JP5778404B2 - Water-soluble cutting fluid - Google Patents
Water-soluble cutting fluid Download PDFInfo
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- JP5778404B2 JP5778404B2 JP2010225933A JP2010225933A JP5778404B2 JP 5778404 B2 JP5778404 B2 JP 5778404B2 JP 2010225933 A JP2010225933 A JP 2010225933A JP 2010225933 A JP2010225933 A JP 2010225933A JP 5778404 B2 JP5778404 B2 JP 5778404B2
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- 239000002173 cutting fluid Substances 0.000 title claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 238000005260 corrosion Methods 0.000 claims description 24
- 230000007797 corrosion Effects 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 20
- 239000010419 fine particle Substances 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 10
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 7
- 150000001414 amino alcohols Chemical class 0.000 claims description 7
- -1 triazole compound Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004715 keto acids Chemical class 0.000 claims description 2
- 230000002421 anti-septic effect Effects 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000005520 cutting process Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910021392 nanocarbon Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229960000250 adipic acid Drugs 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229960002255 azelaic acid Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Auxiliary Devices For Machine Tools (AREA)
- Lubricants (AREA)
Description
本発明は、水溶性切削液に関し、更に詳しくは、防食性（防錆性）を付与したカーボン微粒子を含有する水溶性切削液に係るものである。 The present invention relates to a water-soluble cutting fluid, and more particularly to a water-soluble cutting fluid containing carbon fine particles imparted with anticorrosive properties (rust prevention properties).
本発明の切削液は、切削加工用ばかりでなく研削加工用のものも含む。 The cutting fluid of the present invention includes not only cutting work but also grinding work.
以下の説明で配合率を示す「％」は、特に断らない限り、「質量％」である。 In the following description, “%” indicating the blending ratio is “mass%” unless otherwise specified.
水溶性切削液としては、エマルションタイプ（ＪＩＳ Ｋ２２４１切削油剤：Ａ１種）、ソルブルタイプ（ＪＩＳ Ｋ２２４１切削油剤：Ａ２種）、ソリューションタイプ（ＪＩＳ Ｋ２２４１切削油剤：Ａ３種）の３種類がある。 There are three types of water-soluble cutting fluid: emulsion type (JIS K2241 cutting fluid: A1 type), solve type (JIS K2241 cutting fluid: Type A2), and solution type (JIS K2241 cutting fluid: Type A3).
このうち、難加工向けには、油成分（硫黄系極圧剤、リン系極圧剤、鉱物油、合成油等）を界面活性剤で分散させたエマルションタイプ（Ａ１種）、ソルブルタイプ（Ａ２種）が使用される。 Among these, for difficult processing, an emulsion type (A1 type), a solve type (in which oil components (sulfur extreme pressure agent, phosphorus extreme pressure agent, mineral oil, synthetic oil, etc.) are dispersed with a surfactant. A2 type) is used.
これらのタイプの切削液は、油成分を潤滑主成分としているため液安定性に問題点がある。このため、切削液が不安定な状態で液表面に油分が浮遊してくると、液の腐敗が発生し易くなる。 Since these types of cutting fluids have an oil component as a main component for lubrication, there is a problem in fluid stability. For this reason, when the oil component floats on the surface of the liquid in an unstable state, the liquid is likely to be spoiled.
また、油成分を実質的に含有していないソリューションタイプは、液安定性に優れ、腐敗しにくい半面、難加工に対しては潤滑不足で加工範囲に制約が発生する。 In addition, the solution type that does not substantially contain an oil component has excellent liquid stability and is difficult to be spoiled. On the other hand, for difficult processing, the processing range is limited due to insufficient lubrication.
従来技術として、カーボン分散液のみで切削加工を実施した事例がある（本発明者らが知る限り、直接的に記載した先行技術文献は存在しない。）。カーボン分散液で切削加工すると、現用エマルションョンタイプと同等の切削加工性を得られるが、被切削材及び工作機械における腐食（錆）発生のため使用されていないのが現状であると見聞している。 As a prior art, there is an example in which cutting is performed only with a carbon dispersion (as far as the present inventors know, there is no prior art document described directly). Cutting with a carbon dispersion gives the same machinability as the current emulsion type, but I heard that it is not used because of corrosion (rust) in the work material and machine tool. ing.
