JP6126377B2 - Method for improving flash point of oil or oil composition and oil-based composition with improved flash point - Google Patents
Method for improving flash point of oil or oil composition and oil-based composition with improved flash point Download PDFInfo
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- Organic Insulating Materials (AREA)
Description
本発明は、油類又は油類組成物に対する引火点を向上させる方法及び引火点が向上された油性組成物に関し、特に、消防法に定める危険物第４類の引火性流体及び指定可燃物の可燃性液体類に対する引火点向上方法などに係わり、更に詳しくは、１気圧・温度２０℃において液体であって、引火点が１５０℃以上の第三石油類及び引火点が２００〜２５０℃の第四石油類、又は引火点が２５０℃以上の可燃性液体類に対する引火点を向上させる方法及び引火点が向上された油性組成物に関する。 The present invention relates to a method for improving the flash point of oils or oil compositions, and an oily composition having an improved flash point, and more particularly, to a flammable fluid of Class 4 flammable fluids and designated combustibles specified in the Fire Service Act. The present invention relates to a method for improving the flash point for flammable liquids, and more specifically, a third petroleum having a flash point of 150 ° C. or higher and a flash point of 200 to 250 ° C. The present invention relates to a method for improving the flash point of four petroleums or flammable liquids having a flash point of 250 ° C. or higher, and an oily composition having an improved flash point.
消防法によって危険物第４類に規定されている引火性流体や、指定可燃物に規定されている可燃性液体類には、主として石油類や動植物油等の油類が含まれている。これらのものは引火性があるために消防法によって危険物に指定されているが、引火点が低いほど火災のリスクが高いことから、引火点に応じて、その取り扱いや貯蔵量などについて法的な規制が行われている。 The flammable fluids stipulated by the Fire Service Act as Class 4 hazardous materials and the flammable liquids stipulated by designated combustibles mainly contain oils such as petroleum and animal and vegetable oils. Since these are flammable, they are designated as dangerous goods by the Fire Service Act. However, the lower the flash point, the higher the risk of fire, so depending on the flash point, the handling and storage amount is legal. Regulations are in place.
引火点が上昇することは、火気取扱い上も安全性を増し、その貯蔵や管理などの取り扱いも容易になるから、貯蔵に要する設備や管理コストを低減することができることとなる。このように引火点が高いほど安全性が高くなり、貯蔵や管理も容易かつ経済的に取り扱うことができるところから、石油類の引火点を向上させるために種々の方法が採られてきたが、従来、主として、石油類の低蒸気圧成分への改質や蒸留による高蒸気圧成分の除去などによって行われてきた。 An increase in the flash point increases safety in handling the fire and facilitates handling such as storage and management, so that facilities and management costs required for storage can be reduced. In this way, the higher the flash point, the higher the safety, and the easier it is to handle storage and management easily and economically, so various methods have been adopted to improve the flash point of petroleum. Conventionally, it has been carried out mainly by reforming petroleum to low vapor pressure components or removing high vapor pressure components by distillation.
しかし、上記従来の方法は石油類の分子構造や構成成分を変化させる必要があるため、石油類の製造段階において物理的・化学的操作を行う必要があり、そのために製造や精製設備に高いコストを必要とするものであった。更に、石油類の分子構造や構成成分の変化によって、引火点以外の物理的・化学的特性にも変化を引き起こすこともあって、その処理操作に困難を伴う点もあった。 However, the conventional methods described above require changes in the molecular structure and constituents of petroleum, so that it is necessary to perform physical and chemical operations in the petroleum production stage, which results in high costs for production and refining equipment. Was necessary. In addition, changes in the molecular structure and constituents of petroleum may cause changes in physical and chemical properties other than the flash point, and the treatment operation is difficult.
また、添加物を使用するものとしては、変圧器油又は絶縁油に、有機フッ素化合物であるペルフルオロアルキルプロミドなどの着火抑制剤を添加して、電気機器において短絡が生じたときのアークが鉱油を発火させ爆発や火災を起すことを抑制するものも知られている。（特許文献１） In addition, as for the use of additives, an arc inhibitor when a short circuit occurs in an electrical device by adding an ignition suppression agent such as perfluoroalkylpromide which is an organic fluorine compound to transformer oil or insulating oil is a mineral oil. Some have been known to suppress the occurrence of explosions and fires. (Patent Document 1)
上記の如く、油類又は油類組成物の引火点を上昇させる為には、油類の製造、精製段階から対応する必要があり、既に製造、精製された油類又は油類組成物の引火点を上昇させるための有効な手段がなかったが、これを簡易な手段によって行えるようにしようとするものである。 As described above, in order to increase the flash point of oils or oil compositions, it is necessary to respond from the production and refining stages of oils, and the flash points of oils or oil compositions that have already been produced and refined. There was no effective means for raising the point, but this is intended to be done by simple means.
本発明者らは、油類又は油類組成物の引火点を上昇させるために、種々の検討と研究を重ねていたが、ある種のシリコーン化合物を油類又は油類組成物に少量加えたところ引火点が上昇することを見出し、こうした知見に基づいて本発明を完成した。
一般に、シリコーン化合物は、絶縁油、ダンパー油、熱媒体油等の各種潤滑油の組成材料、樹脂や液体の潤滑性付与剤や消泡剤など工業製品の添加剤として広く使用されているが、本発明は、ジアルキルポリシロキサンの少なくとも１種を有効成分として、少量を油類又は油類組成物に加えて、それらの引火点を向上させるようにしたものである。
In order to increase the flash point of oils or oil compositions, the present inventors have made various studies and researches, but added a small amount of certain silicone compounds to oils or oil compositions. However, the present inventors have found that the flash point is increased and completed the present invention based on such knowledge.
Generally, silicone compounds are widely used as additives for industrial products such as composition materials for various lubricating oils such as insulating oil, damper oil, heat medium oil, resin and liquid lubricity imparting agents and antifoaming agents. In the present invention, at least one dialkylpolysiloxane is used as an active ingredient, and a small amount is added to oils or oil compositions to improve their flash points.
上記ジアルキルポリシロキサンは、２５℃動粘度が５０ｍｍ２／ｓを超えて１０００ｍｍ２／ｓ以下のものが使用される。
こうしたジアルキルポリシロキサンとして、ジメチルポリシロキサンやジエチルポリシロキサンの１つ又は必要により数種のものを適宜に組合わせて、油類又は油類組成物に１〜１００質量ｐｐｍ程度の少量を添加することにより引火点を上昇させる。
As the dialkylpolysiloxane, those having a kinematic viscosity at 25 ° C. of more than 50 mm 2 / s and 1000 mm 2 / s or less are used.
As such a dialkylpolysiloxane, one of dimethylpolysiloxane and diethylpolysiloxane or a combination of several kinds as required is appropriately added, and a small amount of about 1 to 100 ppm by mass is added to oils or oil compositions. To raise the flash point.
本発明によれば、引火性を有する油類又は油類組成物に上記した引火点向上剤を添加することによって、物理的・化学的な特性の双方に大きな変化を引き起こすことなく引火点を容易に上昇させることができる。これにより、この引火点向上剤を添加するという簡易な方法で、油類又は油類組成物の安全性を高め、貯蔵や管理も容易で、経済的に取り扱うことができるようになる。 According to the present invention, by adding the above-mentioned flash point improver to flammable oils or oil compositions, the flash point can be easily increased without causing a large change in both physical and chemical properties. Can be raised. Thereby, by the simple method of adding this flash point improving agent, the safety | security of oil or oil composition can be improved, a storage and management are also easy and can be handled economically.
本発明における、引火性を有する油類又は油類組成物としては、主として、消防法に定める引火点が７０℃以上の第三石油類、引火点が２００〜２５０℃の第四石油類や動植物油類、又は引火点が２５０℃以上の可燃性液体類などがある。また、この油類又は油類組成物としては、特に、飲食に供されないものに対して有効である。 In the present invention, the flammable oil or oil composition mainly includes third oils having a flash point of 70 ° C. or higher as defined by the Fire Service Act, fourth oils and animals and plants having a flash point of 200 to 250 ° C. There are oils or flammable liquids having a flash point of 250 ° C. or higher. Moreover, as this oil or oil composition, it is effective especially with respect to what is not provided to food and drink.
上記第三石油類、第四石油類、動植物油類、又は可燃性液体類は、引火点が比較的高く、加熱しない限り引火する危険性は少ないが、一旦火災になった場合には液温が非常に高くなるため、消火が困難な状況になることもある引火性液体類である。
第三石油類は、１気圧・温度２０℃において液体であって、引火点が７０℃以上で２００℃未満の引火性液体類であり、例えば、ＩＳＯ粘度グレード１０〜２２の鉱油若しくは合成炭化水素、脂肪酸エステル系の潤滑油基油、及びこれらを基油組成物として使った潤滑油などがある。本発明において引火点を上昇させる油類として、第三石油類の中でも好ましくは引火点が１５０℃以上で２００℃未満の油類を挙げることができる。
The third petroleums, fourth petroleums, animal and vegetable oils, or flammable liquids have a relatively high flash point, and there is little risk of igniting unless heated. Are very flammable liquids that can be difficult to extinguish.
