JP5877610B2 - Water-soluble processing oil composition for super finishing - Google Patents
Water-soluble processing oil composition for super finishing Download PDFInfo
- Publication number
- JP5877610B2 JP5877610B2 JP2012128195A JP2012128195A JP5877610B2 JP 5877610 B2 JP5877610 B2 JP 5877610B2 JP 2012128195 A JP2012128195 A JP 2012128195A JP 2012128195 A JP2012128195 A JP 2012128195A JP 5877610 B2 JP5877610 B2 JP 5877610B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- salt
- oil composition
- sodium
- superfinishing
- 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.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 47
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 20
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 159000000000 sodium salts Chemical class 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 239000007769 metal material Substances 0.000 claims description 9
- 239000001488 sodium phosphate Substances 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 9
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 8
- 235000011008 sodium phosphates Nutrition 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 7
- 235000011009 potassium phosphates Nutrition 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 6
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 6
- 229910021538 borax Inorganic materials 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 claims description 4
- MSACGCINQCCHBD-UHFFFAOYSA-N 2,4-dioxo-4-(4-piperidin-1-ylphenyl)butanoic acid Chemical compound C1=CC(C(=O)CC(=O)C(=O)O)=CC=C1N1CCCCC1 MSACGCINQCCHBD-UHFFFAOYSA-N 0.000 claims description 4
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 claims description 4
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 claims description 4
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 150000004677 hydrates Chemical class 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- -1 hydrogen salt Chemical class 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- MXWVLJGUIUZJSQ-UHFFFAOYSA-N [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] MXWVLJGUIUZJSQ-UHFFFAOYSA-N 0.000 description 1
- XLLZUKPXODPNPP-UHFFFAOYSA-N [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] XLLZUKPXODPNPP-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
本発明は、炭素鋼、特殊鋼等の金属材料のホーニング加工、超仕上げ加工として使用するのに好適な、超仕上げ加工用水溶性加工油剤組成物に関する。 The present invention relates to a water-soluble processing oil composition for superfinishing suitable for use in honing and superfinishing of metal materials such as carbon steel and special steel.
小径ベアリング等の精密な研摩加工を行う場合、ホーニング加工または超仕上げ（スーパーフェニッシュとも呼ぶ）加工を行う。超仕上げ加工は精密加工方法の一種である。加工圧力が低いために、最初工作物の表面が粗い間は砥粒による切削作用を行うが、面が平滑になってくると、自動的に目詰まりを起こし、磨き作用を行なうようになり、容易に鏡面が得られる（機械工学便覧 日本機械学会編 Ｂ２−１４９頁）。一度目詰まりを起こしても、次の工作物の表面の粗さの山頂がとがったままの状態のため、砥石表面が削られ目詰まりが解消し、切削作用を行うようになる。加工中に適度な目詰まりが発生し、それが解消されるというサイクルをとるのが超仕上げ加工の特徴であり、他の研削加工と異なる点である。この超仕上げ加工には、不水溶性加工油剤を用いるのが一般的である。
しかしながら、不水溶性加工油剤では、加工熱、摩擦熱により火災が発生する危険性が高い。また、工場内にオイルミストが充満し、作業環境が悪化する。
水溶性加工油剤を用いると砥石がより激しく目詰まりし、目詰まりすると砥石が隠れ、砥石の摩耗量は減少するが、研削量が減少し加工が進まなくなる。更に、次の工作物の表面粗さによる目詰まりの解消が十分に行われなくなるため、より目詰まりが進行し、正常に加工できなくなる事があるからである。
この対策として、水を含有する不水加工油剤（含水不水）（特許文献１）、アルコールとアルキルエーテルを含有した水溶性加工油剤（特許文献２）が提案されている。
その含水不水加工油剤では、加工熱等により水が蒸発するが、実加工ラインでの水含有量の管理は困難なため、引火する危険は避けられなかった。また、水含有量を多くすると粘度上昇が大きくなるため、加工時の油剤持ち去り量が多くなるという問題があった。アルコールとアルキルエーテルを含有する水溶性加工油剤では、十分な加工精度が得られていない。
When performing precise polishing of small diameter bearings, honing or super-finishing (also called super finish) is performed. Superfinishing is a kind of precision machining method. Since the processing pressure is low, the cutting action with abrasive grains is performed while the surface of the workpiece is rough at first, but when the surface becomes smooth, clogging occurs automatically and the polishing action is performed. A mirror surface can be easily obtained (Handbook of Mechanical Engineering, edited by the Japan Society of Mechanical Engineers, B2-149). Even if clogging occurs once, the crest of the surface of the next workpiece remains sharp, so the surface of the grindstone is removed, clogging is eliminated, and cutting action is performed. The characteristic of superfinishing is that it takes a cycle in which moderate clogging occurs during processing and is eliminated, which is different from other grinding processes. For this superfinishing process, a water-insoluble processing oil is generally used.
However, water-insoluble processing oils have a high risk of fire due to processing heat and frictional heat. In addition, the factory is filled with oil mist, which deteriorates the working environment.
When the water-soluble processing oil is used, the grindstone is clogged more severely, and when clogged, the grindstone is hidden and the wear amount of the grindstone is reduced, but the grinding amount is reduced and the processing does not proceed. Furthermore, since clogging due to the surface roughness of the next workpiece is not sufficiently eliminated, clogging further proceeds and normal machining may not be possible.
As countermeasures, non-water processing oil containing water (hydrous non-water) (Patent Document 1) and water-soluble processing oil containing alcohol and alkyl ether (Patent Document 2) have been proposed.
In the water-containing non-water processing oil, water evaporates due to processing heat or the like, but it is difficult to manage the water content in the actual processing line, so the risk of ignition is inevitable. In addition, when the water content is increased, the increase in viscosity is increased, so that there is a problem that the amount of oil taken away during processing increases. With water-soluble processing oils containing alcohol and alkyl ether, sufficient processing accuracy is not obtained.
従って、本発明により、砥石の目詰まりの少ない、超仕上げ加工用水溶性加工油剤組成物を提供する。 Accordingly, the present invention provides a water-soluble processing oil composition for super-finishing processing with less clogging of a grindstone.
不水溶性油剤の目詰まりが少ないのは、水溶性油剤のエマルションのような分散層がなく、すべて均一層から構成されているためである。（切削・研削油剤その選択と使い方 竹山秀彦 監修 工業調査会 １５６頁）
本発明者らは、特定の無機塩を選定し、かつｐＨを１０以上の水溶性加工油剤組成物とすることにより、砥石の目詰まりを抑え、オイルミストによる作業環境の低下及び加工熱や摩擦熱による火災の発生を抑制した、超仕上げ加工を可能とした。
すなわち、本発明により、以下の組成物、該組成物を使用する金属材料加工品の製造方法及び該製造方法により得られた金属材料加工品を提供する：
（１）組成物の全量を基準として１〜４０質量％の塩と、
組成物の全量を基準として６０〜９９質量％の水とを含有し、
前記塩が、リン酸、炭酸、ケイ酸及びホウ酸のナトリウム塩またはカリウム塩からなる群から選ばれる少なくとも２種のみからなる無機塩からなり、
組成物の５％希釈液の２５℃におけるｐＨが１０〜１４である、超仕上げ加工用水溶性加工油剤組成物。
（２）前記無機塩が、リン酸、炭酸又はホウ酸のナトリウム塩またはカリウム塩からなる群から選ばれる少なくとも２種のみからなる前記（１）項記載の超仕上げ用加工用水溶性加工油剤組成物。
（３）前記無機塩が、リン酸又はホウ酸のナトリウム塩またはカリウム塩からなる群から選ばれる少なくとも２種のみからなる前記（１）項記載の超仕上げ用加工用水溶性加工油剤組成物。
（４）前記無機塩が、リン酸ナトリウムと、リン酸カリウムと、ホウ酸ナトリウムと、ホウ酸カリウムとの組み合わせである前記（１）項記載の超仕上げ用加工用水溶性加工油剤組成物。
（５）前記無機塩が、リン酸二水素ナトリウム・２水和物と、リン酸三カリウムと、四ホウ酸ナトリウム・１０水和物と、四ホウ酸カリウム・４水和物との組み合わせである前記（１）項記載の超仕上げ用加工用水溶性加工油剤組成物。
（６）前記無機塩の少なくとも１種が、リン酸ナトリウム又はリン酸カリウム塩である前記（１）項記載の超仕上げ用加工用水溶性加工油剤組成物。
（７）前記無機塩の１種が、正塩である、前記（１）項記載の超仕上げ用加工用水溶性加工油剤組成物。
（８）一つの無機塩の含有量が０．１質量％以上である、前記（１）〜（７）のいずれか１項記載の超仕上げ用加工用水溶性加工油剤組成物。
（９）更なる水で２〜２０％に希釈した前記（１）〜（８）のいずれか１項記載の超仕上げ用加工用水溶性加工油剤組成物。
（１０）前記（１）〜（９）のいずれか１項記載の超仕上げ加工用水溶性加工油剤組成物を使用して、砥石により金属材料を加工する工程を含む、金属材料加工品の製造方法。
（１１）前記（１０）記載の製造方法により得られた金属材料加工品。
The reason why the water-insoluble oil agent is not clogged is that there is no dispersed layer like an emulsion of the water-soluble oil agent, and all the layers are composed of a uniform layer. (Selection and usage of cutting and grinding fluids Hidehiko Takeyama, Industrial Research Committee, page 156)
By selecting a specific inorganic salt and using a water-soluble processing oil composition having a pH of 10 or more, the present inventors suppress clogging of the grindstone, reduce the working environment due to oil mist, and reduce processing heat and friction. Super-finishing is possible, suppressing the occurrence of fire due to heat.
That is, the present invention provides the following composition, a method for producing a processed metal material using the composition, and a processed metal material obtained by the production method:
(1) 1 to 40% by weight of salt based on the total amount of the composition;
60 to 99% by weight of water based on the total amount of the composition,
The salt comprises an inorganic salt consisting of at least two selected from the group consisting of sodium salt or potassium salt of phosphoric acid, carbonic acid, silicic acid and boric acid,
A water-soluble processing oil composition for superfinishing, wherein the 5% dilution of the composition has a pH of 10 to 14 at 25 ° C.
(2) The water-soluble processing oil composition for superfinishing processing according to (1), wherein the inorganic salt is composed of at least two selected from the group consisting of sodium salt or potassium salt of phosphoric acid, carbonic acid or boric acid. .
(3) The water-soluble processing oil composition for superfinishing processing according to (1), wherein the inorganic salt is composed of at least two kinds selected from the group consisting of sodium salt or potassium salt of phosphoric acid or boric acid.
(4) The water-soluble processing oil composition for superfinishing processing according to (1), wherein the inorganic salt is a combination of sodium phosphate, potassium phosphate, sodium borate, and potassium borate.
(5) The inorganic salt is a combination of sodium dihydrogen phosphate dihydrate, tripotassium phosphate, sodium tetraborate decahydrate, and potassium tetraborate tetrahydrate. A water-soluble processing oil composition for processing for superfinishing as described in (1) above.
(6) The water-soluble processing oil composition for superfinishing processing according to (1), wherein at least one of the inorganic salts is sodium phosphate or potassium phosphate.
(7) The water-soluble processing oil composition for superfinishing processing according to (1), wherein one of the inorganic salts is a normal salt.
(8) The water-soluble processing oil composition for superfinishing processing according to any one of (1) to (7), wherein the content of one inorganic salt is 0.1% by mass or more.
(9) The water-soluble processing oil composition for superfinishing processing according to any one of (1) to (8), diluted to 2 to 20% with further water.
(10) A method for producing a processed metal material product, comprising a step of processing a metal material with a grindstone using the water-soluble processing oil composition for superfinishing according to any one of (1) to (9). .
(11) A processed metal material obtained by the production method according to (10).
本発明の超仕上げ用水溶性加工油剤組成物は、従来の水溶性加工油と比べ、目詰まりが少なく、目詰まり防止に優れる。本発明の水溶性加工油剤組成物はまた、不水溶性加工油剤と比べて火災の危険性が少ない。本発明の組成物はまた、加工精度が良く鏡面が得られるという優れた効果を有する。本発明の組成物は防錆性にも優れる。 The water-soluble processing oil composition for superfinishing of the present invention has less clogging and excellent clogging prevention compared to conventional water-soluble processing oils. The water-soluble processing oil composition of the present invention also has a low risk of fire compared to a water-insoluble processing oil. The composition of the present invention also has an excellent effect that a mirror surface is obtained with good processing accuracy. The composition of the present invention is also excellent in rust prevention.
＜塩＞
本発明において用いることのできる塩は、リン酸、炭酸、ケイ酸又はホウ酸のナトリウム塩またはカリウム塩の少なくとも２種のみからなる無機塩からなる。無機塩の組み合わせは、例えば、リン酸のナトリウムとリン酸のカリウム塩との組み合わせのように、一種類の酸のナトリウム塩及びカリウム塩でもよいし、リン酸のナトリウム塩と炭酸のナトリウム塩との組み合わせのように、異なる種類の酸のナトリウム塩又はカリウム塩でもよい。炭酸ナトリウムと炭酸水素ナトリウムのように、一種類の酸のナトリウム塩又はカリウム塩の組み合わせでもよい。
本発明において用いる無機塩は、正塩でも、酸性塩（水素塩）でも、塩基性塩でもよい。正塩が好ましい。
本発明において用いる無機塩はまた、無水物でも水和物でも良い。
本発明の組成物は、他の無機塩、例えば塩酸塩、硝酸塩、硫酸塩を含まない。錆が発生し易いためである。ナトリウム及びカリウム以外のアルカリ金属の塩は、使用することが難しい。リチウム塩は水の溶解度が低いためである。ルビジウム塩及びセシウム塩は一般的な工業グレードがなく、入手困難であるためである。他方、アルカリ土類金属は水に不溶のため使用できない。
本発明の組成物はまた、アミン塩又はアンモニウム塩等の有機塩も含まない。
<Salt>
The salt that can be used in the present invention consists of an inorganic salt consisting of at least two of sodium salt or potassium salt of phosphoric acid, carbonic acid, silicic acid or boric acid. The combination of inorganic salts may be, for example, a single acid sodium salt and potassium salt, such as a combination of sodium phosphate and potassium phosphate, or sodium phosphate and sodium carbonate. The sodium salt or potassium salt of different types of acids may be used. A combination of a sodium salt or a potassium salt of one kind of acid may be used, such as sodium carbonate and sodium hydrogen carbonate.
The inorganic salt used in the present invention may be a normal salt, an acidic salt (hydrogen salt), or a basic salt. A normal salt is preferred.
The inorganic salt used in the present invention may be an anhydride or a hydrate.
The composition of the present invention does not contain other inorganic salts such as hydrochloride, nitrate, sulfate. This is because rust is likely to occur. Alkali metal salts other than sodium and potassium are difficult to use. This is because lithium salts have low water solubility. This is because rubidium salt and cesium salt have no general industrial grade and are difficult to obtain. On the other hand, alkaline earth metals cannot be used because they are insoluble in water.
The compositions of the present invention also do not contain organic salts such as amine salts or ammonium salts.
リン酸のナトリウム塩またはカリウム塩としては、リン酸二水素ナトリウム、リン酸水素二ナトリウム、リン酸三ナトリウム、リン酸二水素カリウム、リン酸水素二カリウム、リン酸三カリウム及びこれらの水和物などがあげられる。このうち、リン酸二水素ナトリウム、リン酸三カリウム及びこれらの水和物が好ましい。リン酸二水素ナトリウム・２水和物、リン酸三カリウムがより好ましい。
炭酸のナトリウム塩またはカリウム塩としては、炭酸水素ナトリウム、炭酸ナトリウム、炭酸二水素カリウム、炭酸水素カリウム、炭酸カリウム及びこれらの水和物などがあげられる。炭酸ナトリウム、炭酸カリウムが好ましい。
ケイ酸のナトリウム塩としては、JIS K 1408-1966に定められたケイ酸ソーダ１号、２号、３号、メタ珪酸ソーダ１種、２種及びこれらの水和物などがあげられる。ケイ酸のカリウム塩としては、K2O・ｎSiO2と表した時、n=２〜４のケイ酸のカリウム塩があげられる。メタ珪酸ソーダ１種が好ましい。
ホウ酸のナトリウム塩またはカリウム塩としては、メタホウ酸ナトリウム、四ホウ酸ナトリウム、八ホウ酸ナトリウム、メタホウ酸カリウム、四ホウ酸カリウム、八ホウ酸カリウム及びこれらの水和物などがあげられる。四ホウ酸ナトリウム、四ホウ酸カリウム及びこれらの水和物が好ましい。四ホウ酸ナトリウム・１０水和物、四ホウ酸カリウム・４水和物がより好ましい。
Examples of sodium salt or potassium salt of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate and hydrates thereof. Etc. Of these, sodium dihydrogen phosphate, tripotassium phosphate and hydrates thereof are preferable. Sodium dihydrogen phosphate dihydrate and tripotassium phosphate are more preferable.
Examples of the sodium salt or potassium salt of carbonic acid include sodium hydrogen carbonate, sodium carbonate, potassium dihydrogen carbonate, potassium hydrogen carbonate, potassium carbonate, and hydrates thereof. Sodium carbonate and potassium carbonate are preferred.
Examples of the sodium salt of silicic acid include sodium silicate No. 1, No. 2, No. 3, No. 1 and 2 kinds of sodium metasilicate as defined in JIS K 1408-1966, and hydrates thereof. Examples of the potassium salt of silicic acid include potassium salt of silicic acid having n = 2 to 4 when expressed as K2O.nSiO2. One kind of sodium metasilicate is preferred.
Examples of the sodium salt or potassium salt of boric acid include sodium metaborate, sodium tetraborate, sodium octaborate, potassium metaborate, potassium tetraborate, potassium octaborate and hydrates thereof. Sodium tetraborate, potassium tetraborate and hydrates thereof are preferred. Sodium tetraborate decahydrate and potassium tetraborate tetrahydrate are more preferable.
中でも、リン酸、炭酸又はホウ酸のナトリウム塩またはカリウム塩が好ましい。リン酸又はホウ酸のナトリウム塩またはカリウム塩がより好ましい。リン酸ナトリウムと、リン酸カリウムと、ホウ酸ナトリウムと、ホウ酸カリウムとの組み合わせが特に好ましい。リン酸二水素ナトリウム・２水和物と、リン酸三カリウムと、四ホウ酸ナトリウム・１０水和物と、四ホウ酸カリウム・４水和物との組み合わせが最も好ましい。少なくとも１種が、リン酸ナトリウム又はリン酸カリウム塩であるのもまた好ましい。
本発明の組成物中の無機塩の含有量は、組成物の全量を基準として１〜４０質量％であり、５〜４０質量％が好ましく、１５〜４０質量％がさらに好ましい。４０質量％を超えると、無機塩の全量が水に溶解しない場合がある。１質量％未満では、加工精度が悪くなる。また、希釈しないで使用した場合や、希釈倍率が低い場合（例えば、原液１、水１）にも所定の加工精度が得られるよう、１質量％以上とした。
一つの無機塩の含有量は０．１質量％以上が好ましく、０．５質量％以上がより好ましい。一つの無機塩の含有量が０．１質量％以上であることにより、加工精度が向上し、加工物を鏡面に仕上げることができる。
Of these, sodium salt or potassium salt of phosphoric acid, carbonic acid or boric acid is preferable. The sodium salt or potassium salt of phosphoric acid or boric acid is more preferable. A combination of sodium phosphate, potassium phosphate, sodium borate and potassium borate is particularly preferred. A combination of sodium dihydrogen phosphate dihydrate, tripotassium phosphate, sodium tetraborate decahydrate, and potassium tetraborate tetrahydrate is most preferred. It is also preferred that at least one is sodium phosphate or potassium phosphate.
Content of the inorganic salt in the composition of this invention is 1-40 mass% on the basis of the whole quantity of a composition, 5-40 mass% is preferable, and 15-40 mass% is more preferable. When it exceeds 40 mass%, the whole quantity of inorganic salt may not melt | dissolve in water. If it is less than 1% by mass, the machining accuracy is deteriorated. In addition, when it is used without being diluted or when the dilution ratio is low (for example, undiluted solution 1, water 1), it is set to 1% by mass or more so as to obtain a predetermined processing accuracy.
The content of one inorganic salt is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. When the content of one inorganic salt is 0.1% by mass or more, the processing accuracy is improved, and the workpiece can be finished to a mirror surface.
＜水＞
本発明において用いる水は、工業用水、水道水、市水、純水のいずれでもよい。
本発明の組成物中の水の含有量は、６０〜９９質量％であり、６５〜８５質量％が好ましい。
<Water>
The water used in the present invention may be industrial water, tap water, city water, or pure water.
Content of the water in the composition of this invention is 60-99 mass%, and 65-85 mass% is preferable.
＜ｐＨ＞
本発明の組成物の５％希釈液のｐＨ（２５℃）は１０〜１４であり、好ましいのは１１〜１４である。１０未満では砥石の目詰まりが発生する恐れがある。
＜その他添加剤＞
必要に応じて添加剤を含ませても良い。添加剤としては、例えば、防腐剤、防錆剤、消泡剤があげられる。
＜使用法＞
本発明の組成物は、工業用水、水道水、市水、純水等に希釈して使用することができる。希釈濃度は２〜２０％が一般的だが、２〜１００％（希釈しない原液）でも使用可能である。
＜適用範囲＞
本発明の組成物は、炭素鋼、特殊鋼等の金属材料のホーニング加工、超仕上げ加工として使用することができる。
<PH>
The pH (25 ° C.) of the 5% diluted solution of the composition of the present invention is 10-14, and preferably 11-14. If it is less than 10, clogging of the grindstone may occur.
<Other additives>
You may include an additive as needed. Examples of the additive include antiseptics, rust inhibitors, and antifoaming agents.
<Usage>
The composition of the present invention can be used after diluted with industrial water, tap water, city water, pure water or the like. The dilution concentration is generally 2 to 20%, but 2 to 100% (undiluted stock solution) can also be used.
<Scope of application>
The composition of the present invention can be used as a honing process or superfinishing process for metal materials such as carbon steel and special steel.
実施例１〜７、比較例１〜７を表1の実施例及び表２の比較例に示す。
尚、表１〜２に例示した組成物（原液）の組成は質量％である。実際の機械加工で使用している場合と同様に、この原液を水道水で１０倍に希釈したものについて以下の試験を行った。
[ｐＨ]
ＪＩＳ Ｚ ８８０２に基づいて、ガラス電極を用いて５％希釈液の２５℃におけるｐＨを測定した。
Examples 1 to 7 and Comparative Examples 1 to 7 are shown in Examples in Table 1 and Comparative Examples in Table 2.
In addition, the composition of the composition (stock solution) illustrated in Tables 1 and 2 is mass%. As in the case of actual machining, the following test was conducted on a 10-fold dilution of this stock solution with tap water.
[pH]
Based on JIS Z 8802, the pH at 25 ° C. of a 5% diluted solution was measured using a glass electrode.
[研削性]
Ｆａｌｅｘ Ｒｉｎｇ ａｎｄ Ｂｌｏｃｋ Ｔｅｓｔ Ｍａｃｈｉｎｅのブロック（ＳＡＥ０１）を砥石で作成し、ＡＳＴＭ Ｄ３７０４に従って実施、砥石目詰まりと、リング研削量で評価した。
砥 石：ＷＡ３０００ ＲＨ−６０Ｖ（硫黄処理）
リング：ＳＡＥ４６２０ φ３５×８．１５ｍｍ
回転数：２７５０ｒｐｍ
荷 重：１．５ｌｂ
時 間：１０秒×２０／１油剤
試験温度：２５℃
油 剤：２００ｍｌ、完全浸漬
[Grindability]
A block (SAE01) of Falex Ring and Block Test Machine was prepared with a grindstone, and it was performed according to ASTM D3704, and evaluated by clogging of the grindstone and ring grinding amount.
Whetstone: WA3000 RH-60V (sulfur treatment)
Ring: SAE4620 φ35 × 8.15mm
Rotation speed: 2750 rpm
Load: 1.5 lb
Time: 10 seconds x 20/1 Oil Test temperature: 25 ° C
Oil: 200ml, complete immersion
[砥石目詰まり]
砥石目詰まりを肉眼で観察し、目詰まり面積により判定した。
判定基準
○：０％（目詰まり発生なし）から５％未満
□：５％以上２０％未満
△：２０％以上５０％未満
×：５０％以上
○及び□を合格、△及び×を不合格とした。
各判断基準における目詰まり例を図１に示す。
[Whetstone clogging]
The clogging of the grindstone was observed with the naked eye and judged by the clogging area.
Judgment criteria ○: 0% (no clogging) to less than 5% □: 5% or more and less than 20% △: 20% or more and less than 50% ×: 50% or more ○ and □ pass, △ and × pass did.
An example of clogging according to each criterion is shown in FIG.
[リング研削量]
試験前後のリング重量の差から求める。
リング研削量＝試験前リング重量−試験後リング重量
判定基準
○：２０ｍｇ以上
□：１５ｍｇ以上２０ｍｇ未満
△：１０ｍｇ以上１５ｍｇ未満
×：１０ｍｇ未満
○及び□を合格、△及び不合格とした。
[Ring grinding amount]
Obtained from the difference in ring weight before and after the test.
Ring grinding amount = Ring weight before test−Ring weight after test Judgment criteria ○: 20 mg or more □: 15 mg or more and less than 20 mg Δ: 10 mg or more and less than 15 mg ×: less than 10 mg ○ and □ are regarded as pass, Δ and fail.
[防錆試験]
ドライ切削したＦＣ２００鋳物切屑２０ｇを直径６０ｍｍ×高さ１５ｍｍのガラスシャーレに採り、実施例及び比較例の組成物の１０倍希釈液を、切屑が完全に浸漬するまで加え、１０分間静置した。その後、該希釈液をデカントし、シャーレを振動させて切屑表面が平らになるようにした。蓋をして室温で２４時間放置し、発錆状態を肉眼で観察し、切屑表面に発生した錆の面積により防錆性を判定した。
[Rust prevention test]
20 g of dry-cut FC200 casting chips were taken in a glass petri dish having a diameter of 60 mm and a height of 15 mm, and 10-fold diluted solutions of the compositions of Examples and Comparative Examples were added until the chips were completely immersed, and allowed to stand for 10 minutes. Thereafter, the diluted solution was decanted, and the petri dish was vibrated so that the chip surface was flattened. The lid was covered and allowed to stand at room temperature for 24 hours. The rusting state was observed with the naked eye, and the rust prevention property was determined by the area of rust generated on the chip surface.
判定基準
○：０％（発錆なし）
□：０％超え２０％未満
△：２０％以上５０％未満
×：５０％以上
○及び□を合格、△及び×を不合格とした。
Judgment criteria ○: 0% (no rusting)
□: More than 0% and less than 20% △: 20% or more and less than 50% ×: 50% or more ○ and □ were accepted, and Δ and x were rejected.
Claims (10)
組成物の全量を基準として６０〜９９質量％の水とを含有し、
前記塩が、リン酸、炭酸、ケイ酸及びホウ酸のナトリウム塩またはカリウム塩からなる群から選ばれる少なくとも２種のみからなる無機塩からなり、
組成物の５％希釈液の２５℃におけるｐＨが１０〜１４である、超仕上げ加工用水溶性加工油剤組成物。 1 to 40% by weight of salt, based on the total amount of the composition,
60 to 99% by weight of water based on the total amount of the composition,
The salt comprises an inorganic salt consisting of at least two selected from the group consisting of sodium salt or potassium salt of phosphoric acid, carbonic acid, silicic acid and boric acid,
A water-soluble processing oil composition for superfinishing, wherein the 5% dilution of the composition has a pH of 10 to 14 at 25 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012128195A JP5877610B2 (en) | 2012-06-05 | 2012-06-05 | Water-soluble processing oil composition for super finishing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012128195A JP5877610B2 (en) | 2012-06-05 | 2012-06-05 | Water-soluble processing oil composition for super finishing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013253138A JP2013253138A (en) | 2013-12-19 |
| JP5877610B2 true JP5877610B2 (en) | 2016-03-08 |
Family
ID=49950947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012128195A Active JP5877610B2 (en) | 2012-06-05 | 2012-06-05 | Water-soluble processing oil composition for super finishing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5877610B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004026943A (en) * | 2002-06-24 | 2004-01-29 | Kozgro Japan Co Ltd | Cutting agent or polishing agent composition |
-
2012
- 2012-06-05 JP JP2012128195A patent/JP5877610B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013253138A (en) | 2013-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102703196B (en) | Environment-friendly water-based metal cutting fluid | |
| CN105358664B (en) | Processability after moisture absorption and resistance to slagging block the excellent metal material water-base lubricant for plastic forming of property | |
| CN104498163A (en) | Water-soluble total-synthesis metal working fluid and application thereof | |
| CN104277902A (en) | Heavy-load metal machining total synthesis cutting fluid as well as preparation method and application thereof | |
| CN104004579B (en) | Machining center rust coolant liquid | |
| CN106398849A (en) | A cutting fluid specially used for a diamond cutting line and a preparing method thereof | |
| CN106318592A (en) | Aqueous cutting fluid for hard and brittle material multi-line cutting and preparation method thereof | |
| CN102899154A (en) | Fully synthetic cutting solution | |
| KR100525973B1 (en) | Metal working fluid | |
| JP6162649B2 (en) | Super finishing method | |
| JP6025662B2 (en) | Water-soluble grinding oil | |
| TW539744B (en) | Aqueous lubricant of one process type used for high efficient cold forging | |
| US7811975B2 (en) | Metalworking and machining fluids | |
| JP5877610B2 (en) | Water-soluble processing oil composition for super finishing | |
| TWI649416B (en) | Water-soluble cutting oil stock solution composition, cutting oil composition and cutting processing method | |
| CN107312595B (en) | Steel ball grinding fluid and preparation method thereof | |
| JP4974150B2 (en) | Water-soluble processing oil | |
| CN104877737B (en) | Aerospace equipment special material emulsion cutting fluid and preparation method and purposes | |
| CN112805358B (en) | Water soluble metalworking concentrates | |
| WO2019167540A1 (en) | Polishing composition, method for producing polishing composition, and polishing method | |
| CN103451000B (en) | A kind of automobile brake disc fully synthetic cutting fluid and preparation method thereof | |
| KR20210127136A (en) | Lubricant for hot forming of metal | |
| CN102911778B (en) | Multi-effect completely-synthesized cutting fluid | |
| JPS60141795A (en) | Cutting and grinding oil for material difficult to work | |
| JP4076635B2 (en) | Water-soluble oil for machining cemented carbide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150414 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150930 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20151013 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151208 |
|
| 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: 20160104 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160125 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5877610 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |