JP2012251232A - Steel sheet for hot pressing and method for producing hot pressed member using same - Google Patents
Steel sheet for hot pressing and method for producing hot pressed member using same Download PDFInfo
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- 239000010959 steel Substances 0.000 title claims abstract description 80
- 238000007731 hot pressing Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000007747 plating Methods 0.000 claims abstract description 41
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- 239000000314 lubricant Substances 0.000 claims abstract description 19
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- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Mounting, Exchange, And Manufacturing Of Dies (AREA)
Abstract
Description
本発明は、自動車の足廻り部材や車体構造部材などを熱間プレスで製造するのに適した熱間プレス用鋼板およびそれを用いた熱間プレス部材の製造方法に関する。 The present invention relates to a steel sheet for hot pressing suitable for manufacturing an automobile underbody member, a vehicle body structural member, and the like by hot pressing, and a method for manufacturing a hot pressing member using the same.
従来から、自動車の足廻り部材や車体構造部材などの多くは、所定の強度を有する鋼板をプレス加工して製造されている。近年、地球環境の保全という観点から、自動車車体の軽量化が熱望され、使用する鋼板を高強度化して、その板厚を低減する努力が続けられている。しかし、鋼板の高強度化に伴ってそのプレス加工性が低下するため、鋼板を所望の部材形状に加工することが困難になる場合が多くなっている。 2. Description of the Related Art Conventionally, many undercarriage members and body structure members of automobiles are manufactured by pressing a steel plate having a predetermined strength. In recent years, from the viewpoint of the preservation of the global environment, there has been a strong desire to reduce the weight of automobile bodies, and efforts have been made to increase the strength of steel sheets to be used and to reduce their thickness. However, as the strength of the steel plate increases, the press workability decreases, and it is often difficult to process the steel plate into a desired member shape.
そのため、特許文献1には、ダイとパンチからなる金型を用いて加熱された鋼板を加工すると同時に急冷することにより加工の容易化と高強度化の両立を可能にした熱間プレスと呼ばれる加工技術が提案されている。しかし、この熱間プレスでは、熱間プレス前に鋼板を950℃前後の高い温度に加熱するため、鋼板表面にはスケール(鉄酸化物)が生成し、そのスケールが熱間プレス時に剥離して、金型を損傷させる、または熱間プレス後の部材表面を損傷させるという問題がある。また、部材表面に残ったスケールは、外観不良や塗装密着性の低下の原因にもなる。このため、通常は酸洗やショットブラストなどの処理を行って部材表面のスケールは除去されるが、これは製造工程を複雑にし、生産性の低下を招く。さらに、自動車の足廻り部材や車体構造部材などには優れた耐食性も必要とされるが、上述のような工程により製造された熱間プレス部材ではめっき層などの防錆皮膜が設けられていないため、耐食性が甚だ不十分である。 Therefore, Patent Document 1 describes a process called a hot press that enables both easy processing and high strength by simultaneously processing a heated steel sheet using a die and punch die and simultaneously cooling it. Technology has been proposed. However, in this hot press, the steel plate is heated to a high temperature of around 950 ° C before hot pressing, so scale (iron oxide) is generated on the surface of the steel plate and the scale peels off during hot pressing. There is a problem that the mold is damaged or the surface of the member after hot pressing is damaged. In addition, the scale remaining on the surface of the member also causes poor appearance and poor paint adhesion. For this reason, the scale on the surface of the member is usually removed by processing such as pickling or shot blasting, but this complicates the manufacturing process and causes a decrease in productivity. Furthermore, although excellent corrosion resistance is required for automobile undercarriage members and vehicle body structural members, hot press members manufactured by the above-described processes are not provided with a rust preventive film such as a plating layer. Therefore, the corrosion resistance is very insufficient.
このようなことから、熱間プレス前の加熱時にスケールの生成を抑制するとともに、熱間プレス後の部材の耐食性を向上させることが可能な熱間プレス技術が要望され、表面にめっき層などの皮膜を設けた鋼板やそれを用いた熱間プレス方法が提案されている。例えば、特許文献2には、ZnまたはZnベース合金で被覆された鋼板を熱間プレスし、Zn-Feベース化合物またはZn-Fe-Alベース化合物を表面に設けた耐食性に優れる熱間プレス部材の製造方法が開示されている。 Therefore, there is a demand for hot press technology that can suppress the formation of scale during heating before hot pressing and improve the corrosion resistance of members after hot pressing. A steel sheet provided with a film and a hot pressing method using the same have been proposed. For example, Patent Document 2 discloses a hot-pressed member excellent in corrosion resistance, in which a steel sheet coated with Zn or a Zn-based alloy is hot-pressed and a Zn-Fe-based compound or a Zn-Fe-Al-based compound is provided on the surface. A manufacturing method is disclosed.
しかしながら、特許文献2に記載の方法で製造された熱間プレス部材では、スケールの生成に起因する外観不良や塗装密着性低下を引き起こし、ZnOの生成に起因する耐食性劣化を招く場合がある。 However, the hot-pressed member manufactured by the method described in Patent Document 2 may cause poor appearance and reduced coating adhesion due to scale generation, and may lead to corrosion resistance deterioration due to ZnO generation.
また、最近では、熱間プレス前に冷間プレスを加えて所望の形状に加工する熱間プレス技術も検討されており、冷間プレス性に優れる熱間プレス用鋼板への要望も高まっている。 Recently, a hot press technology for processing into a desired shape by adding a cold press before hot pressing has been studied, and the demand for a steel sheet for hot press excellent in cold pressability is also increasing. .
本発明は、熱間プレス時にスケールやZnOの生成を抑制可能で耐酸化性に優れるとともに、冷間プレス性にも優れる熱間プレス用鋼板およびそれを用いた熱間プレス部材の製造方法を提供することを目的とする。 The present invention provides a steel sheet for hot pressing that can suppress the formation of scale and ZnO during hot pressing, has excellent oxidation resistance, and is also excellent in cold pressability, and a method for manufacturing a hot press member using the same. The purpose is to do.
本発明者らは、上記の目的とする熱間プレス用鋼板について鋭意検討を行った結果、以下の知見を得た。
i) スケールの生成は、めっき層の欠陥部や、熱間プレスにより加熱時に形成されたZn-Fe金属化合物を起点に発生したクラックのような局所的な部位で起きやすい。
ii) スケールやZnOの生成は、融点が700℃未満の低いZn系めっき層で起きやすい。
iii) スケールやZnOの生成を抑制するには、融点が高い10〜25質量%のNiを含み、残部がZnおよび不可避的不純物からなるめっき層とすることが効果的である。
iv) 優れた冷間プレス性を付与するには、めっき層上に、固形潤滑剤を含む潤滑層を設けることが効果的である。
As a result of intensive studies on the steel sheet for hot pressing that is the above object, the present inventors have obtained the following knowledge.
i) Scale formation is likely to occur at local sites such as cracks originating from a defective portion of the plating layer or a Zn-Fe metal compound formed during heating by hot pressing.
ii) Scale and ZnO are likely to occur in a Zn-based plating layer with a melting point lower than 700 ° C.
iii) In order to suppress the formation of scale and ZnO, it is effective to form a plating layer containing 10 to 25% by mass of Ni having a high melting point and the balance being Zn and inevitable impurities.
iv) In order to provide excellent cold pressability, it is effective to provide a lubricating layer containing a solid lubricant on the plating layer.
本発明は、このような知見に基づきなされたもので、鋼板表面に、順に、10〜25質量%のNiを含み、残部がZnおよび不可避的不純物からなり、付着量が10〜90g/m2のめっき層と、固形潤滑剤を含む潤滑層とを有することを特徴とする熱間プレス用鋼板を提供する。 The present invention has been made on the basis of such knowledge, and the steel sheet surface contains, in order, 10 to 25% by mass of Ni, the balance consisting of Zn and inevitable impurities, and the adhesion amount is 10 to 90 g / m 2. There is provided a hot-press steel sheet characterized by having a plating layer of the above and a lubricating layer containing a solid lubricant.
本発明の熱間プレス用鋼板では、めっき層と潤滑層との間に、さらに、Si含有化合物層、Ti含有化合物層、Al含有化合物層、Zr含有化合物層のうちから選ばれた少なくとも一種の化合物層を有することが好ましい。 In the hot-press steel sheet of the present invention, between the plating layer and the lubricating layer, at least one selected from a Si-containing compound layer, a Ti-containing compound layer, an Al-containing compound layer, and a Zr-containing compound layer. It is preferable to have a compound layer.
本発明は、また、鋼板表面に、順に、10〜25質量%のNiを含み、残部がZnおよび不可避的不純物からなり、付着量が10〜90g/m2のめっき層と、固形潤滑剤を含み、Si含有化合物層、Ti含有化合物層、Al含有化合物層、Zr含有化合物層のうちから選ばれた少なくとも一種の化合物層とを有することを特徴とする熱間プレス用鋼板を提供する。 The present invention also includes, on the surface of the steel sheet, in order, a plating layer containing 10 to 25% by mass of Ni, the balance consisting of Zn and inevitable impurities, and an adhesion amount of 10 to 90 g / m 2 , and a solid lubricant. A hot-press steel sheet is provided that includes at least one compound layer selected from a Si-containing compound layer, a Ti-containing compound layer, an Al-containing compound layer, and a Zr-containing compound layer.
本発明の熱間プレス用鋼板におけるめっき層の下地鋼板としては、質量%で、C:0.15〜0.5%、Si:0.05〜2.0%、Mn:0.5〜3%、P:0.1%以下、S:0.05%以下、Al:0.1%以下、N:0.01%以下を含有し、残部がFeおよび不可避的不純物からなる成分組成を有する鋼板を用いることができる。この下地鋼板には、さらに、質量%で、Cr:0.01〜1%、Ti:0.2%以下、B:0.0005〜0.08%のうちから選ばれた少なくとも一種やSb:0.003〜0.03%が、個別にあるいは同時に含有されることが好ましい。 As the base steel sheet of the plating layer in the hot-press steel sheet of the present invention, in mass%, C: 0.15-0.5%, Si: 0.05-2.0%, Mn: 0.5-3%, P: 0.1% or less, S: A steel plate containing 0.05% or less, Al: 0.1% or less, and N: 0.01% or less, with the balance being composed of Fe and inevitable impurities can be used. In this base steel sheet, in addition, by mass%, Cr: 0.01 to 1%, Ti: 0.2% or less, B: 0.0005 to 0.08% or Sb: 0.003 to 0.03% individually Or it is preferable to contain simultaneously.
本発明は、さらに、上記のような熱間プレス用鋼板を、冷間プレス後、Ac3変態点〜1000℃の温度範囲に加熱後、熱間プレスすることを特徴とする熱間プレス部材の製造方法を提供する。 The present invention further provides a hot press member characterized in that the hot press steel sheet as described above is hot pressed after being cold pressed and then heated to a temperature range of Ac 3 transformation point to 1000 ° C. A manufacturing method is provided.
本発明により、熱間プレス時にスケールやZnOの生成を抑制可能で耐酸化性に優れるとともに、冷間プレス性にも優れる熱間プレス用鋼板を製造できるようになった。本発明である熱間プレス用鋼板を用い、本発明である熱間プレス部材の製造方法で製造した熱間プレス部材は、外観が良好であり、優れた塗装密着性や耐食性を有するので、自動車の足廻り部材や車体構造部材に好適である。 According to the present invention, it is possible to produce a steel sheet for hot pressing that can suppress the formation of scale and ZnO during hot pressing, has excellent oxidation resistance, and is excellent in cold pressability. The hot press member manufactured by the hot press member manufacturing method of the present invention using the hot press steel plate of the present invention has a good appearance and has excellent paint adhesion and corrosion resistance. It is suitable for the underbody member and the vehicle body structural member.
1) 熱間プレス用鋼板
1-1) めっき層
本発明では、熱間プレス時にスケールやZnOの生成を抑制するために、鋼板表面に10〜25質量%以上のNiを含み、残部がZnおよび不可避的不純物からなるめっき層を設ける。めっき層のNi含有率を10〜25質量%とすることによりNi2Zn11、NiZn3、Ni5Zn21のいずれかの結晶構造を有する融点が881℃と高いγ相が形成されるので、加熱時におけるスケールやZnOの生成反応を最小限に抑制することができる。また、加熱時にはZn-Fe金属化合物が形成されないため、クラックの発生に伴うスケールの生成も抑制される。さらには、熱間プレス完了後にも、めっき層はγ相として残存するため、Znの犠牲防食効果により優れた耐食性を発揮する。なお、Ni量が10〜25質量%におけるγ相の形成は、Ni-Zn合金の平衡状態図とは必ずしも一致しないが、これは電気めっき法などで行われるめっき層の形成反応が非平衡で進行するためと考えられる。Ni2Zn11、NiZn3、Ni5Zn21のγ相は、X線回折法やTEM(Transmission Electron Microscopy)を用いた電子線回折法により確認できる。また、めっき層のNi量を10〜25質量%とすることにより上述のとおりγ相が形成されるが、電気めっきの条件等によっては多少のη相が混在することがある。このとき、加熱過程におけるめっき層表面での酸化亜鉛形成反応を最小限に抑制するために、η相の量は5質量%以下であることが好ましい。η相の量は、めっき層の全重量に対するη相の重量比で定義され、例えばアノード溶解法などにより定量することができる。
1) Hot press steel sheet
1-1) Plating layer In the present invention, in order to suppress the formation of scale and ZnO during hot pressing, the surface of the steel plate contains 10 to 25% by mass or more of Ni, and the balance is made of Zn and inevitable impurities. Is provided. By setting the Ni content of the plating layer to 10 to 25% by mass, a γ phase having a high melting point of 881 ° C. having a crystal structure of Ni 2 Zn 11 , NiZn 3 or Ni 5 Zn 21 is formed. Scale and ZnO formation reaction during heating can be minimized. Further, since no Zn—Fe metal compound is formed during heating, the generation of scale associated with the occurrence of cracks is also suppressed. Furthermore, since the plating layer remains as a γ phase even after the hot pressing is completed, excellent corrosion resistance is exhibited due to the sacrificial anticorrosive effect of Zn. Note that the formation of the γ phase when the Ni content is 10 to 25% by mass does not necessarily match the equilibrium diagram of the Ni-Zn alloy, but this is because the formation reaction of the plating layer performed by electroplating is not balanced. It is thought to progress. The γ phase of Ni 2 Zn 11 , NiZn 3 and Ni 5 Zn 21 can be confirmed by an X-ray diffraction method or an electron diffraction method using TEM (Transmission Electron Microscopy). Moreover, although the γ phase is formed as described above by setting the Ni content of the plating layer to 10 to 25% by mass, some η phase may be mixed depending on the conditions of electroplating. At this time, in order to minimize the zinc oxide formation reaction on the surface of the plating layer during the heating process, the amount of η phase is preferably 5% by mass or less. The amount of the η phase is defined by the weight ratio of the η phase to the total weight of the plating layer, and can be quantified by, for example, the anodic dissolution method.
めっき層の片面当たりの付着量は、10g/m2未満ではZnの犠牲防食効果が十分に発揮されず、90g/m2を超えるとその効果が飽和し、コストアップを招くので、10〜90g/m2とする。 Coating weight per one surface of the plated layer, the sacrificial protection effect of Zn is less than 10 g / m 2 is not sufficiently exhibited, greater than 90 g / m 2 when the effect is saturated, so increase the cost, 10～90G / m 2
こうしためっき層の形成方法は特に限定されるものではないが、公知の電気めっき法が好適である。 A method for forming such a plating layer is not particularly limited, but a known electroplating method is preferable.
1-2) 潤滑層
優れた冷間プレス性を付与するために、めっき層上に固形潤滑剤を含む潤滑層を設ける。潤滑層を設けることにより、動摩擦係数が低下し、冷間プレス性の向上が図れる。
1-2) Lubricating layer In order to provide excellent cold pressability, a lubricating layer containing a solid lubricant is provided on the plating layer. By providing the lubricating layer, the dynamic friction coefficient is reduced, and the cold press property can be improved.
固形潤滑剤としては、例えば、以下のようなものが挙げられ、これらの少なくとも一種を用いることができる。
(1) ポリオレフィンワックス、パラフィンワックス: 例えば、ポリエチレンワックス、合成パラフィン、天然パラフィン、マイクロワックス、塩素化炭化水素など
(2) フッ素樹脂: 例えば、ポリフルオロエチレン樹脂(ポリ4フッ化エチレン樹脂など)、ポリフッ化ビニル樹脂、ポリフッ化ビニリデン樹脂など
(3) 脂肪酸アミド系化合物： 例えば、ステアリン酸アミド、パルミチン酸アミド、メチレンビスステアロアミド、エチレンビスステアロアミド、オレイン酸アミド、エシル酸アミド、アルキレンビス脂肪酸アミドなど
(4) 金属石けん類： 例えば、ステアリン酸カルシウム、ステアリン酸鉛、ラウリン酸カルシウム、パルミチン酸カルシウムなど
(5) 金属硫化物： 例えば、二硫化モリブデン、二硫化タングステンなど
(6) その他： グラファイト、フッ化黒鉛、窒化ホウ素、ホウ砂、ポリアルキレングリコール、アルカリ金属硫酸塩など
こうした固形潤滑剤の中でも、特に、ポリエチレンワックス、フッ素樹脂が好適である。ポリエチレンワックスとしては、例えば、クラリアントジャパン(株)製のセリダスト 9615A、セリダスト 3715、セリダスト 3620、セリダスト3910 (いずれも商品名)、三洋化成(株)製のサンワックス 131-P、サンワックス 161-P (いずれも商品名)、三井化学(株)製のケミパール W-100、ケミパール W-200、ケミパール W-500、ケミパール W-800、ケミパール W-950 (いずれも商品名)などを用いることができる。また、フッ素樹脂としては、ポリ4フッ化エチレン樹脂が最も好ましく、例えば、ダイキン工業(株)製のルブロン L-2、ルブロン L-5 (いずれも商品名)、三井・デュポン(株)製のMP1100、MP1200 (いずれも商品名)、旭硝子(株)製のフルオンディスパージョン AD1、フルオンディスパージョン AD2、フルオン L141J、フルオンL150J、フルオン L170J (いずれも商品名)などが好適である。
Examples of the solid lubricant include the following, and at least one of them can be used.
(1) Polyolefin wax, paraffin wax: For example, polyethylene wax, synthetic paraffin, natural paraffin, micro wax, chlorinated hydrocarbon, etc.
(2) Fluorine resin: For example, polyfluoroethylene resin (polytetrafluoroethylene resin, etc.), polyvinyl fluoride resin, polyvinylidene fluoride resin, etc.
(3) Fatty acid amide compounds: For example, stearic acid amide, palmitic acid amide, methylene bisstearamide, ethylene bisstearamide, oleic acid amide, esylic acid amide, alkylene bis fatty acid amide, etc.
(4) Metal soaps: For example, calcium stearate, lead stearate, calcium laurate, calcium palmitate, etc.
(5) Metal sulfide: For example, molybdenum disulfide, tungsten disulfide, etc.
(6) Others: Graphite, fluorinated graphite, boron nitride, borax, polyalkylene glycol, alkali metal sulfate, etc. Among these solid lubricants, polyethylene wax and fluororesin are particularly suitable. Examples of the polyethylene wax include Clariant Japan Co., Ltd.'s Ceridust 9615A, Celidust 3715, Celidust 3620, Celidust 3910 (all trade names), Sanyo Chemical Co., Ltd. Sunwax 131-P, Sunwax 161-P (All trade names), Chemipearl W-100, Chemipearl W-200, Chemipearl W-500, Chemipearl W-800, Chemipearl W-950 (all trade names) manufactured by Mitsui Chemicals, Inc. can be used. . Further, as the fluororesin, polytetrafluoroethylene resin is most preferable. For example, Lubron L-2 and Lubron L-5 (both trade names) manufactured by Daikin Industries, Ltd., Mitsui DuPont Co., Ltd. MP1100, MP1200 (both are trade names), Asahi Glass Co., Ltd. full-on dispersion AD1, full-on dispersion AD2, full-on L141J, full-on L150J, and full-on L170J (all are trade names) are suitable.
こうした固形潤滑剤を含む潤滑層を形成するには、有機樹脂をバインダーとして固形潤滑剤を添加した組成物をめっき層上に付着処理した後、水洗することなく加熱乾燥すればよい。なお、有機樹脂をバインダーとして用いることにより優れた塗装密着性も得られる。このような組成物の付着処理は塗布法、浸漬法、スプレー法のいずれでもよく、ロールコーター、スクイズコーター、ダイコーターなどを用いることができる。このとき、スクイズコーターなどによる塗布、浸漬、スプレーの処理後に、エアナイフ法やロール絞り法により塗布量の調整、外観の均一化、厚みの均一化を行うことも可能である。 In order to form a lubricating layer containing such a solid lubricant, a composition to which a solid lubricant is added using an organic resin as a binder is adhered onto the plating layer, and then heat dried without washing. In addition, the outstanding coating adhesiveness is also obtained by using organic resin as a binder. Such an adhesion treatment of the composition may be any of a coating method, a dipping method, and a spray method, and a roll coater, a squeeze coater, a die coater, or the like can be used. At this time, after applying, dipping, and spraying with a squeeze coater or the like, it is possible to adjust the coating amount, uniform appearance, and uniform thickness by an air knife method or roll drawing method.
潤滑層のバインダーである有機樹脂としては、エポキシ樹脂、変性エポキシ樹脂、ポリヒドロキシポリエーテル樹脂、ポリアルキレングリコール変性エポキシ樹脂、ウレタン変性エポキシ樹脂、およびこれらをさらに変性させた樹脂、ポリエステル樹脂、ウレタン樹脂、アクリル樹脂、ポリオレフィン樹脂から選ばれた少なくとも一種を用いることが適当である。また、これらの樹脂にメラミン樹脂、イソシアネート樹脂などの公知の硬化剤を併用してもよい。また、有機樹脂の末端にOH基を付加し、冷間プレス後にアルカリ水溶液で溶解・脱層できるものでもよい。 Examples of organic resins that are binders for the lubricating layer include epoxy resins, modified epoxy resins, polyhydroxy polyether resins, polyalkylene glycol-modified epoxy resins, urethane-modified epoxy resins, and resins obtained by further modifying these resins, polyester resins, and urethane resins. It is appropriate to use at least one selected from acrylic resins and polyolefin resins. Moreover, you may use together well-known hardening | curing agents, such as a melamine resin and an isocyanate resin, in these resins. Further, an OH group may be added to the end of the organic resin, and the resin may be dissolved / delayered with an alkaline aqueous solution after cold pressing.
潤滑層中の固形潤滑剤の配合量は、有機樹脂をバインダーとした組成物100質量部(固形分)に対して、1〜20質量部(固形分)が好ましく、1〜10質量部(固形分)がより好ましい。固形潤滑剤の配合量が1質量部以上であれば潤滑効果が高く、20質量部以下であれば塗装密着性が低下することがない。 The blending amount of the solid lubricant in the lubricating layer is preferably 1 to 20 parts by mass (solid content) and 1 to 10 parts by mass (solid content) with respect to 100 parts by mass (solid content) of the composition using an organic resin as a binder. Min) is more preferred. If the blending amount of the solid lubricant is 1 part by mass or more, the lubricating effect is high, and if it is 20 parts by mass or less, the coating adhesion does not deteriorate.
潤滑層の乾燥後の層厚は0.1〜2.0μmとすることが好ましい。層厚が0.1μm以上であれば冷間プレス性の向上効果が十分となり、2.0μm以下であれば熱間プレスの際に有機樹脂成分の熱分解生成物が多く発生することがない。 The thickness of the lubrication layer after drying is preferably 0.1 to 2.0 μm. If the layer thickness is 0.1 μm or more, the effect of improving the cold press property is sufficient, and if it is 2.0 μm or less, many thermal decomposition products of the organic resin component are not generated during hot pressing.
1-3) 化合物層
めっき層と潤滑層との間には、さらに、Si含有化合物層、Ti含有化合物層、Al含有化合物層、Zr含有化合物層のうちから選ばれた少なくとも一種の化合物層を設けると優れた塗装密着性が得られる。こうした効果を得るには、化合物層の厚みを0.1μm以上にすることが好ましいが、3.0μmを超えると化合物層が脆くなって塗装密着性の低下を招く場合があるので、3.0μm以下にすることが好ましい。より好ましくは0.4〜2.0μmである。
1-3) Compound layer Further, at least one compound layer selected from a Si-containing compound layer, a Ti-containing compound layer, an Al-containing compound layer, and a Zr-containing compound layer is further provided between the plating layer and the lubricating layer. When provided, excellent paint adhesion can be obtained. In order to obtain such an effect, the thickness of the compound layer is preferably 0.1 μm or more. However, if the thickness exceeds 3.0 μm, the compound layer may become brittle and decrease paint adhesion. It is preferable. More preferably, it is 0.4 to 2.0 μm.
Si含有化合物としては、例えば、シリコーン樹脂、リチウムシリケート、珪酸ソーダ、コロイダルシリカ、シランカップリング剤などを適用できる。Ti含有化合物としては、例えば、チタン酸リチウムやチタン酸カルシウムなどのチタン酸塩、チタンアルコキシドやキレート型チタン化合物を主剤とするチタンカップリング剤などを適用できる。Al含有化合物としては、例えば、アルミン酸ナトリウムやアルミン酸カルシウムなどのアルミン酸塩、アルミニウムアルコキシドやキレート型アルミニウム化合物を主剤とするアルミニウムカップリング剤などを適用できる。Zr含有化合物としては、例えば、ジルコン酸リチウムやジルコン酸カルシウムなどのジルコン酸塩、ジルコニウムアルコキシドやキレート型ジルコニウム化合物を主剤とするジルコニウムカップリング剤などを適用できる。 As the Si-containing compound, for example, silicone resin, lithium silicate, sodium silicate, colloidal silica, silane coupling agent and the like can be applied. As the Ti-containing compound, for example, a titanate such as lithium titanate or calcium titanate, a titanium coupling agent mainly containing a titanium alkoxide or a chelate-type titanium compound can be applied. As the Al-containing compound, for example, an aluminate such as sodium aluminate or calcium aluminate, an aluminum coupling agent mainly composed of an aluminum alkoxide or a chelate-type aluminum compound can be applied. As the Zr-containing compound, for example, a zirconate salt such as lithium zirconate or calcium zirconate, a zirconium coupling agent mainly composed of a zirconium alkoxide or a chelate-type zirconium compound can be applied.
めっき層上にこうした化合物層を形成するには、上記のSi含有化合物、Ti含有化合物、Al含有化合物、Zr含有化合物のうちから選ばれた少なくとも一種の化合物をめっき層上に付着処理した後、水洗することなく加熱乾燥すればよい。これらの化合物の付着処理は塗布法、浸漬法、スプレー法のいずれでもよく、ロールコーター、スクイズコーター、ダイコーターなどを用いればよい。このとき、スクイズコーターなどによる塗布処理、浸漬処理、スプレー処理の後に、エアナイフ法やロール絞り法により塗布量の調整、外観の均一化、厚みの均一化を行うことも可能である。また、加熱乾燥は鋼板最高到達温度が40〜200℃となるように行うことが好ましい。60〜160℃で行うことがより好ましい。 In order to form such a compound layer on the plating layer, after depositing on the plating layer at least one compound selected from the Si-containing compound, Ti-containing compound, Al-containing compound, Zr-containing compound, What is necessary is just to heat-dry without washing with water. The adhesion treatment of these compounds may be any of a coating method, a dipping method, and a spray method, and a roll coater, a squeeze coater, a die coater, or the like may be used. At this time, it is also possible to adjust the coating amount, make the appearance uniform, and make the thickness uniform by an air knife method or roll drawing method after the coating treatment, dipping treatment, and spraying treatment with a squeeze coater. Moreover, it is preferable to perform heat drying so that the maximum reached temperature of a steel plate may be 40-200 degreeC. It is more preferable to carry out at 60 to 160 ° C.
また、めっき層上にこうした化合物層を形成するには、Si、Ti、Al、Zrのうちから選ばれた少なくとも一種のカチオンを含有し、リン酸イオン、フッ素酸イオン、フッ化物イオンのうちから選ばれた少なくとも一種のアニオンを含有する酸性の水溶液にめっき層を有する鋼板を浸漬する反応型処理を行った後、水洗するかまたは水洗することなく加熱乾燥する方法によっても可能である。 Further, in order to form such a compound layer on the plating layer, it contains at least one cation selected from Si, Ti, Al, and Zr, and is selected from among phosphate ions, fluoric acid ions, and fluoride ions. It is also possible to perform a reactive treatment in which a steel sheet having a plating layer is immersed in an acidic aqueous solution containing at least one kind of anion, and then wash with water or heat and dry without washing.
なお、潤滑層を設ける代わりに、上記のような固形潤滑剤をこの化合物層に含有させても、優れた冷間プレス性を付与できる。 It should be noted that excellent cold pressability can be imparted even if a solid lubricant as described above is contained in the compound layer instead of providing the lubricating layer.
化合物層中への固形潤滑剤の配合量は、化合物100質量部(固形分)に対して、1〜20質量部(固形分)が好ましく、1〜10質量部(固形分)がより好ましい。固形潤滑剤の配合量が1質量部以上であれば潤滑効果が優れ、20質量部以下であれば塗装密着性が低下することがない。 The compounding amount of the solid lubricant in the compound layer is preferably 1 to 20 parts by mass (solid content) and more preferably 1 to 10 parts by mass (solid content) with respect to 100 parts by mass (solid content) of the compound. If the blending amount of the solid lubricant is 1 part by mass or more, the lubricating effect is excellent, and if it is 20 parts by mass or less, the coating adhesion does not deteriorate.
1-4) 下地鋼板
980MPa以上の強度を有する熱間プレス部材を得るには、めっき層の下地鋼板として、例えば、質量%で、C:0.15〜0.5%、Si:0.05〜2.0%、Mn:0.5〜3%、P:0.1%以下、S:0.05%以下、Al:0.1%以下、N:0.01%以下を含有し、残部がFeおよび不可避的不純物からなる成分組成を有する熱延鋼板や冷延鋼板を用いることができる。各成分元素の限定理由を、以下に説明する。ここで、成分の含有量を表す「%」は、特に断らない限り「質量%」を意味する。
1-4) Base steel plate
In order to obtain a hot pressed member having a strength of 980 MPa or more, for example, as a base steel plate of a plating layer, in mass%, C: 0.15-0.5%, Si: 0.05-2.0%, Mn: 0.5-3%, P : Hot rolled steel sheet or cold rolled steel sheet having a component composition containing 0.1% or less, S: 0.05% or less, Al: 0.1% or less, N: 0.01% or less, the balance being Fe and inevitable impurities may be used. it can. The reason for limitation of each component element is demonstrated below. Here, “%” representing the content of a component means “% by mass” unless otherwise specified.
C:0.15〜0.5%
Cは、鋼の強度を向上させる元素であり、熱間プレス部材のTSを980MPa以上にするには、その量を0.15%以上とする必要がある。一方、C量が0.5%を超えると、素材の鋼板のブランキング加工性が著しく低下する。したがって、C量は0.15〜0.5%とする。
C: 0.15-0.5%
C is an element that improves the strength of steel. In order to increase the TS of a hot-pressed member to 980 MPa or more, the amount needs to be 0.15% or more. On the other hand, if the amount of C exceeds 0.5%, the blanking workability of the steel plate as the material will be significantly reduced. Therefore, the C content is 0.15 to 0.5%.
Si:0.05〜2.0%
Siは、C同様、鋼の強度を向上させる元素であり、熱間プレス部材のTSを980MPa以上にするには、その量を0.05%以上とする必要がある。一方、Si量が2.0%を超えると、熱間圧延時に赤スケールと呼ばれる表面欠陥の発生が著しく増大するとともに、圧延荷重が増大したり、熱延鋼板の延性の劣化を招く。さらに、Si量が2.0%を超えると、Znを主体としためっき皮膜を鋼板表面に形成するめっき処理を施す際に、めっき処理性に悪影響を及ぼす場合がある。したがって、Si量は0.05〜2.0%とする。
Si: 0.05-2.0%
Si, like C, is an element that improves the strength of steel. In order to increase the TS of a hot-pressed member to 980 MPa or more, the amount needs to be 0.05% or more. On the other hand, when the Si content exceeds 2.0%, the occurrence of surface defects called red scale during hot rolling is remarkably increased, the rolling load is increased, and the ductility of the hot-rolled steel sheet is deteriorated. Furthermore, when the Si content exceeds 2.0%, the plating processability may be adversely affected when a plating process for forming a plating film mainly composed of Zn on the steel sheet surface is performed. Therefore, the Si content is 0.05 to 2.0%.
Mn:0.5〜3%
Mnは、フェライト変態を抑制して焼入れ性を向上させるのに効果的な元素であり、また、Ac3変態点を低下させるので、熱間プレス前の加熱温度を低下するにも有効な元素である。このような効果の発現のためには、その量を0.5%以上とする必要がある。一方、Mn量が3%を超えると、偏析して素材の鋼板および熱間プレス部材の特性の均一性が低下する。したがって、Mn量は0.5〜3%とする。
Mn: 0.5-3%
Mn is an effective element for improving the hardenability by suppressing the ferrite transformation, and also an element effective for lowering the heating temperature before hot pressing because it lowers the Ac 3 transformation point. is there. In order to exhibit such an effect, the amount needs to be 0.5% or more. On the other hand, when the amount of Mn exceeds 3%, segregation occurs and the uniformity of the characteristics of the raw steel plate and the hot press member decreases. Therefore, the amount of Mn is 0.5 to 3%.
P:0.1%以下
P量が0.1%を超えると、偏析して素材の鋼板および熱間プレス部材の特性の均一性が低下するとともに、靭性も著しく低下する。したがって、P量は0.1%以下とする。
P: 0.1% or less
When the amount of P exceeds 0.1%, segregation occurs and the uniformity of the characteristics of the raw steel plate and hot-pressed member decreases, and the toughness also decreases significantly. Therefore, the P content is 0.1% or less.
S:0.05%以下
S量が0.05%を超えると、熱間プレス部材の靭性が低下する。したがって、S量は0.05%以下とする。
S: 0.05% or less
When the amount of S exceeds 0.05%, the toughness of the hot pressed member decreases. Therefore, the S content is 0.05% or less.
Al:0.1%以下
Al量が0.1%を超えると、素材の鋼板のブランキング加工性や焼入れ性を低下させる。したがって、Al量は0.1%以下とする。
Al: 0.1% or less
If the Al content exceeds 0.1%, blanking workability and hardenability of the steel sheet will be reduced. Therefore, the Al content is 0.1% or less.
N:0.01%以下
N量が0.01%を超えると、熱間圧延時や熱間プレス前の加熱時にAlNの窒化物を形成し、素材の鋼板のブランキング加工性や焼入れ性を低下させる。したがって、N量は0.01%以下とする。
N: 0.01% or less
If the N content exceeds 0.01%, an AlN nitride is formed during hot rolling or heating before hot pressing, and the blanking workability and hardenability of the raw steel sheet are reduced. Therefore, the N content is 0.01% or less.
残部はFeおよび不可避的不純物であるが、以下の理由により、Cr:0.01〜1%、Ti:0.2%以下、B:0.0005〜0.08%のうちから選ばれた少なくとも一種や、Sb:0.003〜0.03%が、個別にあるいは同時に含有されることが好ましい。 The balance is Fe and inevitable impurities, but for the following reasons, at least one selected from Cr: 0.01 to 1%, Ti: 0.2% or less, B: 0.0005 to 0.08%, Sb: 0.003 to 0.03 % Are preferably contained individually or simultaneously.
Cr:0.01〜1%
Crは、鋼を強化するとともに、焼入れ性を向上させるのに有効な元素である。こうした効果の発現のためには、Cr量を0.01%以上とすることが好ましい。一方、Cr量が1%を超えると、著しいコスト高を招くため、その上限は1%とすることが好ましい。
Cr: 0.01-1%
Cr is an element effective for strengthening steel and improving hardenability. In order to exhibit such an effect, the Cr content is preferably 0.01% or more. On the other hand, if the Cr content exceeds 1%, the cost is significantly increased, so the upper limit is preferably 1%.
Ti:0.2%以下
Tiは、鋼を強化するとともに、細粒化により靭性を向上させるのに有効な元素である。また、次に述べるBよりも優先して窒化物を形成して、固溶Bによる焼入れ性の向上効果を発揮させるのに有効な元素でもある。しかし、Ti量が0.2%を超えると、熱間圧延時の圧延荷重が極端に増大し、また、熱間プレス部材の靭性が低下するので、その上限は0.2%とすることが好ましい。
Ti: 0.2% or less
Ti is an element effective for strengthening steel and improving toughness by refining. It is also an element effective for forming a nitride in preference to B, which will be described next, and exhibiting the effect of improving hardenability by solid solution B. However, if the amount of Ti exceeds 0.2%, the rolling load during hot rolling is extremely increased and the toughness of the hot pressed member is lowered, so the upper limit is preferably 0.2%.
B:0.0005〜0.08%
Bは、熱間プレス時の焼入れ性や熱間プレス後の靭性向上に有効な元素である。こうした効果の発現のためには、B量を0.0005%以上とすることが好ましい。一方、B量が0.08%を超えると、熱間圧延時の圧延荷重が極端に増大し、また、熱間圧延後にマルテンサイト相やベイナイト相が生じて鋼板の割れなどが生じるので、その上限は0.08%とすることが好ましい。
B: 0.0005-0.08%
B is an element effective for improving the hardenability during hot pressing and toughness after hot pressing. In order to exhibit such an effect, the B content is preferably 0.0005% or more. On the other hand, if the amount of B exceeds 0.08%, the rolling load during hot rolling is extremely increased, and the martensite phase and bainite phase occur after hot rolling, resulting in cracks in the steel sheet, so the upper limit is It is preferable to set it to 0.08%.
Sb:0.003〜0.03%
Sbは、熱間プレス前に鋼板を加熱してから熱間プレスの一連の処理によって鋼板を冷却するまでの間に鋼板表層部に生じる脱炭層を抑制する効果を有する。このような効果の発現のためにはその量を0.003%以上とする必要がある。一方、Sb量が0.03%を超えると、圧延荷重の増大を招き、生産性を低下させる。したがって、Sb量は0.003〜0.03%とすることが好ましい。
Sb: 0.003-0.03%
Sb has an effect of suppressing a decarburized layer generated in the steel sheet surface layer portion between the time when the steel plate is heated before hot pressing and the time when the steel plate is cooled by a series of processes of hot pressing. In order to exhibit such an effect, the amount needs to be 0.003% or more. On the other hand, if the Sb content exceeds 0.03%, the rolling load increases and the productivity decreases. Accordingly, the Sb content is preferably 0.003 to 0.03%.
2) 熱間プレス部材の製造方法
上記した本発明の熱間プレス用鋼板は、冷間プレス後、Ac3変態点〜1000℃の温度範囲に加熱後熱間プレスされて熱間プレス部材となる。熱間プレス前にAc3変態点以上に加熱するのは、熱間プレス時の急冷でマルテンサイト相などの硬質相を形成し、部材の高強度化を図るためである。また、加熱温度の上限を1000℃としたのは、1000℃を超えるとめっき層表面に多量のZnOが生成するためである。なお、ここでいう加熱温度とは鋼板の最高到達温度のことをいう。
2) Manufacturing method of hot-pressed member The hot-pressed steel sheet of the present invention described above is hot-pressed after being cold-pressed and then heated to a temperature range of Ac 3 transformation point to 1000 ° C to become a hot-pressed member. . The reason for heating above the Ac 3 transformation point before hot pressing is to form a hard phase such as a martensite phase by rapid cooling during hot pressing, thereby increasing the strength of the member. The upper limit of the heating temperature is set to 1000 ° C. because when the temperature exceeds 1000 ° C., a large amount of ZnO is generated on the surface of the plating layer. In addition, the heating temperature here means the highest temperature reached of the steel sheet.
熱間プレス前の加熱時の平均昇温速度は、特に限定されるものではないが、例えば2〜200℃/sが好適である。めっき層表面におけるZnOの生成やめっき層の欠陥部における局所的なスケールの生成は、鋼板が高温条件下に晒される高温滞留時間が長くなるほど増大するため、平均昇温速度が速いほど好適である。また、最高到達板温における保持時間についても特に限定されるものではないが、上記と同じ理由により短時間とする方が好適であり、好ましくは300s以下、より好ましくは120s以下、さらに好ましくは10s以下とする。 The average rate of temperature rise during heating before hot pressing is not particularly limited, but is preferably 2 to 200 ° C./s, for example. Formation of ZnO on the surface of the plating layer and generation of local scale in the defective portion of the plating layer increase as the high-temperature residence time during which the steel sheet is exposed to high-temperature conditions increases. . Further, the holding time at the maximum plate temperature is not particularly limited, but it is preferable to shorten the holding time for the same reason as described above, preferably 300 s or less, more preferably 120 s or less, more preferably 10 s. The following.
熱間プレス前の加熱方法としては、電気炉やガス炉などによる加熱、火炎加熱、通電加熱、高周波加熱、誘導加熱などを例示できる。 Examples of the heating method before hot pressing include heating by an electric furnace or a gas furnace, flame heating, energization heating, high frequency heating, induction heating, and the like.
下地鋼板として、質量%で、C:0.23%、Si:0.25%、Mn:1.2%、P:0.01%、S:0.01%、Al:0.03%、N：0.005%、Cr:0.2%、Ti:0.02%、B:0.0022%、Sb:0.008%を含有し、残部がFeおよび不可避的不純物からなる成分組成を有し、Ac3変態点が820℃で、板厚1.6mmの冷延鋼板を用いた。この冷延鋼板の表面に、200g/Lの硫酸ニッケル六水和物および10〜100g/Lの硫酸亜鉛七水和物を含有するpH1.5、温度50℃のめっき浴中で電流密度を5〜100A/dm2と変化させて電気めっき処理を施して、表1、2に示すようなNi含有量(残部はZnおよび不可避的不純物)と付着量およびη相含有量のめっき層を形成した。さらに、一部の場合を除き、めっき層上に、表1、2に示す固形潤滑剤と化合物または有機バインダーを含み残部溶媒からなる組成物(固形分割合15%)を塗布後、到達鋼板温度が140℃となる条件で乾燥し、表1、2に示す厚みの化合物層または潤滑層を形成し、鋼板No.1〜22を作製した。なお、化合物としてシリコーン樹脂を使用する場合および有機バインダーとしてジエタノール変性エポキシ樹脂を使用する場合の溶媒はエチレングリコールモノブチルエーテル：石油系ナフサを55：45(質量比)のシンナーとした。また、化合物としてシランカップリング剤を使用する場合および有機バインダーとしてエチレンアイオノマーを使用する場合の溶媒は脱イオン水とした。ここで、鋼板No.1〜11、16〜22は固形潤滑剤を含む化合物層を設けた例、鋼板No.12、13は潤滑層を設けた例、鋼板No.14は化合物層上に潤滑層を設けた例、鋼板No.15は化合物層も潤滑層も設けてない例である。 As a base steel sheet, in mass%, C: 0.23%, Si: 0.25%, Mn: 1.2%, P: 0.01%, S: 0.01%, Al: 0.03%, N: 0.005%, Cr: 0.2%, Ti: A cold-rolled steel sheet containing 0.02%, B: 0.0022%, Sb: 0.008%, the balance being composed of Fe and inevitable impurities, an Ac 3 transformation point of 820 ° C, and a thickness of 1.6 mm is used. It was. The surface of this cold-rolled steel sheet has a current density of 5 in a plating bath containing 200 g / L nickel sulfate hexahydrate and 10 to 100 g / L zinc sulfate heptahydrate at a pH of 1.5 and a temperature of 50 ° C. Electroplating treatment was performed with a change of ~ 100 A / dm 2 to form a plating layer with Ni content (the balance was Zn and inevitable impurities), adhesion amount and η phase content as shown in Tables 1 and 2 . Further, except in some cases, after applying a composition (solid content ratio 15%) comprising the solid lubricant and the compound or organic binder shown in Tables 1 and 2 and the remaining solvent on the plating layer, the steel plate temperature reached Was dried under conditions of 140 ° C. to form compound layers or lubricating layers having thicknesses shown in Tables 1 and 2, and steel plates Nos. 1 to 22 were produced. In the case of using a silicone resin as the compound and a diethanol-modified epoxy resin as the organic binder, the solvent was ethylene glycol monobutyl ether: petroleum naphtha, 55:45 (mass ratio) thinner. Further, when using a silane coupling agent as a compound and when using an ethylene ionomer as an organic binder, the solvent was deionized water. Here, steel plates No. 1 to 11 and 16 to 22 are examples in which a compound layer containing a solid lubricant is provided, steel plates No. 12 and 13 are examples in which a lubrication layer is provided, and steel plate No. 14 is lubricated on the compound layer. An example in which a layer is provided, steel plate No. 15 is an example in which neither a compound layer nor a lubricating layer is provided.
なお、潤滑層の固形潤滑剤、有機樹脂バインダー、化合物層の化合物として以下のものを用いた。
シリコーン樹脂：信越化学(株)製 KR-242A
ポリエチレンワックス1：クラリアントジャパン(株)製 セリダスト3620
フッ素樹脂：ポリ4フッ化エチレン樹脂 旭硝子(株)製 フルオン L170J
二硫化モリブデン：大東潤滑(株)製 LM-13
グラファイト：日立化成工業(株)製 GP-60S
窒化ホウ素：水島合金鉄(株)製 FS-1
ジエタノール変性エポキシ樹脂：関西ペイント(株)製 ER-007
ブロックイソシアネート：旭化成工業(株)製 デュラネートMF-K60X
エチレンアイオノマー：三井化学工業(株)製 ケミパールS650
ポリエチレンワックス2：三井化学工業(株)製 ケミパールW950
シランカップリング剤：信越化学(株)製 KBE-403
このようにして得られた表1、2に示す鋼板No.1〜22について、次に示す冷間プレス性、熱間プレス時の耐酸化性および熱間プレス後の塗装密着性の評価を行った。ここで、熱間プレスは、電気炉または直接通電により表1、2に示す加熱条件で加熱後、Al製金型で挟み込んで冷却速度50℃/sで冷却してシミュレートした。
冷間プレス性：図1に模式的に示した摩擦係数測定装置を用いて動摩擦係数を測定して、冷間プレス性を評価した。まず、作製ままの鋼板から採取したサンプル1を、スライドテーブル3の上面に固定されている試料台2に設置する。スライドテーブル3は、その下方にあるスライドテーブル支持台5上面に設けられたローラ4により水平移動可能である。次に、上下移動可能なスライドテーブル支持台5を上方へ移動させることにより上方に設けられた図2に示す形状のビード6の下面にサンプル1を押し付ける。このとき、スライドテーブル支持台5に取り付けられている第一ロードセル7によりサンプル1への押し付け荷重Nを測定する。最後に、一定の押し付け荷重N(=400kgf)を作用させた状態でスライドテーブル3を移動速度100cm/minでレール9上を水平移動させ、スライドテーブル3の一方の端部に取り付けられている第二ロードセル8により摺動抵抗力Fを測定し、室温(25℃)での動摩擦係数μ=F/Nを求める。なお、潤滑油としてスギムラ化学工業(株)製のプレス用洗浄油プレトンR352Lをサンプル1の表面に塗布して試験を行った。算出したμを以下の基準で評価し、◎、○であれば、冷間プレス性に優れるとした。
◎：μ<0.1
○：0.1≦μ<0.15
△：0.15≦μ<0.2
×：0.2≦μ
耐酸化性：表1、2に示す加熱条件で加熱後、鋼板の重量を測定し、加熱前との重量変化を測定した。ここで、重量変化は、スケールやZnOの生成による重量増加と生成したZnOの飛散による重量減少の和であるが、その絶対値が小さいほど耐酸化性に優れるとし、以下の基準で評価し、◎、○であれば本発明の目的を満足しているとした。
◎：重量変化の絶対値≦3g/m2
○：3g/m2<重量変化の絶対値≦5g/m2
×：5g/m2<重量変化の絶対値
塗装密着性：熱処理後の鋼板からサンプルを採取し、日本パーカライジング(株)製PB-SX35を使用して標準条件で化成処理を施した後、関西ペイント(株)製電着塗料GT-10HTグレーを170℃×20分間の焼付け条件で膜厚20μm成膜して、塗装試験片を作製した。そして、作製した試験片の化成処理および電着塗装を施した面に対してカッターナイフで碁盤目(10×10個、1mm間隔)の鋼素地まで到達するカットを入れ、接着テープにより貼着・剥離する碁盤目テープ剥離試験を行った。以下の基準で評価し、◎、○であれば塗装密着性に優れるとした。
◎：剥離なし
○：1〜10個の碁盤目で剥離
△：11〜30個の碁盤目で剥離
×：31個以上の碁盤目で剥離
結果を表3に示す。本発明例では、冷間プレス性、熱間プレス時の耐酸化性に優れるとともに、熱間プレス後の塗装密着性にも優れていることがわかる。
In addition, the following were used as the solid lubricant of the lubricating layer, the organic resin binder, and the compound of the compound layer.
Silicone resin: KR-242A manufactured by Shin-Etsu Chemical Co., Ltd.
Polyethylene wax 1: Celidust 3620, manufactured by Clariant Japan
Fluororesin: Polytetrafluoroethylene resin Asahi Glass Co., Ltd. Fullon L170J
Molybdenum disulfide: LM-13 manufactured by Daito Lubrication Co., Ltd.
Graphite: GP-60S manufactured by Hitachi Chemical Co., Ltd.
Boron nitride: FS-1 made by Mizushima Alloy Iron Co., Ltd.
Diethanol-modified epoxy resin: ER-007 manufactured by Kansai Paint Co., Ltd.
Block isocyanate: Duranate MF-K60X manufactured by Asahi Kasei Corporation
Ethylene ionomer: Chemipearl S650 manufactured by Mitsui Chemicals, Inc.
Polyethylene wax 2: Chemipearl W950 manufactured by Mitsui Chemicals, Inc.
Silane coupling agent: KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.
For the steel plates Nos. 1 to 22 shown in Tables 1 and 2 thus obtained, the following cold press properties, oxidation resistance during hot pressing, and coating adhesion after hot pressing were evaluated. It was. Here, the hot press was simulated by heating with an electric furnace or direct energization under the heating conditions shown in Tables 1 and 2, and then sandwiching with an Al mold and cooling at a cooling rate of 50 ° C./s.
Cold pressability: The dynamic friction coefficient was measured using the friction coefficient measuring apparatus schematically shown in FIG. 1 to evaluate the cold pressability. First, the sample 1 collected from the as-prepared steel plate is placed on the sample stage 2 fixed to the upper surface of the slide table 3. The slide table 3 can be moved horizontally by a roller 4 provided on the upper surface of the
A: μ <0.1
○: 0.1 ≦ μ <0.15
Δ: 0.15 ≦ μ <0.2
×: 0.2 ≦ μ
Oxidation resistance: After heating under the heating conditions shown in Tables 1 and 2, the weight of the steel sheet was measured and the change in weight before heating was measured. Here, the weight change is the sum of the weight increase due to the scale and ZnO generation and the weight decrease due to the scattering of the generated ZnO, but the smaller the absolute value, the better the oxidation resistance. If ◎ or ○, the object of the present invention was satisfied.
A: Absolute value of weight change ≦ 3 g / m 2
○: 3 g / m 2 <absolute value of weight change ≦ 5 g / m 2
×: 5g / m 2 <Absolute value of weight change Paint adhesion: A sample was taken from the heat-treated steel sheet and subjected to chemical conversion treatment under standard conditions using PB-SX35 manufactured by Nihon Parkerizing Co., Ltd. An electrodeposition paint GT-10HT gray made by Paint Co., Ltd. was formed into a film with a thickness of 20 μm under a baking condition of 170 ° C. for 20 minutes to prepare a coating test piece. Then, a cut that reaches the steel substrate of the grid pattern (10 x 10 pieces, 1 mm interval) with a cutter knife is put on the surface that has been subjected to chemical conversion treatment and electrodeposition coating of the prepared test piece, and is attached with an adhesive tape. A cross-cut tape peeling test was conducted. Evaluation was made according to the following criteria, and ◎ and ○ were considered excellent in paint adhesion.
A: No peeling B: Peeling at 1 to 10 grids Δ: Peeling at 11 to 30 grids x: Peeling at 31 or more grids Table 3 shows the results. In the example of this invention, it turns out that it is excellent also in the coating press adhesiveness after a hot press while being excellent in cold press property and the oxidation resistance at the time of hot press.
なお、本実施例では実際に冷間プレスや熱間プレスによる加工を行っていないが、上述したように、耐酸化性や塗装密着性は熱間プレス前の加熱によるめっき層の変化、特にめっき層中のZnの挙動に左右されるので、本実施例の結果で耐酸化性や塗装密着性を評価できることになる。 In this example, processing by cold pressing or hot pressing is not actually performed, but as described above, oxidation resistance and coating adhesion are affected by changes in the plating layer due to heating before hot pressing, particularly plating. Since it depends on the behavior of Zn in the layer, the oxidation resistance and paint adhesion can be evaluated by the results of this example.
1 サンプル(鋼板)
2 試料台
3 スライドテーブル
4 ローラ
5 スライドテーブル支持台
6 ビード
7 第一ロードセル
8 第二ロードセル
9 レール
1 sample (steel plate)
2 Sample stage
3 Slide table
4 Roller
5 Slide table support
6 beads
7 First load cell
8 Second load cell
9 rails
Claims (7)
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011126941A JP5187414B2 (en) | 2011-06-07 | 2011-06-07 | Steel sheet for hot press and method for producing hot press member using the same |
| MYPI2013003930A MY154406A (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot pressing and process for manufacturing hot pressed member using the steel sheet |
| MX2013014294A MX344422B (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot pressing and method for producing hot pressed member using same. |
| CA2836119A CA2836119C (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot pressing and process for manufacturing hot pressed member using the steel sheet |
| CN201280028256.2A CN103597117B (en) | 2011-06-07 | 2012-05-23 | Hot pressing steel plate and use the manufacture method of hot press parts of this hot pressing steel plate |
| CN201610269427.0A CN105908226B (en) | 2011-06-07 | 2012-05-23 | Hot pressing steel plate |
| AU2012268278A AU2012268278B2 (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot pressing and process for manufacturing hot pressed member using the steel sheet |
| KR1020137030642A KR101447408B1 (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot pressing and process for manufacturing hot pressed member using the steel sheet |
| RU2013158293/02A RU2591905C2 (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot forming and method of producing parts from steel sheet by hot forming |
| PCT/JP2012/063824 WO2012169389A1 (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot pressing and method for producing hot pressed member using same |
| KR1020147015264A KR101789366B1 (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot pressing and process for manufacturing hot pressed member using the steel sheet |
| EP12796728.9A EP2719796B1 (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot pressing and process for manufacturing hot pressed member using the steel sheet |
| US14/123,872 US10100381B2 (en) | 2011-06-07 | 2012-05-23 | Steel sheet for hot pressing and process for manufacturing hot pressed member using the steel sheet |
| TW101118522A TWI441960B (en) | 2011-06-07 | 2012-05-24 | Steel sheet for hot pressing and process for manufacturing hot pressed member using the steel sheet |
| ARP120101989A AR086681A1 (en) | 2011-06-07 | 2012-06-06 | STEEL SHEET FOR HOT MOLDING AND PROCEDURE FOR MANUFACTURING A HOT MOLDED MEMBER USING THE STEEL SHEET |
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| JP2011126941A JP5187414B2 (en) | 2011-06-07 | 2011-06-07 | Steel sheet for hot press and method for producing hot press member using the same |
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| WO2015001705A1 (en) * | 2013-07-02 | 2015-01-08 | Ｊｆｅスチール株式会社 | Method of manufacturing hot press member |
| KR101528057B1 (en) * | 2013-11-27 | 2015-06-10 | 주식회사 포스코 | Steel for hot press forming with excellent formability and method for manufacturing the same |
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|---|---|---|---|---|
| JP2004124207A (en) * | 2002-10-04 | 2004-04-22 | Nippon Steel Corp | Zn-PLATED STEEL SHEET FOR HOT-PRESS, AND CAR COMPONENTS WITH HIGH STRENGTH USING IT |
| JP2005240072A (en) * | 2004-02-24 | 2005-09-08 | Nippon Steel Corp | Zinc-base plated hot press steel |
| JP2011074409A (en) * | 2009-09-29 | 2011-04-14 | Jfe Steel Corp | Plated steel sheet for hot press forming, and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004124207A (en) * | 2002-10-04 | 2004-04-22 | Nippon Steel Corp | Zn-PLATED STEEL SHEET FOR HOT-PRESS, AND CAR COMPONENTS WITH HIGH STRENGTH USING IT |
| JP2005240072A (en) * | 2004-02-24 | 2005-09-08 | Nippon Steel Corp | Zinc-base plated hot press steel |
| JP2011074409A (en) * | 2009-09-29 | 2011-04-14 | Jfe Steel Corp | Plated steel sheet for hot press forming, and method for manufacturing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015001705A1 (en) * | 2013-07-02 | 2015-01-08 | Ｊｆｅスチール株式会社 | Method of manufacturing hot press member |
| JP6020589B2 (en) * | 2013-07-02 | 2016-11-02 | Ｊｆｅスチール株式会社 | Manufacturing method of hot press member |
| JPWO2015001705A1 (en) * | 2013-07-02 | 2017-02-23 | Ｊｆｅスチール株式会社 | Manufacturing method of hot press member |
| US10384254B2 (en) | 2013-07-02 | 2019-08-20 | Jfe Steel Corporation | Method of manufacturing hot-pressed member |
| KR101528057B1 (en) * | 2013-11-27 | 2015-06-10 | 주식회사 포스코 | Steel for hot press forming with excellent formability and method for manufacturing the same |
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| JP5187414B2 (en) | 2013-04-24 |
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