JP4299644B2 - Hydrophilic stainless steel sheet and method for producing the same - Google Patents
Hydrophilic stainless steel sheet and method for producing the same Download PDFInfo
- Publication number
- JP4299644B2 JP4299644B2 JP2003403196A JP2003403196A JP4299644B2 JP 4299644 B2 JP4299644 B2 JP 4299644B2 JP 2003403196 A JP2003403196 A JP 2003403196A JP 2003403196 A JP2003403196 A JP 2003403196A JP 4299644 B2 JP4299644 B2 JP 4299644B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- mass
- steel sheet
- less
- atomic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 37
- 239000010935 stainless steel Substances 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 23
- 238000000137 annealing Methods 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 14
- 239000010959 steel Substances 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 description 12
- 238000005097 cold rolling Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910001566 austenite Inorganic materials 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002436 steel type Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Heat Treatment Of Sheet Steel (AREA)
Description
本発明は、業務用あるいは家庭用の冷蔵庫，冷凍庫，製氷機，流し台，テーブル，棚，ワゴンなどの厨房機器などに好適なステンレス鋼板であり、鋼板表面に付着する種々の汚れを、布巾などによる水拭きにより容易に除去できる親水性ステンレス鋼板に関するものである。 The present invention is a stainless steel plate suitable for commercial or household refrigerators, freezers, ice machines, sinks, tables, shelves, kitchen equipment such as wagons, etc. The present invention relates to a hydrophilic stainless steel plate that can be easily removed by wiping with water.
従来、ステンレス鋼板は耐食性に優れるとともに、研磨仕上や光沢仕上などによる様々な意匠性を持つ美麗な外観と清潔感を有することから、各種業務用あるいは家庭用の厨房機器などに使用されている。
しかし、これらの用途においては、人の手肌による接触にさらされるために手垢などの汚れが付着しやすく、また食材，調味料などにより汚れる機会が多くなっている。このため、洗剤を用いた清掃などのメンテナンスを常に心がけないと、外観上の美麗さを失うばかりでなく、汚れを起点とした錆の発生を招きやすいという問題があった。
Conventionally, a stainless steel plate is excellent in corrosion resistance and has a beautiful appearance and cleanliness with various design properties such as a polished finish and a gloss finish, and thus has been used in various commercial and household kitchen appliances.
However, in these applications, dirt such as dirt is likely to adhere because it is exposed to contact with human hand skin, and there are many opportunities to get dirty with foods, seasonings and the like. For this reason, if maintenance such as cleaning with a detergent is not always taken care of, there is a problem that not only the appearance is lost but also rust is likely to be generated starting from dirt.
このような問題を解決する手段の一つとして、付着した汚れを簡単な水洗で除去できるように、ステンレス鋼板の表面を親水化する技術がある。
ステンレス鋼板の表面を親水化する手段としては、表面に適度な凹凸を形成して親水性を高める方法、表面に親水性物質をコーティングする方法、あるいは熱処理により表面に特定の元素を濃化させて親水性を付与する方法などが提案されている。
例えば、特許文献１には、酸洗により表面に微細な凹凸を形成することで親水性を高めた高強度複相組織のステンレス鋼板が示されている。また特許文献２には、塩化第二鉄液のスプレーエッチングにより粗化面を形成することによって親水性を付与したオフセット印刷機用ステンレス平板が示されている。
As one means for solving such a problem, there is a technique for making the surface of a stainless steel plate hydrophilic so that attached dirt can be removed by simple water washing.
As a means for hydrophilizing the surface of a stainless steel plate, a method for increasing the hydrophilicity by forming appropriate irregularities on the surface, a method for coating the surface with a hydrophilic substance, or a method for concentrating a specific element on the surface by heat treatment. A method for imparting hydrophilicity has been proposed.
For example, Patent Document 1 discloses a stainless steel plate having a high-strength multiphase structure in which hydrophilicity is enhanced by forming fine irregularities on the surface by pickling. Patent Document 2 discloses a stainless steel plate for an offset printing press to which hydrophilicity is imparted by forming a roughened surface by spray etching of a ferric chloride solution.
特許文献３には、ステンレス鋼やガラス，プラスチックなどの基材表面に親水性を付与するために塗布する親水性ビニルモノマー含有親水滑水性表面処理剤が示されており、特許文献４には、同様にフッ素系ビニルモノマーを含有する表面処理剤が示されている。特許文献５には、表面にケイ酸ナトリウムなどの水ガラスやコロイダルシリカ，アルミナゾルなどの親水化処理剤を塗布する親水化ステンレス鋼の製造方法が示されている。
また、特許文献６，７には、アナターゼ型チタン酸化物などの光半導体を含有した層を表面に形成した部材あるいはステンレス鋼が示されている。
さらに、特許文献８には、研磨仕上したステンレス鋼板を光輝焼鈍して、表面酸化皮膜中の原子濃度比（Ｃｒ＋Ｓｉ＋Ａｌ）／Ｆｅを０．４以上にするとともに、研磨目に直角方向の中心線粗さＲａを０．３０μｍ以下とすることにより汚れ除去性を改善することが示されている。
Patent Document 3 discloses a hydrophilic vinyl monomer-containing hydrophilic sliding surface treatment agent that is applied to impart hydrophilicity to the surface of a base material such as stainless steel, glass, or plastic. Similarly, a surface treating agent containing a fluorinated vinyl monomer is shown. Patent Document 5 discloses a method for producing hydrophilized stainless steel, in which a hydrophilic glass such as sodium silicate, colloidal silica, alumina sol or the like is applied to the surface.
