JPH0860301A - Martensitic stainless steel having antibacterial characteristic and its production - Google Patents
Martensitic stainless steel having antibacterial characteristic and its productionInfo
- Publication number
- JPH0860301A JPH0860301A JP21055594A JP21055594A JPH0860301A JP H0860301 A JPH0860301 A JP H0860301A JP 21055594 A JP21055594 A JP 21055594A JP 21055594 A JP21055594 A JP 21055594A JP H0860301 A JPH0860301 A JP H0860301A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- potential
- concentration
- surface layer
- martensitic stainless
- 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.)
- Pending
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 40
- 229910001105 martensitic stainless steel Inorganic materials 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000002344 surface layer Substances 0.000 claims abstract description 24
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 22
- 239000010935 stainless steel Substances 0.000 claims abstract description 22
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 18
- 239000010959 steel Substances 0.000 claims abstract description 17
- 238000002161 passivation Methods 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- 239000003242 anti bacterial agent Substances 0.000 description 12
- 241000894006 Bacteria Species 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000012937 correction Methods 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 5
- 230000002411 adverse Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000002503 metabolic effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000644 propagated effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 241000288673 Chiroptera Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、抗菌性が高められたマ
ルテンサイト系ステンレス鋼及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to martensitic stainless steel having enhanced antibacterial properties and a method for producing the same.
【０００２】[0002]
【従来の技術】雑菌が繁殖し易い場所や雑菌の発生が好
ましくない場所に使用される硬質材料として、耐食性に
優れたマルテンサイト系ステンレス鋼が使用されてい
る。しかし、雑菌の繁殖による汚染，悪臭，ぬめり等が
人体，動物，製品等に与える悪影響を懸念する傾向が強
くなってきている。特に清潔さが要求される厨房，医療
機関，多数の人が集まる建造物等では、雑菌に対して抵
抗力のある材料に対する要求が強い。この種の要求に答
えるため、抗菌剤を配合した樹脂をマルテンサイト系ス
テンレス鋼の表面に塗布積層する方法や、マトリックス
中に抗菌剤成分を含むめっきを施す方法等が特開平５−
２２８２０２号公報，特開平６−１０１９１号公報等で
紹介されている。2. Description of the Related Art Martensitic stainless steel having excellent corrosion resistance is used as a hard material used in a place where various bacteria are easily propagated or where the generation of various bacteria is not preferable. However, there is an increasing tendency to be concerned about the adverse effects of contamination, malodor, slimyness, etc. due to the propagation of various bacteria on human bodies, animals, products and the like. Especially in kitchens, medical institutions, buildings where many people gather, where cleanliness is required, there is a strong demand for materials that are resistant to various bacteria. In order to meet this kind of demand, there is a method of coating and laminating a resin containing an antibacterial agent on the surface of martensitic stainless steel, a method of plating an antibacterial agent component in a matrix, and the like.
It is introduced in Japanese Unexamined Patent Publication No. 228202, Japanese Unexamined Patent Publication No. 6-10191, and the like.
【０００３】[0003]
【発明が解決しようとする課題】抗菌剤を配合した樹脂
をマルテンサイト系ステンレス鋼の表面に塗布積層する
と、ステンレス鋼特有の金属光沢が失われ、商品価値を
下げる。しかも、抗菌性皮膜は、加工時や使用中に割
れ，欠損，摩耗等の損傷を受け、湿潤雰囲気に曝される
とき抗菌性成分が溶出し、外観が劣化するばかりでな
く、本来の抗菌作用が損なわれる。また、抗菌剤が枯渇
したとき、残った皮膜が却って雑菌の栄養分となり、雑
菌の繁殖を促進させる原因にもなる。抗菌剤成分を混入
した複合めっきを施したものでは、めっき層の密着性が
十分でなく、加工性を低下させる欠点がある。また、皮
膜の溶解，摩耗，欠損等に起因して外観が低下すると共
に、抗菌作用が低下する場合がある。When a resin containing an antibacterial agent is applied and laminated on the surface of martensitic stainless steel, the metallic luster peculiar to stainless steel is lost and the commercial value is lowered. Moreover, the antibacterial film is damaged during processing or during use, such as cracking, chipping, and abrasion, and when exposed to a humid atmosphere, the antibacterial components are eluted and the appearance is deteriorated. Is damaged. In addition, when the antibacterial agent is exhausted, the remaining film is rather a nutrient for miscellaneous bacteria, which also promotes the growth of miscellaneous bacteria. In the case where the composite plating containing the antibacterial agent component is applied, there is a drawback that the adhesion of the plating layer is not sufficient and the workability is deteriorated. In addition, the appearance may be deteriorated due to dissolution, wear, and defects of the film, and the antibacterial action may be decreased.
【０００４】しかも、何れの方法も抗菌剤を使用してい
ることから、溶出した抗菌剤が人体や環境に悪影響を及
ぼす虞れがある。そこで、抗菌剤成分を被覆する方法に
代え、ステンレス鋼自体に抗菌性を付与するとこが望ま
れている。本発明は、このような要求に応えるべく案出
されたものであり、表面層のＣｕ濃度を高めることによ
り、マルテンサイト系ステンレス鋼自体に抗菌性をもた
せ、ステンレス鋼特有の美麗な外観や加工性等の諸特性
を損なうことなく、長期にわたって優れた抗菌性を維持
し、しかも人体や環境に対して安全なマルテンサイト系
ステンレス鋼を提供することを目的とする。In addition, since the antibacterial agent is used in each of the methods, the eluted antibacterial agent may adversely affect the human body and the environment. Therefore, it is desired to impart antibacterial properties to the stainless steel itself, instead of coating the antibacterial agent component. The present invention has been devised in order to meet such a requirement. By increasing the Cu concentration in the surface layer, the martensitic stainless steel itself has antibacterial properties, and has a beautiful appearance and processing peculiar to stainless steel. It is an object of the present invention to provide a martensitic stainless steel that maintains excellent antibacterial properties for a long period of time without impairing various properties such as properties and is safe for the human body and environment.
【０００５】[0005]
【課題を解決するための手段】本発明のマルテンサイト
系ステンレス鋼は、その目的を達成するため、５重量％
以下のＣｕを含むステンレス鋼を下地とし、表面から５
０Åまでの深さにある表層部のＣｕ濃度が０．１原子％
以上であることを特徴とする。下地鋼としては、Ｃｕ含
有量が０．０１〜５重量％の範囲にあるものが好まし
い。表層部のＣｕ濃度Ｃ1 は、必要とする抗菌性を得る
上から、下地鋼のＣｕ含有量Ｃ2 を基準として次式
（１）の範囲に調整される。 Ｃ1 ／Ｃ2 ≧０．２ ・・・・（１）The martensitic stainless steel of the present invention has a content of 5% by weight in order to achieve its object.
From the surface of the following stainless steel containing Cu, 5 from the surface
Cu concentration in the surface layer at a depth of 0Å is 0.1 atom%
It is characterized by the above. The base steel preferably has a Cu content in the range of 0.01 to 5% by weight. The Cu concentration C 1 of the surface layer portion is adjusted within the range of the following formula (1) based on the Cu content C 2 of the base steel in order to obtain the required antibacterial property. C 1 / C 2 ≧ 0.2 ··· (1)
【０００６】表層部のＣｕ濃度は、Ｃｕを含むマルテン
サイト系ステンレス鋼を交番電解処理し、表層部のＣｕ
濃度を０．１原子％以上に高めることにより調整され
る。すなわち、Ｃｒの不動態化電位より卑の電位範囲と
Ｆｅの自然電位からＦｅの不動態化完了電位までの貴の
電位範囲との間で振幅する方形波電位を５重量％以下の
Ｃｕを含むマルテンサイト系ステンレス鋼に印加すると
き、貴の電位で溶出したＣｕイオンが卑の電位で鋼表面
に析出し、表層部のＣｕ濃度を上昇させる。このとき、
下地鋼のＣｕ含有量を考慮して電解処理時間を設定する
ことにより、Ｃｕ濃度０．１原子％以上の表層部が形成
される。表層部のＣｕ濃度は、Ｘ線光電子分光分析装置
を使用して測定することができる。たとえば、脱脂後の
清浄表面にＭｇｋαＸ線を照射し、各ピークの面積強度
を測定し、相対感度指数を用いて算出される。The Cu concentration in the surface layer is obtained by subjecting martensitic stainless steel containing Cu to an electrolytic treatment by alternating electrolysis.
It is adjusted by increasing the concentration to 0.1 atom% or more. That is, a square-wave potential oscillating between a base potential range lower than the passivation potential of Cr and a noble potential range from the natural potential of Fe to the passivation completion potential of Fe contains 5 wt% or less of Cu. When applied to martensitic stainless steel, Cu ions eluted at a noble potential are deposited on the steel surface at a base potential to increase the Cu concentration in the surface layer portion. At this time,
By setting the electrolytic treatment time in consideration of the Cu content of the base steel, the surface layer portion having a Cu concentration of 0.1 atom% or more is formed. The Cu concentration in the surface layer portion can be measured using an X-ray photoelectron spectroscopy analyzer. For example, the clean surface after degreasing is irradiated with Mgkα X-rays, the area intensity of each peak is measured, and the relative sensitivity index is used for calculation.
【０００７】Ｃｕは、非常に優れた抗菌性を呈すること
が知られている。Ｃｕの抗菌性は、イオン化したＣｕが
細胞の呼吸，代謝酵素中のチオールと効率よく反応し、
チオールを不活化させることに起因するものと考えられ
ており、抗菌性シリカゲル，抗菌性ゼオライト等のＣｕ
を担持した抗菌剤として使用されている。しかし、マル
テンサイト系ステンレス鋼自体に含まれているＣｕに関
しては、抗菌性の観点から検討されていない。本発明者
等は、このマルテンサイト系ステンレス鋼自体に含まれ
ているＣｕにも抗菌性があることを見い出し、鋼表面の
Ｃｕ濃度を所定範囲に維持することによって鋼自体であ
っても優れた抗菌性が発現されることを確認した。Cu is known to exhibit a very good antibacterial property. The antibacterial property of Cu is that ionized Cu efficiently reacts with thiols in respiration and metabolic enzymes of cells,
It is considered to be caused by inactivating thiol, and Cu such as antibacterial silica gel, antibacterial zeolite, etc.
Is used as an antibacterial agent. However, Cu contained in the martensitic stainless steel itself has not been studied from the viewpoint of antibacterial property. The present inventors have found that Cu contained in the martensitic stainless steel itself also has antibacterial properties, and by maintaining the Cu concentration on the steel surface within a predetermined range, the steel itself is excellent. It was confirmed that antibacterial properties were expressed.
【０００８】マルテンサイト系ステンレス鋼に含まれて
いるＣｕが抗菌性を発現する機構は、次のように推察さ
れる。細菌が繁殖し易い湿潤環境下では、マルテンサイ
ト系ステンレス鋼のＣｕ含有量が少ない場合であって
も、鋼表面のＣｕ濃度を増加させることにより、ステン
レス鋼表面にある僅かな水分で極微量のＣｕがイオン化
する。Ｃｕは、抗菌効果が高いことから、極微量であっ
ても、鋼表面の近傍に存在する細菌細胞の呼吸や代謝酵
素と効率よく反応し、不活化する。その結果、細菌の繁
殖を抑え、殺菌する。鋼表面に接する雰囲気のｐＨや水
分中の塩濃度等の使用環境によってＣｕのイオン化反応
が影響され、結果としてＣｕの抗菌効果が変わる。しか
し、鋼表面から５０Åまでの深さにある表層部のＣｕ濃
度を０．１原子％以上にするとき、通常の環境で十分な
抗菌性を発現させることができる。The mechanism by which Cu contained in martensitic stainless steel exhibits antibacterial properties is presumed as follows. In a humid environment in which bacteria are easily propagated, even if the Cu content of martensitic stainless steel is low, increasing the Cu concentration on the steel surface allows a very small amount of water to be present on the stainless steel surface for a very small amount of water. Cu is ionized. Since Cu has a high antibacterial effect, even if it is an extremely small amount, Cu efficiently reacts with the respiratory and metabolic enzymes of bacterial cells existing near the steel surface and is inactivated. As a result, bacterial growth is suppressed and sterilized. The ionization reaction of Cu is affected by the use environment such as the pH of the atmosphere in contact with the steel surface and the salt concentration in water, and as a result, the antibacterial effect of Cu changes. However, when the Cu concentration in the surface layer portion at a depth of up to 50 Å from the steel surface is set to 0.1 atom% or more, sufficient antibacterial property can be exhibited in a normal environment.
【０００９】Ｃｕの抗菌効果は、マルテンサイト系ステ
ンレス鋼に含まれているＣｕが多量になるほど強力にな
る。抗菌性の観点からすると、Ｃｕ含有量が高いほど好
ましい。また、マルテンサイト相に過飽和状態でＣｕを
含ませ、その後の時効処理によってＣｕリッチの相を微
細分散析出させることにより、硬度の上昇にも有効に働
く。しかし、５重量％を超える多量のＣｕが含まれる
と、ステンレス鋼の熱間加工性が阻害される。したがっ
て、下地鋼となるマルテンサイト系ステンレス鋼のＣｕ
含有量は、０．０１〜５重量％に範囲にあることが要求
される。この範囲でＣｕを含むマルテンサイト系ステン
レス鋼は、通常のＣｕを含んでいないものと外観に変わ
りはない。しかも、鋼材自体に抗菌性を付与しているこ
とから、疵付き，摩耗等に対して抵抗力のある表面をも
ち、高位に安定した抗菌性が長期間にわたって持続され
る。更に、食器，容器等にも広く使用されているように
Ｃｕは通常の使用環境下では人体等に対し無害であるこ
とから、Ｃｕ添加したマルテンサイト系ステンレス鋼も
人体や環境に対して悪影響を与えることはない。The antibacterial effect of Cu becomes stronger as the amount of Cu contained in martensitic stainless steel increases. From the viewpoint of antibacterial properties, the higher the Cu content, the more preferable. Further, by including Cu in a supersaturated state in the martensite phase and finely dispersing and precipitating a Cu-rich phase in the subsequent aging treatment, the hardness is effectively increased. However, when a large amount of Cu exceeding 5% by weight is contained, the hot workability of stainless steel is impaired. Therefore, Cu of the martensitic stainless steel to be the base steel
The content is required to be in the range of 0.01 to 5% by weight. The martensitic stainless steel containing Cu in this range has the same appearance as that of ordinary one not containing Cu. Moreover, since the steel material itself is provided with antibacterial properties, it has a surface resistant to flaws, abrasion, etc., and the highly stable antibacterial properties are maintained for a long period of time. Further, as Cu is widely used for tableware, containers, etc., Cu is harmless to the human body in a normal use environment, so that martensitic stainless steel containing Cu also has an adverse effect on the human body and the environment. Never give.
【００１０】Ｃｕ以外に含まれる合金元素としては、
０．０１５〜０．０７０重量％のＣ，０．０５〜２．０
重量％のＳｉ，０．１０〜１．０重量％のＭｎ，０．０
１重量％以下のＳ，０．０４０重量％以下のＰ，１２〜
１７重量％のＣｒ，０．０５〜８．０重量％のＮｉ等が
ある。また、必要に応じ０．５〜１．５重量％のＡｌ，
０．１５〜０．６５重量％のＴｉ，０．００８〜０．０
３０重量％のＮ，０．３０〜２．５重量％のＭｏ，０．
１０〜０．５０重量％のＮｂ，０．１０〜０．５０重量
％のＴａを１種又は２種以上を添加しても良い。マルテ
ンサイト系ステンレス鋼を交番電解処理するとき、表層
部のＣｕ濃度を高めることができる。交番電解処理で
は、たとえばＣｕ含有ステンレス鋼を酸性電解液に浸漬
し、Ｃｒの不動態化電位より卑の電位範囲とＦｅの自然
電位からＦｅの不動態化完了電位までの貴の電位範囲と
の間で振幅する方形波電位をステンレス鋼に印加する。As alloy elements other than Cu,
0.015-0.070 wt% C, 0.05-2.0
% Si, 0.10 to 1.0% Mn, 0.0
1% by weight or less S, 0.040% by weight or less P, 12-
17 wt% Cr, 0.05 to 8.0 wt% Ni, and the like. If necessary, 0.5 to 1.5% by weight of Al,
0.15 to 0.65 wt% Ti, 0.008 to 0.0
30 wt% N, 0.30-2.5 wt% Mo, 0.
One or two or more of Nb of 10 to 0.50% by weight and Ta of 0.10 to 0.50% by weight may be added. When the martensitic stainless steel is subjected to the alternating electrolysis treatment, the Cu concentration in the surface layer portion can be increased. In the alternating electrolysis treatment, for example, Cu-containing stainless steel is dipped in an acidic electrolytic solution to obtain a base potential range lower than the Cr passivation potential and a noble potential range from the Fe natural potential to the Fe passivation completion potential. A square wave potential oscillating between is applied to stainless steel.
【００１１】貴の電位範囲における電解では、ステンレ
ス鋼に含まれている金属元素が溶出する。このとき、主
としてＦｅ及びＣｒが活性溶解し、Ｎｉも自然電位以下
で活性溶解する。ステンレス鋼に含まれているＣｕは、
Ｆｅ，Ｃｒ，Ｎｉ等と同様に貴の電位範囲で溶解する
が、他の金属に比較して貴な金属であることから卑の電
位範囲になったとき優先的に析出する。この溶解・析出
が繰り返されることにより、ステンレス鋼表面のＣｕ濃
度が上昇する。すなわち、鋼表面にＣｕが濃縮され、抗
菌性が高められる。このようにして表層部のＣｕ濃度が
高められたマルテンサイト系ステンレス鋼は、Ｃｕの抗
菌作用を活用し、包丁，替え刃等の刃物、スプーン，ナ
イフ，フォーク等の洋食器、メス，ハサミ，滅菌装置，
手洗器，バット等の医療用機械器具、便座等のサニタリ
ー用器具、ボールペン，筆記具のグリップ等の文房具、
各種食品の製造機器・機材，運搬用機器・機材等として
広範な分野で使用される。In electrolysis in the noble potential range, the metal element contained in stainless steel is eluted. At this time, mainly Fe and Cr are actively dissolved, and Ni is also actively dissolved at the natural potential or lower. Cu contained in stainless steel is
Like Fe, Cr, Ni, etc., it dissolves in the noble potential range, but since it is a noble metal compared to other metals, it preferentially precipitates in the base potential range. By repeating this dissolution / precipitation, the Cu concentration on the surface of the stainless steel increases. That is, Cu is concentrated on the steel surface and antibacterial property is enhanced. In this way, the martensitic stainless steel with the increased Cu concentration in the surface layer makes use of the antibacterial action of Cu, and uses knife such as kitchen knives, spare blades, Western tableware such as spoons, knives, forks, scalpels, scissors, Sterilizer,
Hand washers, medical instruments such as bats, sanitary instruments such as toilet seats, ballpoint pens, stationery such as grips for writing instruments,
It is used in a wide range of fields as various food manufacturing equipment / equipment, transportation equipment / equipment, etc.
【００１２】[0012]
実施例１：Ｃ：０．６４重量％，Ｓｉ：１．３１重量
％，Ｓ：０．００１重量％，Ｐ：０．０２９重量％，Ｃ
ｒ：１４．５２重量％及びＮｉ：６．８０重量％を含
み、Ｃｕ含有量を０．４３〜３．０２重量％の範囲で調
整したものを使用した。各ステンレス鋼の表面元素濃度
をＸＰＳで測定した。測定結果を、表１に示す。なお、
表１における比較例３は、Ｃｕを含まないステンレス鋼
を使用した場合である。Example 1: C: 0.64% by weight, Si: 1.31% by weight, S: 0.001% by weight, P: 0.029% by weight, C
r: 14.52 wt% and Ni: 6.80 wt% were used, and the Cu content adjusted in the range of 0.43 to 3.02 wt% was used. The surface element concentration of each stainless steel was measured by XPS. The measurement results are shown in Table 1. In addition,
Comparative Example 3 in Table 1 is a case where stainless steel containing no Cu is used.
【００１３】各試験片の抗菌性を、次のように調査し
た。Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ ＩＦＯ ３３
０１（大腸菌）及びＳｔａｐｈｙｌｏｃｏｃｃｕｓ ａ
ｕｒｅｕｓ ＩＦＯ １２７３２（黄色ブドウ球菌）そ
れぞれについて普通ブイヨン培地で３５℃，１６〜２０
時間振盪培養し、培養液を用意した。培養液を滅菌リン
酸緩衝液で２０，０００倍に希釈することにより、菌液
を調製した。菌液を試験片の表面に１ｍｌ滴下し、２５
℃で２４時間保存した。保存後、試験片をＳＣＤＬＰ培
地で洗い出し、得られた液について標準寒天培地を用い
た混釈平板培養法（３５℃，２日間培養）により生菌数
を測定した。この試験方法によるとき、初期の生菌数よ
り２４時間後の生菌数が減少しているほど、抗菌性の強
い材料であるといえる。また、試験に異常がないことを
確認するため、参照としてシャーレに菌液を直接滴下
し、同様に菌数を測定した。参照の生菌数に大きな増減
がないとき、試験結果が信頼性の高いものと評価され
る。The antibacterial property of each test piece was investigated as follows. Escherichia coli IFO 33
01 (E. coli) and Staphylococcus a
ureus IFO 12732 (Staphylococcus aureus) in ordinary broth medium at 35 ° C., 16-20
After culturing with shaking for a period of time, a culture solution was prepared. The bacterial solution was prepared by diluting the culture solution 20,000 times with sterile phosphate buffer. Drop 1 ml of the bacterial solution on the surface of the test piece, and
Stored at 24 ° C for 24 hours. After storage, the test piece was washed out with SCDLP medium, and the number of viable cells in the obtained liquid was measured by the pour plate culture method (culture at 35 ° C. for 2 days) using a standard agar medium. According to this test method, it can be said that a material having a stronger antibacterial property is obtained as the viable cell count after 24 hours is decreased from the initial viable cell count. In addition, in order to confirm that there was no abnormality in the test, the bacterial solution was directly dropped on the petri dish as a reference, and the number of bacteria was measured in the same manner. The test results are evaluated as highly reliable when there is no significant increase or decrease in the reference viable cell count.
【００１４】[0014]
【表１】 [Table 1]
【００１５】試験結果を示す表１から明らかなように、
表層部のＣｕ濃度が０．１原子％以上と高くなっている
試験番号１〜４では、何れの試験片も２４時間後の生菌
数が少なく、良好な抗菌性を呈していることが判る。こ
れに対し、表層部のＣｕ濃度が０．１原子％に満たない
試験番号５，６では、２４時間後にも多量の大腸菌及び
黄色ブドウ球菌が生存していた。As is clear from Table 1 showing the test results,
In Test Nos. 1 to 4 in which the Cu concentration in the surface layer portion is as high as 0.1 atom% or more, it can be seen that all the test pieces have a small number of viable bacteria after 24 hours and exhibit good antibacterial properties. . In contrast, in Test Nos. 5 and 6 in which the Cu concentration in the surface layer portion was less than 0.1 atomic%, a large amount of Escherichia coli and Staphylococcus aureus survived even after 24 hours.
【００１６】実施例２：Ｃｕ含有量０．２０重量％のマ
ルテンサイト系ステンレス鋼及びＣｕを含まないステン
レス鋼ＳＵＳ４０３を１００ｍｍ×１００ｍｍのサイズ
に切り出し、試験片を作成した。試験片の表面をジクロ
ルメタンの液及び蒸気で脱脂した後、２５℃に保持した
０．５ｌｍｏｌ／ｍ3 の硫酸液を電解浴として交番電解
処理した。交番電解処理では、表２に示す貴の電位ＥH
での電解時間ｔH 及び卑の電位ＥL での電解時間ｔL を
何れも０．１秒に設定した方形波電位を印加した。Example 2 A martensitic stainless steel having a Cu content of 0.20% by weight and a stainless steel SUS403 containing no Cu were cut into a size of 100 mm × 100 mm to prepare a test piece. The surface of the test piece was degreased with a solution of dichloromethane and steam, and then subjected to an alternating electrolysis treatment using a 0.5 lmol / m 3 sulfuric acid solution kept at 25 ° C. as an electrolytic bath. In alternating electrolysis, the noble potential E H shown in Table 2
A square-wave potential was applied in which the electrolysis time t H in (1) and the electrolysis time t L in the base potential E L were both set to 0.1 seconds.
【００１７】[0017]
【表２】 [Table 2]
【００１８】交番電解処理後の各試験片について、実施
例１と同様な条件下で抗菌性試験を行った。試験結果を
示す表３にみられるように、表層部のＣｕ濃度を０．１
原子％以上に高めた試験番号７〜１２の試験片では、何
れも良好な抗菌性を示した。これに対し、Ｃｕを含まな
い下地鋼を使用した試験番号１３，１４、Ｃｒの不動態
化電位より低い卑の電位ＥL 又はＦｅの不動態化完了電
位より高い貴の電位ＥH で交番電解した試験番号１５〜
１７の試験片では、交番電解処理後に表層部のＣｕ濃縮
が検出されず、良好な抗菌性が得られなかった。Each test piece after the alternating electrolysis treatment was subjected to an antibacterial test under the same conditions as in Example 1. As shown in Table 3 showing the test result, the Cu concentration in the surface layer portion was set to 0.1.
The test pieces of Test Nos. 7 to 12, which had been increased to at least atomic%, all showed good antibacterial properties. On the other hand, test Nos. 13 and 14 using the base steel containing no Cu, the base potential E L lower than the passivation potential of Cr or the noble potential E H higher than the passivation completion potential of Fe, alternate electrolysis. Test number 15-
In the test piece of No. 17, no Cu concentration in the surface layer was detected after the alternating electrolysis treatment, and good antibacterial properties were not obtained.
【００１９】[0019]
【表３】 [Table 3]
【００２０】[0020]
【発明の効果】以上に説明したように、本発明のマルテ
ンサイト系ステンレス鋼は、表層部のＣｕ濃度を０．１
原子％以上とすることにより、外観，加工性等の本来要
求される特性を損なうことなく、長期にわたって高位に
安定した抗菌性を維持する。また、Ｃｕの析出硬化を利
用して表面の硬質化を図ることもできる。このようにし
て抗菌性が高められたステンレス鋼は、衛生面を重視し
た刃物，洋食器，医療用機器，サニタリー器具，食品関
連機器等として広範な分野で使用される。As described above, the martensitic stainless steel of the present invention has a Cu concentration of 0.1 at the surface layer portion.
By adjusting the content to be atomic% or more, the highly stable antibacterial property can be maintained for a long period of time without impairing the originally required properties such as appearance and processability. Further, the surface can be hardened by utilizing the precipitation hardening of Cu. The stainless steel thus improved in antibacterial property is used in a wide range of fields such as cutting tools, Western tableware, medical equipment, sanitary equipment, food-related equipment, etc. that emphasize hygiene.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年３月１日[Submission date] March 1, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００４[Correction target item name] 0004
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００４】しかも、何れの方法も抗菌剤を使用してい
ることから、溶出した抗菌剤が人体や環境に悪影響を及
ぼす虞れがある。そこで、抗菌剤成分を被覆する方法に
代え、ステンレス鋼自体に抗菌性を付与することが望ま
れている。本発明は、このような要求に応えるべく案出
されたものであり、表面層のＣｕ濃度を高めることによ
り、マルテンサイト系ステンレス鋼自体に抗菌性をもた
せ、ステンレス鋼特有の美麗な外観や加工性等の諸特性
を損なうことなく、長期にわたって優れた抗菌性を維持
し、しかも人体や環境に対して安全なマルテンサイト系
ステンレス鋼を提供することを目的とする。In addition, since the antibacterial agent is used in each of the methods, the eluted antibacterial agent may adversely affect the human body and the environment. Therefore, it is desired to impart antibacterial properties to the stainless steel itself, instead of coating the antibacterial agent component. The present invention has been devised in order to meet such a requirement. By increasing the Cu concentration in the surface layer, the martensitic stainless steel itself has antibacterial properties, and has a beautiful appearance and processing peculiar to stainless steel. It is an object of the present invention to provide a martensitic stainless steel that maintains excellent antibacterial properties for a long period of time without impairing various properties such as properties and is safe for the human body and environment.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】[0012]
【実施例】 実施例１：Ｃ：０．０６４重量％，Ｓｉ：１．３１重量
％，Ｓ：０．００１重量％，Ｐ：０．０２９重量％，Ｃ
ｒ：１４．５２重量％及びＮｉ：６．８０重量％を含
み、Ｃｕ含有量を０．４３〜３．０２重量％の範囲で調
整したものを使用した。各ステンレス鋼の表面元素濃度
をＸＰＳで測定した。測定結果を、表１に示す。なお、
表１における比較例３は、Ｃｕを含まないステンレス鋼
を使用した場合である。EXAMPLES Example 1: C: 0.064% by weight, Si: 1.31% by weight, S: 0.001% by weight, P: 0.029% by weight, C
r: 14.52 wt% and Ni: 6.80 wt% were used, and the Cu content adjusted in the range of 0.43 to 3.02 wt% was used. The surface element concentration of each stainless steel was measured by XPS. The measurement results are shown in Table 1. In addition,
Comparative Example 3 in Table 1 is a case where stainless steel containing no Cu is used.
フロントページの続き (72)発明者 福本 博光 千葉県市川市高谷新町７番１号 日新製鋼 株式会社鉄鋼研究所内Front page continued (72) Inventor Hiromitsu Fukumoto 7-1 Takaya Shinmachi, Ichikawa City, Chiba Nisshin Steel Co., Ltd.
Claims (2)
レス鋼を下地とし、表面から５０Åまでの深さにある表
層部のＣｕ濃度が０．１原子％以上で、該表層部のＣｕ
濃度Ｃ1 と下地鋼のＣｕ含有量Ｃ2 との間にＣ1 ／Ｃ2
≧０．２の関係が成立している抗菌性を有するマルテン
サイト系ステンレス鋼。1. Cu: 0.01 to 5% by weight of stainless steel as a base, and the Cu concentration of the surface layer portion at a depth of 50 Å from the surface is 0.1 atom% or more, and the Cu of the surface layer portion is
Between the concentration C 1 and the Cu content C 2 of the base steel C 1 / C 2
A martensitic stainless steel having an antibacterial property satisfying a relationship of ≧ 0.2.
Ｆｅの自然電位からＦｅの不動態化完了電位までの貴の
電位範囲との間で振幅する方形波電位を５重量％以下の
Ｃｕを含むマルテンサイト系ステンレス鋼に印加し、表
層部のＣｕ濃度を０．１原子％以上に高める交番電解処
理することを特徴とする抗菌性を有するマルテンサイト
系ステンレス鋼の製造方法。2. A square wave potential oscillating between a base potential range lower than the Cr passivation potential and a noble potential range from the Fe natural potential to the Fe passivation completion potential is 5% by weight or less. A method for producing martensitic stainless steel having antibacterial properties, which is characterized in that it is applied to martensitic stainless steel containing Cu and subjected to an alternating electrolysis treatment for increasing the Cu concentration in the surface layer portion to 0.1 atom% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21055594A JPH0860301A (en) | 1994-08-11 | 1994-08-11 | Martensitic stainless steel having antibacterial characteristic and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21055594A JPH0860301A (en) | 1994-08-11 | 1994-08-11 | Martensitic stainless steel having antibacterial characteristic and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0860301A true JPH0860301A (en) | 1996-03-05 |
Family
ID=16591266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21055594A Pending JPH0860301A (en) | 1994-08-11 | 1994-08-11 | Martensitic stainless steel having antibacterial characteristic and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0860301A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022080273A1 (en) * | 2020-10-15 | 2022-04-21 | 昭和電工株式会社 | Gas-filled container and method of storing (e)-1,1,1,4,4,4-hexafluoro-2-butene |
-
1994
- 1994-08-11 JP JP21055594A patent/JPH0860301A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022080273A1 (en) * | 2020-10-15 | 2022-04-21 | 昭和電工株式会社 | Gas-filled container and method of storing (e)-1,1,1,4,4,4-hexafluoro-2-butene |
| JPWO2022080273A1 (en) * | 2020-10-15 | 2022-04-21 | ||
| KR20230058526A (en) * | 2020-10-15 | 2023-05-03 | 가부시끼가이샤 레조낙 | Gas filled container and storage method of (E)-1,1,1,4,4,4-hexafluoro-2-butene |
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