なお、本発明の特許性に影響を与えるものではないが、カーボン微粒子（ナノカーボン）を含有した水溶性切削液を使用した、下記構成の鉄系被削材の切削方法が特許文献１で提案されている（特許文献１特許請求の範囲等）。 Although not affecting the patentability of the present invention, Patent Document 1 proposes a method for cutting an iron-based work material having the following configuration using a water-soluble cutting fluid containing carbon fine particles (nanocarbon). (Patent Document 1 claims, etc.).
「ナノカーボンを含有した水溶性切削液を電解させ、電解した水溶性切削液を、ダイヤモンド切削工具と鉄系被削材との切削点に供給しながら、ダイヤモンド切削工具により鉄系被削材を切削することを特徴とする。」 “While electrolyzing a water-soluble cutting fluid containing nanocarbon and supplying the electrolyzed water-soluble cutting fluid to the cutting point between the diamond cutting tool and the iron-based work material, the diamond-cutting tool It is characterized by cutting. "
特許文献１に記載された水溶性切削液の作用は下記の如くである旨記載されている（段落００２９参照）。 It is described that the action of the water-soluble cutting fluid described in Patent Document 1 is as follows (see paragraph 0029).
カーボン微粒子（ナノカーボン）が切削工具の切刃表面に付着して形成されたカーボンの被覆層が、固体潤滑剤として機能することにより切刃表面の表面摩擦係数を下げて、切りくずの切削工具への付着を防止するとともに、切刃保護層としても機能して、切削工具の摩耗を防止する。この炭素微粒子の作用は、本発明における作用と同様であると考えられる。 The carbon coating layer formed by carbon fine particles (nanocarbon) adhering to the cutting blade surface of the cutting tool functions as a solid lubricant, thereby reducing the surface friction coefficient of the cutting blade surface and cutting the chip. As well as preventing adhesion to the cutting tool, it also functions as a cutting edge protective layer to prevent wear of the cutting tool. The action of the carbon fine particles is considered to be the same as the action in the present invention.
しかし、特許文献１に記載された水溶性切削液は、後述の本発明の目的である被切削体（被削材）の防錆を意図したものではない。特許文献１段落００３０には下記内容の記載がある。 However, the water-soluble cutting fluid described in Patent Document 1 is not intended for rust prevention of a workpiece (workpiece), which is an object of the present invention described later. Patent Document 1 paragraph 0030 has the following description.
「腐食作用を有する化合物を有する切削液を電解して切削点に供給することにより、表面の結晶構造を脆くして、切削性能を向上させるものである。」 “By electrolyzing a cutting fluid having a compound having a corrosive action and supplying it to the cutting point, the surface crystal structure becomes brittle and the cutting performance is improved.”
なお、特許文献１の実施例で「ナノカーボンを含有した水溶性切削液」として使用されている「Aqua-Black 162」（登録商標）は、「ナノカーボン濃度20wt％、ｐH７」とされている（段落００３５）。 In addition, “Aqua-Black 162” (registered trademark) used as “a water-soluble cutting fluid containing nanocarbon” in the example of Patent Document 1 is set to “nanocarbon concentration 20 wt%, pH 7”. (Paragraph 0035).
そして、東海カーボン株式会社のホームページ「親水性カーボンブラックAqua-Black 162および001特性一覧表」によれば、ナノカーボンの分散性を確保するために、カルボキシル基（官能基）が導入されており、各カルボキシル基の水素がアルカリ金属置換されている。「Aqua-Black」（商標）は、インクとしての使用を想定しており、酸性では使用できないためと考えられる。このため、アルカリ金属置換される前の「Aqua-Black」（親水性カーボンブラック；カーボン分散液）は、ｐH：２〜３であったと推定される。ｐH：２〜３の当該カーボン分散液を切削液として使用していたため、被削材および工作機械における腐食・錆発生の問題がより発生し易かったと推定される。 And according to Tokai Carbon Co., Ltd. website “Hydrophilic Carbon Black Aqua-Black 162 and 001 Properties Table”, carboxyl groups (functional groups) have been introduced to ensure the dispersibility of nanocarbons, The hydrogen of each carboxyl group is substituted with an alkali metal. “Aqua-Black” (trademark) is assumed to be used as an ink, and it is considered that it cannot be used in an acidic state. For this reason, it is estimated that “Aqua-Black” (hydrophilic carbon black; carbon dispersion) before the alkali metal substitution was pH: 2 to 3. Since the carbon dispersion having a pH of 2 to 3 was used as a cutting fluid, it is estimated that the problem of corrosion and rust generation in the work material and machine tool was more likely to occur.
また、ソリューションタイプである水溶性切削液（A3種）では、ＪＩＳ Ｋ２２４１で規定されている如く、1号（鋼板）ではｐH８．５〜１０．５、２号（アルミニウム板および銅板）ではｐH８．０〜１０．５と規定されている。 In addition, the solution type water-soluble cutting fluid (type A3) has a pH of 8.5 to 10.5 for No. 1 (steel plate) and a pH of 8 for No. 2 (aluminum plate and copper plate) as defined in JIS K2241. It is defined as 0 to 10.5.
なお、本発明の特許性に影響を与えるものではないが、本発明に使用可能な酸化処理されたカーボン微粒子を記載した文献として特許文献２〜３等が存在する。 In addition, although it does not affect the patentability of this invention, patent documents 2-3 etc. exist as literature which described the oxidized carbon fine particle which can be used for this invention.
本発明は、上記にかんがみて、カーボン微粒子を含有する水溶性切削液において、エマルションタイプ（ＪＩＳ Ｋ２２４１切削油剤；Ａ１種）と同等の切削加工性（機械加工性）を維持しながら、被切削材および工作機械における実用的な耐腐食性が達成できる水溶性切削液を提供することを目的とする。 In view of the above, the present invention, in a water-soluble cutting fluid containing carbon fine particles, maintains a cutting workability (machining workability) equivalent to that of an emulsion type (JIS K2241 cutting fluid; class A1), while cutting the work material. And it aims at providing the water-soluble cutting fluid which can achieve practical corrosion resistance in a machine tool.
本発明者らは、上記課題を解決するために、機械加工性（切削・研削）を阻害せずに、かつ、ｐＨをＪＩＳ Ｋ２２４１に規定するｐＨ８．０以上に調整可能な各種腐食抑制剤（インヒビター）の組合わせを種々検討した結果、下記構成の水溶性切削液に想到した。 In order to solve the above-mentioned problems, the present inventors have various corrosion inhibitors that can be adjusted to pH 8.0 or higher as defined in JIS K2241 without impairing machinability (cutting / grinding). As a result of various studies on combinations of inhibitors, the inventors have come up with a water-soluble cutting fluid having the following constitution.
酸化処理されたカーボン微粒子０．０５〜６．０ｗｔ％を分散含有し、腐食抑制剤（インヒビター）が添加されてなる水溶性切削液であって、
前記腐食抑制剤として、アミノアルコール（但し、Ｃ：１〜５）および脂肪族カルボン酸（但し、Ｃ：４〜１６）を含有して、ｐＨ：８．０〜１０．５に調節されてなる、ことを特徴とする。
A water-soluble cutting fluid containing 0.05 to 6.0 wt% of oxidized carbon fine particles dispersed therein, and having a corrosion inhibitor (inhibitor) added thereto,
As the corrosion inhibitor, it contains amino alcohol (C: 1 to 5) and aliphatic carboxylic acid (C: 4 to 16), and is adjusted to pH: 8.0 to 10.5. It is characterized by that.
酸化処理されたカーボン微粒子は、通常、カーボン分散液（自己分散型カーボンブラック）の形態で配合する。 The oxidized carbon fine particles are usually blended in the form of a carbon dispersion (self-dispersing carbon black).
カーボン微粒子の酸化処理としては、特許文献２段落００２１に記載されている如く、下記のような手段により可能であるが、炭素陽極の電解酸化処理が望ましい。 As described in paragraph 0021 of Patent Document 2, the oxidation treatment of the carbon fine particles can be performed by the following means, but the electrolytic oxidation treatment of the carbon anode is desirable.
(1)酸化剤による化学的酸化、(2)オゾンによる酸化、(3)放電酸化又はプラズマ放電酸化、(4)電子ビーム照射による酸化。 (1) chemical oxidation with an oxidizing agent, (2) oxidation with ozone, (3) discharge oxidation or plasma discharge oxidation, and (4) oxidation by electron beam irradiation.
電解酸化の概要は下記のごとくである（特許文献２段落００２２から引用）。
「塩化リチウムのような少量の塩を含んだ電解液、成形し焼結した炭素粒子から精製したアノード(陽極)とプラチナカソード(陰極)である。電極間の電圧は電解液にとって十分に高い電圧とした。電気分解がすすむにつれ、炭素粒子は懸濁する。溶液のｐＨ値が2.5に減少するまで電気分解は続ける。炭素粒子は溶液中で何ら他の分散剤なしに懸濁する。炭素粒子の沈降は調整の10日後でも見られない。」
The outline of the electrolytic oxidation is as follows (cited from Patent Document 2, paragraph 0022).
“An electrolyte containing a small amount of salt, such as lithium chloride, an anode (anode) purified from shaped and sintered carbon particles and a platinum cathode (cathode). The voltage between the electrodes is high enough for the electrolyte. As the electrolysis progresses, the carbon particles suspend, and the electrolysis continues until the pH value of the solution decreases to 2.5.The carbon particles suspend in the solution without any other dispersant. No sedimentation is seen even after 10 days of adjustment. "
また、前述の「Aqua-Black」等および均等のカーボン分散液も使用可能である。このカーボン分散液のカーボン微粒子濃度は、０．１〜１０．０％、望ましくは、０．５〜５％とする。また、カーボン分散液のｐＨは、ｐＨ７．０〜８．０に限らず、表面官能基（カルボキシル基）の末端水素が１価イオンで置換されていないｐＨ２．０〜３．０のものも使用可能である。さらには、カーボン分散液を、一旦、乾燥させてカーボン微粒子とし、再度、他の成分とともに、水分散させてもよい。 Moreover, the above-mentioned “Aqua-Black” and the like and an equivalent carbon dispersion can also be used. The carbon fine particle concentration of this carbon dispersion is 0.1 to 10.0%, preferably 0.5 to 5%. Further, the pH of the carbon dispersion is not limited to 7.0 to 8.0, and the carbon dispersion having pH 2.0 to 3.0 in which the terminal hydrogen of the surface functional group (carboxyl group) is not substituted with a monovalent ion is used. Is possible. Furthermore, the carbon dispersion liquid may be once dried to form carbon fine particles, and again dispersed with water together with other components.
上記電解酸化カーボンからなるカーボン分散液は、他のカーボン分散液（例えば、「Aqua-Black」）に比して、分散安定性および潤滑性に優れており望ましい。 The carbon dispersion composed of the above electrolytically oxidized carbon is desirable because it is superior in dispersion stability and lubricity as compared with other carbon dispersions (for example, “Aqua-Black”).
ちなみに、電解酸化カーボンで調製したカーボン微粒子の粒径は、二軸平均径：３００〜１０００ｎｍである。 Incidentally, the particle diameter of the carbon fine particles prepared with electrolytically oxidized carbon is biaxial average diameter: 300 to 1000 nm.
カーボン分散液の配合比率は、通常、４０〜７０％、望ましくは４５〜５５％とする。切削液（原液）組成でカーボン微粒子０．０４〜７．０％、望ましくは０．１〜５．０％、さらに望ましくは０．１〜２．０％となる量とする。 The blending ratio of the carbon dispersion is usually 40 to 70%, preferably 45 to 55%. The amount of carbon fine particles is 0.04 to 7.0%, preferably 0.1 to 5.0%, more preferably 0.1 to 2.0% in the cutting fluid (stock solution) composition.
アミノアルコールと脂肪族カルボン酸と併用することにより、アミノアルコールがカルボン酸と反応して、酸アミドが生成する。この結果、防錆（防食）性を向上できることは勿論、カーボン分散性を維持しながら、ｐＨを８以上に調整可能となる。 By using amino alcohol and aliphatic carboxylic acid in combination, amino alcohol reacts with carboxylic acid to produce acid amide. As a result, the rust prevention (corrosion prevention) can be improved, and the pH can be adjusted to 8 or more while maintaining the carbon dispersibility.
上記アミノアルコールとしては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン等、第１・２・３級アミンタイプのものを好適に使用できる。これらのうちで、第１級タイプと第２級タイプを併用することが、ｐＨ調整が容易となり望ましい。 As the amino alcohol, those of primary, secondary and tertiary amine types such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine can be suitably used. Among these, it is desirable to use the primary type and the secondary type in combination because pH adjustment is easy.
上記アミノアルコールの配合量は、第１級タイプ：１〜８％、第２級タイプ：４〜１６％、第１級タイプ／第２級タイプ＝１／５〜１／２とする。 The compounding amount of the amino alcohol is primary type: 1 to 8%, secondary type: 4 to 16%, primary type / secondary type = 1/5 to 1/2.
上記脂肪族カルボン酸（但し、Ｃ：４〜１６）としては、モノカルボン酸でもよいが、ジカルボン酸が、モノカルボン酸に比して溶解度が高く、キレート作用も期待でき、防錆性にも優れており望ましい。 The aliphatic carboxylic acid (C: 4 to 16) may be a monocarboxylic acid, but the dicarboxylic acid has higher solubility than the monocarboxylic acid, can be expected to have a chelating action, and has an antirust property. Excellent and desirable.
ジカルボン酸としては、ヘキサン二酸（Ｃ６）、ヘプタン二酸（Ｃ７）、オクタン二酸（Ｃ８）、ノナン二酸（Ｃ９）、デカン二酸（Ｃ１０）、ドデカン二酸（Ｃ１２）等を好適に使用できる。 Preferred dicarboxylic acids include hexanedioic acid (C6), heptanedioic acid (C7), octanedioic acid (C8), nonanedioic acid (C9), decanedioic acid (C10), dodecanedioic acid (C12), and the like. Can be used.
このジカルボン酸の配合量は、２〜１５％、望ましくは８〜１２％とする。 The blending amount of this dicarboxylic acid is 2 to 15%, desirably 8 to 12%.
さらに、希釈使用時の切削液の表面張力の調整剤として、液状多価アルコールを配合させることが望ましい。液状多価アルコールは、非鉄金属に対する腐食防止性を増大させる腐食抑制剤としての作用も奏する。 Furthermore, it is desirable to mix liquid polyhydric alcohol as a regulator of the surface tension of the cutting fluid during dilution use. The liquid polyhydric alcohol also has an action as a corrosion inhibitor that increases the corrosion resistance against non-ferrous metals.
上記液状多価アルコールとしては、グリセリン、ジグセリン、エチレングリコール、ジエチレングリコール、液状ポリエチレングリコール（液状ＰＥＧ）、プロピレングリコール、ジプロピレングリコールおよび液状ポリプロピレングリコール（液状ＰＰＧ）等を好適に使用できる。これらの内で、液状ＰＰＧ、液状ＰＥＧ等は、各種分子量・粘度のものが上市されており、好適に使用できる。なお、液状多価アルコールの一部を界面活性剤に置換してもよい。界面活性剤としては、アニオン系、カチオン系、ノニオン系を問わない。 As said liquid polyhydric alcohol, glycerin, diglycerin, ethylene glycol, diethylene glycol, liquid polyethylene glycol (liquid PEG), propylene glycol, dipropylene glycol, liquid polypropylene glycol (liquid PPG), etc. can be used conveniently. Among these, liquid PPG, liquid PEG, and the like having various molecular weights and viscosities are marketed and can be preferably used. A part of the liquid polyhydric alcohol may be replaced with a surfactant. The surfactant may be an anionic type, a cationic type, or a nonionic type.
上記液状多価アルコールは、その配合量は、５〜１５％、望ましくは７〜１３％とする。 The amount of the liquid polyhydric alcohol is 5 to 15%, preferably 7 to 13%.
また、腐食抑制剤として、通常、鉄系防食剤（防錆剤）として慣用されている、ベンゼン環縮合系のトリアゾール化合物を含有させることで、銅系金属腐食防止作用も付加できる。特に、後述の試験例で示す如く、ベンゾトリアゾールとトリルトリアゾールとを併用することにより、ベンゾトリアゾール単独に比して、銅系金属の防食性ばかりでなく、アルミ系金属の防食性が向上するとともに、エンドミル加工性も向上することを確認している。 Moreover, the copper metal corrosion prevention effect | action can also be added by containing the triazole compound of a benzene ring condensation type | system | group normally used as a corrosion inhibitor (usually an iron type anticorrosive agent). In particular, as shown in the test examples described later, the combined use of benzotriazole and tolyltriazole improves not only the corrosion resistance of copper-based metals but also the corrosion resistance of aluminum-based metals compared to benzotriazole alone. It has been confirmed that the end mill workability is also improved.
更に、防錆性向上のための腐食抑制剤として、珪酸塩、リン酸塩、ホウ酸塩、モリブデン酸塩等の酸化作用を有しないオキソ酸の無機塩（以下「非酸化性無機塩」という。）を添加してもよい。それらの配合量は、０．１〜２％とする。 Furthermore, as a corrosion inhibitor for improving rust prevention properties , inorganic salts of oxo acids having no oxidizing action such as silicates, phosphates, borates and molybdates (hereinafter referred to as “non-oxidizing inorganic salts”) .) May be added. Their blending amount is 0.1 to 2%.
更に、通常、水溶性切削液に使用されている、汎用の防腐剤（防カビ剤）を含有させる。この防腐剤の配合量は、０．０１〜０．１％とする。 Furthermore, a general-purpose preservative (antifungal agent) usually used in water-soluble cutting fluid is contained. The preservative content is 0.01-0.1%.
上記各成分の組成は、纏めると下記の如くになる。
・カーボン分散液 ４０〜７０％
・脂肪族カルボン酸（但し、Ｃ：４〜１６） ２〜１５％
・アミノアルコール（但し、Ｃ：１〜５） ５〜２０％
・液状多価アルコール ５〜１５％
・ベンゼン環縮合系のトリアゾール化合物 ０．５〜５％
・非酸化性無機塩 ０．１〜２％
・水その他 残部
The composition of each of the above components is summarized as follows.
・ Carbon dispersion 40-70%
Aliphatic carboxylic acid (however, C: 4-16) 2-15%
・ Amino alcohol (C: 1-5) 5-20%
・ Liquid polyhydric alcohol 5-15%
・ Triazole compound of benzene ring condensation system 0.5-5%
・ Non-oxidizing inorganic salt 0.1-2%
・ Water and other balance
そして、本発明の水溶性切削液（原液）は、通常、１０〜２０倍に希釈して、慣用法により機械加工（切削・研削）における潤滑剤乃至冷却剤として使用する。 The water-soluble cutting fluid (stock solution) of the present invention is usually diluted 10 to 20 times and used as a lubricant or coolant in machining (cutting / grinding) by a conventional method.
以下、本発明を、実施例・比較例に基づいて、更に、詳細に説明する。 Hereinafter, the present invention will be described in more detail based on examples and comparative examples.
１）カーボン分散液：
実施例の電解カーボン分散液は、特許文献２の実施例１で調製したものを、カーボン分散量（濃度）：０．２％に希釈したものを使用した。なお、電解カーボン粒子形態は、顕微鏡で観察したところ、扁平状、粒径指数：二軸平均５００ｎｍであった。
1) Carbon dispersion:
As the electrolytic carbon dispersion liquid of the examples, the one prepared by diluting the carbon dispersion amount (concentration) prepared in Example 1 of Patent Document 2 to 0.2% was used. In addition, when the electrolytic carbon particle form was observed with a microscope, it was flat, particle size index: biaxial average 500 nm.
特許文献２の段落００５３から分散液（懸濁液）の調製方法を次に引用する。
「水(ｐＨ：７)を電解液にして、ステンレスのメッシュ板を折り曲げて作った直径100mmの円筒状の陰極の中に、直径20mm、長さ100mmの黒鉛の棒を陽極にしていれ、直流電流３Ａを24時間流してコロイド状の炭素懸濁液を作った。この炭素懸濁液は10日間放置しても粉末の沈降は無く、炭素粉末が炭素コロイドとして分散していた。懸濁液中の炭素粉末の濃度は3.1wt％であった。電解液のｐＨは2.5に変化した。」
The method for preparing a dispersion (suspension) is referred to from paragraph 0053 of Patent Document 2.
“In a 100 mm diameter cylindrical cathode made by bending a stainless steel mesh plate with water (pH: 7) as an electrolyte, a graphite rod with a diameter of 20 mm and a length of 100 mm is used as the anode. A colloidal carbon suspension was made by applying an electric current of 3 A for 24 hours, and the carbon suspension did not settle even when left for 10 days, and the carbon powder was dispersed as a carbon colloid. The concentration of the carbon powder inside was 3.1 wt%, and the pH of the electrolyte changed to 2.5. "
２）切削液の調製：
実施例組成は、表１に示す処方で、カーボン分散液と、その他成分の水系分散液とを質量比１：１で、常温で攪拌して調製した。
2) Preparation of cutting fluid:
The composition of the examples was prepared by stirring the carbon dispersion and the aqueous dispersion of other components at a mass ratio of 1: 1 at room temperature according to the formulation shown in Table 1.
３）耐腐食性（防錆性・防食性）試験：
ＪＩＳ Ｋ２２３４ ８．６に準拠した金属腐食試験条件で各種金属を評価した。
3) Corrosion resistance (rust resistance / corrosion resistance) test:
Various metals were evaluated under metal corrosion test conditions in accordance with JIS K2234 8.6.
試験温度８８℃、試験時間１０００時間後の錆、腐食の状態で判定した。 The test temperature was 88 ° C. and the test time was 1000 hours.
４）機械加工性試験：
各実施例・比較例の切削液を１０倍希釈して、下記各条件の機械加工に適用して、切削加工性（潤滑性能・冷却性能等）を総合評価した。
4) Machinability test:
The cutting fluid of each Example / Comparative Example was diluted 10 times and applied to machining under the following conditions to comprehensively evaluate cutting workability (lubrication performance, cooling performance, etc.).
・ドリル加工・・・加工材：ＡＤＣ１２、切削速度：２５０ｍ／ｍｉｎ、送り量：０．１ｍｍ／ｒｅｖ
・エンドミル加工・・・加工材：ＳＣＭ−４２０Ｈ、切削速度：７０ｍ／ｍｉｎ、回転数：５３０ｍｉｎ-1
・ Drilling: Work material: ADC12, Cutting speed: 250 m / min, Feed rate: 0.1 mm / rev
End mill processing: Work material: SCM-420H, cutting speed: 70 m / min, rotation speed: 530 min −1
＜実施例の試験結果＞
実施例の試験結果を表２に示す。
<Test results of examples>
The test results of the examples are shown in Table 2.
ＰＥＧ系を添加した実施例２・３について、鋼、鋳鉄で若干錆の発生が認められた。ＰＰＧ系を添加した実施例４・５及び段落００５３に示されている実施例１に関しては、鋼、鋳鉄の耐腐食性（防食性）に優れた結果が得られた。 About Example 2 * 3 which added PEG type | system | group, generation | occurrence | production of some rust was recognized by steel and cast iron. With respect to Examples 4 and 5 to which PPG system was added and Example 1 shown in paragraph 0053, excellent results were obtained in the corrosion resistance (corrosion resistance) of steel and cast iron.
銅系・アルミニウム系に関しては、全組成共に良好で有るが、特にベンゾトリアゾールとトリルトリアゾールの組み合わせた実施例２・４が効果的な結果が得られた。 Regarding copper-based and aluminum-based materials, all the compositions were good, but effective results were obtained particularly in Examples 2 and 4 in which benzotriazole and tolyltriazole were combined.
実施例１と、比較例１の評価結果より、カーボン分散液の潤滑性が確認された。 From the evaluation results of Example 1 and Comparative Example 1, the lubricity of the carbon dispersion liquid was confirmed.
実施例１〜６および比較例１の結果から、高分子ポリマー添加による相乗効果も確認された。 From the results of Examples 1 to 6 and Comparative Example 1, a synergistic effect due to the addition of the polymer was also confirmed.
多価アルコールおよび非酸化性無機塩（珪酸ソーダ）を不使用の場合は、非鉄耐腐食性が低下するとともに、リーマ加工、エンドミル加工において若干低下する。その理由は、表面張力が大きくなるためと考えられる。 When polyhydric alcohol and non-oxidizing inorganic salt (sodium silicate) are not used, non-ferrous corrosion resistance is lowered, and it is slightly lowered in reaming and end milling. The reason is considered that the surface tension is increased.
ＰＥＧ添加の実施例２、３は、耐腐食性（防食性）が若干低下する傾向があり多価アルコールとしては、ＰＰＧが有効と考えられる。 In Examples 2 and 3 to which PEG was added, corrosion resistance (anticorrosion) tends to be slightly lowered, and PPG is considered to be effective as a polyhydric alcohol.
実施例１・４・５を用いてソリューション（合成系）、ソルブルタイプ（合成系）の水溶性切削液を設計することにより、被切削材・機械に対する耐腐食性、切削液の耐腐敗、切削加工性の向上が見込める。 By designing solutions (synthetic system) and soluble type (synthetic system) water-soluble cutting fluids using Examples 1, 4 and 5, corrosion resistance to the work material and machine, anti-corrosion of the cutting fluid, Expected to improve machinability.
Claims (8)
前記カーボン微粒子が電解酸化粉末であるとともに、
前記腐食抑制剤として、アミノアルコール（但し、Ｃ：１〜５）および脂肪族カルボン酸（但し、Ｃ：４〜１６）を含有して、ｐＨ：８．０〜１０．５に調節されてなる、
ことを特徴とする水溶性切削液。 A water-soluble cutting fluid containing 0.04 to 7.0 wt% of oxidized carbon fine particles dispersed therein, to which a corrosion inhibitor (inhibitor) is added,
The carbon fine particles are electrolytically oxidized powder,
As the corrosion inhibitor, it contains amino alcohol (C: 1 to 5) and aliphatic carboxylic acid (C: 4 to 16), and is adjusted to pH: 8.0 to 10.5. ,
A water-soluble cutting fluid characterized by that.
・カーボン分散液 ４０〜７０質量％
・脂肪族カルボン酸（但し、Ｃ：４〜１６） ２〜１５質量％
・アミノアルコール（但し、Ｃ：１〜５） ５〜２０質量％
・液状多価アルコール ５〜１５質量％
・ベンゼン環縮合系のトリアゾール化合物 ０．５〜５質量％
・酸化作用を有しないオキソ酸の無機塩 ０．１〜２質量％
・水その他 残部 The water-soluble cutting fluid according to claim 4, which has the following composition.
Carbon dispersion 40-70% by mass
Aliphatic carboxylic acid (however, C: 4 to 16) 2 to 15% by mass
-Amino alcohol (however, C: 1-5) 5-20 mass%
・ Liquid polyhydric alcohol 5-15% by mass
-Benzene ring condensation system triazole compound 0.5-5 mass%
・ Inorganic salt of oxo acid having no oxidizing action 0.1 to 2% by mass
・ Water and other balance
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| JP2013077341A (en) * | 2011-09-29 | 2013-04-25 | Alphana Technology Co Ltd | Method for manufacturing rotary apparatus and rotary apparatus manufactured by the manufacturing method |
| CN103555396B (en) * | 2013-10-30 | 2015-04-22 | 沈阳航空航天大学 | Water-based cutting fluid |
| JP6586621B2 (en) * | 2015-10-30 | 2019-10-09 | パレス化学株式会社 | Aqueous lubricant composition and metal working method using the same |
| CN115786028B (en) | 2017-10-06 | 2024-04-02 | 卡斯特罗尔有限公司 | Metal working fluid additive composition |
| CN115820331B (en) * | 2022-11-23 | 2023-07-28 | 俄美达（武汉）有限公司 | Cutting fluid for precious stone processing and preparation method thereof |
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| JPS6140400A (en) * | 1984-08-02 | 1986-02-26 | Idemitsu Kosan Co Ltd | Water-soluble lubricant |
| JP3244996B2 (en) * | 1995-02-24 | 2002-01-07 | ユシロ化学工業株式会社 | Water-soluble metalworking oil |
| JP4974150B2 (en) * | 2007-02-19 | 2012-07-11 | 株式会社興人 | Water-soluble processing oil |
| JP2009173814A (en) * | 2008-01-25 | 2009-08-06 | Yushiro Chem Ind Co Ltd | Aqueous lubricant composition and working method |
| JP5394691B2 (en) * | 2008-08-22 | 2014-01-22 | 出光興産株式会社 | Water-soluble metalworking fluid and metalworking coolant |
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