Patent Documents 6 and 7 disclose a member or stainless steel in which a layer containing an optical semiconductor such as anatase-type titanium oxide is formed on the surface.
Furthermore, in Patent Document 8, a polished stainless steel plate is brightly annealed so that the atomic concentration ratio (Cr + Si + Al) / Fe in the surface oxide film is 0.4 or more, and the center line roughness in the direction perpendicular to the polishing surface is increased. It has been shown that when the thickness Ra is set to 0.30 μm or less, the soil removability is improved.
しかしながら、特許文献１，２で提案されている技術では、表面の凹凸形態を調整することにより親水性を付与する方法であるため、研磨仕上や鏡面仕上などの外観上の意匠性が要求される用途には適用できない。
また、引用文献３〜７で提案されている技術では、ステンレス鋼板の親水化処理としての適用を考えた場合に、処理剤を塗布するための設備・機器が別途必要なためにコストアップに繋がることになる。しかも、非金属である樹脂やセラミックスを被覆することになるためにリサイクル性に劣ることや環境負荷が大きくなるという問題点を内包することになる。
さらに、特許文献８で提案された技術では、研磨仕上にしか適用できないため、用途が限られるという欠点を有している。
However, since the techniques proposed in Patent Documents 1 and 2 are methods for imparting hydrophilicity by adjusting the surface irregularity form, design on the appearance such as polishing finish or mirror finish is required. It is not applicable for use.
Moreover, in the technique proposed by the cited documents 3-7, when the application as a hydrophilization process of a stainless steel plate is considered, since the equipment and apparatus for apply | coating a processing agent are needed separately, it leads to a cost increase. It will be. In addition, since non-metallic resin and ceramics are coated, problems such as inferior recyclability and increased environmental load are involved.
Furthermore, since the technique proposed in Patent Document 8 can be applied only to the polishing finish, it has a drawback that its use is limited.
このように、従来の技術では親水性を付与することによりコストアップを招いたり、リサイクルの観点から環境負荷を増加させたりする場合が多かった。また、上記技術で得られる親水性のレベルは、近年要求されてきている耐汚染性やメンテナンスフリー性に対して必ずしも十分ではなかった。
そこで、本発明は、このような問題を解消すべく案出されたものであり、耐汚染性，メンテナンスフリー性に優れ、低コストで、しかもリサイクル性にも優れた親水性ステンレス鋼板を提供することを目的とする。
As described above, the conventional techniques often increase the cost by imparting hydrophilicity, or increase the environmental load from the viewpoint of recycling. Further, the level of hydrophilicity obtained by the above technique is not always sufficient for the stain resistance and maintenance-free properties that have been required in recent years.
Accordingly, the present invention has been devised to solve such problems, and provides a hydrophilic stainless steel sheet that is excellent in contamination resistance, maintenance-free properties, low cost, and excellent in recyclability. For the purpose.
本発明の親水性ステンレス鋼板は、その目的を達成するため、０．０６〜０．０８質量％のＣ，０．１８〜２．０質量％のＳｉ，０．２８〜０．３１質量％のＭｎ，０．０３０〜０．０３３質量％のＰ，０．００８〜０．００９質量％のＳ，１７．７７〜１７．８１質量％のＣｒ，０．２０〜０．２３質量％のＮｉ，０．３９〜０．４２質量％のＮｂを含有し、残部がＦｅ及び不可避的不純物からなるステンレス鋼板の表面に形成された皮膜が、Ｃを除きＳｉ：１５原子％以上，Ｎｂ：５原子％以下，Ｎ：３原子％以下，残部がＡｌ，Ｍｎ，Ｃｒ，Ｆｅ，Ｏからなる組成を有するＳｉＯ２主体の酸化物からなり、かつ鋼板表面における結晶面方位（１１０），（２００），（２１１），（２２０），（３１０），（２２２）の相対強度の総和に対して、結晶面方位（１１０），（２１１）及び（３１０）の相対強度比の合計が２０％以上を占めることを特徴とする。
ステンレス鋼板としては、０．２０〜２．０質量％のＳｉを含有しているものが好ましい。
このような表面特性を有するステンレス鋼板は、仕上光輝焼鈍前の冷間圧延を、圧延率９０％以下で施した冷延ステンレス鋼板を、窒素比率１５体積％以下の水素−窒素混合ガス雰囲気にて、温度Ｔ（℃）と露点Ｄ（℃）の間で、Ｄ≦０．０６７×Ｔ−１０７，Ｄ≦−４０，かつＴ≧８５０の関係を満たす温度，湿度条件で仕上光輝焼鈍することにより得られる。
In order to achieve the object, the hydrophilic stainless steel sheet according to the present invention has 0.06 to 0.08 mass% C, 0.18 to 2.0 mass% Si, and 0.28 to 0.31 mass%. Mn, 0.030 to 0.033 mass% P, 0.008 to 0.009 mass% S, 17.77 to 17.81 mass% Cr, 0.20 to 0.23 mass% Ni, A film formed on the surface of a stainless steel plate containing 0.39 to 0.42% by mass of Nb, the balance being Fe and inevitable impurities , except for C: Si: 15 atomic% or more, Nb: 5 atomic% Hereinafter, N: 3 atomic% or less, the balance being composed of an oxide mainly composed of SiO 2 having a composition of Al, Mn, Cr, Fe, O, and crystal plane orientations (110), (200), ( 211), (220), (310), (222) Respect, the crystal plane orientation (110), characterized in that occupy a total 20% or more of the relative intensity ratio of (211) and (310).
The stainless steel plate, 0. What contains 20-2.0 mass% Si is preferable.
A stainless steel sheet having such surface characteristics is obtained by subjecting a cold-rolled stainless steel sheet, which has been cold-rolled before finish bright annealing, to a rolling rate of 90% or less in a hydrogen-nitrogen mixed gas atmosphere having a nitrogen ratio of 15% by volume or less. By finish bright annealing between temperature T (° C.) and dew point D (° C.) under the temperature and humidity conditions satisfying the relationship of D ≦ 0.067 × T−107, D ≦ −40, and T ≧ 850 can get.
本発明者等は、ステンレス鋼板を光輝焼鈍したときに鋼板表面に生成する酸化皮膜に着目して調査・研究を行った結果、表面酸化皮膜の組成と特定結晶面方位の集積度を適正化することにより、親水性を著しく向上できることを見いだした。
そして、表面酸化皮膜の組成および特定結晶面方位の集積度の適正化が、仕上光輝焼鈍時の雰囲気含有窒素量，温度及び露点と、仕上光輝焼鈍前に実施する冷間圧延時の圧延率の調整で行えることを見いだしたものである。
したがって、本発明により、冷延条件の調整及び光輝焼鈍の調整という簡便な手段のみで、親水性に優れたステンレス鋼板を得ることが可能になる。これにより、鋼板表面に付着する種々の汚れを、布巾などにより水拭きにより容易に除去できるので、各種厨房機器などに好適なステンレス鋼板を低コストで提供することが可能となる。
As a result of investigation and research focusing on the oxide film formed on the steel sheet surface when the stainless steel sheet is brightly annealed, the present inventors optimize the composition of the surface oxide film and the degree of integration of the specific crystal plane orientation. Thus, it was found that the hydrophilicity can be remarkably improved.
And the optimization of the composition of the surface oxide film and the degree of integration of the specific crystal plane orientation are the amount of nitrogen in the atmosphere at the time of finish bright annealing, the temperature and the dew point, and the rolling rate at the time of cold rolling performed before the finish bright annealing. I found out what I can do with the adjustment.
Therefore, according to the present invention, it is possible to obtain a stainless steel plate having excellent hydrophilicity only by simple means of adjusting the cold rolling conditions and adjusting the bright annealing. As a result, various stains adhering to the surface of the steel plate can be easily removed by wiping with a cloth or the like, so that it is possible to provide a stainless steel plate suitable for various kitchen appliances at a low cost.
以下に、本発明の特徴を詳しく説明する。
まず、表面に優れた親水性を付与するためには、表面酸化皮膜の組成を適正化する必要がある。ＳｉＯ2主体の酸化物からなる皮膜であって、Ｃを除きＳｉ：１５原子％以上，Ｎｂ：５原子％以下，Ｎ：３原子％以下，残部がＡｌ，Ｍｎ，Ｃｒ，Ｆｅ，Ｏからなる組成を有することを必須とする。
酸化皮膜組成の同定は、Ｘ線光電子分光法（ＸＰＳ）による酸素スペクトルの解析により、主要な３つの酸化物ＳｉＯ2，Ｃｒ2Ｏ3及びＦｅ2Ｏ3についてのピーク高さの比率を比較して行う。すなわち、図１，２に示すような酸素スペクトルにおいて、結合エネルギー５３２．５ｅＶ位置のＳｉＯ2のピーク高さ比率；ｈＳｉＯ2，結合エネルギー５３０．９ｅＶ位置のＣｒ2Ｏ3のピーク高さ比率；ｈＣｒ2Ｏ3，及び結合エネルギー５３０．３ｅＶ位置のＦｅ2Ｏ3のピーク高さ比率；ｈＦｅ2Ｏ3としたとき、ｈＳｉＯ2，ｈＣｒ2Ｏ3，及びｈＦｅ2Ｏ3を比較する。
そして、ｈＳｉＯ2≧（ｈＣｒ2Ｏ3＋ｈＦｅ2Ｏ3）／２となった場合に、これをＳｉＯ2主体の酸化皮膜と断定する。例示した図１はＳｉＯ2を主体とした酸化物の場合の酸素スペクトルを、図２はＣｒ2Ｏ3及びＦｅ2Ｏ3を主体とした酸化物の場合の酸素スペクトルを表わしている。
The features of the present invention will be described in detail below.
First, in order to impart excellent hydrophilicity to the surface, it is necessary to optimize the composition of the surface oxide film. It is a film made of an oxide mainly composed of SiO 2 , except for C, Si: 15 atomic% or more, Nb: 5 atomic% or less, N: 3 atomic% or less, and the balance is made of Al, Mn, Cr, Fe, O It is essential to have a composition.
The oxide film composition is identified by comparing the peak height ratios for the three main oxides SiO 2 , Cr 2 O 3 and Fe 2 O 3 by analyzing the oxygen spectrum by X-ray photoelectron spectroscopy (XPS). Do it. That is, in the oxygen spectra as shown in FIGS. 1 and 2 , the peak height ratio of SiO 2 at the binding energy 532.5 eV position; hSiO 2 , the peak height ratio of Cr 2 O 3 at the binding energy 530.9 eV position; hCr The peak height ratio of Fe 2 O 3 at the position of 2 O 3 and a binding energy of 530.3 eV; where hFe 2 O 3 is used, hSiO 2 , hCr 2 O 3 , and hFe 2 O 3 are compared.
When hSiO 2 ≧ (hCr 2 O 3 + hFe 2 O 3 ) / 2, this is determined to be an oxide film mainly composed of SiO 2 . Illustrated FIG. 1 represents an oxygen spectrum in the case of an oxide mainly composed of SiO 2 , and FIG. 2 represents an oxygen spectrum in the case of an oxide mainly composed of Cr 2 O 3 and Fe 2 O 3 .
ＳｉＯ2を主体とした酸化皮膜を形成したものにあっても、優れた親水性を持たせるには、Ｃを除いたＳｉ，Ｎｂ，Ｎ，Ａｌ，Ｍｎ，Ｃｒ，Ｆｅ，Ｏを表面皮膜形成元素としたとき、皮膜中のＳｉ量を原子％で１５％以上とすることが必要である。１５原子％に満たないと酸化皮膜はＣｒ及びＦｅ酸化物を主体としたものになって、親水性が得られない。
なお、本明細書中での表面皮膜組成の分析値は、Ｘ線光電子分光法による各元素スペクトルの積分面積に基づいた半定量分析値により算出した値である。
ＳｉＯ2主体の酸化皮膜により親水性が向上する理由については、次のようなことが考えられよう。一般的に、ＳｉＯ2は酸化物の中ではイオン結合性が比較的大きいことが知られている。これらの酸化物ではその最表面において分極した−ＯＨ基が配列しているため、やはり分極した水分子との間に引力が働くことにより親水性を示すものと思われる。反対に、皮膜中にイオン結合の小さいＣｒ，Ｆｅ等の酸化物を主体とした酸化皮膜では水分子との親和力が低く親水性が得られないと考えられる。
Even in the case where an oxide film mainly composed of SiO 2 is formed, in order to have excellent hydrophilicity, a surface film is formed of Si, Nb, N, Al, Mn, Cr, Fe, O excluding C. When used as an element, the amount of Si in the film must be 15% or more in atomic%. If it is less than 15 atomic%, the oxide film is mainly composed of Cr and Fe oxide, and hydrophilicity cannot be obtained.
In addition, the analysis value of the surface film composition in this specification is a value calculated by a semi-quantitative analysis value based on the integrated area of each element spectrum by X-ray photoelectron spectroscopy.
The reason why the hydrophilicity is improved by the oxide film mainly composed of SiO 2 can be considered as follows. In general, it is known that SiO 2 has a relatively large ionic bond among oxides. In these oxides, since —OH groups polarized on the outermost surface are arranged, it is considered that hydrophilicity is exhibited by an attractive force acting on polarized water molecules. On the contrary, it is considered that an oxide film mainly composed of an oxide such as Cr or Fe having a small ionic bond in the film has a low affinity for water molecules and a hydrophilic property cannot be obtained.
ところで、ステンレス鋼には、含有されているＣ，Ｎを固定して耐食性や加工性を向上させる目的でＮｂが添加されている場合がある。
このＮｂは、光輝焼鈍時に焼鈍条件によっては窒素と反応して窒化物を形成し、表面皮膜中Ｎｂ窒化物を混入させることになる。表面皮膜中のＮｂ窒化物量が多くなると親水性が低下する。これは、Ｎｂ窒化物のイオン結合が小さいために、その表面占有率が高くなるほど水分子との親和力を低下させるためと考えられる。本発明者等は、各種予備実験から、皮膜中のＮｂ量が５原子％を越え、かつＮ量が３原子％を超えると、所望の親水性が得られないことを確認した。
したがって、本発明では、皮膜中のＮｂ量を５原子％以下，Ｎ量を３原子％以下と規定している。
By the way, Nb may be added to stainless steel for the purpose of fixing the contained C and N and improving the corrosion resistance and workability.
This Nb reacts with nitrogen to form a nitride depending on the annealing conditions during bright annealing, and Nb nitride is mixed in the surface film. As the amount of Nb nitride in the surface film increases, the hydrophilicity decreases. This is thought to be due to the fact that the ionic bond of Nb nitride is small, so that the affinity with water molecules decreases as the surface occupancy increases. The present inventors have confirmed from various preliminary experiments that the desired hydrophilicity cannot be obtained when the Nb content in the coating exceeds 5 atomic% and the N content exceeds 3 atomic%.
Therefore, in the present invention, the Nb content in the film is defined as 5 atomic% or less, and the N content is defined as 3 atomic% or less.
上記したようにステンレス鋼板に親水性を持たせるためには、光輝焼鈍後の表面皮膜中のＳｉＯ2量を多くすることが好ましい。一般的には、原板であるステンレス鋼板としては、含有Ｓｉ量が多いものほど好ましいことになる。鋼中に含まれるＳｉ量が少ないと、皮膜中のＳｉ比率が低くなりＳｉＯ2を主体とした酸化皮膜は形成されなくなる。親水性を得るためには、原板としてはＳｉ含有量０．２質量％以上のものが好ましい。なお、Ｓｉ含有量が２．０質量％を超えると冷間加工性が低下するため、原板としてはＳｉ含有量２．０質量％以下のものを用いることが好ましい。 As described above, in order to impart hydrophilicity to the stainless steel plate, it is preferable to increase the amount of SiO 2 in the surface film after bright annealing. In general, as the stainless steel plate as the original plate, the one having a larger content of Si is preferable. If the amount of Si contained in the steel is small, the Si ratio in the coating becomes low and an oxide coating mainly composed of SiO 2 cannot be formed. In order to obtain hydrophilicity, the original plate preferably has a Si content of 0.2% by mass or more. In addition, since cold workability will fall when Si content exceeds 2.0 mass%, it is preferable to use a Si content 2.0 mass% or less as an original plate.
表面に優れた親水性を付与するためには、表面皮膜の組成を調整するだけでなく、鋼板表面における特定の結晶面方位を集積する必要がある。
すなわち、鋼板表面における結晶面方位（１１０），（２００），（２１１），（２２０），（３１０），（２２２）の相対強度の総和に対して、結晶面方位（１１０），（２１１）及び（３１０）の相対強度比の合計を２０％以上にすると、仕上光輝焼鈍時に形成される酸化皮膜中のＳｉＯ2比率が高くなって、親水性が向上する。なお、ここでの相対強度比とは、Ｘ線ディフラクトメーターにより測定した結晶面方位（ｕｖｗ）の積分強度Ｉ（ｕｖｗ）を、結晶面方位が完全にランダムである標準試料の積分強度Ｉ0（ｕｖｗ）で除した相対強度を求め、上記６面の相対強度の総和に対する各面の百分率と定義する。
In order to impart excellent hydrophilicity to the surface, it is necessary not only to adjust the composition of the surface film but also to accumulate specific crystal plane orientations on the steel sheet surface.
That is, the crystal plane orientation (110), (211) with respect to the sum of the relative intensities of the crystal plane orientations (110), (200), (211), (220), (310), (222) on the steel sheet surface. And when the total of the relative intensity ratios of (310) is 20% or more, the SiO 2 ratio in the oxide film formed during the finish bright annealing is increased, and the hydrophilicity is improved. Here, the relative intensity ratio is the integrated intensity I (uvw) of the crystal plane orientation (uvw) measured by an X-ray diffractometer, and the integrated intensity I 0 of a standard sample whose crystal plane orientation is completely random. The relative intensity divided by (uvw) is obtained and defined as the percentage of each surface with respect to the sum of the relative intensities of the six surfaces.
特定の結晶面方位の集積度が大きい場合にＳｉＯ2比率が高くなる理由は定かではないが、次のような事象に類似しているものと考えられる。
すなわち、塗装に先立って鉄鋼材料の表面に施されるリン酸塩処理においては、予め原板表面に（１１１）面の集積度を高めることが行われている。これにより酸に解けにくいγ−Ｆｅ2Ｏ3皮膜厚を薄くすることができ、かつリン酸塩の析出核密度を高めて緻密な結晶を得ることができる。
本発明における結晶面方位制御による親水性の向上も、緻密なＳｉＯ2皮膜が選択的に生成することによるものと推察される。
The reason why the SiO 2 ratio increases when the degree of integration of a specific crystal plane orientation is large is not clear, but is thought to be similar to the following phenomenon.
That is, in the phosphate treatment applied to the surface of the steel material prior to coating, the degree of integration of the (111) plane is increased in advance on the surface of the original plate. This makes it possible to reduce the thickness of the γ-Fe 2 O 3 film that is difficult to dissolve by an acid, and to increase the density of precipitation nuclei of phosphate to obtain dense crystals.
The improvement in hydrophilicity by controlling the crystal plane orientation in the present invention is also presumed to be due to the selective generation of a dense SiO 2 film.
次に上記のような表面特性を有するステンレス鋼板の製造方法について説明する。
通常通りに均熱後に熱間圧延したステンレス鋼の熱延鋼帯を、焼鈍後、冷間圧延と仕上げの光輝焼鈍を行う。
鋼板表面の結晶面方位（１１０），（２１１）及び（３１０）の相対強度比の合計を２０％以上としてＳｉＯ2を主体とする酸化皮膜を形成するためには、仕上焼鈍前の冷間圧延での冷延率を９０％以下にする必要がある。９０％を超える圧延率では、焼鈍後に（１１１）の発達が著しくなり、（１１０），（２１１）及び（３１０）の合計が２０％未満になってしまう。このため、ＳｉＯ2を主体とする酸化皮膜が形成されにくくなる。
Next, the manufacturing method of the stainless steel plate which has the above surface characteristics is demonstrated.
As usual, the hot rolled steel strip of stainless steel that has been hot rolled after soaking is subjected to cold rolling and bright annealing for finishing after annealing.
In order to form an oxide film mainly composed of SiO 2 with the sum of the relative strength ratios of crystal plane orientations (110), (211) and (310) on the steel sheet surface being 20% or more, cold rolling before finish annealing is performed. It is necessary to make the cold rolling rate at 90% or less. When the rolling rate exceeds 90%, the development of (111) becomes remarkable after annealing, and the sum of (110), (211) and (310) becomes less than 20%. For this reason, it becomes difficult to form an oxide film mainly composed of SiO 2 .
ステンレス鋼板の表面に形成される皮膜の組成に最も影響を及ぼすのは、仕上光輝焼鈍を行う際の焼鈍条件である。
水素−窒素からなる雰囲気ガス中の窒素比率が大きくなると、Ｎｂ窒化物の生成量が増加して親水性を低下させることになる。素材のＮｂ含有量にもよるが、窒素比率が１５体積％以下の雰囲気であれば、Ｎｂ窒化物の影響は認められない。
It is the annealing conditions when performing the finish bright annealing that has the greatest influence on the composition of the film formed on the surface of the stainless steel plate.
When the nitrogen ratio in the atmosphere gas composed of hydrogen-nitrogen increases, the amount of Nb nitride produced increases and the hydrophilicity decreases. Although depending on the Nb content of the material, the influence of Nb nitride is not recognized if the nitrogen ratio is 15 vol% or less.
ＳｉＯ2を主体とする酸化皮膜を形成するためには、温度Ｔ（℃）、露点Ｄ（℃）としたとき、Ｄ≦０．０６７×Ｔ−１０７，Ｄ≦−４０，かつＴ≧８５０の条件を満たす温度，湿度条件で焼鈍する必要がある。
露点Ｄ（℃）が−４０℃を超えると酸化皮膜が厚くなりすぎて干渉色による着色（テンパーカラー）を生じる。また、温度Ｔ（℃）が８５０℃未満ではＳｉが酸化皮膜中に十分に濃化せず、ＳｉＯ2を主体とする酸化皮膜が形成されない。さらに、露点Ｄ（℃）が０．０６７×Ｔ−１０７を超える条件で光輝焼鈍すると、酸化皮膜がＣｒ及びＦｅ主体の酸化物となって、所望の親水性は得られない。これらの条件は、各種予備実験を繰り返すことにより、実験的に確認したものである。
In order to form an oxide film mainly composed of SiO 2 , assuming that the temperature T (° C.) and the dew point D (° C.), D ≦ 0.067 × T−107, D ≦ −40, and T ≧ 850. It is necessary to anneal at the temperature and humidity conditions that satisfy the conditions.
When the dew point D (° C.) exceeds −40 ° C., the oxide film becomes too thick and coloration with an interference color (temper color) occurs. Further, when the temperature T (° C.) is less than 850 ° C., Si is not sufficiently concentrated in the oxide film, and an oxide film mainly composed of SiO 2 is not formed. Further, when bright annealing is performed under a condition where the dew point D (° C.) exceeds 0.067 × T-107, the oxide film becomes an oxide mainly composed of Cr and Fe, and the desired hydrophilicity cannot be obtained. These conditions were experimentally confirmed by repeating various preliminary experiments.
なお、本発明におけるステンレス鋼板には、一般的なステンレス鋼の分類による、オーステナイト系，フェライト系，マルテンサイト系，フェライト＋マルテンサイト系，オーステナイト＋フェライト系，あるいは高Ｍｎオーステナイト系などのいずれの鋼種を適用しても良い。 The stainless steel plate in the present invention includes any steel type such as austenite, ferrite, martensite, ferrite + martensite, austenite + ferrite, or high Mn austenite according to the general stainless steel classification. May be applied.
Ｃｒを１７．８質量％程度，Ｎｂを０．４質量％程度含有し、その他の含有元素がＳＵＳ４３０の規格の範囲内にあるフェライト系ステンレス鋼について、Ｓｉ含有量を変えた３種類の鋼を準備した（表１参照）。これらの鋼を常法にて溶製し、鍛造及び熱間圧延により板厚３ｍｍの熱延鋼帯にした。溶態化処理と酸洗を施した後、表２に示す種々の条件による仕上冷間圧延、仕上光輝焼鈍を施して板厚０．８ｍｍとした後、切り板サンプルを採取した。
各サンプルについて、表面をＸ線光電子分光法により皮膜最表面での原子比率及び酸素スペクトルから酸化物ピーク高さ比率を測定した。また、Ｘ線ディフラクトメーターで表面での結晶面方位を測定した。さらに、各サンプルについて、静滴法によりイオン交換水０．１ｍｌの液滴との接触角を測定し、接触角が５０度以下の場合を親水性が優れるものとして評価した。
For ferritic stainless steels containing about 17.8% by mass of Cr, about 0.4% by mass of Nb, and other elements within the range of SUS430, three types of steels with different Si contents are used. Prepared (see Table 1). These steels were melted by a conventional method and formed into a hot-rolled steel strip having a plate thickness of 3 mm by forging and hot rolling. After solution treatment and pickling, finish cold rolling and finish bright annealing under various conditions shown in Table 2 were performed to obtain a plate thickness of 0.8 mm, and then a cut plate sample was collected.
About each sample, the oxide peak height ratio was measured from the atomic ratio and oxygen spectrum in the outermost surface of a film | membrane by the X ray photoelectron spectroscopy about the surface. Further, the crystal plane orientation on the surface was measured with an X-ray diffractometer. Further, the contact angle of each sample with a 0.1 ml droplet of ion-exchanged water was measured by a sessile drop method, and the case where the contact angle was 50 degrees or less was evaluated as having excellent hydrophilicity.
各サンプルの表面皮膜組成，酸化物ピーク高さ比及び結晶面方位、並びにそれぞれのサンプルの接触角を表３に示す。
本発明例である試験Ｎｏ．１〜８では、ＳｉＯ2を主体とした適正な酸化物皮膜が形成されており、接触角が５０度以下となって優れた親水性を示していた。Ｓｉ含有量が比較的少ない鋼種を素材としたものであっても、適切な条件で冷間圧延と光輝焼鈍を施せば（試験Ｎｏ．７，８参照）、表面にはＳｉＯ2を主体とする酸化皮膜が形成され、所望の親水性を発揮できている。
これに対して、比較例の試験Ｎｏ．９では、雰囲気ガス中の窒素比率が高いために、表面皮膜におけるＮｂ及びＮの比率が高くなって、接触角が大きくなっている。また、試験Ｎｏ．１０〜１２では、光輝焼鈍の温度，湿度の条件が本発明範囲外であるために、皮膜最表面におけるＳｉ比率が低く、Ｃｒ及びＦｅ主体の酸化皮膜が形成されて接触角が５０度を超えるようになっている。さらに、試験Ｎｏ．１３では、仕上冷延時の圧延率が高いために、結晶面方位の相対的強度比（１１０）＋（２１１）＋（３１０）の合計が２０％に満たず、ＳｉＯ2主体の酸化部皮膜が形成されず親水性を示さなかった。
Table 3 shows the surface film composition, oxide peak height ratio and crystal plane orientation of each sample, and the contact angle of each sample.
Test No. which is an example of the present invention. In Nos. 1 to 8, an appropriate oxide film mainly composed of SiO 2 was formed, and the contact angle was 50 degrees or less, indicating excellent hydrophilicity. Even if it is made of a steel type having a relatively small Si content, if it is subjected to cold rolling and bright annealing under appropriate conditions (see Test Nos. 7 and 8), the surface is mainly composed of SiO 2. An oxide film is formed and desired hydrophilicity can be exhibited.
In contrast, Test No. of the comparative example. In No. 9, since the nitrogen ratio in the atmospheric gas is high, the ratio of Nb and N in the surface film is high, and the contact angle is large. In addition, Test No. 10 to 12, the conditions of the bright annealing temperature and humidity are outside the scope of the present invention, so the Si ratio on the outermost surface of the film is low, an oxide film mainly composed of Cr and Fe is formed, and the contact angle exceeds 50 degrees. It is like that. Furthermore, test no. In No. 13, since the rolling ratio at the time of finish cold rolling is high, the total of the relative strength ratios (110) + (211) + (310) of the crystal plane orientation does not reach 20%, and the oxide part film mainly composed of SiO 2 It was not formed and did not show hydrophilicity.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003403196A JP4299644B2 (en) | 2003-12-02 | 2003-12-02 | Hydrophilic stainless steel sheet and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003403196A JP4299644B2 (en) | 2003-12-02 | 2003-12-02 | Hydrophilic stainless steel sheet and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005163102A JP2005163102A (en) | 2005-06-23 |
| JP4299644B2 true JP4299644B2 (en) | 2009-07-22 |
Family
ID=34726574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003403196A Expired - Lifetime JP4299644B2 (en) | 2003-12-02 | 2003-12-02 | Hydrophilic stainless steel sheet and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4299644B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119856A (en) * | 2005-10-28 | 2007-05-17 | Nisshin Steel Co Ltd | Hydrophilic stainless steel sheet and its manufacturing method |
| JP4826372B2 (en) * | 2006-07-14 | 2011-11-30 | 住友金属工業株式会社 | Stainless steel sheet having uniform film and method for producing the same |
| JP5274047B2 (en) * | 2008-02-23 | 2013-08-28 | 日新製鋼株式会社 | Ferritic stainless steel material, manufacturing method thereof, and automobile muffler |
| JP2016196019A (en) * | 2015-04-03 | 2016-11-24 | 日新製鋼株式会社 | Ferritic stainless steel sheet, cover member and method for manufacturing ferritic stainless steel sheet |
| JP2016196682A (en) * | 2015-04-03 | 2016-11-24 | 日新製鋼株式会社 | Austenitic stainless steel sheet, cover member, and method for producing the austenitic stainless steel sheet |
-
2003
- 2003-12-02 JP JP2003403196A patent/JP4299644B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005163102A (en) | 2005-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3739887B2 (en) | Polished stainless steel sheet excellent in dirt removal and method for producing the same | |
| WO2014103722A1 (en) | Ferritic stainless steel sheet having excellent anti-bacterial activity, and method for producing same | |
| TW201508098A (en) | Hot stamped body and method for producing hot stamped body | |
| KR20200093002A (en) | High-strength steel sheet and its manufacturing method | |
| JP2007119856A (en) | Hydrophilic stainless steel sheet and its manufacturing method | |
| JP4299644B2 (en) | Hydrophilic stainless steel sheet and method for producing the same | |
| JP4809664B2 (en) | Method for producing low-carbon steel cold-rolled steel strip with excellent surface smoothness | |
| JP4238153B2 (en) | High-strength electrogalvanized steel sheet excellent in uniform appearance and method for producing the same | |
| JP2013173976A (en) | Method for manufacturing cold rolled steel sheet and manufacturing facility of the same | |
| JP2005240062A (en) | Hydrophilic stainless steel plate, and method for manufacturing the same | |
| JP2004211151A (en) | Al-plated steel sheet for high-temperature press forming superior in lubricity | |
| JP4306411B2 (en) | Steel plate for heat treatment and its manufacturing method | |
| JP2991928B2 (en) | Cr-Ni diffusion treated steel sheet excellent in workability and corrosion resistance and method for producing the same | |
| JP4465853B2 (en) | Ferritic stainless steel cold rolled steel for jar pot containers and ferritic stainless steel containers for jar pots with excellent corrosion resistance and scale adhesion | |
| JP6911597B2 (en) | Unidirectional silicon steel plate with excellent film adhesion and its manufacturing method | |
| JPS58100622A (en) | Production of silicon-manganese high strength steel plate having excellent suitability to chemical conversion | |
| JP2648679B2 (en) | Manufacturing method of painted aluminum plated steel sheet with excellent corrosion resistance and workability | |
| JP4782057B2 (en) | High-strength steel sheet with excellent scale adhesion during hot pressing and manufacturing method thereof | |
| JP5655717B2 (en) | Method for producing cold-rolled steel sheet with excellent press formability, chemical conversion treatment and post-coating corrosion resistance | |
| JP2000063985A (en) | Cold rolled steel sheet for porcelain enameling, hardly causing strength reduction after firing | |
| JPH07113142A (en) | Stainless steel plate for architectural material, excellent in contamination resistance and corrosion resistance | |
| KR101066579B1 (en) | Surface treatment method for ferritic stainless hot-rolled steel plate | |
| JP5245323B2 (en) | Electrical steel sheet for etching | |
| US4612095A (en) | Method for improving corrosion resistance of bright annealed stainless steel | |
| JP3862836B2 (en) | Mirror finish multi-phase stainless steel plate with excellent scratch resistance and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061128 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20070411 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20070417 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20070417 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081224 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090106 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090309 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090331 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090417 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4299644 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120424 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130424 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140424 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |