JP4471686B2 - Cemented carbide penball with excellent corrosion resistance - Google Patents
Cemented carbide penball with excellent corrosion resistance Download PDFInfo
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- JP4471686B2 JP4471686B2 JP2004069360A JP2004069360A JP4471686B2 JP 4471686 B2 JP4471686 B2 JP 4471686B2 JP 2004069360 A JP2004069360 A JP 2004069360A JP 2004069360 A JP2004069360 A JP 2004069360A JP 4471686 B2 JP4471686 B2 JP 4471686B2
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- cemented carbide
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- 230000007797 corrosion Effects 0.000 title claims description 15
- 238000005260 corrosion Methods 0.000 title claims description 15
- 239000002131 composite material Substances 0.000 claims description 21
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 4
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 239000000976 ink Substances 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 15
- 239000011651 chromium Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Pens And Brushes (AREA)
Description
本発明はボールペン用の耐食性に優れる超硬合金製ペンボールに関する。その中でも特に水溶性インクを用いる水性ボールペン用の超硬合金製ペンボールに関する。 The present invention relates to a cemented carbide pen ball excellent in corrosion resistance for a ballpoint pen. In particular, the present invention relates to a cemented carbide penball for a water-based ballpoint pen that uses water-soluble ink.
超硬合金製ペンボールは硬さが高いため摩耗しにくく、ボールペン用として優れた性能を発揮するが、長年使用する間にインクにより結合相が徐々に腐食してボール形状が変化し、ボールペンの書き味が低下してしまう。超硬合金製ペンボールの結合相の耐食性を向上させた従来技術として、ＷＣ−Ｃｏ合金に炭化クロムを添加した超硬合金製ペンボールがある（例えば、特許文献１参照。）。また、ＷＣ−Ｃｒ3Ｃ2−Ｃｏ合金にＶＣを添加した超硬合金製ペンボールがある（例えば、特許文献２参照。）。さらに、ＷＣ−ＴｉＣ−Ｎｉ合金の結合相に、Ｎｉ、Ｍｏ、Ｃｒを含有させる超硬合金製ペンボールがある（例えば、特許文献３参照。）。 Cemented carbide penballs are hard to wear out and exhibit excellent performance for ballpoint pens, but during many years of use, the binder phase gradually corrodes by ink and the shape of the ball changes. Written taste will deteriorate. As a conventional technique for improving the corrosion resistance of the binder phase of a cemented carbide penball, there is a cemented carbide penball in which chromium carbide is added to a WC-Co alloy (for example, see Patent Document 1). In addition, there is a cemented carbide pen ball in which VC is added to a WC—Cr 3 C 2 —Co alloy (for example, see Patent Document 2). Further, there is a cemented carbide pen ball containing Ni, Mo, Cr in the binder phase of the WC-TiC-Ni alloy (see, for example, Patent Document 3).
近年、改良されたインク、特に水溶性インクは超硬合金の結合相を腐食しやすいため、従来の超硬合金製ペンボールでは、要求性能に十分に応えられなくなってきた。そこで、本発明はインクに対し耐食性に優れる超硬合金製ペンボールの提供を目的とする。 In recent years, improved inks, particularly water-soluble inks, tend to corrode the cemented carbide binder phase, and conventional cemented carbide penballs have been unable to adequately meet the required performance. Accordingly, an object of the present invention is to provide a cemented carbide pen ball that is excellent in corrosion resistance to ink.
インクは染料に由来する有機電解質を含むため、Ｃｏを主成分とする金属からなる結合相は腐食しやすい。腐食により結合相が優先的に除去されると、ＷＣからなる硬質相の一部が脱落して表面粗さが粗くなってインク切れを招き、筆記中の書き味が低下する。さらに腐食が進むと硬質相の脱落が多くなり、ボールと軸との隙間が大きくなり、インクの染み出しや漏れが生じる。 Since the ink contains an organic electrolyte derived from a dye, a binder phase made of a metal containing Co as a main component is easily corroded. When the binder phase is preferentially removed due to corrosion, a part of the hard phase composed of WC falls off, the surface roughness becomes rough, ink is run out, and writing quality during writing is lowered. As the corrosion further progresses, the hard phase drops off, the gap between the ball and the shaft increases, and ink oozes out and leaks.
本発明者らは、腐食によるペン先のボール沈み問題を解決するため種々検討した結果、ＮｉおよびＣｏの１種または２種とＣｒとＷとＣからなりＣを２５〜５０モル％含有する（Ｃｒ，Ｎｉ，Ｗ）7Ｃ3などの複合炭化物相を析出形成させ，局部的な腐食による超硬合金製ペンボールの形状変化を防止し、インクの染み出しや漏れを無くすことができるという知見を得た。 As a result of various investigations to solve the ball sinking problem of the nib due to corrosion, the inventors of the present invention are composed of one or two of Ni and Co, Cr, W, and C, and contain 25 to 50 mol% of C ( The knowledge that precipitation of complex carbide phases such as (Cr, Ni, W) 7 C 3 prevents the shape change of cemented carbide penballs due to local corrosion and eliminates ink leakage and leakage. Got.
すなわち、本発明の耐食性に優れる超硬合金製ペンボールは、ＮｉおよびＣｏのうち１種または２種とＣｒとＷとＣを主成分としてＣを２５〜５０モル％含有する複合炭化物相：１〜２５体積％と、Ｎｉおよび／またはＣｏを主成分とする結合相：３〜２３体積％と、ＷＣからなる硬質相：残部とで構成されることを特徴とする。 That is, the cemented carbide penball excellent in corrosion resistance according to the present invention is a composite carbide phase containing 25 to 50 mol% of C with one or two of Ni and Co, Cr, W and C as main components: ˜25% by volume, a binder phase mainly composed of Ni and / or Co: 3 to 23% by volume, and a hard phase composed of WC: the balance.
本発明の超硬合金製ペンボールの複合炭化物相は、ＮｉおよびＣｏの１種または２種とＣｒとＷとＣを主成分として、複合炭化物相全体に対してＣを２５〜５０モル％含有する複合炭化物相である。本発明において、ＮｉおよびＣｏの１種または２種とＣｒとＷとＣを主成分とする複合炭化物相とは、ＮｉおよびＣｏの１種または２種とＣｒとＷとＣとを合計で９０重量％以上含む複合炭化物相を示し、残部としてＴｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，Ｍｏの中の少なくとも１種を１０重量％未満含んでもよい。具体的には、（Ｃｒ，Ｎｉ，Ｗ）7Ｃ3、（Ｃｒ，Ｃｏ，Ｗ）7Ｃ3、（Ｃｒ，Ｎｉ，Ｃｏ，Ｗ）7Ｃ3などを挙げることができる。複合炭化物相の結晶型は、立方晶相と異なりＮａＣｌ構造ではなく、複合炭化物相は、インク、特に水溶性インクに対して腐食しにくい性質を持つ。複合炭化物相は、硬質相および立方晶相を取り込むように大きな斑状に分布している。このため結合相の腐食が進み硬質相、立方晶相の脱落が生じても，斑状に分布している複合炭化物相は腐食しにくいためマクロにはボール形状が維持され、インク染み出しや漏れを抑制することができる。 The composite carbide phase of the cemented carbide penball of the present invention contains one or two of Ni and Co, Cr, W, and C as main components, and contains 25 to 50 mol% of C with respect to the entire composite carbide phase. It is a composite carbide phase. In the present invention, one or two kinds of Ni and Co, and a composite carbide phase mainly composed of Cr, W, and C are a total of 90 kinds of one or two kinds of Ni and Co, Cr, W, and C. A composite carbide phase containing at least% by weight is shown, and the balance may contain less than 10% by weight of at least one of Ti, Zr, Hf, V, Nb, Ta, and Mo. Specifically, (Cr, Ni, W) 7 C 3 , (Cr, Co, W) 7 C 3 , (Cr, Ni, Co, W) 7 C 3 and the like can be mentioned. Unlike the cubic phase, the crystal form of the composite carbide phase is not an NaCl structure, and the composite carbide phase has a property that it is difficult to corrode with respect to ink, particularly water-soluble ink. The composite carbide phase is distributed in large spots so as to incorporate a hard phase and a cubic phase. For this reason, even if the corrosion of the binder phase progresses and the hard phase and cubic phase fall off, the complex carbide phase distributed in patches is difficult to corrode, so the ball shape is maintained in the macro, and ink seepage and leakage are prevented. Can be suppressed.
複合炭化物相の大きさの平均は、硬質相の平均粒径の３倍〜２５０μｍが好ましく、具体的には、２〜２５０μｍが好ましい。これは、２μｍ未満であるとボール外径を維持する効果が少なく、２５０μｍを超えると強度が低下するためである。その中でも５〜１５０μｍがさらに好ましく、１０〜４０μｍがさらに好ましい。複合炭化物相は、超硬合金製ペンボール全体に対して１体積％未満であると、十分な効果を発揮せず、２５体積％を超えると超硬合金製ペンボールの強度が低下するため、１〜２５体積％と定めた。 The average size of the composite carbide phase is preferably 3 to 250 [mu] m of the average particle size of the hard phase, specifically 2 to 250 [mu] m. This is because if it is less than 2 μm, the effect of maintaining the outer diameter of the ball is small, and if it exceeds 250 μm, the strength decreases. Among these, 5 to 150 μm is more preferable, and 10 to 40 μm is more preferable. If the composite carbide phase is less than 1% by volume with respect to the entire cemented carbide penball, the sufficient effect is not achieved, and if it exceeds 25% by volume, the strength of the cemented carbide penball decreases. It was defined as 1 to 25% by volume.
本発明の超硬合金製ペンボールの結合相は、Ｎｉおよび／またはＣｏを主成分とする結合相である。Ｎｉおよび／またはＣｏを主成分とする結合相とは、Ｎｉ、Ｃｏ、Ｎｉ−Ｃｏ合金およびこれらの金属に周期律表４ａ、５ａ、６ａ族元素、炭素、窒素の中の少なくとも１種が０．１〜５０重量％固溶した合金を示す。結合相が、超硬合金製ペンボール全体に対して３体積％未満では靭性が低く、２３体積％を超えると十分な耐摩耗性が得られない。そのため、結合相は３〜２３体積％と定めた。 The binder phase of the cemented carbide pen ball of the present invention is a binder phase mainly composed of Ni and / or Co. The binder phase containing Ni and / or Co as a main component means that Ni, Co, Ni—Co alloys and these metals contain at least one of the periodic table 4a, 5a, and 6a group elements, carbon, and nitrogen. .1 to 50% by weight of solid solution alloy. If the binder phase is less than 3% by volume relative to the entire cemented carbide pen ball, the toughness is low, and if it exceeds 23% by volume, sufficient wear resistance cannot be obtained. Therefore, the binder phase is determined to be 3 to 23% by volume.
本発明の超硬合金製ペンボールの硬質相はＷＣからなり、超硬合金製ペンボールの硬さを上げ、耐摩耗性を向上させる作用がある。 The hard phase of the cemented carbide penball of the present invention is made of WC, and has the effect of increasing the hardness of the cemented carbide penball and improving the wear resistance.
本発明の超硬合金製ペンボールの硬質相の一部を置換して、立方晶相を超硬合金製ペンボール全体に対して０．１〜２０体積％含有させると、インクのノリを改善するため好ましい。立方晶相は、周期律表４ａ、５ａ、６ａ族元素の炭化物、窒化物およびこれらの相互固溶体の中から選ばれた少なくとも１種の立方晶相でありＮａＣｌ構造を有する。具体的には、（Ｗ，Ｔｉ）Ｃ、（Ｗ，Ｔａ，Ｔｉ）Ｃ、（Ｗ，Ｔｉ，Ｔａ，Ｎｂ）Ｃなどを挙げることができる。立方晶相が０．１体積％未満では、その効果が少なく、２０体積％を超えると超硬合金製ペンボールの強度が低下するため、０．１〜２０体積％が好ましい。その中でも２〜１６体積％が好ましい。 Replacing a part of the hard phase of the cemented carbide penball of the present invention and containing the cubic phase in an amount of 0.1 to 20% by volume based on the entire cemented carbide penball improves the ink paste. Therefore, it is preferable. The cubic phase is at least one cubic phase selected from carbides, nitrides, and mutual solid solutions of the elements 4a, 5a, and 6a of the periodic table, and has a NaCl structure. Specific examples include (W, Ti) C, (W, Ta, Ti) C, (W, Ti, Ta, Nb) C, and the like. If the cubic phase is less than 0.1% by volume, the effect is small, and if it exceeds 20% by volume, the strength of the cemented carbide pen ball is lowered, so 0.1-20% by volume is preferable. Among these, 2 to 16% by volume is preferable.
超硬合金製ペンボールのビッカース硬さＨｖを１８００〜２３００とすると加工時の変形を低減させることができるため好ましい。 It is preferable to set the Vickers hardness Hv of the cemented carbide penball to 1800 to 2300 because deformation during processing can be reduced.
本発明の超硬合金製ペンボールの製造方法について、超硬合金製ペンボールに添加するＣｒは、金属クロム、炭化クロム、窒化クロムまたはクロムを含有する化合物などいかなる形態で添加してもよい。結合相の主成分であるＣｏ、Ｎｉについては、Ｃｏ粉末、Ｎｉ粉末またはＣｏ−Ｎｉ合金粉末のいずれでもよいが、粉末の平均粒径は０．５〜１．５μｍが好ましい。ＷＣ粉末は、平均粒径０．３〜２μｍが好ましい。また、ＷＣを除く周期律表４ａ、５ａ、６ａ族元素の炭化物、窒化物、炭窒化物の粉末は平均粒径０．５〜４μｍが好ましい。このような原料粉末を配合し、湿式ボールミルにて混合、粉砕、パラフィン添加したのち乾燥、造粒する。その後、脱ワックス工程を経て、真空または不活性ガス中で焼結を行なう。焼結後の冷却過程で、１２５０〜１３５０℃の温度範囲で２時間以上の定温処理を不活性ガス中で行なうと複合炭化物相を所望の形状に析出させることができる。定温処理時間を長くすると複合炭化物相が成長し、複合炭化物相の大きさが増大する。 In the method for producing a cemented carbide penball of the present invention, Cr added to the cemented carbide penball may be added in any form such as metallic chromium, chromium carbide, chromium nitride, or a compound containing chromium. Co and Ni which are the main components of the binder phase may be any of Co powder, Ni powder or Co—Ni alloy powder, but the average particle size of the powder is preferably 0.5 to 1.5 μm. The WC powder preferably has an average particle size of 0.3 to 2 μm. In addition, the carbides, nitrides, and carbonitride powders of the periodic table 4a, 5a, and 6a group elements excluding WC preferably have an average particle size of 0.5 to 4 μm. Such raw material powders are blended, mixed in a wet ball mill, pulverized, added with paraffin, dried and granulated. After that, sintering is performed in a vacuum or an inert gas through a dewaxing process. In the cooling process after sintering, if a constant temperature treatment is performed in an inert gas at a temperature range of 1250 to 1350 ° C. for 2 hours or more, the composite carbide phase can be precipitated in a desired shape. When the constant temperature treatment time is increased, the composite carbide phase grows and the size of the composite carbide phase increases.
本発明の超硬合金製ペンボールの一実施例の断面組識観察を図１に示す。これは、本発明の超硬合金製ペンボールの一実施例の鏡面研磨面を８０℃に加熱した２０重量％塩酸水溶液に２４時間浸してエッチングし、光学顕微鏡で観察したもので、黒色の部分が結合相、灰色の部分がＷＣからなる硬質相、白色の部分が複合炭化物相を示す。組識中の斑状部分は、硬質相とそれを取り込みながら析出した複合炭化物相を示す。この斑状部分の大きさを測定することで、複合炭化物相の大きさを測定できる。 FIG. 1 shows a cross-sectional texture observation of one embodiment of the cemented carbide penball of the present invention. This shows that the mirror-polished surface of one embodiment of the cemented carbide penball of the present invention was etched by immersing it in a 20 wt% hydrochloric acid aqueous solution heated to 80 ° C. for 24 hours and observed with an optical microscope. Indicates a binder phase, a gray portion indicates a hard phase composed of WC, and a white portion indicates a composite carbide phase. The mottled portion in the tissue shows a hard phase and a composite carbide phase that precipitates while incorporating the hard phase. By measuring the size of the patchy portion, the size of the composite carbide phase can be measured.
本発明の超硬合金製ペンボールは、長期間にわたって優れた書き味が得られる。これは、複合炭化物相を形成させることで、硬質相、立方晶相が脱落しなくなったためであり、ボール沈みが無くなりインクの染み出しや漏れの問題を解決できた。書き味の低下とボール沈みを防止することで、ボールペンの寿命を伸ばすことが可能となる。 With the cemented carbide penball of the present invention, excellent writing quality can be obtained over a long period of time. This is because the formation of the composite carbide phase prevented the hard phase and the cubic phase from falling off, eliminating the ball sink and solving the problems of ink bleeding and leakage. It is possible to extend the life of the ball-point pen by preventing the writing taste and the ball sinking.
市販の平均粒径２μｍのＣｒ3Ｃ2粉末、ＴｉＣ粉末、Ｍｏ2Ｃ粉末、平均粒径１μｍのＮｉ粉末、Ｃｏ粉末、表１に示す平均粒径のＷＣ粉末を用意する。表１に示す配合組成に配合した後、湿式ボールミルにて混合、粉砕、パラフィン添加したのち乾燥、造粒する。その後、脱ワックス工程を経て、真空中で１４５０℃、１時間保持の焼結を行なった。焼結後、比較品については不可性ガス雰囲気で冷却したが、発明品については、焼結後の冷却過程の途中で、不活性ガス雰囲気で１３００℃にて２時間以上保持する定温処理を行った。 A commercially available Cr 3 C 2 powder, TiC powder, Mo 2 C powder, Ni powder, Co powder having an average particle diameter of 1 μm, and WC powder having an average particle diameter shown in Table 1 are prepared. After blending to the blending composition shown in Table 1, the mixture is mixed, pulverized and added with paraffin by a wet ball mill, and then dried and granulated. Thereafter, through a dewaxing step, sintering was performed in vacuum at 1450 ° C. for 1 hour. After sintering, the comparative product was cooled in an inferior gas atmosphere, but the invention product was subjected to a constant temperature treatment in an inert gas atmosphere at 1300 ° C. for 2 hours or longer during the cooling process after sintering. It was.
上記のようにして作製した発明品および通常の方法で製造した従来品について、試料中に存在する各相の存在比率および複合炭化物相の大きさを測定した。その結果を表２に示す。また、各試料のビッカース硬さ（Ｈｖ）を測定した結果を表２に示す。 For the inventive product produced as described above and the conventional product produced by the usual method, the abundance ratio of each phase present in the sample and the size of the composite carbide phase were measured. The results are shown in Table 2. Table 2 shows the results of measuring the Vickers hardness (Hv) of each sample.
発明品と比較品の超硬合金製ペンボールの表面粗さＲａが０．００２μｍになるまで加工した後、ボールペンのペン先にセットし、連続筆記試験によりインク切れについての評価およびボール沈み評価を表３に示す。 After processing until the surface roughness Ra of the inventive cemented carbide penball is 0.002 μm, set it on the pen tip of the ballpoint pen, and evaluate the ink out and ball sink by continuous writing test. Table 3 shows.
試験条件
荷重：２．２Ｎ
筆記速度：０．８ｍ／ｓｅｃ
筆記距離：２５００ｍ螺旋筆記
筆記角度：６５度
Test condition load: 2.2N
Writing speed: 0.8m / sec
Writing distance: 2500m Spiral writing angle: 65 degrees
表３の結果から分かるように、発明品のいずれも、長期間にわたって優れた書き味が得られた。ボール沈みが無くなりインクの染み出しを生じにくく、ボールペンの寿命が長くなった。それに対して、比較品はＣｏやＮｉが腐食し、硬質相、立方晶相が脱落して表面粗さが粗くなるため、インク切れを招き、筆記中の書き味が低下した。さらにペン先のボール径が腐食により小さくなることでボールの沈みも大きくなりインクの染み出しや漏れがあった。 As can be seen from the results in Table 3, excellent writing quality was obtained over a long period of time for all of the invention products. Ball sinking disappeared and ink bleed-out hardly occurred, and the life of the ballpoint pen was extended. In contrast, Co and Ni were corroded, the hard phase and the cubic phase were dropped and the surface roughness was roughened, leading to ink shortage and poor writing during writing. Further, as the ball diameter of the nib becomes smaller due to corrosion, the sinking of the ball also increases, and ink oozes out and leaks.
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| JP2004069360A JP4471686B2 (en) | 2004-03-11 | 2004-03-11 | Cemented carbide penball with excellent corrosion resistance |
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| CN102423979A (en) * | 2011-08-25 | 2012-04-25 | 张勇 | Hard alloy ball bead for gel pen and production method thereof |
| JP6182848B2 (en) * | 2012-10-30 | 2017-08-23 | ぺんてる株式会社 | Ball for ballpoint pen |
| JP6303276B2 (en) * | 2013-03-28 | 2018-04-04 | ぺんてる株式会社 | Ball for ballpoint pen |
| JP2020185713A (en) * | 2019-05-14 | 2020-11-19 | 三菱鉛筆株式会社 | Aqueous ball-point pen |
| WO2023095713A1 (en) | 2021-11-26 | 2023-06-01 | 株式会社パイロットコーポレーション | Writing ball, method for manufacturing writing ball, and ballpoint pen with writing ball |
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