JP4780642B2 - Hard coating and method for producing the same - Google Patents
Hard coating and method for producing the same Download PDFInfo
- Publication number
- JP4780642B2 JP4780642B2 JP2005246502A JP2005246502A JP4780642B2 JP 4780642 B2 JP4780642 B2 JP 4780642B2 JP 2005246502 A JP2005246502 A JP 2005246502A JP 2005246502 A JP2005246502 A JP 2005246502A JP 4780642 B2 JP4780642 B2 JP 4780642B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- hard
- hard coating
- hard film
- film
- 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 - Fee Related
Links
Landscapes
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Physical Vapour Deposition (AREA)
Description
本願発明は、優れた潤滑特性と耐欠損性を有し、更に密着性の特性もかね備えた硬質皮膜に関する。 The present invention relates to a hard film having excellent lubrication characteristics and fracture resistance, and also having adhesion properties.
下記の特許文献は、C添加の硬質皮膜に関する技術を開示している。 The following patent document discloses a technique related to a C-added hard film.
特許文献1、2に開示されるDLC系の硬質皮膜は、非常に高硬度であることが開示されている。特許文献3、4は、TiAlCN、特許文献5、6は、(TiAlSi)(CN)は、高硬度化を目的に研究がなされており、潤滑特性に優れる記載はないが、Cを硬質皮膜中に添加することにより潤滑性の向上しているものと考えられる。特許文献7は、B4C、BN、TiB2などといった硬質粒子を含有させる手法で高硬度硬質皮膜を得ており、特に潤滑に関する説明はない。
本発明の目的は、硬質皮膜の有する密着性を犠牲にすることが無く、特に硬質皮膜の潤滑特性と耐欠損性を改善することである。またこの硬質皮膜の製造方法を提供することである。
Patent Documents 1 and 2 disclose that DLC-based hard coatings have extremely high hardness. Patent Documents 3 and 4 are TiAlCN, and Patent Documents 5 and 6 are (TiAlSi) (CN), which has been studied for the purpose of increasing the hardness and is not described as having excellent lubrication properties. It is considered that the lubricity is improved by adding to. Patent Document 7 obtains a high-hardness hard film by a method of containing hard particles such as B 4 C, BN, TiB 2 and the like, and there is no description regarding lubrication.
An object of the present invention is to improve the lubrication characteristics and fracture resistance of a hard coating without sacrificing the adhesion of the hard coating. Moreover, it is providing the manufacturing method of this hard film.
本願発明は、硬質皮膜は、4a、5a、6a族、Al、B、Siから選択される1種以上の金属元素と、Cを含みN、Oから選択される1種以上の非金属元素によって構成され、該硬質皮膜は、C成分に組成差を有し、C含有量が多い第2の層と、該第2の層よりもC含有量が少ない第1の層の積層構造で、該硬質皮膜は柱状組織構造を有し、該柱状組織構造の結晶粒は、該第1の層と第2の層の積層構造を有し、且つ、該第1の層、第2の層の層間の境界領域で少なくとも結晶格子縞が連続している領域があり、該第1の層、第2の層の厚みT(nm)が0.1≦T≦30.4、であることを特徴とする硬質皮膜である。更に、本願発明の硬質皮膜を物理蒸着法(以下、PVD法と記す。)により被覆する際には、アーク放電型イオンプレーティング法(以下、AIP法と記す。)とマグネトロンスパッタリング法(以下、MS法と記す。)を併用し、両者の蒸着源を同一チャンバー内で同時に放電させることにより積層構造を有する硬質皮膜を製造する方法である。本構成を採用することによって、密着性が優れ、特に潤滑特性や耐欠損性などの衝撃に対する強度を有する硬質皮膜を提供することができる。 In the present invention, the hard coating is composed of one or more metal elements selected from Group 4a, 5a, 6a, Al, B, and Si, and one or more non-metal elements selected from N and O containing C. The hard coating is composed of a second layer having a compositional difference in the C component, a second layer having a high C content, and a first layer having a lower C content than the second layer, The hard coating has a columnar structure, and the crystal grains of the columnar structure have a laminated structure of the first layer and the second layer, and the layers between the first layer and the second layer. In the boundary region, there is a region where at least crystal lattice fringes are continuous, and the thickness T (nm) of the first layer and the second layer is 0.1 ≦ T ≦ 30.4 Hard film. Further, when the hard coating of the present invention is coated by a physical vapor deposition method (hereinafter referred to as PVD method), an arc discharge ion plating method (hereinafter referred to as AIP method) and a magnetron sputtering method (hereinafter referred to as “PVD method”). This is a method for producing a hard film having a laminated structure by simultaneously discharging both vapor deposition sources in the same chamber. By adopting this configuration, it is possible to provide a hard film having excellent adhesion and particularly strength against impacts such as lubrication characteristics and fracture resistance.
本願発明の硬質皮膜は、硬質皮膜と基体との密着性が優れ、特に潤滑特性、耐欠損性に優れた硬質皮膜である。更に該硬質皮膜の製造方法を提供することができた。本願発明の硬質皮膜を、例えば切削工具等に適用した場合、溶着の激しいダイカスト金型用鋼の乾式高能率切削加工をはじめ、金型加工時の断続切削状況下においても安定性と、長い工具寿命が得られ、切削加工における生産性の向上に極めて有効である。 The hard coating of the present invention is a hard coating excellent in adhesion between the hard coating and the substrate, and particularly excellent in lubrication characteristics and fracture resistance. Furthermore, the manufacturing method of this hard film could be provided. When the hard coating of the present invention is applied to, for example, a cutting tool or the like, it is stable and long tool even under intermittent cutting conditions at the time of die processing, including dry high-efficiency cutting of die casting steel for severe welding It has a long life and is extremely effective for improving productivity in cutting.
本願発明は、硬質皮膜にCを含有させることで、潤滑特性を改善することができる。硬質皮膜がCを含有することによって、300℃程度の比較的低温条件であっても硬質皮膜表面に酸化現象を発生する。この酸化現象が、硬質皮膜表面の保護膜として機能し、更に摩擦係数を低下させ、潤滑特性が著しく向上する。例えば、本願発明の硬質皮膜を切削工具に適用した場合、大気中における切削温度近傍における硬質皮膜の摩擦係数は、Cを含有しない場合と比較して著しく低減する。更に酸化現象による保護膜は、被加工物の溶着を抑制し、切削熱など酸化雰囲気の高温下における被加工物の硬質皮膜中への内向拡散を防ぐことから、結果的に耐摩耗性や耐欠損性に優れ、安定した切削加工を可能にする効果がある。
本願発明の硬質皮膜は、柱状組織構造を有し、結晶粒成長方向に対して界面を形成することなく境界領域で結晶粒が連続的に成長した硬質皮膜である。ここで、柱状組織構造とは、膜厚方向に伸びた縦長成長結晶組織である。該硬質皮膜は多結晶材料であるが、結晶粒1つ1つの単位で捉えれば、単結晶材料の成長に類似した形態となっている。しかも、該硬質皮膜の柱状組織構造における結晶粒は、結晶粒成長方向に対してC成分に組成差を有する積層構造であって、少なくとも該積層構造における層間の境界領域で結晶格子縞が連続している領域がある。硬質皮膜の結晶粒がC成分に組成差を有する積層構造であることによって、硬質皮膜全体として靭性を持たせることができる。例えば、C成分の含有量が多い層では、比較的軟らかい硬質皮膜が形成される。この軟らかい層が、潤滑特性を向上させるだけでなく、他の比較的硬い層の層間に存在するとクッション効果を示し、硬質皮膜全体として靭性に富むようになる。更に、最適化された硬質皮膜を用いてCの特徴である高潤滑特性と融合させることによって、強靭性による耐欠損性、且つ高潤滑特性を有する硬質皮膜を得ることができる。しかし、この時の好ましいC成分の組成差は、最大でも10%である。
本願発明における硬質皮膜の各層の厚みT(nm)が0.1≦T≦30.4、となっていることが好ましい。Tが30.4nmを超えると、各層の境界領域に歪が発生し、結晶粒中の格子縞が不連続となり、硬質皮膜の機械的強度が低下するため不都合である。特に金属成分とC、Nを硬質皮膜にした場合、金属成分とNの硬質皮膜より、原子半径の差から結晶格子の歪が大きくなりやすい。その結果、場合によっては格子縞が不連続となることがある。そのような場合、例えば本願発明の硬質皮膜を切削工具に適用すると、切削初期において硬質皮膜表面に切削衝撃による皮膜の層状破壊が発生し、硬質皮膜の機械的強度に問題がある。各層の境界領域の歪発生を回避することは、硬質皮膜と基体との密着性の改善に有効である。一方、Tの下限値を0.1nmとしたのは、現在の層構造を確認する手段にX線回折装置や透過電子顕微鏡を用いた場合、層構造を確認できる最小厚みが0.1nmである。また、被覆を行う際に0.1nm未満の積層周期で被覆を行うと、皮膜特性のばらつきが発生し、安定品質の製品を供給することが出来ない。そこで、Tの下限値を0.1nmに規定した。
In the present invention, lubrication characteristics can be improved by adding C to the hard coating. When the hard film contains C, an oxidation phenomenon occurs on the surface of the hard film even under a relatively low temperature condition of about 300 ° C. This oxidation phenomenon functions as a protective film on the surface of the hard coating, further reduces the friction coefficient, and remarkably improves the lubrication characteristics. For example, when the hard coating of the present invention is applied to a cutting tool, the friction coefficient of the hard coating in the vicinity of the cutting temperature in the atmosphere is significantly reduced as compared with the case where C is not contained. Furthermore, the protective film due to the oxidation phenomenon suppresses welding of the work piece and prevents inward diffusion of the work piece into the hard film at high temperatures in an oxidizing atmosphere such as cutting heat. It has excellent chipping properties and has the effect of enabling stable cutting.
The hard film of the present invention is a hard film having a columnar structure and having crystal grains continuously grown in the boundary region without forming an interface with respect to the crystal grain growth direction. Here, the columnar structure is a vertically grown crystal structure extending in the film thickness direction. The hard coating is a polycrystalline material, but has a form similar to the growth of a single crystal material if it is grasped in units of crystal grains. In addition, the crystal grains in the columnar structure of the hard film have a laminated structure having a compositional difference in the C component with respect to the crystal grain growth direction, and crystal lattice fringes are continuous at least in the boundary region between the layers in the laminated structure. There is an area. When the hard coating crystal grains have a laminated structure having a composition difference in the C component, the entire hard coating can be provided with toughness. For example, in a layer having a high C component content, a relatively soft hard film is formed. This soft layer not only improves the lubrication characteristics, but also presents a cushioning effect when present between other relatively hard layers, so that the entire hard coating is rich in toughness. Furthermore, by using an optimized hard film and fusing with the high lubrication characteristics that are characteristic of C, a hard film having fracture resistance due to toughness and high lubrication characteristics can be obtained. However, the preferable difference in the composition of the C component at this time is 10% at the maximum.
It is preferable that the thickness T (nm) of each layer of the hard coating in the present invention is 0.1 ≦ T ≦ 30.4 . If T exceeds 30.4 nm, distortion occurs in the boundary region between the layers, the lattice stripes in the crystal grains become discontinuous, and this is disadvantageous because the mechanical strength of the hard coating is reduced. In particular, when the metal component and C and N are hard coatings, the distortion of the crystal lattice tends to be larger due to the difference in atomic radius than the metal component and N hard coating. As a result, the lattice fringes may become discontinuous in some cases. In such a case, for example, when the hard coating of the present invention is applied to a cutting tool, a laminar fracture of the coating due to a cutting impact occurs on the surface of the hard coating at the beginning of cutting, and there is a problem in the mechanical strength of the hard coating. Avoiding the occurrence of distortion in the boundary region of each layer is effective in improving the adhesion between the hard film and the substrate. On the other hand, the lower limit of T is set to 0.1 nm when the X-ray diffractometer or the transmission electron microscope is used as the means for confirming the current layer structure, and the minimum thickness for confirming the layer structure is 0.1 nm. . In addition, when coating is performed with a lamination period of less than 0.1 nm when coating is performed, variations in film characteristics occur, and stable quality products cannot be supplied. Therefore, the lower limit value of T is defined as 0.1 nm.
本願発明硬質皮膜のC含有量は原子%で、0.1%以上、30%以下であることが好ましい。0.1%未満の含有量では、汎用の分析機器を用いた検出が困難であること、また測定誤差の判断も難しく量産管理性が乏しくなる。そのため、簡易的に検出可能な0.1%以上とした。一方、C含有量が30%を超えると、硬質皮膜の結晶組織が柱状晶形態からアモルファス状の微細組織に変化し、更に積層構造を有する各層の格子縞が不連続になるといった不都合が生じる。その結果、硬質皮膜の機械的強度が低下すること、硬質皮膜の硬度低下や密着性低下に大きく影響を及ぼす残留圧縮応力が著しく大きくなり、外部からの強い衝撃により硬質皮膜の剥離が発生すること、などの不都合な現象が多く発生する。これらの理由から、C含有量は30%以下であることが好ましい。より好ましくは、0.1%以上、20%以下の範囲に制御することである。 The C content of the hard coating of the present invention is atomic%, preferably 0.1% or more and 30% or less. When the content is less than 0.1%, detection using a general-purpose analytical instrument is difficult, and determination of measurement error is difficult, and mass production controllability becomes poor. Therefore, it was set to 0.1% or more that can be easily detected. On the other hand, if the C content exceeds 30%, the crystal structure of the hard coating changes from a columnar crystal form to an amorphous microstructure, and further, the lattice stripes of each layer having a laminated structure become discontinuous. As a result, the mechanical strength of the hard coating decreases, the residual compressive stress that greatly affects the hardness reduction and adhesion deterioration of the hard coating increases remarkably, and the hard coating peels off due to a strong external impact. Many inconvenient phenomena occur. For these reasons, the C content is preferably 30% or less. More preferably, it is controlled within the range of 0.1% or more and 20% or less.
本願発明の硬質皮膜の被覆方法としてPVD法を採用し、該PVD法はAIP法とMS法である。更に該AIP法と該MS法とを併用し、両者の蒸着源を同一チャンバー内で同時に放電させることである。この理由は、AIP法とMS法とを同時に行うことにより、硬質皮膜の結晶粒成長方向に対して界面を形成させることなく結晶が連続的に成長した硬質皮膜を得ることが可能となるからである。これにより、硬質皮膜内部の結晶そのものの機械的強度がより強固になる。また、プラズマ密度の異なる成膜方式を同時に使用すると、夫々の放電により発生したプラズマから価数の異なるイオンが同時に基体表面に到達する。プラズマ密度の高いAIP法の蒸着源近傍では、硬質結晶が主体の第1の層をなし、プラズマ密度の低いMS法の蒸着源近傍では、軟質結晶が主体の第2の層をなす。更に両方の蒸着源からの影響を受ける第3の層が形成され、これらが積層構造を有する。即ち第1の層、第2の層と第3の層とが積層する。第2の層が第1の層間にサンドイッチされた状態で存在すると、第2の層がクッション効果を示し、硬質皮膜全体として靭性に富むようになる。更に、第3の層の存在によって、MS法の蒸着源から供給される成分が硬質皮膜中で組成変調することに、硬質皮膜の密着性の改善効果を有する。
Cの添加方法は、4a、5a、6a族、B、Si、Alから選択される元素が主体のターゲットを用いたAIP法による硬質皮膜被覆工程と、Cを含有したターゲットを用いたMS法による硬質皮膜被覆工程とを両者同時に行うことである。この理由は、MS法の発生するプラズマ密度が比較的低いため、硬質皮膜に容易にCを添加できるからである。MS法によってターゲット材より蒸発したC成分は、一旦はイオンレベルにまで分解される。この状態でC成分は基体表面に到達すると、AIP法によって蒸発した他の金属イオンやガス成分のイオンとともに結晶粒を構成する。この時、結晶粒は界面を形成することなく連続的に成長し、C成分は原子レベルで結晶粒の構造内に取り込まれてゆくのである。
本願発明の硬質皮膜の柱状組織構造からなる結晶粒はC成分に組成差を有し、これを最大でも10%に制御し、更にTを30.4nm以下に制御し、且つ結晶格子縞が連続して成長し積層構造を有するためには、MS法の蒸着源の放電出力を8.5kW以下に設定することが望ましい。MS法による蒸着源に設置される炭化物の放電によって得られる硬質皮膜は、AIP法主体で得られる硬質皮膜よりも若干軟らかい。特にC含有量が多い領域では、比較的軟らかい硬質皮膜が形成される。このように最適化された硬質皮膜を用いれば被覆部材の耐衝撃特性が向上して、強靭性、且つ高潤滑特性を有する硬質皮膜を得ることが可能となる。一方、プラズマ密度が比較的高いAIP法は、放電時のエネルギーが非常に大きいため、硬質皮膜にCを添加させるためには、炭化水素系の反応ガスを用いることが一般的である。しかし、AIP法の場合、プラズマ中で炭化水素系のガス成分をもイオン価させなければならない。炭化水素系のガスをイオン価させるためには、AIP蒸着源に取り付けられる金属ターゲットを放電させるのに非常に不安定な領域の低反応圧力状態が好ましい。したがって、AIP蒸着源における放電安定性が低下することになり、その蒸着源に設置するターゲットの金属種によっては、放電が困難である。また放電によって得られた硬質皮膜の表面にマクロパーティクルが多くなり、品位上の問題が発生する。更には、低反応圧力領域によって得られる硬質皮膜は残留圧縮応力が非常に大きく、密着性を劣化させる。炭化水素系のガスを取り扱うにあたり、環境上の面、また安全性など取り扱いの制約を受ける。そのため、硬質皮膜中にCを添加させる手段としては、MS法の蒸着源に設置される金属ターゲット材にあらかじめCを添加したものを使用することが望ましい。しかもMS法を利用すれば、C、TiC、WC、CrCなどターゲット材単体を用いることができる。AIP法では、Cを含むターゲット材単体は、融点の問題から放電が非常に困難である。そのためMS蒸着源に設置されるターゲット種は、4a、5a、6a族、B、Si、Alから選択される1種以上の金属マトリックス中にC添加したターゲット材、もしくはC単体のターゲットを用いる必要がある。PVD法に対して化学蒸着法では、AIP法同様、やはり炭化水素系のガスを使用することが一般的である。この場合、環境上、また安全性など問題がある。硬質皮膜中にCを添加させると、硬質皮膜表面に酸化物層を形成しやすくなるが、このような有効な物理現象を考慮して、あらかじめ酸素を含む硬質皮膜を表面に被覆しても効果がある。硬質皮膜に酸化物を形成させるためには、主体となる反応ガス中にOを含有させて得ることが好ましい。
AIP法とMS法とを同時に行うことにより得られる硬質皮膜は、結晶格子縞が連続した積層構造を有する。更にこれによって得られる硬質皮膜は、結晶格子縞が連続した積層構造を有する。しかし、両者を間欠的に用いた場合、例えばAIP法とMS法とを交互に放電させることによってCを添加すると、界面をもつ積層構造が生じ、その界面に発生する歪が影響して、各層の接合が脆弱化するため好ましくない。
本願発明の硬質皮膜を例えば切削工具等、高硬度が要求される耐摩耗部材や耐熱部材の表面に適用すると、特に潤滑特性が著しく向上するため、切削加工の高温状態での耐溶着性並びに硬質皮膜への被削材元素の拡散を抑制することができる。更に、切削加工の乾式化、高速化、高送り化に対応する硬質皮膜被覆工具を提供することができる。ここでの高送り加工とは、切削条件における1刃当たりの送り量が0.3mm/刃を超えるような切削を言う。
The PVD method is adopted as the method for coating the hard film of the present invention, and the PVD method is an AIP method and an MS method. Further, the AIP method and the MS method are used in combination, and both vapor deposition sources are discharged simultaneously in the same chamber. This is because by simultaneously performing the AIP method and the MS method, it is possible to obtain a hard film in which crystals are continuously grown without forming an interface with respect to the crystal growth direction of the hard film. is there. Thereby, the mechanical strength of the crystal inside the hard coating becomes stronger. In addition, when film forming methods having different plasma densities are used at the same time, ions having different valences simultaneously reach the substrate surface from the plasma generated by the respective discharges. In the vicinity of the AIP deposition source having a high plasma density, a hard crystal is the first layer, and in the vicinity of the MS plasma deposition source having a low plasma density, the soft crystal is the second layer. In addition, a third layer is formed which is influenced by both vapor deposition sources and has a laminated structure. That is, the first layer, the second layer, and the third layer are stacked. When the second layer is sandwiched between the first layers, the second layer exhibits a cushioning effect, and the entire hard coating is rich in toughness. Further, the presence of the third layer has an effect of improving the adhesion of the hard film by the composition modulation of the component supplied from the vapor deposition source of the MS method in the hard film.
The addition method of C is based on a hard film coating step by an AIP method using a target mainly composed of an element selected from the group 4a, 5a, 6a, B, Si, and Al, and an MS method using a target containing C. The hard film coating process is performed at the same time. This is because the plasma density generated by the MS method is relatively low, so that C can be easily added to the hard coating. The C component evaporated from the target material by the MS method is once decomposed to the ion level. When the C component reaches the substrate surface in this state, it forms crystal grains together with other metal ions and gas component ions evaporated by the AIP method. At this time, the crystal grains continuously grow without forming an interface, and the C component is taken into the structure of the crystal grains at the atomic level.
The crystal grains comprising the columnar structure of the hard coating of the present invention have a compositional difference in the C component, which is controlled to 10% at the maximum, T is further controlled to 30.4 nm or less, and crystal lattice fringes are continuous. In order to grow and have a laminated structure, it is desirable to set the discharge output of the MS deposition source to 8.5 kW or less. The hard film obtained by the discharge of the carbide placed in the vapor deposition source by the MS method is slightly softer than the hard film obtained mainly by the AIP method. In particular, in a region having a high C content, a relatively soft hard film is formed. If the hard coating optimized in this way is used, the impact resistance characteristics of the covering member are improved, and a hard coating having toughness and high lubricating characteristics can be obtained. On the other hand, since the AIP method having a relatively high plasma density has a very large energy during discharge, it is common to use a hydrocarbon-based reaction gas in order to add C to the hard coating. However, in the case of the AIP method, the hydrocarbon gas component must be ionized in the plasma. In order to ionize the hydrocarbon-based gas, a low reaction pressure state in a region that is very unstable for discharging a metal target attached to the AIP deposition source is preferable. Therefore, the discharge stability in the AIP vapor deposition source is lowered, and discharge is difficult depending on the metal species of the target installed in the vapor deposition source. In addition, macro particles increase on the surface of the hard film obtained by the discharge, which causes a quality problem. Furthermore, the hard film obtained by the low reaction pressure region has a very large residual compressive stress, which deteriorates the adhesion. Handling of hydrocarbon gases is subject to environmental restrictions and handling restrictions such as safety. Therefore, as a means for adding C to the hard coating, it is desirable to use a metal target material that has been added in advance to a metal target material installed in a vapor deposition source of the MS method. In addition, if the MS method is used, a single target material such as C, TiC, WC, or CrC can be used. In the AIP method, a single target material containing C is very difficult to discharge due to a melting point problem. Therefore, it is necessary to use a target material added with C in one or more kinds of metal matrices selected from 4a, 5a, 6a group, B, Si, and Al, or a target of C alone, as a target type installed in the MS evaporation source. There is. In contrast to the PVD method, the chemical vapor deposition method generally uses a hydrocarbon-based gas as in the AIP method. In this case, there are environmental and safety problems. When C is added to the hard film, it becomes easier to form an oxide layer on the surface of the hard film, but in consideration of such an effective physical phenomenon, it is also effective to coat the surface with a hard film containing oxygen in advance. There is. In order to form an oxide on the hard coating, it is preferable to obtain O by inclusion in the main reaction gas.
A hard film obtained by simultaneously performing the AIP method and the MS method has a laminated structure in which crystal lattice stripes are continuous. Furthermore, the hard coating obtained thereby has a laminated structure in which crystal lattice stripes are continuous. However, when both are used intermittently, for example, when C is added by alternately discharging the AIP method and the MS method, a laminated structure having an interface is formed, and the strain generated at the interface affects each layer. This is not preferable because the bonding of the material becomes weak.
When the hard coating of the present invention is applied to the surface of an abrasion-resistant member or heat-resistant member that requires high hardness, such as a cutting tool, the lubrication characteristics are particularly improved. Diffusion of the work material element into the film can be suppressed. Furthermore, it is possible to provide a hard film coated tool that can cope with dry cutting, high speed, and high feed of cutting. The high feed processing here refers to cutting in which the feed amount per blade under the cutting conditions exceeds 0.3 mm / tooth.
本願発明の硬質皮膜の被覆には、小型真空装置内にAIP方式の蒸着源と、MS方式の蒸着源とを併設した装置を用いて。基体は超硬合金製インサートを用い、反応ガスはN2ガス、Ar/O2混合ガスから目的の皮膜が得られるものを選択した。反応圧力は、真空装置内で両者の成膜法が同時にプラズマを発生させることが可能な圧力範囲を選定し、2種の蒸着源を同時に放電させるために反応圧力は3.0Paに設定した。基体温度は400℃、バイアス電圧は−40Vから−150Vの範囲の電圧を印加した。蒸着源は各種合金製ターゲットが選択可能であり、AIP蒸着源には所定組成の合金ターゲット材、MS蒸着源にはCを含むターゲット材を用いた。硬質皮膜にCを効果的に添加するために、AIP蒸着源とMS蒸着源とを同時に放電させた。得られた硬質皮膜の評価は、以下に示す切削条件にて切削試験を行った。切削試験で用いた被削材は、ダイカスト金型用鋼種として用いられるSKD61、硬さはHRC45、を選択した。本鋼種は、切削加工初期に刃先部における溶着現象が発生し、被覆インサート刃先部の硬質皮膜尊損傷が激しくなる。評価方法は、この被削材表面を高能率加工条件にて切削を行う事により、インサートが切削初期に発生する溶着がもたらす摩耗やヒートクラックによって欠損に至るまでの切削可能長を評価した。表1、2に本発明例、参考例、比較例及び従来例に関する硬質皮膜の詳細、使用したターゲット材組成及び切削試験の結果を示す。 For the coating of the hard film of the present invention, an apparatus in which an AIP deposition source and an MS deposition source are provided in a small vacuum apparatus is used. The substrate used was a cemented carbide insert, and the reaction gas was selected from N 2 gas and Ar / O 2 mixed gas to obtain the desired film. As the reaction pressure, a pressure range in which both film forming methods can simultaneously generate plasma in a vacuum apparatus was selected, and the reaction pressure was set to 3.0 Pa in order to simultaneously discharge two kinds of vapor deposition sources. The substrate temperature was 400 ° C., and the bias voltage was a voltage in the range of −40V to −150V. Various alloy targets can be selected as the deposition source, an alloy target material having a predetermined composition was used as the AIP deposition source, and a target material containing C was used as the MS deposition source. In order to effectively add C to the hard coating, the AIP vapor deposition source and the MS vapor deposition source were simultaneously discharged. Evaluation of the obtained hard film performed the cutting test on the cutting conditions shown below. As the work material used in the cutting test, SKD61 used as a steel type for die casting molds and HRC45 as the hardness were selected. In this steel type, a welding phenomenon occurs at the cutting edge portion in the early stage of cutting, and the hard coating is severely damaged at the coated insert cutting edge portion. In the evaluation method, the length of the work material was evaluated by cutting the surface of the work material under high-efficiency machining conditions, so that the insert could be damaged due to wear or heat crack caused by welding generated in the early stage of cutting. Tables 1 and 2 show the details of the hard coating, the composition of the target material used, and the results of the cutting test for the inventive examples , reference examples, comparative examples and conventional examples.
(切削条件)
工具:正面フライス
インサート形状:SDE53タイプ特殊形状
切削方法:センターカット方式
被削材形状:巾100mm×長さ250mm
被削材:SKD61、硬さ、HRC45
切り込み量:1.5mm
切削速度:100m/min
1刃送り量:0.6mm/刃
切削油:なし
表2は、評価結果であり、参考例1から4、本発明例5、参考例6から8、本発明例9、参考例10、本発明例11から14、比較例15から28、従来例29から35を示す。表2の結果より、本発明例5、9及び11から14は、硬質皮膜が柱状組織構造を有し、結晶粒がC成分に組成差を有する積層構造を有し、少なくとも該積層構造における層間の境界領域で結晶格子縞が連続している領域があり、各層の厚みT(nm)が0.1≦T≦30.4を満たすことによって、優れた切削性能を有することを確認した。2種以上の物理蒸着源を用いてCを硬質皮膜に添加させた時のC含有量の範囲が、切削性能に影響を及ぼすことも確認した。本発明例5、9及び11から14に示した様に、本願発明の硬質皮膜は、従来実現が困難であった切削加工を行うことが可能となった。本発明例9に示したグラファイトターゲットによってCが添加された硬質皮膜は、今回の評価の中で最も良い結果を示した。本発明例9の硬質皮膜を成膜するにあたり、グラファイトターゲットの放電出力を6.5kWに設定した。その結果、硬質皮膜を全体的に見た場合、C含有量は4.8%であり、本願発明で規定するC添加量の範囲内であった。図1に示す様に、硬質皮膜の破断面組織を倍率15000倍で観察した結果、柱状組織構造であった。従って、高送り加工などの衝撃の激しい切削加工において、せん断方向に対する機械的強度も得られた。図2は、本発明例9の硬質皮膜の破面を透過電子顕微鏡により2万倍で観察した結果であり、硬質皮膜の柱状組織構造を有する結晶粒は積層構造を有していた。図3は、図2に示した結晶粒の1部を更に拡大して20万倍で観察を行った結果であり、結晶粒はコントラストの異なる黒色層と灰色層とが複数存在している積層構造を有していることを確認した。ここで、1つ1つの結晶粒は同一方向に結晶成長したものであり、電子回折によって確認することができる。ここで、図2の観察で見られたコントラストの縞模様の数と、図3の観察で見られたコントラストの縞模様の数との間には、観察倍率が異なっている点から相関性は無い。また図2に示したコントラストの縞模様から、膜厚方向の層の厚さを得ることができる。測定の結果、各層の層厚は、3から4nm程度であった。図3の観察状態から更に観察倍率を高くして、結晶格子縞の状態を200万倍で観察した。この時の観察結果を図4に示す。図4の観察領域は、図3の観察形態を参照しながら進めていった。即ち、図3で見られた黒色層と灰色層とが交互に積層されている領域を確認し、観察倍率を高くした場合でも観察視野には、常に黒色層、灰色層とその境界領域とが含まれるように配慮した。図4に便宜的に示した線は、夫々黒色層と灰色層とに対応する領域を区別するために使用した。更に、図5に図4の概略図を示した。図4より、積層構造における層間の境界領域で結晶格子縞が連続している領域があることを確認した。ここで、格子縞の連続性はすべての境界領域で成立する必要はなく、透過電子顕微鏡により層の境界領域を観察した時に、格子縞の連続性が認められる領域が存在すれば本願発明の優れた作用効果を得ることができる。図4には、左側の領域の1部に黒色のコントラストを示す領域が存在しているが、これは図5に示した黒色層、灰色層とは観察倍率が異なっている点から関連はない。更に、図4で観察した領域に配慮しながら、電子回折像を調べた。電子回折像を調べるにあたり、調査領域が、黒色層と灰色層との境界領域となるように配慮した。観察によって得られた電子回折像を図6に示す。図6では、略単一の電子回折像が得られた。この観察結果について考察を行うと、略単一の電子回折像が得られたことは、図7の概略図で示す様に、星印で示した黒色層の電子回折図形と、丸印で示した灰色層の電子回折図形とが一致していることを示し、これよりこの調査領域ではエピタキシャルな関係により格子縞が連続していることを確認した。従って、積層構造を有する結晶粒について層の境界領域の電子回折を行った結果、マクロ的には多結晶構造ではあるが、ミクロ的な観察により単結晶の様な形態をなしていることを見いだしたのである。更に、表3は本発明例9の積層構造の各層における組成分析を行った結果である。
(Cutting conditions)
Tool: Face mill Insert shape: SDE53 type special shape Cutting method: Center cut method Workpiece shape: width 100mm x length 250mm
Work material: SKD61, hardness, HRC45
Cutting depth: 1.5mm
Cutting speed: 100 m / min
1-blade feed amount: 0.6 mm / blade Cutting oil: None Table 2 shows the evaluation results, Reference Examples 1 to 4, Invention Examples 5 and Reference Examples 6 to 8, Invention Example 9, Reference Example 10, and this Invention Examples 11 to 14, Comparative Examples 15 to 28 , and Conventional Examples 29 to 35 are shown. From the results of Table 2, Invention Examples 5, 9 and 11 to 14 have a laminate structure in which the hard coating has a columnar structure and crystal grains have a composition difference in the C component, and at least the interlayer in the laminate structure. In the boundary region, there was a region where crystal lattice stripes were continuous, and it was confirmed that the cutting performance was excellent when the thickness T (nm) of each layer satisfied 0.1 ≦ T ≦ 30.4 . It was also confirmed that the range of the C content when C was added to the hard coating using two or more physical vapor deposition sources had an effect on the cutting performance. As shown in Examples 5, 9 and 11 to 14 of the present invention, the hard coating of the present invention can perform cutting which has been difficult to realize in the past. The hard film to which C was added by the graphite target shown in Example 9 of the present invention showed the best result in this evaluation. In forming the hard coating of Invention Example 9, the discharge output of the graphite target was set to 6.5 kW. As a result, when the hard coating was viewed as a whole, the C content was 4.8%, which was within the range of the C addition specified in the present invention. As shown in FIG. 1, as a result of observing the fracture surface structure of the hard film at a magnification of 15000, it was a columnar structure. Therefore, the mechanical strength with respect to the shearing direction was also obtained in cutting with high impact such as high feed machining. FIG. 2 shows the result of observing the fracture surface of the hard film of Example 9 of the present invention at a magnification of 20,000 with a transmission electron microscope, and the crystal grains having the columnar structure of the hard film had a laminated structure. FIG. 3 is a result of further enlarging a part of the crystal grain shown in FIG. 2 and observing it at a magnification of 200,000. The crystal grain is a laminate in which a plurality of black layers and gray layers having different contrasts exist. It was confirmed to have a structure. Here, each crystal grain is grown in the same direction, and can be confirmed by electron diffraction. Here, the correlation between the number of contrast stripes seen in the observation of FIG. 2 and the number of contrast stripes seen in the observation of FIG. No. Further, the thickness of the layer in the film thickness direction can be obtained from the contrast stripe pattern shown in FIG. As a result of the measurement, the layer thickness of each layer was about 3 to 4 nm. The observation magnification of the observation state in FIG. 3 was further increased, and the state of crystal lattice fringes was observed at 2 million times. The observation result at this time is shown in FIG. The observation region in FIG. 4 was advanced with reference to the observation form in FIG. That is, the region where the black layer and the gray layer seen in FIG. 3 are alternately stacked is confirmed, and even when the observation magnification is increased, the observation visual field always includes the black layer, the gray layer, and the boundary region. Considered to be included. For convenience, the lines shown in FIG. 4 were used to distinguish the areas corresponding to the black and gray layers, respectively. Further, FIG. 5 shows a schematic diagram of FIG. From FIG. 4, it was confirmed that there was a region where crystal lattice fringes continued in the boundary region between layers in the laminated structure. Here, it is not necessary for the continuity of the lattice fringes to be established in all the boundary regions, and if the region where the continuity of the lattice fringes is observed when the boundary region of the layer is observed with a transmission electron microscope, the excellent effect of the present invention can be obtained. An effect can be obtained. In FIG. 4, there is an area showing black contrast in a part of the left area, but this is not related to the black layer and the gray layer shown in FIG. 5 because the observation magnification is different. . Further, an electron diffraction image was examined while considering the region observed in FIG. In examining the electron diffraction image, consideration was given so that the investigation region was a boundary region between the black layer and the gray layer. The electron diffraction image obtained by observation is shown in FIG. In FIG. 6, a substantially single electron diffraction image was obtained. Considering this observation result, the fact that a substantially single electron diffraction image was obtained is indicated by a black layer electron diffraction pattern indicated by a star and a circle as shown in the schematic diagram of FIG. It was confirmed that the electron diffraction pattern of the gray layer coincided with this, and from this, it was confirmed that lattice fringes were continuous due to the epitaxial relationship in this investigation region. Therefore, as a result of electron diffraction in the boundary region between the layers of the crystal grains having a laminated structure, it was found that the macroscopically polycrystalline structure, but a single crystal-like form was formed by microscopic observation. It was. Further, Table 3 shows the results of composition analysis in each layer of the laminated structure of Example 9 of the present invention.
分析は透過電子顕微鏡に付設されるエネルギー分散型X線分析装置(以下、EDXと記す。)にて行った。分析した領域は、図4の観察による黒色層と灰色層との領域に配慮した。表3の分析領域を図4の点P、点Qに示す。分析結果から、添加したC成分の組成差が確認された。C含有量が10%を超えると、結晶組織が微細化するため、組成差は、最大でも10%以内に制御しなければならない。本発明例9は、放電させるグラファイト(C)の放電出力を6.5kWに設定したため、C含有量差は4.0%に制御できた。図8には、摩擦係数の測定結果を示す。摩擦係数の測定は、ボールオンディスク方式の摩擦摩耗試験機を用い、大気中600℃の高温下における摩擦係数の測定を行った。その結果、硬質皮膜にCを添加することにより、潤滑特性が大幅に向上することが確認した。Ti、Crなどの炭化物の形も潤滑特性に優れることが確認された。切削が安定し、しかも優れた切削性能を発揮させるために、ターゲット材としてはグラファイト(C)が適している傾向にあった。これより、溶着が激しく発生する金属の加工においては、本願発明の構成要素を満たす硬質皮膜によって十分に満足の行くが結果が得られた。今回の切削試験価で最も良好な本発明例9は、他の条件として、金型で見られる固定穴等、切削加工においては断続となる部位の加工も行った。その結果、適正な膜厚を有した積層構造を形成していたため、硬質皮膜の靭性が著しく向上し、激しい衝撃に対しても欠損することなく、安定した切削を行うことができた。これは、2種以上のプラズマ密度の異なる成膜方式を同時に使用すると、それぞれの放電により発生したプラズマから価数の異なるイオンが同時に基体表面に到達する。第1の層はAIP方式の蒸着源近傍で硬質結晶が主体に層をなし、第2の層はMS方式の蒸着源近傍で軟質結晶が主体の層をなして積層構造を有する。第1の層と第2の層とが混在して基体表面で層として堆積する。その際に、第2の層が第1の層の結晶間に存在するとクッション効果を示し、その結果、皮膜全体として靭性に富むようになる。このようにして被覆部材の耐衝撃特性が向上した。本願発明の特徴である優れた潤滑特性を有し、かつ耐欠損特性にも優れた硬質皮膜を得ることができた。 The analysis was performed with an energy dispersive X-ray analyzer (hereinafter referred to as EDX) attached to the transmission electron microscope. In the analyzed region, the region of the black layer and the gray layer observed in FIG. 4 was considered. The analysis areas in Table 3 are indicated by points P and Q in FIG. From the analysis results, the difference in composition of the added C component was confirmed. If the C content exceeds 10%, the crystal structure becomes finer, so the compositional difference must be controlled within 10% at the maximum. In Invention Example 9, since the discharge output of graphite (C) to be discharged was set to 6.5 kW, the C content difference could be controlled to 4.0%. FIG. 8 shows the measurement results of the friction coefficient. The coefficient of friction was measured using a ball-on-disk type friction and wear tester at a high temperature of 600 ° C. in the atmosphere. As a result, it was confirmed that by adding C to the hard coating, the lubrication characteristics are greatly improved. It was confirmed that the shape of carbides such as Ti and Cr is also excellent in lubrication characteristics. In order to achieve stable cutting and excellent cutting performance, graphite (C) tends to be suitable as a target material. As a result, in the processing of a metal in which welding is severely generated, a satisfactory result was obtained with a hard coating satisfying the constituent elements of the present invention. In Invention Example 9, which is the best in the cutting test value this time, as other conditions, parts such as fixing holes found in the mold were intermittently processed in the cutting process. As a result, since a laminated structure having an appropriate film thickness was formed, the toughness of the hard coating was remarkably improved, and stable cutting could be performed without loss even with severe impact. When two or more kinds of film forming methods having different plasma densities are used at the same time, ions having different valences simultaneously reach the substrate surface from the plasma generated by each discharge. The first layer is mainly composed of hard crystals in the vicinity of the AIP deposition source, and the second layer has a laminated structure in which soft crystals are mainly composed in the vicinity of the MS deposition source. The first layer and the second layer are mixed and deposited as a layer on the substrate surface. At that time, if the second layer exists between the crystals of the first layer, a cushioning effect is exhibited, and as a result, the entire film becomes rich in toughness. Thus, the impact resistance characteristics of the covering member were improved. It was possible to obtain a hard film having excellent lubrication characteristics, which is a feature of the present invention, and excellent in fracture resistance.
比較例15、16、18から20、24から26、28はC含有量が多く、30%以上であった。比較例20はC含有量が34%と多量に添加されていた。この破断面組織を確認した結果、図9に示す様なアモルファス状の微細組織になっていた。硬質皮膜の硬度も26GPa程度と軟質化傾向にあった。積層構造における1層の厚みが本願発明の規定範囲内であっても、切削特性に満足の行く結果は得られなかった。従って、C含有量の適正な制御も大切な項目であり、過酷な使用状況下に耐えるだけの機械的強度が得られなくなるのである。比較例17は、AIP方式とMS方式とを同時に放電させて得られた硬質皮膜が有する積層構造の1層の厚みが30.4nmを超えてしまった。この時、MS方式の蒸着源の放電出力は8.6kWであった。その結果、積層構造の各層の結晶格子縞に歪が発生し、格子縞が不連続となり硬質皮膜の結晶組織が微細化し早期摩耗に至った。比較例23は、硬質皮膜のC含有量が7.0%、積層構造の1層の厚みが30.6nmであり、成膜時に使用する反応ガスを0.8Paに設定したため、破断面組織が厚膜方向に分断されていた。C添加の効果によってある程度の切削性能は得られたものの、切削初期に発生する溶着の抑制には不十分であった。比較例21、22は、夫々の成膜で使用したSiC、Cを放電させるときの放電出力を0.2kWに落として被覆した。その結果、積層構造における1層の厚みは夫々確認限界に近い0.2nm、0.8nmであった。得られたC含有量は、XPS分析などの分析装置を使用してもCの検出が不可能なほど少量であった。そのため、切削初期の溶着が激しく発生した。特に比較例22は火花が発生し、評価を途中で中止した。硬質皮膜へのC含有量、結合状態や積層周期となる1層の厚みを制御することは、大切なことである。 In Comparative Examples 15, 16, 18 to 20, 24 to 26, and 28, the C content was large and was 30% or more. In Comparative Example 20, the C content was as large as 34%. As a result of confirming the fracture surface structure, an amorphous microstructure as shown in FIG. 9 was obtained. The hardness of the hard film was also about 26 GPa and was in a softening tendency. Even if the thickness of one layer in the laminated structure is within the specified range of the present invention, a satisfactory result in cutting characteristics was not obtained. Therefore, proper control of the C content is also an important item, and mechanical strength sufficient to withstand severe use conditions cannot be obtained. In Comparative Example 17, the thickness of one layer of the laminated structure of the hard coating obtained by discharging the AIP method and the MS method simultaneously exceeded 30.4 nm. At this time, the discharge output of the MS deposition source was 8.6 kW. As a result, distortion occurred in the crystal lattice fringes of each layer of the laminated structure, the lattice fringes became discontinuous, and the crystal structure of the hard coating became finer, leading to early wear. In Comparative Example 23, the hard film had a C content of 7.0%, the thickness of one layer of the laminated structure was 30.6 nm, and the reaction gas used during film formation was set to 0.8 Pa. It was divided in the thick film direction. Although some cutting performance was obtained by the effect of addition of C, it was insufficient for suppressing welding occurring at the initial stage of cutting. In Comparative Examples 21 and 22, the discharge output when discharging SiC and C used in the respective film formations was reduced to 0.2 kW and the coating was performed. As a result, the thickness of one layer in the laminated structure was 0.2 nm and 0.8 nm, which were close to the confirmation limit, respectively. The obtained C content was so small that C could not be detected even using an analyzer such as XPS analysis. Therefore, intense welding occurred at the initial stage of cutting. In particular, in Comparative Example 22, a spark occurred, and the evaluation was stopped midway. It is important to control the C content in the hard film, the bonding state, and the thickness of one layer that is the lamination cycle.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005246502A JP4780642B2 (en) | 2005-08-26 | 2005-08-26 | Hard coating and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005246502A JP4780642B2 (en) | 2005-08-26 | 2005-08-26 | Hard coating and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2007056356A JP2007056356A (en) | 2007-03-08 |
JP4780642B2 true JP4780642B2 (en) | 2011-09-28 |
Family
ID=37920084
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2005246502A Expired - Fee Related JP4780642B2 (en) | 2005-08-26 | 2005-08-26 | Hard coating and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4780642B2 (en) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE59106090D1 (en) * | 1991-01-21 | 1995-08-31 | Balzers Hochvakuum | Coated, highly wear-resistant tool and physical coating process for coating highly wear-resistant tools. |
JP3914687B2 (en) * | 2000-04-11 | 2007-05-16 | 住友電工ハードメタル株式会社 | Cutting tool and manufacturing method thereof |
-
2005
- 2005-08-26 JP JP2005246502A patent/JP4780642B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2007056356A (en) | 2007-03-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100937072B1 (en) | Hard coating having excellent wear resistance and oxidation resistance and target for forming the same, and hard coating having excellent high-temperature lubricating ability and wear resistance and target for forming the same | |
KR101701186B1 (en) | Cutting tool | |
KR101170396B1 (en) | Hard coating and its production method | |
JP5382580B2 (en) | Surface coated cutting tool | |
JP2008162008A (en) | Coated cutting tool | |
JP4304170B2 (en) | Hard coating | |
JP2011011287A (en) | Surface coated cutting tool | |
JP3963354B2 (en) | Coated cutting tool | |
JP2017064845A (en) | Surface coating cutting tool excellent in chipping resistance and abrasion resistance | |
EP3456867B1 (en) | Coated drill | |
JP4850189B2 (en) | Coated tool | |
JP6529262B2 (en) | Coated tools | |
JP6709536B2 (en) | Surface coated cutting tool with excellent hard coating layer and chipping resistance | |
JP2007046103A (en) | Hard film | |
JP4304179B2 (en) | Hard coating and method for producing the same | |
JP2019084671A (en) | Surface-coated cutting tool having hard coating layer exerting excellent chipping resistance and wear resistance | |
JP4780642B2 (en) | Hard coating and method for producing the same | |
JP4615259B2 (en) | Manufacturing method of hard coating | |
JP4663336B2 (en) | Hard coating and method for manufacturing hard coating | |
JP2007056324A (en) | Hard film | |
JP4304175B2 (en) | Hard coating and method for producing the same | |
JP2007056354A (en) | Hard film and its manufacturing method | |
JP2007056323A (en) | Hard film | |
JP2018144115A (en) | Surface-coated cutting tool having hard coating layer excellent in chipping resistance and peeling resistance | |
JP2006307242A (en) | Hard film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080718 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100826 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100831 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101018 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110223 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110310 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110527 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110527 |
|
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: 20110630 |
|
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: 20110630 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140715 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
LAPS | Cancellation because of no payment of annual fees |