JP4277264B2 - Tool member with excellent high-temperature strength characteristics and method for producing the same - Google Patents
Tool member with excellent high-temperature strength characteristics and method for producing the same Download PDFInfo
- Publication number
- JP4277264B2 JP4277264B2 JP2003327038A JP2003327038A JP4277264B2 JP 4277264 B2 JP4277264 B2 JP 4277264B2 JP 2003327038 A JP2003327038 A JP 2003327038A JP 2003327038 A JP2003327038 A JP 2003327038A JP 4277264 B2 JP4277264 B2 JP 4277264B2
- Authority
- JP
- Japan
- Prior art keywords
- tool member
- tool
- grain size
- oxide
- powder
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000013078 crystal Substances 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 26
- 238000005496 tempering Methods 0.000 claims description 24
- 238000010791 quenching Methods 0.000 claims description 18
- 230000000171 quenching effect Effects 0.000 claims description 18
- 229910001566 austenite Inorganic materials 0.000 claims description 15
- 238000003701 mechanical milling Methods 0.000 claims description 13
- 229910001315 Tool steel Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 10
- 238000005728 strengthening Methods 0.000 description 9
- 229910000997 High-speed steel Inorganic materials 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 150000001247 metal acetylides Chemical class 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000760 Hardened steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000161 steel melt Substances 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Heat Treatment Of Articles (AREA)
Description
本発明は、プレス金型、ダイカスト金型、押出し工具、切削工具、パンチおよびダイスといった多種の工具部材に最適な、高温強度を改善させた工具部材およびその製造方法に関するものである。 The present invention relates to a tool member improved in high-temperature strength and suitable for a variety of tool members such as a press die, a die-casting die, an extrusion tool, a cutting tool, a punch and a die, and a manufacturing method thereof.
従来、温熱間工具や切削工具等の分野には、ＪＩＳ鋼種であるＳＫＤ６１系の合金工具鋼やＳＫＨ２系の高速度鋼が用いられていた。通常、このような工具部材は、その工具鋼素材を焼きなまし（低硬度）状態で製品形状に機械加工し、その後に焼入れ焼戻しして硬さ調整が行なわれ、仕上げ加工を経て製品工具にされる。（プリハードン鋼の場合は焼入れ焼戻し状態で製品形状に機械加工・仕上げ加工を経て製品工具にされる。） Conventionally, SKD61-based alloy tool steel and SKH2-based high-speed steel, which are JIS steel types, have been used in the fields of hot tools and cutting tools. Usually, such a tool member is machined into a product shape in the annealed (low hardness) state of the tool steel material, and then the hardness is adjusted by quenching and tempering, and then the finished product is processed into a product tool. . (In the case of pre-hardened steel, the product shape is machined and finished into a product tool in the quenched and tempered state.)
そして、このような部材において、例えば高速度鋼の機械的性質を改善する手法が提案されている（特許文献１参照）。この提案は炭化物径および結晶粒径を微細化して室温強度を上昇させるという点で優れたものである。
上述した特許文献１に開示される手法は、室温強度を上昇させる点では有利であるものの、高温強度の点では、強度を担う炭化物が高温で成長し強度を維持できなくなることが懸念される。工具を用いて製造する製品のコストを低減するためには、使用する工具の長寿命化を達成し、高負荷化に耐える工具部材を開発する必要があり、その上で上記の高温強度の向上は大きな課題となる。 Although the method disclosed in Patent Document 1 described above is advantageous in terms of increasing the room temperature strength, there is a concern that in terms of high temperature strength, carbides that bear the strength grow at high temperatures and cannot maintain the strength. In order to reduce the cost of products manufactured using tools, it is necessary to develop a tool member that can extend the life of the tool used and withstand high loads, and then improve the high-temperature strength described above. Is a big challenge.
本発明の目的は、従来の技術に対し、強度を担う炭化物が高温で成長し強度を維持できなくなるという問題を解決して、さらに結晶粒を微細化して強度（高温強度含む）を向上させた工具部材およびその製造方法を提供することである。 The object of the present invention is to solve the problem that the carbide responsible for the strength grows at a high temperature and cannot maintain the strength, and further refines the crystal grains to improve the strength (including the high temperature strength). It is providing a tool member and its manufacturing method.
本発明者は、強度を担う粒子として主に導入されていた炭化物が、高温で成長し強度を維持できなくなるという問題を検討し、高温でも安定であまり成長しない酸化物を微細に分散させることを採用した。そして、最適組成および製造方法を鋭意研究することによって、炭化物量を減少させても強度（高温強度含む）および靭性を大きく改善できることを見いだし本発明に到達した。 The present inventor studied the problem that carbides mainly introduced as particles responsible for strength grow at high temperatures and cannot maintain strength, and finely disperse oxides that are stable at high temperatures and do not grow much. Adopted. And by intensively studying the optimum composition and manufacturing method, the inventors have found that the strength (including high temperature strength) and toughness can be greatly improved even if the amount of carbide is reduced, and have reached the present invention.
すなわち、本発明は、焼入れ焼戻しされた工具部材であって、質量％でＣ：０．１〜３．０％、Ｃｒ：１．０〜１８．０％を含むＪＩＳにより工具鋼に分類される組成に、Ｙ ２ Ｏ ３ からなる酸化物が０．３〜５．０体積％混合された組成よりなり、組織中には、最大径が１５ｎｍ以下で１μｍ ３ あたり２００００個以上の酸化物が分散し、かつ旧オーステナイト粒界による結晶粒径が最大０．５μｍである高温強度特性に優れた工具部材である。 That is, the present invention is a tool member that has been quenched and tempered, and is classified as tool steel by JIS including C: 0.1 to 3.0% and Cr: 1.0 to 18.0% by mass. The composition consists of a composition in which 0.3 to 5.0% by volume of an oxide composed of Y 2 O 3 is mixed. In the structure, the maximum diameter is 15 nm or less, and 20000 or more oxides are dispersed per 1 μm 3. In addition, the tool member is excellent in high-temperature strength characteristics and has a maximum crystal grain size of 0.5 μm due to prior austenite grain boundaries .
そして、本発明の高温強度特性に優れた工具部材の製造方法は、質量％でＣ：０．１〜３．０％、Ｃｒ：１．０〜１８．０％を含むＪＩＳにより工具鋼に分類される組成に、Ｙ ２ Ｏ ３ からなる酸化物が０．３〜５．０体積％になるように混合された工具鋼粉末と酸化物粉末の混合粉末をメカニカルミリングした後、固化成形し、焼入れ焼戻しして、最大径が１５ｎｍ以下で１μｍ ３ あたり２００００個以上の酸化物が分散し、かつ旧オーステナイト粒界による結晶粒径が最大０．５μｍである組織を得るものである。また、必要に応じて本発明の工具部材の製造方法は、焼入れ焼戻しの前に、機械加工することができ、所定の形状の工具部材に加工するものである。 And the manufacturing method of the tool member excellent in the high temperature strength characteristic of this invention classify | categorized into tool steel by JIS containing C: 0.1-3.0% and Cr: 1.0-18.0% in the mass%. After mechanically milling the mixed powder of the tool steel powder and the oxide powder mixed so that the oxide made of Y 2 O 3 is 0.3 to 5.0% by volume in the composition to be solidified, solidified and molded, By quenching and tempering , a structure is obtained in which the maximum diameter is 15 nm or less, 20000 or more oxides are dispersed per 1 μm 3 , and the crystal grain size due to prior austenite grain boundaries is 0.5 μm at maximum . Moreover, the manufacturing method of the tool member of this invention can be machined before hardening and tempering as needed, and is processed into the tool member of a predetermined shape.
本発明によれば、工具部材の結晶粒を非常に微細化でき、かつ高温強度特性を飛躍的に改善することができる。よって、製品コスト低減のために、使用する工具の長寿命化・高負荷化に耐える工具部材の実用化にとって欠くことのできない技術となる。 According to the present invention, the crystal grains of the tool member can be made very fine and the high-temperature strength characteristics can be dramatically improved. Therefore, in order to reduce the product cost, it becomes an indispensable technique for practical use of a tool member that can withstand long life and high load of a tool to be used.
上述したように、本発明の重要な特徴は、工具部材の強度、とりわけ高温強度の向上手段として、その組織中に酸化物を微細に分散させる手法を採用したことにある。 As described above, an important feature of the present invention is that a technique for finely dispersing oxide in the structure is adopted as means for improving the strength of the tool member, particularly the high temperature strength.
最初に本発明の根幹をなす酸化物を微細に分散させる理由について説明する。酸化物を微細に分散させることによって、母材の結晶粒成長を効果的に抑制することができる。結晶粒を微細に維持することで、結晶粒微細化強化を利用することができ、従来材で強度を担っていた炭化物による析出強化を代替することができる。析出強化を利用して強度を上昇させると靭性が劣化する傾向にあるのに対して、本発明の結晶粒微細化強化では靭性をあまり損なわないかまたは改善できる作用があるため、工具部材の靭性改善にとっては有効である。 First, the reason why the oxide that forms the basis of the present invention is finely dispersed will be described. By finely dispersing the oxide, crystal grain growth of the base material can be effectively suppressed. By maintaining the crystal grains fine, the grain refinement strengthening can be used, and the precipitation strengthening by the carbide that has been responsible for the strength of the conventional material can be substituted. While increasing the strength using precipitation strengthening tends to deteriorate the toughness, the toughening of the crystal grain refinement of the present invention has the effect of not significantly impairing or improving the toughness. It is effective for improvement.
さらに、イットリウム系（Ｙ２Ｏ３）やチタン系（ＴｉＯ２）、アルミ系（Ａｌ２Ｏ３）といった酸化物は、通常、工具部材中に形成される炭化物に比べて、その高温での熱処理中や使用中でもあまり成長しないことから、従来材では炭化物の成長が起こって析出強化量が著しく減少するような高温域でも、結晶粒微細化強化を利用でき、飛躍的に高温強度を高めることができる。 Furthermore, oxides such as yttrium (Y 2 O 3 ), titanium (TiO 2 ), and aluminum (Al 2 O 3 ) are usually heat treated at higher temperatures than carbides formed in tool members. Since it does not grow so much even during use or in use, the conventional material can use grain refinement strengthening at a high temperature range where carbide growth occurs and the amount of precipitation strengthening is significantly reduced, dramatically increasing the high temperature strength. it can.
よって、上述の効果を有効に利用するためには、組織中に分散させる酸化物の大きさおよび個数密度を同時に調整することが重要となる。本願発明の工具部材の場合、その酸化物の分散状態は粒径２５ｎｍ以下の酸化物を１μｍ３あたり７５０個以上分散させるものであり、好ましくは酸化物自体の最大径が２５ｎｍ以下となるようにする。特に好ましくは、酸化物の最大径が１５ｎｍ以下で１μｍ３中に２００００個以上となるようにする。 Therefore, in order to effectively use the above effects, it is important to simultaneously adjust the size and number density of oxides dispersed in the structure. In the case of the tool member of the present invention, the dispersion state of the oxide is such that 750 or more oxides having a particle size of 25 nm or less are dispersed per 1 μm 3 , and preferably the maximum diameter of the oxide itself is 25 nm or less. To do. Particularly preferably, the maximum diameter of the oxide is 15 nm or less and 20000 or more in 1 μm 3 .
なお、酸化物の分散状態の評価は、透過型電子顕微鏡を用いた薄膜観察の結果から行なえば良い。該手段によって組織中に酸化物が分散していることが確認でき、例えば４０万倍の暗視野像（図１）および元素分布マッピングを行ないＦｅの透過電子線のみで結像したエレメントイメージ（図２）をそれぞれ１視野用いることで、酸化物の大きさ（最大径）および個数密度を得ることができる。Ｆｅのエレメントイメージを用いることで酸化物の個数を精度良く観察できる。 Note that the oxide dispersion state may be evaluated from the results of thin film observation using a transmission electron microscope. By this means, it can be confirmed that oxides are dispersed in the structure. For example, a dark field image (Fig. 1) of a magnification of 400,000 times and an element image (Fig. 1) imaged with only a transmission electron beam of Fe by performing element distribution mapping. By using 1 field of view 2), the size (maximum diameter) and number density of the oxide can be obtained. By using the Fe element image, the number of oxides can be accurately observed.
すなわち、暗視野像中の酸化物の最長方向の長さを計り、ＡＳＴＭの切断法から公称粒径を求めてそれを粒径とすれば良く、最も大きな酸化物の最長方向の長さについてその公称粒径を最大径とすれば良い。また、Ｆｅのエレメントイメージ中の直径２ｍｍ以上に写っている酸化物の個数を数えて、それを観察体積（観察面積×薄膜試料厚さ）で割って酸化物の個数密度とすれば良い。なお、図１，２の電子像は、後の（実施例１）で評価した供試材Ａの、５００℃で焼戻したときのものである。 That is, the longest length of the oxide in the dark field image is measured, the nominal particle size is obtained from the ASTM cutting method, and it is used as the particle size. The nominal particle diameter may be the maximum diameter. Further, the number of oxides in the Fe element image having a diameter of 2 mm or more may be counted and divided by the observation volume (observation area × thin film sample thickness) to obtain the oxide number density. In addition, the electronic images of FIGS. 1 and 2 are those when the specimen A evaluated in the following (Example 1) is tempered at 500 ° C.
以下に、本発明の効果を最大限に活用するのに好ましい、工具部材の成分や結晶粒径を限定した理由について詳細に説明する。 The reason why the components of the tool member and the crystal grain size are limited to make the best use of the effects of the present invention will be described below.
ＣやＣｒは焼入れ性を高める元素であり、本発明の根幹をなす焼入れ焼戻しされた工具部材を製造する上で非常に重要である。このような焼入れ性を高める元素は、本発明の工具部材として成立させるために、必ず十分な焼入れ性が確保できるように成分調整される必要がある。 C and Cr are elements that enhance the hardenability, and are very important in producing a quenched and tempered tool member that forms the basis of the present invention. In order to establish such a hardenability element as the tool member of the present invention, it is necessary to adjust the components so as to ensure sufficient hardenability.
・Ｃ：０．１〜３．０質量％
Ｃは、一部が基地中に固溶して強度を付与し、一部は炭化物を形成することで耐摩耗性や耐焼付き性を高める重要な元素であることから、本発明の対象を温熱間工具や切削工具といった工具部材とする場合には、特に本発明の有用性を向上させる。また、固溶した侵入型原子であるＣは、ＣｒなどのＣと親和性の大きい置換型原子と共添加した場合、Ｉ（侵入型原子）−Ｓ（置換型原子）効果；溶質原子の引きずり抵抗として作用し高強度化する作用も期待される。ただし、含有量が０．１質量％未満では工具部材として十分な硬さ、耐摩耗性を確保できなくなる。他方、過度の添加は靭性や熱間強度の低下を招くため上限を３．０質量％とする。
C: 0.1-3.0% by mass
C is an important element that enhances the wear resistance and seizure resistance by partly forming a solid solution in the base to impart strength, and partly forming carbides. In the case of a tool member such as an interstitial tool or a cutting tool, the usefulness of the present invention is particularly improved. Further, when C, which is a solid interstitial atom, is co-added with a substitution atom having a high affinity with C, such as Cr, I (interstitial atom) -S (substitution atom) effect; solute atom dragging The effect of increasing the strength by acting as a resistance is also expected. However, if the content is less than 0.1% by mass, sufficient hardness and wear resistance as a tool member cannot be secured. On the other hand, excessive addition causes a decrease in toughness and hot strength, so the upper limit is made 3.0% by mass.
・Ｃｒ：１．０〜１８．０質量％
Ｃｒは焼入れ性を高めて、また、炭化物を形成して基地の強化や耐摩耗性を向上させる効果を有することから、本発明の対象を温熱間工具や切削工具といった工具部材とする場合には、特に本発明の有用性を向上させる元素であり、少なくとも１．０質量％添加する必要がある。ただし、過度の添加は焼入れ性や熱間強度の低下を招くため、上限を１８．０質量％とする。
・ Cr: 1.0-18.0 mass%
Since Cr has the effect of improving hardenability and forming carbides to improve the reinforcement of the base and wear resistance, when the object of the present invention is a tool member such as a hot tool or a cutting tool In particular, it is an element that improves the usefulness of the present invention, and it is necessary to add at least 1.0% by mass. However, excessive addition causes a decrease in hardenability and hot strength, so the upper limit is made 18.0% by mass.
・旧オーステナイト粒界による結晶粒径が最大１０μｍ以下
焼入れ焼戻しされて使用される工具部材にとって、本発明の酸化物の導入による結晶粒微細化効果は、その焼入れ焼戻し後の“旧オーステナイト粒界による結晶粒径”に反映されている。通常の工具部材の場合、その旧オーステナイト粒界による結晶粒径は小さくても２０μｍ程度であるが、結晶粒微細化による強化量が大きくなるのは平均結晶粒径１０μｍ以下の領域である。結晶粒微細化強化を利用して強化を図るため、本発明にかかる工具部材の結晶粒径は最大１０μｍ以下とする。好ましくは５μｍ以下、さらに好ましくは１μｍ以下とする。
The maximum grain size of the prior austenite grain boundaries is 10 μm or less. For tool members used after quenching and tempering, the effect of crystal grain refinement by the introduction of the oxide of the present invention is due to the “old austenite grain boundaries after quenching and tempering” This is reflected in the “crystal grain size”. In the case of a normal tool member, the crystal grain size due to the prior austenite grain boundary is about 20 μm at the minimum, but the amount of strengthening due to crystal grain refinement is large in the region where the average crystal grain size is 10 μm or less. In order to reinforce using the refinement of crystal grains, the tool member according to the present invention has a maximum crystal grain size of 10 μm or less. The thickness is preferably 5 μm or less, more preferably 1 μm or less.
なお、本発明の旧オーステナイト粒界による結晶粒径の評価は、透過型電子顕微鏡を用いた薄膜観察の結果（例えば４万倍の暗視野像を４視野）から行なえばよい。すなわち、暗視野像中のもっとも大きな結晶粒の最長方向の長さを計り、ＡＳＴＭの切断法から公称粒径を求めて、それを最大粒径とすればよい。図３に示す暗視野像は、後の（実施例１）で評価した供試材Ａの、５００℃で焼戻したときのものである。 The evaluation of the crystal grain size by the prior austenite grain boundary of the present invention may be performed from the result of thin film observation using a transmission electron microscope (for example, 40000 times dark field image is 4 fields). That is, the length in the longest direction of the largest crystal grain in the dark field image is measured, the nominal grain size is obtained from the ASTM cutting method, and it is set as the maximum grain size. The dark field image shown in FIG. 3 is the one when the specimen A evaluated in the following (Example 1) is tempered at 500 ° C.
また、本発明の工具部材の成分組成は、質量％でＣ：０．１〜３．０％、Ｃｒ：１．０〜１８．０％を含む以外には、例えば必要に応じてＭｏ，Ｗ，Ｖ，Ｎｉ，Ｃｏなどを添加することができ、ＪＩＳに記載されるような工具鋼組成の適用が可能である。 Moreover, the component composition of the tool member of the present invention includes, for example, Mo and W as necessary, except that C: 0.1 to 3.0% and Cr: 1.0 to 18.0% are contained in mass%. , V, Ni, Co, etc. can be added, and the tool steel composition as described in JIS can be applied.
次に、本発明の工具部材の製造方法について述べる。
本発明の微細な結晶粒組織を有した工具部材の達成には、例えばメカニカルミリング法で作製した粉末を固化成形する手法が適用でき、これは最終的には焼入れ焼戻しされることで結晶粒の成長が起こり得る工具部材の製造方法に好ましい手法である。すなわち、質量％でＣ：０．１〜３．０％、Ｃｒ：１．０〜１８．０％を含むＪＩＳにより工具鋼に分類される組成にＹ ２ Ｏ ３ からなる酸化物が０．３〜５．０体積％になるように混合された工具鋼粉末と酸化物粉末の混合粉末をメカニカルミリングした後、固化成形し、焼入れ焼戻しして、最大径が１５ｎｍ以下で１μｍ ３ あたり２００００個以上の酸化物が分散し、かつ旧オーステナイト粒界による結晶粒径が最大０．５μｍである組織を得る工具部材の製造方法であり、必要に応じてその焼入れ焼戻しの前に機械加工することで、所定の形状の工具部材とすることができる。
Next, the manufacturing method of the tool member of this invention is described.
In order to achieve the tool member having a fine grain structure of the present invention, for example, a method of solidifying and forming a powder produced by a mechanical milling method can be applied, and this is finally quenched and tempered. This is a preferred method for a method of manufacturing a tool member that can grow. That is, an oxide composed of Y 2 O 3 in a composition classified as tool steel by JIS containing C: 0.1 to 3.0% and Cr: 1.0 to 18.0% by mass is 0.3. After mechanical milling of mixed powder of tool steel powder and oxide powder mixed to be ~ 5.0% by volume, solidified and molded, quenched and tempered , maximum diameter is 15 nm or less, and 20000 or more per 1 μm 3 Is a manufacturing method of a tool member that obtains a structure having a maximum crystal grain size of 0.5 μm due to the prior austenite grain boundaries, by machining before quenching and tempering as necessary, A tool member having a predetermined shape can be obtained.
従来、アトライタやボールミル等の装置によるメカニカルミリング法は、そのミリングに供される原料粉末の結晶粒径を微細にできる手段として使用されており、工具鋼の分野でも提案されている（特許文献１参照）。本発明も、このメカニカルミリング法による処理後粉末を固化成形するものであるが、ここで本発明の場合、メカニカルミリング前の原料粉末としてさらに酸化物粉末を混ぜた混合粉末とし、原子レベルまで機械的に混合することで、高温でも安定した酸化物粒子による結晶粒微細化強化と分散強化を達成できる。 Conventionally, a mechanical milling method using an apparatus such as an attritor or a ball mill has been used as a means for reducing the crystal grain size of a raw material powder used for the milling, and has also been proposed in the field of tool steel (Patent Document 1). reference). The present invention also solidifies and molds the powder after the treatment by the mechanical milling method. In the present invention, the mixed powder is further mixed with the oxide powder as the raw material powder before the mechanical milling. By mixing them together, it is possible to achieve grain refinement strengthening and dispersion strengthening with oxide particles that are stable even at high temperatures.
・酸化物：０．３〜５．０体積％
酸化物は高温でも熱的に安定なため、工具部材の熱処理時や高温での使用時の結晶粒成長を効果的に抑制する上で重要な物質であり、微細粒組織を維持するために最低０．３体積％は必要である。しかし酸化物の量が多すぎると固化成形時の成形性が悪くなることに加えて、工具部材の靭性劣化を招くため、上限を５．０体積％とする。
・ Oxide: 0.3-5.0% by volume
Since oxide is thermally stable even at high temperatures, it is an important material for effectively suppressing crystal grain growth during heat treatment of tool members and when used at high temperatures, and it is the minimum to maintain a fine grain structure. 0.3% by volume is necessary. However, if the amount of the oxide is too large, the formability during solidification molding is deteriorated and the toughness of the tool member is deteriorated. Therefore, the upper limit is set to 5.0% by volume.
次に、メカニカルミリング法によって処理された粉末は固化成形するが、粉末を固化成形し、後工程では焼入れ焼戻しする際の熱処理によって、結晶粒は成長する。つまり、本発明によって作製される工具部材の結晶粒径を微細にするためには、その原料となるメカニカルミリング法で作製した粉末の結晶粒径は微細であることが望ましい。そのため、メカニカルミリング法による粉末の結晶粒の超微細化は好ましくは平均で１００ｎｍ以下、さらに好ましくは５０ｎｍ以下である。 Next, although the powder processed by the mechanical milling method is solidified and formed, crystal grains grow by heat treatment when the powder is solidified and formed and quenched and tempered in a subsequent process. That is, in order to make the crystal grain size of the tool member produced by the present invention fine, it is desirable that the crystal grain size of the powder produced by the mechanical milling method as the raw material is fine. Therefore, the ultrafine refinement of the powder crystal grains by the mechanical milling method is preferably 100 nm or less on average, and more preferably 50 nm or less.
なお、固化成形手段には例えば焼結やＨＩＰ、温熱間圧延、温熱間押出し等の高温固化が適用でき、ＨＩＰや温熱間圧延、温熱間押出しが完全に緻密な材料を得易い点で好ましい。そして、その固化成形された素材については、後は必要であれば通常の鍛造・圧延工程、焼きなまし状態での機械加工を適用し、焼入れ焼戻しして工具部材に仕上げる。 Note that high-temperature solidification such as sintering, HIP, hot-rolling, and hot-extrusion can be applied to the solidification forming means, and HIP, hot-rolling, and hot-extrusion are preferable in that it is easy to obtain a completely dense material. The solidified material is then subjected to a normal forging / rolling process and machining in an annealed state, if necessary, and quenched and tempered to finish a tool member.
また、本発明の工具部材が焼入れ焼戻しのできる素材であることは、高温強度特性に優れた工具部材を製造する上でも非常に重要である。すなわち、高合金系の工具部材や、大きな工具にも十分に対応できるだけの、体積寸法が大きい工具部材を効率的に製造するためには、上記の固化成形時の温度が高いほど良い。しかし、９００℃を超えるような高温域では、鉄系の材料ではほとんどの成分系で相変態が起こり、結晶粒が成長してしまう。しかも、昇温時と降温時の二回の相変態が起こることによって、極端に大きな結晶粒サイズになってしまう。この点、焼入れできる素材の場合、結晶粒成長が起こる相変態は昇温時の一回のみとなり、降温時に結晶粒成長は起こらないことから微細な結晶粒サイズを維持でき、結晶粒微細化強化を利用できる。 In addition, the fact that the tool member of the present invention is a material that can be quenched and tempered is also very important in producing a tool member having excellent high-temperature strength characteristics. That is, in order to efficiently produce a tool member having a large volume dimension that can sufficiently handle a high-alloy tool member or a large tool, the higher the temperature during the above solidification molding, the better. However, in a high temperature range exceeding 900 ° C., phase transformation occurs in most component systems in iron-based materials, and crystal grains grow. Moreover, an extremely large crystal grain size is caused by two phase transformations at the time of temperature rise and temperature fall. In this regard, in the case of a material that can be hardened, the phase transformation in which crystal grain growth occurs is only once at the time of temperature increase, and since crystal grain growth does not occur at the time of temperature decrease, a fine crystal grain size can be maintained, and grain refinement strengthening Can be used.
表１に示した供試材Ａは、ガスアトマイズ法で作製した合金粉末と市販のＹ２Ｏ３酸化物粉末の混合粉末を遊星型ボールミル装置を用いて回転数２３００ｒｐｍで１００時間のメカニカルミリング処理によって作製した粉末である。組成はＳＫＤ６１に相当し、これにＹ２Ｏ３酸化物が全体積の３％になるよう添加されている。 Specimen A shown in Table 1 is a mechanical milling treatment of a mixed powder of an alloy powder produced by a gas atomizing method and a commercially available Y 2 O 3 oxide powder at a rotational speed of 2300 rpm for 100 hours using a planetary ball mill device. It is the produced powder. The composition corresponds to SKD61, and Y 2 O 3 oxide is added to this so as to be 3% of the total volume.
メカニカルミリングの条件は、その処理後粉末の平均結晶粒径が１００ｎｍ以下になるよう装置因子を調整しており、透過型電子顕微鏡を用いた観察（１０万倍の暗視野像を１視野）およびＸ線回折法による半価幅を利用して算出した供試材Ａの処理後粉末の平均結晶粒径は約３０ｎｍであった。 The mechanical milling conditions are such that the device factor is adjusted so that the average crystal grain size of the treated powder is 100 nm or less, observation using a transmission electron microscope (one field of 100,000 times dark field image) and The average crystal grain size of the treated powder of the sample material A calculated using the half width by the X-ray diffraction method was about 30 nm.
つぎに、供試材Ａの上記処理後粉末を金属製の容器に入れて１０００℃で圧延することで固化成形したのち、比較材として表１に別に準備したＳＫＤ６１溶製材と共に、ＳＫＤ６１の標準的な焼入れ焼戻し温度である１０２０℃での焼入れ処理と、５００℃および５５０℃での焼戻しを行った。そして、その焼入れ焼戻し後の旧オーステナイト粒径の最大結晶粒径、粒径２５ｎｍ以下の酸化物については、その最大径および単位体積当たりの個数、そして焼入れ状態および焼戻し後の硬さを測定した。結晶粒径の評価は透過型電子顕微鏡を用いた薄膜観察の結果（４万倍を４視野）から行った。酸化物の評価は透過型電子顕微鏡を用いた薄膜観察の結果（最大径：４０万倍の暗視野像を１視野、単位体積あたりの個数：４０万倍のＦｅのエレメントイメージを１視野）から行った。硬度測定はマイクロビッカース硬度計を用いて測定した。結果を表２に示す。 Next, the processed powder of the test material A is put in a metal container and solidified by rolling at 1000 ° C. Then, together with the SKD61 melted material prepared separately in Table 1 as a comparative material, the standard of SKD61 A quenching treatment at 1020 ° C., which is a quenching and tempering temperature, and tempering at 500 ° C. and 550 ° C. were performed. And about the maximum crystal grain size of the prior austenite grain size after the quenching and tempering, and the oxide having a grain size of 25 nm or less, the maximum diameter and the number per unit volume, the quenching state, and the hardness after tempering were measured. The crystal grain size was evaluated from the results of thin film observation using a transmission electron microscope (40,000 times 4 views). Oxide evaluation is based on the results of thin film observation using a transmission electron microscope (maximum diameter: one field of dark field image with a magnification of 400,000 times, number per unit volume: one element image of Fe with a magnification of 400,000 times) went. The hardness was measured using a micro Vickers hardness meter. The results are shown in Table 2.
供試材Ａの焼戻し組織は、焼戻し温度に関わらず、およそ０．１〜０．５μｍのサイズの旧オーステナイト結晶粒からなっており、その測定による最大の結晶粒径は０．５μｍであった。一方、溶製法で作製したＳＫＤ６１の焼戻し組織も焼戻し温度に関わらず、旧オーステナイト粒径は平均で２２μｍであり、その一般的な粒径である約２０μｍと比べて、本発明の結晶粒径は極めて微細である。また、供試材Ａの５００℃焼戻し材の酸化物の最大径は９．４ｎｍで１μｍ３当り１２３５７７個存在し、供試材Ａの５５０℃焼戻し材の酸化物の最大径は９．８ｎｍで１μｍ３当り１１８９０４個存在した。なお、両供試材の組織中に粒径２５ｎｍを越える酸化物は確認されなかった。 Regardless of the tempering temperature, the tempered structure of the test material A was composed of prior austenite crystal grains having a size of about 0.1 to 0.5 μm, and the maximum crystal grain size by the measurement was 0.5 μm. . On the other hand, the tempered structure of SKD61 produced by the melting method has an average austenite grain size of 22 μm on average regardless of the tempering temperature, and the crystal grain size of the present invention is about 20 μm, which is a general grain size. Very fine. In addition, the maximum oxide diameter of the tempered material of 500 ° C. of the sample material A is 9.4 nm and 123577 per 1 μm 3 exists, and the maximum diameter of the oxide of the tempered material of 550 ° C. of the sample material A is 9.8 nm. There were 118904 pieces per 1 μm 3 . In addition, oxides having a particle size exceeding 25 nm were not confirmed in the structures of both test materials.
一方、溶製法で作製したＳＫＤ６１の焼戻し材の組織中には１μｍを越える大きな酸化物（アルミナ系など）が極わずかに存在したが、粒径２５ｎｍ以下の酸化物は今回の手法では観察されなかった。 On the other hand, there was very little large oxide (such as alumina) exceeding 1 μm in the structure of the tempered material of SKD61 produced by the melting method, but no oxide having a particle size of 25 nm or less was observed by this method. It was.
そして、本発明材は、結晶粒微細化に起因して焼入れ硬さが非常に高く、さらに温熱間工具がよく使用される温度域でもある５００℃および５５０℃で焼戻しても硬さはほぼ維持されており、高硬度かつ高温強度に優れている。これに対して、比較材は焼戻し後に硬さがかなり低下していることがわかる。本発明材の場合、その焼入れ時の組織も調べたところ、およそ０．１〜０．５μｍのサイズの結晶粒（大角粒）であった。酸化物が非常に微細かつ多数存在することによって、高温での固化成形および焼入れ過程での結晶粒の成長抑制に加えて、焼戻し過程（使用過程）での結晶粒の成長も抑制できていた。 The material of the present invention has a very high quenching hardness due to the refinement of crystal grains, and the hardness is almost maintained even when tempering at 500 ° C. and 550 ° C., which is also a temperature range in which warm tools are often used. It is excellent in high hardness and high temperature strength. On the other hand, it can be seen that the comparative material has a considerably reduced hardness after tempering. In the case of the material of the present invention, the structure at the time of quenching was also examined. As a result, crystal grains (large-angle grains) having a size of about 0.1 to 0.5 μm were obtained. Due to the presence of very fine and numerous oxides, in addition to suppressing the growth of crystal grains in the solidification molding and quenching process at high temperature, the growth of crystal grains in the tempering process (use process) could be suppressed.
表３に示した供試材Ｂは、ガスアトマイズ法で作製した合金粉末と市販のＹ２Ｏ３酸化物粉末の混合粉末を遊星型ボールミル装置を用いて回転数２３００ｒｐｍで１００時間のメカニカルミリング処理によって作製した粉末である。組成は一次炭化物をほとんど含まない高速度鋼（以下マトリクス高速度鋼と記す）に相当し、これにＹ２Ｏ３酸化物が全体積の３％になるよう添加されている。メカニカルミリングの条件設定は（実施例１）に従うものであり、透過型電子顕微鏡を用いた観察（１０万倍の暗視野像を１視野）およびＸ線回折法による半価幅を利用して算出した供試材Ｂの処理後粉末の平均結晶粒径は約２０ｎｍであった。 Specimen B shown in Table 3 is a mechanical milling treatment of a mixed powder of an alloy powder produced by a gas atomizing method and a commercially available Y 2 O 3 oxide powder at a rotational speed of 2300 rpm for 100 hours using a planetary ball mill device. It is the produced powder. The composition corresponds to a high-speed steel containing almost no primary carbide (hereinafter referred to as matrix high-speed steel), to which Y 2 O 3 oxide is added so as to be 3% of the total volume. The mechanical milling conditions are set according to (Example 1), and are calculated using observation using a transmission electron microscope (one field of 100,000 times dark field image) and half width by X-ray diffraction method. The average crystal grain size of the processed powder of the test material B was about 20 nm.
つぎに、供試材Ｂの上記処理後粉末を、金属製の容器に入れて１０００℃で圧延することで固化成形したのち、比較材として表３に別に準備したマトリクス高速度鋼の溶製材と共に、該マトリクス高速度鋼の標準的な焼入れ焼戻し温度である１１４０℃での焼入れ処理と、５００℃および５５０℃での焼戻しを行った。そして、（実施例１）に同様にその焼入れ焼戻し後の旧オーステナイト粒径の最大の結晶粒径、粒径２５ｎｍ以下の酸化物については、その最大径および単位体積当たりの個数と、焼入れ状態および焼戻し後の硬さを測定した。結果を表４に示す。 Next, after the above-mentioned treated powder of the test material B is put in a metal container and rolled at 1000 ° C., it is solidified and molded, together with a matrix high-speed steel melt prepared separately in Table 3 as a comparative material The matrix high speed steel was subjected to quenching treatment at 1140 ° C., which is a standard quenching and tempering temperature, and tempering at 500 ° C. and 550 ° C. As in (Example 1), the maximum crystal grain size of the prior austenite grain size after quenching and tempering, and the oxide having a grain size of 25 nm or less, the maximum diameter, the number per unit volume, the quenching state, and The hardness after tempering was measured. The results are shown in Table 4.
供試材Ｂの焼戻し組織は、焼戻し温度に関わらず、およそ０．１〜０．４μｍのサイズの旧オーステナイト結晶粒からなっており、その測定による最大の結晶粒径は０．４μｍであった。一方、溶製法で作製したマトリクス高速度鋼の焼戻し組織も焼戻し温度に関わらず、旧オーステナイト粒径は平均で２２μｍであり、その一般的な粒径である約２０μｍと比べて、本発明の結晶粒径は極めて微細である。また、供試材Ｂの５００℃焼戻し材の酸化物の最大径は１０．２ｎｍで１μｍ３当り１０９９７１個存在し、供試材Ｂの５５０℃焼戻し材の酸化物の最大径は９．５ｎｍで１μｍ３当り１１４３５７個存在した。なお、両供試材の組織中に粒径２５ｎｍを越える酸化物は確認されなかった。 Regardless of the tempering temperature, the tempered structure of the test material B was composed of prior austenite crystal grains having a size of about 0.1 to 0.4 μm, and the maximum crystal grain size by the measurement was 0.4 μm. . On the other hand, the tempered structure of the matrix high-speed steel produced by the melting method also has a prior austenite grain size of 22 μm on average regardless of the tempering temperature. Compared with the typical grain size of about 20 μm, the crystal of the present invention The particle size is very fine. In addition, the maximum oxide diameter of the tempered material of 500 ° C. of the sample material B is 10.971 nm per 10 μm 3 at 10.2 nm, and the maximum diameter of the oxide of the 550 ° C. tempered material of the sample material B is 9.5 nm. There were 114357 per 1 μm 3 . In addition, oxides having a particle size exceeding 25 nm were not confirmed in the structures of both test materials.
一方、溶製法で作製したマトリクス高速度鋼の焼戻し材の組織中には１μｍを越える大きな酸化物（アルミナ系など）が極わずかに存在したが、粒径２５ｎｍ以下の酸化物は今回の手法では観察されなかった。 On the other hand, in the tempered material of matrix high-speed steel produced by the melting method, there were very few large oxides (such as alumina) exceeding 1 μm. Not observed.
そして、本発明材は、結晶粒微細化に起因して焼入れ硬さが非常に高く、さらに温熱間工具がよく使用される温度域でもある５００℃および５５０℃の焼戻し後にはむしろやや上昇している。これに対して、比較材は焼戻し後に硬さがかなり低下していることがわかる。なお、供試材Ｂの場合も、その焼入れ時の組織はおよそ０．１〜０．４μｍのサイズの結晶粒（大角粒）からなっていた。 The material of the present invention has a very high quenching hardness due to the refinement of crystal grains, and further increases slightly after tempering at 500 ° C. and 550 ° C., which is also a temperature range in which hot tools are often used. Yes. On the other hand, it can be seen that the comparative material has a considerably reduced hardness after tempering. In the case of Specimen B, the quenched structure was composed of crystal grains (large-angle grains) having a size of about 0.1 to 0.4 μm.
本発明によって、工具部材の結晶粒を非常に微細化し、かつ高温強度特性を飛躍的に改善することによって、従来材よりも非常に長寿命になるだけでなく、従来材では耐えられないような高負荷環境にも適用できる。 According to the present invention, the crystal grains of the tool member are made very fine and the high temperature strength characteristics are drastically improved, so that not only is the life much longer than that of the conventional material, but the conventional material cannot be tolerated. Applicable to high load environment.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003327038A JP4277264B2 (en) | 2003-05-13 | 2003-09-19 | Tool member with excellent high-temperature strength characteristics and method for producing the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003133882 | 2003-05-13 | ||
| JP2003327038A JP4277264B2 (en) | 2003-05-13 | 2003-09-19 | Tool member with excellent high-temperature strength characteristics and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004360062A JP2004360062A (en) | 2004-12-24 |
| JP4277264B2 true JP4277264B2 (en) | 2009-06-10 |
Family
ID=34067154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003327038A Expired - Fee Related JP4277264B2 (en) | 2003-05-13 | 2003-09-19 | Tool member with excellent high-temperature strength characteristics and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4277264B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5088532B2 (en) * | 2006-04-05 | 2012-12-05 | 日立金属株式会社 | High-strength tool with excellent softening and surface finish characteristics and manufacturing method thereof |
| WO2007119722A1 (en) * | 2006-04-11 | 2007-10-25 | Hitachi Metals, Ltd. | Process for producing steel material |
| JP5590496B2 (en) * | 2008-06-26 | 2014-09-17 | 日立金属株式会社 | Mold with excellent high-temperature strength and surface finish characteristics and method for producing the same |
| JP5896296B2 (en) * | 2011-06-24 | 2016-03-30 | 日立金属株式会社 | Manufacturing method of high-strength mold with excellent high-temperature softening resistance |
| CN104388819B (en) * | 2014-10-31 | 2016-06-29 | 新昌县大市聚镇海房机械厂 | A kind of powdered metallurgical material for cutting tool and preparation method thereof |
-
2003
- 2003-09-19 JP JP2003327038A patent/JP4277264B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004360062A (en) | 2004-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Suryanarayana et al. | Nanostructured materials and nanocomposites by mechanical alloying: an overview | |
| RU2324576C2 (en) | Nanocristallic metal material with austenic structure possessing high firmness, durability and viscosity, and method of its production | |
| DE69400848T2 (en) | Titanium aluminide alloys with good creep resistance | |
| JPWO2019220917A1 (en) | Laminated modeling hot tool and its manufacturing method, and metal powder for laminated modeling hot tool | |
| JP5110398B2 (en) | Iron-based sintered alloy, method for producing iron-based sintered alloy, and connecting rod | |
| EP0475101B1 (en) | High strength aluminum-based alloys | |
| DE69315492T2 (en) | Nitrogen-compressed aluminum-based sintered alloys and manufacturing process | |
| JP5590496B2 (en) | Mold with excellent high-temperature strength and surface finish characteristics and method for producing the same | |
| JP2007092117A (en) | High strength and low specific gravity aluminum alloy | |
| JP5212774B2 (en) | Hot tool steel excellent in toughness and high temperature strength and method for producing the same | |
| JP2019116688A (en) | Powder high speed tool steel | |
| JP4277264B2 (en) | Tool member with excellent high-temperature strength characteristics and method for producing the same | |
| JP6345945B2 (en) | Powdered high-speed tool steel with excellent wear resistance and method for producing the same | |
| JP6230885B2 (en) | α + β type titanium alloy and method for producing the same | |
| JP6930590B2 (en) | Alloy steel powder for powder metallurgy and iron-based mixed powder for powder metallurgy | |
| JP4764094B2 (en) | Heat-resistant Al-based alloy | |
| JP5088532B2 (en) | High-strength tool with excellent softening and surface finish characteristics and manufacturing method thereof | |
| JP4281857B2 (en) | Sintered tool steel and manufacturing method thereof | |
| JP4008597B2 (en) | Aluminum-based composite material and manufacturing method thereof | |
| JP5896296B2 (en) | Manufacturing method of high-strength mold with excellent high-temperature softening resistance | |
| JP2004219323A (en) | Method of evaluating iron base material | |
| Khalil et al. | Application of Al-Si Semi-solid Reaction for fabricating harmonic structured Al based alloy | |
| JP2005281768A (en) | Nanocrystal white cast iron powder having high hardness, tough nanocrystal white cast iron bulk material having high hardness and high strength and production method therefor | |
| JP2004339532A (en) | Method of producing tool steel | |
| JP2001073100A (en) | Fe-based sintered body, powder for producing Fe-based sintered body, and method for producing Fe-based sintered body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060810 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080624 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081114 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090105 |
|
| 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: 20090213 |
|
| 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: 20090226 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120319 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4277264 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: 20120319 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130319 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140319 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |