理の後、リン酸亜鉛処理、有機樹脂系処理、有機系後処理を順次行い試験板を調整した。
リン酸亜鉛処理は、市販のＴｉＯ２コロイド系表面調整処理の後、表２に示すように調製した浴を使用して、スプレー法により、温度４５℃で処理時間１〜１０秒間で行い、更に、水洗して乾燥した。
有機樹脂系処理の構成成分及び組成をそれぞれ表３に示す。処理はすべてロールコーターを用いて塗布し、熱風乾燥器で到達板温１５０℃にて乾燥後水冷し、乾燥放置させた。
一方、有機系後処理の構成成分及び組成をそれぞれ表４に示す。処理はすべてロールコーターを用いて塗布し、熱風乾燥器で到達板温１１０℃にて乾燥後室内放冷させた。
EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail, this invention is not limited only to these Examples.
(Processing method for galvanized steel sheet)
Table 1 shows the plating plate used. After the alkaline degreasing treatment, the test plate was prepared by sequentially performing zinc phosphate treatment, organic resin treatment, and organic post treatment.
Zinc phosphate treatment is carried out at a temperature of 45 ° C. at a treatment time of 1 to 10 seconds by a spray method using a bath prepared as shown in Table 2 after a commercially available TiO 2 colloidal surface conditioning treatment, Washed with water and dried.
Table 3 shows the components and composition of the organic resin treatment. All treatments were applied using a roll coater, dried with a hot air drier at an ultimate plate temperature of 150 ° C., then cooled with water and left to dry.
On the other hand, Table 4 shows the components and compositions of the organic post-treatment. All treatments were applied using a roll coater, dried with a hot air drier at an ultimate plate temperature of 110 ° C., and then allowed to cool indoors.
実施例１〜２３、３４〜５６及び比較例２４〜３３、５７〜６６
表５−１、５−２に示した条件（原板の種類、リン酸亜鉛処理の種類と皮膜量、有機樹脂系処理の種類と皮膜量、有機系後処理の種類と皮膜量）となるように試験板を製造した。原板としては表１中のＥＧ２０又はＧＩ７０を使用し、リン酸亜鉛処理浴としては表２中のＮｏ．１〜３を使用し、有機樹脂系処理剤としては表３中のＮｏ．１〜１０を使用し、有機系後処理剤としては表４中のＮｏ．１〜７を使用した。
Examples 1 to 23, 34 to 56 and Comparative Examples 24 to 33, 57 to 66
The conditions shown in Tables 5-1 and 5-2 (the type of the original plate, the type and coating amount of the zinc phosphate treatment, the type and coating amount of the organic resin processing, the type and coating amount of the organic post-treatment) A test plate was manufactured. EG20 or GI70 in Table 1 is used as the original plate, and No. 1 in Table 2 is used as the zinc phosphate treatment bath. No. 1 to No. 3 in Table 3 are used as organic resin processing agents. No. 1 to No. 10 in Table 4 are used as organic post-treatment agents. 1-7 were used.
リン酸亜鉛処理後の皮膜量は、クロム酸でリン酸亜鉛処理皮膜を溶解し、前後の質量差から算出した。リン酸亜鉛処理後のサンプルに、各有機樹脂系処理剤を塗布し、到達板温１５０℃で乾燥して水冷後、乾燥放置し塗布前後の質量差から有機樹脂系処理皮膜の皮膜量を算出した。同様に、有機樹脂系処理後のサンプルに、各有機系後処理剤を塗布し、到達板温１１０℃で乾燥して室内放冷後、乾燥放置し塗布前後の質量差から有機系後処理皮膜の皮膜量を算出した。 The coating amount after the zinc phosphate treatment was calculated from the difference in mass before and after dissolving the zinc phosphate treatment coating with chromic acid. Apply each organic resin-based treatment agent to the sample after zinc phosphate treatment, dry it at a final plate temperature of 150 ° C, cool with water, leave it to dry, and calculate the coating amount of the organic resin-based treatment film from the mass difference before and after coating. did. Similarly, each organic post-treatment agent is applied to the sample after the organic resin treatment, dried at an ultimate plate temperature of 110 ° C., allowed to cool in the room, and left to dry. The amount of film was calculated.
（ブレード密着性評価方法）
上記の処理された亜鉛メッキ鋼板を２０ｍｍ角のサンプルにシャーせん断し、端面バリの反りが接着面にこないように、あらかじめ１２０℃に加温された湿潤硬化型のウレタン系接着剤をカートリッジ缶の先端から押し出しで被着部に少量のせた後で、すぐにブレード部材であるウレタン系ゴム（厚さ１ｍｍで１０ｍｍ×２０ｍｍの短冊）を押し当てて、４９Ｎ／１００ｍｍ２で数秒間加圧して、ブレード部材と鋼板間の接着剤厚みが０．１±０．０５ｍｍとなるように設定した。この後で、１ｈｒ室内放置後、３５℃、６０％ＲＨの恒温恒湿槽で１ｄａｙエージングを行なった。取り出し後、３ｈｒ室内放置し、ブレード密着性評価を行なった。
(Blade adhesion evaluation method)
The treated galvanized steel sheet is shear sheared into a 20 mm square sample, and a wet-curing urethane adhesive preheated to 120 ° C. is applied to the cartridge can so that end surface burrs do not warp on the adhesive surface. Immediately after placing a small amount on the adherend by extrusion from the tip, immediately press the urethane rubber that is a blade member (10 mm × 20 mm strip with a thickness of 1 mm), pressurize at 49 N / 100 mm 2 for several seconds, The thickness of the adhesive between the blade member and the steel plate was set to be 0.1 ± 0.05 mm. Thereafter, after standing in the room for 1 hr, 1 day aging was performed in a constant temperature and humidity chamber of 35 ° C. and 60% RH. After taking out, it was left in the room for 3 hours to evaluate blade adhesion.
鋼板を治具で水平に固定し、ゴムの短冊長手方向をチャック付き治具でしっかりと挟み込み、チャック付き治具を鋼板と垂直に鉛直方向に１０ｍｍ／ｍｉｎ．の速度で引き上げた。この時、ゴムの剥離が起こり出す初期剥離強度をモニターし、ブレード密着性評価値とした。評価基準は、以下のようにした。
〇；８５Ｎ／１０ｍｍ超
△；７５〜８５Ｎ／１０ｍｍ
×；７５Ｎ／１０ｍｍ未満
The steel plate is fixed horizontally with a jig, and the longitudinal direction of the rubber strip is firmly sandwiched with the jig with the chuck, and the jig with the chuck is 10 mm / min. Raised at the speed of. At this time, the initial peel strength at which the rubber was peeled off was monitored and used as a blade adhesion evaluation value. The evaluation criteria were as follows.
○: Over 85 N / 10 mm Δ: 75-85 N / 10 mm
X: Less than 75N / 10mm
（耐食性評価方法）
上記の処理された亜鉛メッキ鋼板を７０ｍｍ×１５０ｍｍのサンプルにシャーせん断し、サンプル端面および裏面を市販のマスキングテープを用いて、メッキがない端面部や裏面が腐食環境にさらされないようにテープシールした。テープシール後のサンプルを大型塩水噴霧機（スガ試験機製）に冶具を用いて水平から６０°の傾きに立て掛け、ＪＩＳ−Ｚ−２３７１の塩水噴霧試験（ＳＳＴ試験）方法に準じて耐食性試験を行なった。塩水噴霧試験７２ｈｒ後のサンプル表面白錆発生面積率を目視判定により実測した。評価基準は、以下のようにした。
〇；白錆発生なし
△；白錆１０％未満
×；白錆１０％超
(Corrosion resistance evaluation method)
The above-treated galvanized steel sheet was shear-sheared into a 70 mm × 150 mm sample, and the sample end face and back face were tape-sealed using a commercially available masking tape so that the end face and back face without plating were not exposed to the corrosive environment. . The sample after tape sealing is leaned on a large salt sprayer (manufactured by Suga Test Instruments) at an inclination of 60 ° from the horizontal using a jig, and a corrosion resistance test is performed according to the salt spray test (SST test) method of JIS-Z-2371. It was. The sample surface white rust generation area ratio after the salt spray test 72 hours was measured by visual judgment. The evaluation criteria were as follows.
○: No white rust △; White rust less than 10% ×; White rust over 10%
以上の評価結果を表５−１、５−２に示した。
ＥＧ２０、リン酸亜鉛処理浴Ｎо．１〜３、有機樹脂系処理剤Ｎｏ．１〜１０、有機系後処理剤Ｎｏ．１〜５を使用した試験板（実施例１〜２３）は、どの種類の皮膜量の組み合わせにおいてもブレード密着性に優れるものであった。また、ＧＩ７０を使用した場合（実施例４１〜６３）でも、どの種類の皮膜量の組み合わせにおいてもブレード密着性に優れるものを得ることができた（評点△〜○）。また、これらの実施例ではどの種類の皮膜量の組み合わせの場合でもＳＳＴ耐食性に優れていることがわかる（評点△〜○）。
The above evaluation results are shown in Tables 5-1 and 5-2.
EG20, zinc phosphate treatment bath Nо. 1-3, organic resin processing agent No.1. 1 to 10, organic post-treatment agent No. 1 The test plates using Examples 1 to 5 (Examples 1 to 23) were excellent in blade adhesion in any combination of coating amounts. Further, even when GI70 was used (Examples 41 to 63), it was possible to obtain a blade having excellent blade adhesion in any combination of coating amounts (scores Δ to ○). Further, it can be seen that these examples are excellent in SST corrosion resistance in any combination of coating amounts (scores Δ to ○).
一方、ＥＧ２０を使用した場合の比較例２４〜４０、ＧＩ７０を使用した場合の比較例６４〜８０により得られた試験板は、ブレード密着性が優れているものを得ることはできなかった（評点×）。また同時に、これらの比較例では有機樹脂系処理剤での処理を行なっていないため、ＳＳＴ耐食性も優れているものが得られなかった（評点×）。
すなわち、亜鉛系メッキ鋼板の表面の第１層にリン酸亜鉛処理皮膜、第２層に有機樹脂系皮膜、第３層にアミノ基含有シランカップリング剤を１０〜１００質量％、その他のシランカップリング剤及び、または有機アルコキシシラン化合物を０〜９０質量％からなる有機系後処理皮膜を有し、上記リン酸亜鉛処理皮膜量が０．３〜５ｇ／ｍ２、有機樹脂系皮膜量が０．０１〜１ｇ／ｍ２、有機系後処理皮膜量が０．０１〜１ｇ／ｍ２であることで格段のブレード密着性とＳＳＴ耐食性の向上が図られることがわかった。
On the other hand, the test plates obtained in Comparative Examples 24 to 40 using EG20 and Comparative Examples 64 to 80 using GI70 were not able to obtain a blade having excellent blade adhesion (score). X). At the same time, in these comparative examples, no treatment with an organic resin-based treating agent was carried out, and therefore, those having excellent SST corrosion resistance could not be obtained (score x).
That is, a zinc phosphate-treated film on the first layer of the zinc-based plated steel sheet, an organic resin-based film on the second layer, an amino group-containing silane coupling agent in the third layer, 10 to 100% by mass, and other silane cups It has an organic post-treatment film comprising 0 to 90% by mass of a ring agent and / or an organic alkoxysilane compound, the zinc phosphate treatment film amount is 0.3 to 5 g / m 2 , and the organic resin film amount is 0. .01~1g / m 2, the organic post-treatment coating amount was found to be reduced to improve the remarkable blade adhesion and SST corrosion resistance that it is 0.01 to 1 g / m 2.
なお、従来技術相当品にあたる特許文献１、２に準ずる電気亜鉛メッキ鋼板の上にクロメート皮膜と有機潤滑皮膜層を有する鋼板を用いて、上記評価法により耐食性を評価したところ評点は○であったが、密着性評価の評点は×であった。
更に、特許文献３、４の従来技術にあたる新日鉄製ボンデ鋼板と加水分解性有機シラン化合物を含有する湿気硬化型接着剤乃至シランカップリング剤が添加されているホットメルト接着剤を用いて上記評価法に準ずる密着性評価を行なったところ評点は×であった。ただし、耐食性を評価したところ評点は○であった。
In addition, when the corrosion resistance was evaluated by the above evaluation method using a steel sheet having a chromate film and an organic lubricating film layer on an electrogalvanized steel sheet according to Patent Documents 1 and 2 corresponding to the prior art, the score was ○. However, the score of adhesion evaluation was x.
Further, the evaluation method described above using Nippon Steel's bonded steel sheet, which is the prior art of Patent Documents 3 and 4, and a moisture-curable adhesive containing a hydrolyzable organosilane compound or a hot melt adhesive to which a silane coupling agent is added. When the adhesion evaluation according to the above was performed, the score was x. However, when the corrosion resistance was evaluated, the score was ○.
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| JP2004081924A Expired - Fee Related JP4441297B2 (en) | 2004-03-22 | 2004-03-22 | Inorganic organic composite-treated zinc-based plated steel sheet for blade support members |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015510049A (en) * | 2012-01-12 | 2015-04-02 | オーチス エレベータ カンパニーＯｔｉｓ Ｅｌｅｖａｔｏｒ Ｃｏｍｐａｎｙ | Protective covering for cord |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07319354A (en) * | 1994-05-25 | 1995-12-08 | Bando Chem Ind Ltd | Cleaning blade for electrophotographic device and its production |
| JPH0873775A (en) * | 1994-09-02 | 1996-03-19 | Nippon Parkerizing Co Ltd | Metal surface treating agent for forming coating film excellent in fingerprint resistance, corrosion resistance and adhesion of coating film and method of treating therewith |
| JP2001081578A (en) * | 1999-09-17 | 2001-03-27 | Nisshin Steel Co Ltd | Nonchromic coated metallic sheet |
| JP2003195719A (en) * | 2001-12-28 | 2003-07-09 | Canon Chemicals Inc | Blade for electrophotographic device and method producing the blade |
| JP2003253464A (en) * | 2001-12-26 | 2003-09-10 | Sumitomo Metal Ind Ltd | Nonchromium treatment for nonchromic chemical conversion treated steel sheet |
| JP2003311877A (en) * | 2002-04-22 | 2003-11-06 | Nippon Steel Corp | Highly durable coated steel plate |
-
2004
- 2004-03-22 JP JP2004081924A patent/JP4441297B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07319354A (en) * | 1994-05-25 | 1995-12-08 | Bando Chem Ind Ltd | Cleaning blade for electrophotographic device and its production |
| JPH0873775A (en) * | 1994-09-02 | 1996-03-19 | Nippon Parkerizing Co Ltd | Metal surface treating agent for forming coating film excellent in fingerprint resistance, corrosion resistance and adhesion of coating film and method of treating therewith |
| JP2001081578A (en) * | 1999-09-17 | 2001-03-27 | Nisshin Steel Co Ltd | Nonchromic coated metallic sheet |
| JP2003253464A (en) * | 2001-12-26 | 2003-09-10 | Sumitomo Metal Ind Ltd | Nonchromium treatment for nonchromic chemical conversion treated steel sheet |
| JP2003195719A (en) * | 2001-12-28 | 2003-07-09 | Canon Chemicals Inc | Blade for electrophotographic device and method producing the blade |
| JP2003311877A (en) * | 2002-04-22 | 2003-11-06 | Nippon Steel Corp | Highly durable coated steel plate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015510049A (en) * | 2012-01-12 | 2015-04-02 | オーチス エレベータ カンパニーＯｔｉｓ Ｅｌｅｖａｔｏｒ Ｃｏｍｐａｎｙ | Protective covering for cord |
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| JP4441297B2 (en) | 2010-03-31 |
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