JP4236604B2 - W / O emulsion type flame retardant hydraulic fluid - Google Patents
W / O emulsion type flame retardant hydraulic fluid Download PDFInfo
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- JP4236604B2 JP4236604B2 JP2004075575A JP2004075575A JP4236604B2 JP 4236604 B2 JP4236604 B2 JP 4236604B2 JP 2004075575 A JP2004075575 A JP 2004075575A JP 2004075575 A JP2004075575 A JP 2004075575A JP 4236604 B2 JP4236604 B2 JP 4236604B2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 25
- 239000003063 flame retardant Substances 0.000 title claims description 25
- 239000000839 emulsion Substances 0.000 title claims description 23
- 239000012530 fluid Substances 0.000 title claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003242 anti bacterial agent Substances 0.000 claims description 21
- 239000002199 base oil Substances 0.000 claims description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- 150000002780 morpholines Chemical class 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 11
- -1 fatty acid ester Chemical class 0.000 description 10
- 239000010720 hydraulic oil Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000010913 used oil Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LLESIRNXIZQHES-UHFFFAOYSA-N 4-(4-nitrobutyl)morpholine Chemical compound [O-][N+](=O)CCCCN1CCOCC1 LLESIRNXIZQHES-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Description
本発明は、抗菌性に優れたＷ／Ｏエマルション型難燃性油圧作動油に関する。 The present invention relates to a W / O emulsion type flame retardant hydraulic fluid excellent in antibacterial properties.
高熱源雰囲気にさらされる鉄鋼設備、ダイキャストマシーンなどの各種油圧装置に可燃性の鉱物油系油圧作動油を用いると、突発的な油漏れにより火災の危険があるので、従来からこれらの設備には難燃性油圧作動油が用いられている。難燃性油圧作動油には、水‐グリコール型、Ｗ／Ｏエマルション型、Ｏ／Ｗエマルション型などの含水系の難燃性油圧作動油と脂肪酸エステル型、リン酸エステル型などの合成油系のものがある。合成油系の難燃性油圧作動油は，難燃性が充分でなく，また毒性の問題もあり実用性に欠ける。また、水グリコール型は、難燃性に優れるものの、すべて水溶性基材で構成されているため廃水に漏洩した際ＣＯＤが高まり、廃水処理の負荷が多大である。 If flammable mineral oil-based hydraulic fluid is used in various hydraulic equipment such as steel equipment and die-cast machines exposed to high heat source atmosphere, there is a risk of fire due to sudden oil leakage. Flame retardant hydraulic fluid is used. Flame retardant hydraulic fluids include water-glycol type, W / O emulsion type, O / W emulsion type and other water-containing flame retardant hydraulic fluids and synthetic oils such as fatty acid ester type and phosphate ester type. There are things. Synthetic oil-based flame retardant hydraulic fluids have insufficient flame retardancy and are not practical due to toxicity problems. In addition, although the water glycol type is excellent in flame retardancy, since it is composed entirely of a water-soluble substrate, COD increases when it leaks into waste water, and the load of waste water treatment is great.
一方、Ｗ／Ｏエマルション型難燃性作動油は、連続相が油で、水滴が約２μｍで安定に油中に分散しており、廃水に漏洩しても容易に浮上回収ができ、また水中のＣＯＤ増加も極めて少ない廃水処理性に優れた非危険物に分類される難燃性作動油である。近年、環境対応の一環として、このＷ／Ｏ エマルション型難燃性作動油の使用が見直されている。 On the other hand, the W / O emulsion type flame retardant hydraulic oil has a continuous phase of oil, water droplets of approximately 2 μm and is stably dispersed in the oil, and can be easily levitated and recovered even if it leaks into waste water. It is a flame retardant hydraulic oil classified as a non-hazardous material with excellent wastewater treatment properties with very little increase in COD. In recent years, the use of this W / O emulsion type flame retardant hydraulic oil has been reviewed as part of environmental measures.
Ｗ／Ｏエマルション型難燃性油圧作動油は、一般的に、基油約６０容量％に乳化剤を配合し、水約４０容量％を機械的に乳化したもので、作動油としての特性を持たせるため、摩耗防止剤、防錆剤、酸化防止剤、消泡剤を適宜配合したものである。この結果、Ｗ／Ｏエマルション型難燃性油圧作動油は、難燃性、潤滑性、廃水処理性に優れ、上記用途に多用されている。 W / O emulsion-type flame retardant hydraulic fluid is generally composed of about 60% by volume of base oil and mechanically emulsified about 40% by volume of water, and has characteristics as a hydraulic fluid. Therefore, an antiwear agent, an antirust agent, an antioxidant, and an antifoaming agent are appropriately blended. As a result, the W / O emulsion-type flame retardant hydraulic fluid is excellent in flame retardancy, lubricity, and wastewater treatment properties, and is frequently used in the above applications.
一方、近年の傾向として、油圧作動油に対するメンテナンスフリーのニーズは高く、また実際に経費削減や油漏れに対する設備対応が整い、従来に比べ新油の補給量が減少してきた。一般に、含水系難燃性作動油は、水、有機物（鉱物油など）から構成されているため、適度な環境（温度，汚染水の混入、ｐＨなど）が整えば、微生物が生育する。特にカビは糸状であるため、ポンプのストレーナーを閉塞するなどのトラブルを引き起こす。そのため含水系難燃性作動油には抗菌剤が配合され、微生物の発生を抑制している（例えば、特許文献１参照）。抗菌剤は、バクテリア、コウボおよびカビなどの微生物に幅広い抗菌スペクトルを有し、なおかつＷ／Ｏエマルション型難燃性作動油としての特性、例えば、潤滑性、乳化安定性、油圧システムの材料適合性などに悪影響を及ぼさないものが用いられる必要がある。抗菌剤として古くから用いられているトリアジン系化合物は、優れた抗菌性を有するものの金属腐食性（特には、銅など）に大きな課題があった。この金属腐食性を改善するため、腐食防止剤の採用、腐食性の少ない抗菌剤の採用などが検討されている。 On the other hand, as a recent trend, maintenance-free needs for hydraulic fluids are high, and cost reductions and facilities for oil leaks are actually available, so the amount of new oil replenished has decreased. In general, since a water-containing flame-retardant hydraulic oil is composed of water and organic matter (mineral oil or the like), microorganisms grow if an appropriate environment (temperature, contamination water contamination, pH, etc.) is prepared. In particular, mold is thread-like and causes troubles such as blocking the strainer of the pump. Therefore, an antibacterial agent is blended in the water-containing flame retardant hydraulic oil to suppress the generation of microorganisms (see, for example, Patent Document 1). The antibacterial agent has a broad antibacterial spectrum for microorganisms such as bacteria, yeast and mold, and also has properties as a W / O emulsion type flame retardant hydraulic fluid, for example, lubricity, emulsion stability, material compatibility of hydraulic system It is necessary to use those that do not adversely affect the above. Triazine-based compounds that have been used as antibacterial agents for a long time have great problems in metal corrosiveness (especially copper) although they have excellent antibacterial properties. In order to improve the metal corrosivity, the use of a corrosion inhibitor and the use of an antibacterial agent with low corrosivity are being studied.
今後さらに新油の補給自体が少なくなる傾向にあり、現状よりもさらに抗菌性の長期持続性が必要されている。特に、一般的に微生物は中性から酸性域で成育しやすく、また抗菌剤の効力はアルカリ域で発揮される。酸性域でも効果がある抗菌剤もあるが、一般に金属腐食性が高く、好ましいものではない。
本発明は上記課題を解決するもので、本発明の目的は抗菌剤の効能を長期間持続できるＷ／Ｏエマルション型難燃性油圧作動油を提供することにある。 This invention solves the said subject, and the objective of this invention is providing the W / O emulsion type flame-retardant hydraulic fluid which can maintain the effect of an antibacterial agent for a long period of time.
本発明は、界面活性剤を用いて基油に水を分散させたＷ／Ｏ エマルション型難燃性油圧作動油において、油性アルキルアミンまたはモルホリン誘導体である含窒素系抗菌剤を０.０１〜５質量％配合するとともに、前記分散させる水にトリエタノールアミンを０.２〜７質量％添加したＷ／Ｏエマルション型難燃性油圧作動油からなる。 The present invention relates to a W / O emulsion type flame retardant hydraulic fluid in which water is dispersed in a base oil using a surfactant, and 0.01 to 5 nitrogen-containing antibacterial agents which are oily alkylamines or morpholine derivatives. It is composed of a W / O emulsion type flame retardant hydraulic fluid in which 0.2% to 7% by mass of triethanolamine is added to the water to be dispersed.
本発明のＷ／Ｏエマルション型難燃性油圧作動油は、特定の種類の抗菌剤とトリエタノールアミンとを配合したために、長期にわたってアルカリ性を維持し，結果として抗菌剤の効能を長期間持続でき、しかも酸性域に達し微生物が繁殖してしまった使用油に新油を継ぎ足して使用したときでも使用油の抗菌性能を著しく回復できるという格別の効果を奏するものである。 The W / O emulsion-type flame retardant hydraulic fluid of the present invention is blended with a specific type of antibacterial agent and triethanolamine, so it maintains alkalinity for a long period of time, and as a result, the efficacy of the antibacterial agent can be sustained for a long period of time. In addition, the antibacterial performance of the used oil can be remarkably recovered even when the new oil is added to the used oil that has reached the acidic range and the microorganisms have propagated.
本発明の油圧作動油に用いる基油には、鉱油、合成油あるいはこれらの混合油を用いることができる。前記鉱油としては、原油を常圧蒸留及び／又は減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱蝋、水素化脱蝋、水素化精製、硫酸洗浄、白土処理等の潤滑油の精製に用いられる各種の精製処理を適宜組み合わせて得られたものが好適である。 As the base oil used in the hydraulic fluid of the present invention, mineral oil, synthetic oil, or a mixed oil thereof can be used. As the mineral oil, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, hydrodewaxing, hydrorefining, Those obtained by appropriately combining various purification treatments used for the purification of lubricating oil such as sulfuric acid washing and clay treatment are preferred.
また、合成油としては、ポリ-α-オレフィン、低分子量エチレン・α-オレフィン共重合体等を用いることができる。さらに、各種の鉱油基材を混合した混合油、あるいは合成油基材の混合油、およびそれら基材の任意な混合割合の混合油を使用することができる。これらの基油の物性は、特に限定するものではないが、４０℃における動粘度が５〜５０mm2/sのものが好ましく、１０〜３０mm2/sのものがより好ましい。 As synthetic oils, poly-α-olefins, low molecular weight ethylene / α-olefin copolymers, and the like can be used. Furthermore, a mixed oil obtained by mixing various mineral oil base materials, a mixed oil based on synthetic oil base materials, or a mixed oil having an arbitrary mixing ratio of these base materials can be used. The physical properties of these base oils are not particularly limited, but those having a kinematic viscosity at 40 ° C. of 5 to 50 mm 2 / s are preferable, and those of 10 to 30 mm 2 / s are more preferable.
本発明の油圧作動油に用いる水は、特に制限はないが、精製水が好ましい。前記基油への水の配合割合は、１〜７０容量％が好ましく、難燃性、エマルション安定性およびエマルション粘度のバランスからは、水分割合が２０〜５５容量％になるようにすることがより好ましい。 The water used for the hydraulic fluid of the present invention is not particularly limited, but purified water is preferable. The mixing ratio of water to the base oil is preferably 1 to 70% by volume. From the balance of flame retardancy, emulsion stability and emulsion viscosity, the water ratio should be 20 to 55% by volume. preferable.
界面活性剤（乳化剤）としては、非イオン系界面活性剤やイオン系界面活性剤などＷ／Ｏエマルションに用いられている周知のものを適宜用いることができる。具体的には、非イオン系界面活性剤として、アルケニルコハク酸エステル系、アルキル化フェニルエーテル、脂肪酸エステル、ソルビタンエステル系などが挙げられ、また、アニオン系界面活性剤としては、Ｃａスルフォネート、Ｂａスルフォネート、Ｎａスルフォネートなどがその一例として挙げられる。これらのうち、少なくとも１種以上の界面活性剤を、基油に対して０.５〜２０重量％、好ましくは１〜１０重量％添加する。 As the surfactant (emulsifier), known ones used in W / O emulsions such as nonionic surfactants and ionic surfactants can be appropriately used. Specifically, examples of the nonionic surfactant include alkenyl succinate ester, alkylated phenyl ether, fatty acid ester, sorbitan ester, and the like, and anionic surfactants include Ca sulfonate and Ba sulfonate. An example thereof is Na sulfonate. Among these, at least one surfactant is added in an amount of 0.5 to 20% by weight, preferably 1 to 10% by weight, based on the base oil.
本発明では、抗菌剤として、バクテリア、コウボ、カビに幅広い抗菌スペクトルを有し、潤滑性、乳化安定性、さらには銅腐食性の少ない油溶性の含窒素系化合物を用いるものである。油溶性の含窒素化合物としては、炭素数８〜２４の１級アミンやモルホリン誘導体が好適である。
これらの抗菌剤は基油および／または水に添加することが好ましく、０.０１〜５質量％、好ましくは０.１〜３質量％添加する。これよりも少ないと十分な抗菌性能が得られず、多すぎても乳化安定性などへの諸性能へ影響し、かつコスト面で不利となる。
In the present invention, as an antibacterial agent, an oil-soluble nitrogen-containing compound having a broad antibacterial spectrum in bacteria, yeast, and molds, and having low lubricity, emulsion stability, and copper corrosion resistance is used. The nitrogen-containing oil-soluble compound, it is preferred primary amine and morpholine derivative of 8 to 24 carbon atoms.
These antibacterial agents are preferably added to the base oil and / or water, and are added in an amount of 0.01 to 5% by mass, preferably 0.1 to 3% by mass. If it is less than this, sufficient antibacterial performance cannot be obtained, and if it is too much, it affects various performances such as emulsion stability and is disadvantageous in terms of cost.
一方、トリエタノールアミンは、弱塩基性でアルカリ維持剤として添加されるもので、他の添加剤との反応性などが低く、水溶性切削液などで広く用いられている。
トリエタノールアミンは水に対して添加し、水を基準に０.１〜１０質量％、好ましくは０.２〜７質量％添加すると良い。これより少ないと十分なアルカリ維持剤としての効果が認められず、多すぎると乳化安定性やコスト面で不利となる。
On the other hand, triethanolamine is weakly basic and is added as an alkali maintenance agent, has low reactivity with other additives, and is widely used in water-soluble cutting fluids.
Triethanolamine is added to water, and 0.1 to 10% by mass, preferably 0.2 to 7% by mass, based on water. If it is less than this, the effect as a sufficient alkali maintenance agent is not recognized, and if it is too much, it is disadvantageous in terms of emulsion stability and cost.
本発明の作動油には、さらに周知の極圧剤、腐食防止剤、摩耗防止剤、防錆剤、酸化防止剤、及び消泡剤などの添加剤を適宜配合することができる。極圧剤、摩耗防止剤としてジアルキルジチオリン酸亜鉛、硫黄系化合物、リン系化合物など、腐食防止剤としてのチアジアゾール誘導体、防錆剤として金属スルフォネートなど、酸化防止剤としてフェノール系、アミン系化合物など、及び消泡剤としてシリコーン系化合物、ＰＭＡポリマーなどが挙げられる。また、前記各種の添加剤は、数種が予め混合されたいわゆる添加剤パッケージの形で用いることもできる。 Additives such as well-known extreme pressure agents, corrosion inhibitors, antiwear agents, rust inhibitors, antioxidants, and antifoaming agents can be appropriately added to the hydraulic oil of the present invention. Extreme pressure agents, zinc alkyl dithiophosphates, sulfur compounds, phosphorus compounds, etc. as antiwear agents, thiadiazole derivatives as corrosion inhibitors, metal sulfonates, etc., phenols, amine compounds, etc. as antioxidants, Examples of antifoaming agents include silicone compounds and PMA polymers. The various additives can also be used in the form of a so-called additive package in which several kinds are mixed in advance.
上記の各種添加剤を基油、または水に配合し、それぞれ母液を調製し、高速ホモジナイザーなどの撹拌機を用いて、油側母液に水側母液を配合しながら、機械的に乳化することによりＷ／Ｏエマルション型難燃性作動油を得ることができる。Ｗ／Ｏエマルション型難燃性作動油で十分な難燃性を有するためには，通常，水側母液が４０容量％乳化される．この場合、基油には、乳化剤や摩耗防止剤などの油溶性添加剤を、また水には抗菌剤などの水溶性添加剤を配合して、混合することが好ましい。 By blending the above-mentioned various additives into the base oil or water, preparing a mother liquor, and mechanically emulsifying the water-side mother liquor with the oil-side mother liquor using a stirrer such as a high-speed homogenizer. A W / O emulsion type flame-retardant hydraulic oil can be obtained. In order to have sufficient flame retardancy with a W / O emulsion type flame retardant hydraulic oil, the water side mother liquor is usually emulsified by 40% by volume. In this case, it is preferable that the base oil is mixed with an oil-soluble additive such as an emulsifier or an anti-wear agent, and the water is mixed with a water-soluble additive such as an antibacterial agent.
Ｗ／Ｏエマルション型難燃性油圧作動油の供試油を調製するに当たり、次の基材を用いた。
ａ）基油：動粘度（４０℃）が２０mm2/s、粘度指数が１０５、流動点が−１５℃のパラフィン系鉱油。
ｂ）水：精製水
ｃ）添加剤：
(1)抗菌剤Ａ：アルキルアミン系［Ｃ１６〜２２の１級アルキルアミン］
抗菌剤Ｂ：モルホリン誘導体［ニトロブチルモルホリン］
抗菌剤Ｃ：トリアジン系化合物
(2)アルカリ維持剤：トリエタノールアミン
(3)乳化剤：Ｃａスルフォネート系ほか
(4)摩耗防止剤：ＺｎＤＴＰ
(5)腐食防止剤：チアジアゾール
In preparing the test oil of the W / O emulsion type flame retardant hydraulic fluid, the following base materials were used.
a) Base oil: Paraffinic mineral oil having a kinematic viscosity (40 ° C.) of 20 mm 2 / s, a viscosity index of 105, and a pour point of −15 ° C.
b) Water: Purified water c) Additives:
(1) Antibacterial agent A: alkylamine type [C16-22 primary alkylamine]
Antibacterial agent B: morpholine derivative [nitrobutylmorpholine]
Antibacterial agent C: Triazine compound
(2) Alkali maintenance agent: Triethanolamine
(3) Emulsifier: Ca sulfonate and others
(4) Antiwear agent: ZnDTP
(5) Corrosion inhibitor: thiadiazole
これらの基材を、表１に示す割合で混合し、高速ホモジナイザーで機械的に撹拌乳化して供試油１〜３及び比較油１、２のＷ／Ｏエマルション型難燃性油圧作動油を調製した。
これらの供試油及び比較油について、次の評価を行い、この結果を表１に示した。
ａ）ｐＨ
ｂ）全塩基価（ＪＩＳ Ｋ２５０１）
ｃ）潤滑性：シェル４球耐摩耗試験［1800rpm，40kgf/cm2，30min］
摩耗痕（mm）の計測
ｄ）乳化安定性：冷却−加熱サイクル試験［−15℃×72ｈ⇔25℃×24ｈ］
エマルション１００ｍｌにおける水−油分離量（ml）
ｅ）銅腐食性［装置：JIS K2510，銅板：JIS K2514，60℃，1500rpm，168hr］
銅板の腐食減量（mg）
These base materials are mixed in the proportions shown in Table 1, and mechanically stirred and emulsified with a high-speed homogenizer to give the W / O emulsion type flame-retardant hydraulic fluids of test oils 1 to 3 and comparative oils 1 and 2. Prepared.
These test oils and comparative oils were evaluated as follows, and the results are shown in Table 1.
a) pH
b) Total base number (JIS K2501)
c) lubricating: shell 4 Tama耐wear test [1800rpm, 40kgf / cm 2, 30min]
Measurement of wear scar (mm) d) Emulsification stability: Cooling-heating cycle test [-15 ° C x 72h⇔25 ° C x 24h]
Water-oil separation in 100 ml emulsion (ml)
e) Copper corrosive [Equipment: JIS K2510, Copper plate: JIS K2514, 60 ° C, 1500rpm, 168hr]
Copper plate corrosion weight loss (mg)
表１の供試油１〜３が示すようにアルカリ維持剤としてトリエタノールアミンを配合すると、ｐＨがアルカリ側にシフトした。比較油１と比べても、トリエタノールアミンの配合による潤滑性、乳化安定性、銅腐食性などの作動油としての特性に大きな影響がないことが分かる。一方、比較油２に示すように、高アルカリを示す抗菌剤Ｃを用いると銅腐食性の点で問題があることがわかる。 When Triethanolamine was blended as an alkali maintenance agent as shown in Test oils 1 to 3 in Table 1, the pH shifted to the alkali side. Even when compared with Comparative Oil 1, it can be seen that there is no significant influence on characteristics as hydraulic oil such as lubricity, emulsification stability, copper corrosiveness, etc., by blending triethanolamine. On the other hand, as shown in Comparative Oil 2, it is found that there is a problem in terms of copper corrosivity when antibacterial agent C showing high alkali is used.
ｐＨが５.７にまで下がった使用油と上記供試油２又は比較油１を表２に示す割合で配合し、ｐＨの変化を観察した。この結果を表２に示した。 The used oil whose pH was lowered to 5.7 and the above sample oil 2 or comparative oil 1 were blended in the proportions shown in Table 2, and the change in pH was observed. The results are shown in Table 2.
表２に示すように、トリエタノールアミンを配合した供試油２は，比較油１に比べて、混合量に対するｐＨの変化が少なく、良好なアルカリ維持性能を示した。アルカリ性を維持することによって、微生物の繁殖しにくい環境にできるとともに、アルカリ域で効力を発揮する抗菌剤の抗菌性能を長期に渡って維持できることを示すものである As shown in Table 2, the sample oil 2 blended with triethanolamine showed less change in pH with respect to the mixing amount than the comparative oil 1 and showed good alkali maintenance performance. By maintaining the alkalinity, it is possible to create an environment in which microorganisms are difficult to propagate, and also to maintain the antibacterial performance of antibacterial agents that are effective in the alkaline region over a long period of time.
本発明は、特定の種類の抗菌剤とトリエタノールアミンとを配合したために、銅腐食性や潤滑性などの作動油としての性能を損なわずに、また抗菌剤の効能を長期間持続できるアルカリ維持性を高めたものであり、Ｗ／Ｏエマルション型難燃性油圧作動油として非常に有用なものである。 Since the present invention is formulated with a specific type of antibacterial agent and triethanolamine, it maintains alkali so that the performance of the antibacterial agent can be maintained for a long time without impairing the performance as a hydraulic oil such as copper corrosiveness and lubricity. It is highly useful as a W / O emulsion type flame retardant hydraulic fluid.
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