Third petroleums are flammable liquids that are liquid at 1 atm and temperature of 20 ° C. and have a flash point of 70 ° C. or higher and lower than 200 ° C., for example, ISO viscosity grade 10-22 mineral oil or synthetic hydrocarbon And fatty acid ester-based lubricating base oils, and lubricating oils using these as base oil compositions. In the present invention, oils that increase the flash point include oils having a flash point of 150 ° C. or higher and lower than 200 ° C. among the third petroleums.
第四石油類は１気圧・温度２０℃において液体であって、引火点が２００℃以上で２５０℃未満のものであり、例えば、ＳＡＥ粘度グレードが３０、５Ｗ−３０、１０Ｗ−３０、１５Ｗ−４０等のエンジン油や、ＩＳＯ粘度グレードが３２〜６８の鉱油若しくは合成炭化水素、脂肪酸エステル系の潤滑油基油、及びこれらを基油組成物として使った潤滑油などがある。 The fourth petroleum is a liquid at 1 atm and a temperature of 20 ° C., and has a flash point of 200 ° C. or higher and lower than 250 ° C., for example, SAE viscosity grade is 30, 5W-30, 10W-30, 15W- Engine oils such as 40, mineral oils or synthetic hydrocarbons having an ISO viscosity grade of 32-68, fatty acid ester-based lubricating base oils, and lubricating oils using these as base oil compositions.
上記した動植物油類は、動物の脂肉等又は植物の種子若しくは果肉から抽出したものであり、１気圧・温度２０℃において液体であり、引火点が２５０℃未満のものであって、例えば、ヤシ油、アマニ油などが挙げられる。 The above-mentioned animal and vegetable oils are extracted from animal fat or the like or plant seeds or pulp, are liquid at 1 atm / 20 ° C., and have a flash point of less than 250 ° C., for example, Examples include coconut oil and linseed oil.
上記した可燃性液体類は、日本国の「危険物の規制に関する政令」（別表第四）に定義されている通り、１気圧において温度２０℃で液状を示すもので引火点が２５０℃以上のものである。 The flammable liquids described above are liquids at a temperature of 20 ° C at 1 atm as defined in Japan's “Decree on the Regulation of Dangerous Goods” (Appendix Table 4). Is.
上記第三石油類、第四石油類、動植物油類、又は可燃性液体類としては、鉱油又は合成油を挙げることができる。鉱油又は合成油としては、特に、ＡＰＩ（Ａｍｅｒｉｃａｎ Ｐｅｔｒｏｌｅｕｍ Ｉｎｓｔｉｔｕｔｅ，米国石油協会）基油カテゴリーでグループ１、グループ２、グループ３、グループ４などに属する基油、またはこれらの混合物を挙げることができる。 As said 3rd petroleum, 4th petroleum, animal and vegetable oils, or flammable liquids, mineral oil or synthetic oil can be mentioned. Examples of mineral oils or synthetic oils include base oils belonging to Group 1, Group 2, Group 3, Group 4, etc. in the API (American Petroleum Institute, American Petroleum Institute) base oil category, or mixtures thereof.
グループ１基油としては、例えば、原油を常圧蒸留して得られる潤滑油留分に対して、溶剤精製、水素化精製、脱ろうなどの精製手段を適宜組合せて適用することにより得られるパラフィン系鉱油を挙げることができる。
グループ２基油としては、例えば、原油を常圧蒸留して得られる潤滑油留分に対して、水素化分解、脱ろうなどの精製手段を適宜組合せて適用することにより得られたパラフィン系鉱油を挙げることができる。
As Group 1 base oil, for example, paraffin obtained by applying a suitable combination of solvent refining, hydrotreating, dewaxing, etc., to a lubricating oil fraction obtained by atmospheric distillation of crude oil Listed are mineral oils.
Group 2 base oils include, for example, paraffinic mineral oils obtained by appropriately combining refining means such as hydrocracking and dewaxing for lubricating oil fractions obtained by atmospheric distillation of crude oil Can be mentioned.
グループ３基油としては、例えば、原油を常圧蒸留して得られる潤滑油留分に対して、高度水素化精製により製造されるパラフィン系鉱油や、天然ガスの液体燃料化技術のフィッシャートロプッシュ法により合成されたＧＴＬ（ガストゥリキッド）、ワックスおよび脱ろうプロセスにて生成されるワックスをイソパラフィンに変換・脱ろうするＩＳＯＤＥＷＡＸプロセスにより精製された基油や、モービルＷＡＸ異性化プロセスにより精製された基油を挙げることができる。
グループ４基油としては、ポリオレフィンを挙げることができる。
Group 3 base oils include, for example, paraffinic mineral oil produced by advanced hydrorefining of lubricating oil fractions obtained by atmospheric distillation of crude oil, and Fischer Tropu, a natural gas liquid fuel technology. GTL (gas-to-liquid) synthesized by the method, wax and base oil refined by ISODEWAX process that converts and dewaxes wax produced by dewaxing process to isoparaffin, and refined by mobile WAX isomerization process Mention may be made of base oils.
Group 4 base oils include polyolefins.
合成油としては、上記のポリオレフィン、天然ガスの液体燃料化技術のフィッシャートロプッシュ法により合成されたＧＴＬ（ガストゥリキッド）油以外にも、例えば、アルキルベンゼン、アルキルナフタレン、エステル、ポリオキシアルキレングリコール、ポリフェニルエーテル、ジアルキルジフェニルエーテル、含フッ素化合物（パーフルオロポリエーテル、フッ素化ポリオレフィン等）など又はこれらの混合物などを挙げることができる。 Synthetic oils include, for example, alkylbenzene, alkylnaphthalene, ester, polyoxyalkylene glycol, in addition to the above-mentioned polyolefin, GTL (gas-tuly liquid) oil synthesized by the Fischer-Tropsch method of natural gas liquid fuel technology, Examples thereof include polyphenyl ether, dialkyl diphenyl ether, fluorine-containing compounds (perfluoropolyether, fluorinated polyolefin, etc.) and mixtures thereof.
上記第三石油類、第四石油類、動植物油類、又は可燃性液体類は、各種用途に使用することができる。これら用途としては、特に制限されるものではないが、油圧作動油、タービン油、圧縮機油、軸受油（油膜軸受油）、摺動面油、歯車油、真空ポンプ油、冷凍機油、熱媒体油、電気絶縁油等の工業用潤滑油、内燃機関用潤滑油、車両駆動系用潤滑油、車両パワートレイン用潤滑油などの用途が一例として挙げられる。 The third petroleum, fourth petroleum, animal and vegetable oils, or flammable liquids can be used for various applications. These applications are not particularly limited, but hydraulic oil, turbine oil, compressor oil, bearing oil (oil film bearing oil), sliding surface oil, gear oil, vacuum pump oil, refrigerator oil, heat medium oil Examples include industrial lubricating oils such as electrical insulating oils, internal combustion engine lubricating oils, vehicle drive system lubricating oils, vehicle powertrain lubricating oils, and the like.
上記第三石油類、第四石油類、動植物油類、又は可燃性液体類は、性能を向上させるため、種々の添加剤が必要に応じて添加されていてもよい。これら添加剤としては、酸化防止剤、金属不活性剤、極圧剤、油性向上剤、シリコーン系以外のアルコール系消泡剤やポリアクリル酸エチル系消泡剤、粘度指数向上剤、流動点降下剤、清浄分散剤、防錆剤、抗乳化剤等や、その他の公知の添加剤を挙げることができる。 In order to improve the performance of the third petroleums, fourth petroleums, animal and vegetable oils, or flammable liquids, various additives may be added as necessary. These additives include antioxidants, metal deactivators, extreme pressure agents, oiliness improvers, non-silicone alcohol defoamers and polyethyl acrylate defoamers, viscosity index improvers, pour point depressants. Agents, cleaning dispersants, rust inhibitors, demulsifiers, and other known additives.
上記の油類又は油類組成物には、ジアルキルポリシロキサンが添加される。このジアルキルポリシロキサンは２５℃における動粘度が５０ｍｍ２／ｓを超えて１０００ｍｍ２／ｓ以下のものであり、１０００ｍｍ２／ｓ未満のものが好ましいことがある。
また、このジアルキルポリシロキサンの２５℃における動粘度は、好ましくは７０ｍｍ２／ｓ以上で１０００ｍｍ２／ｓ以下（又は１０００ｍｍ２／ｓ未満）、より好ましくは２００ｍｍ２／ｓ以上で１０００ｍｍ２／ｓ以下（又は１０００ｍｍ２／ｓ未満）であってもよい。
A dialkylpolysiloxane is added to the oils or oil compositions. The dialkylpolysiloxane has a kinematic viscosity at 25 ° C. of more than 50 mm 2 / s and 1000 mm 2 / s or less, and preferably less than 1000 mm 2 / s.
The kinematic viscosity of this dialkylpolysiloxane at 25 ° C. is preferably 70 mm 2 / s or more and 1000 mm 2 / s or less (or less than 1000 mm 2 / s), more preferably 200 mm 2 / s or more and 1000 mm 2 / s or less. (Or less than 1000 mm 2 / s).
そして、上記ジアルキルポリシロキサンは、その１種又は複数種のものを適宜に組合せて用いることができる。添加するジアルキルポリシロキサンの動粘度が低すぎる（例えば５０ｍｍ２／ｓ以下となる）と、引火点を向上させる効果が期待できない虞があり、これはジアルキルポリシロキサンの分子量が小さいためと考えられる。 And the said dialkyl polysiloxane can be used combining the 1 type or multiple types of thing suitably. If the kinematic viscosity of the added dialkylpolysiloxane is too low (for example, 50 mm 2 / s or less), there is a possibility that the effect of improving the flash point cannot be expected, which is considered because the molecular weight of the dialkylpolysiloxane is small.
上記ジアルキルポリシロキサンの２５℃比重の値は特に制限されるものではないが、０．９６０を超えていてもよく、好ましくは０．９６５以上、より好ましくは０．９７０以上であってもよい。
上記ジアルキルポリシロキサンの粘度温度係数V.T.Cの値は特に制限されるものではないが、０.５９を超えていてもよく、好ましくは０．６０以上であってもよい。
また、上記ジアルキルポリシロキサンの２５℃屈折率の値は特に制限されるものではないが、１.４０２を超えていてもよく、好ましくは１.４０３以上であってもよい。
The value of the specific gravity at 25 ° C. of the dialkylpolysiloxane is not particularly limited, but may exceed 0.960, preferably 0.965 or more, and more preferably 0.970 or more.
The value of the viscosity temperature coefficient VTC of the dialkylpolysiloxane is not particularly limited, but may exceed 0.59, preferably 0.60 or more.
Further, the value of the 25 ° C. refractive index of the dialkylpolysiloxane is not particularly limited, but may exceed 1.402, and may preferably be 1.403 or more.
上記の粘度温度係数V.T.C（Viscosity Temperature Coefficient）とは、以下の式により算出されるもので、粘度温度係数V.T.Cが小さいほど、温度による粘度変化が小さいことを示している。
V.T.C＝１−〔２１０°F（98.9℃）の動粘度／１００°F（37.8℃）の動粘度〕
The viscosity temperature coefficient VTC (Viscosity Temperature Coefficient) is calculated by the following formula, and indicates that the smaller the viscosity temperature coefficient VTC, the smaller the viscosity change due to temperature.
VTC = 1- [Kinematic viscosity at 210 ° F. (98.9 ° C.) / Kinematic viscosity at 100 ° F. (37.8 ° C.)]
上記ジアルキルポリシロキサンとしては、アルキル基がメチルのジメチルポリシロキサンや、アルキル基がエチルのジエチルポリシロキサンが好ましく用いられ、特に、ジメチルポリシロキサンが好ましい。 As the dialkylpolysiloxane, dimethylpolysiloxane having an alkyl group of methyl and diethylpolysiloxane having an alkyl group of ethyl are preferably used, and dimethylpolysiloxane is particularly preferable.
こうしたジアルキルポリシロキサンは、ホモジナイザー等を使って油類又は油類組成物に直接添加して、溶解又は分散させることによって添加することができる。
また、必要に応じて、ジアルキルポリシロキサンを溶解することができる溶剤によってあらかじめ希釈溶液を作成し、これを油類又は油類組成物に加えて稀釈、分散させて添加することができる。
Such a dialkylpolysiloxane can be added by directly adding to an oil or oil composition using a homogenizer or the like and dissolving or dispersing it.
If necessary, a dilute solution can be prepared in advance with a solvent capable of dissolving the dialkylpolysiloxane, and this can be added to the oil or oil composition, diluted and dispersed.
上記ジメチルポリシロキサンの希釈溶液の作製に用いる溶剤としては、灯油、トルエン、シクロヘキサノン、メチルイソブチルケトン（ＭＩＢＫ）その他が使用できるが、所望のジアルキルポリシロキサンを容易に溶解又は分散できる溶剤であれば特に限定されず、各種のものが使用できる。
また、この溶剤として低引火点のものを使用した場合、希釈溶剤の量が多くなり過ぎると引火点を低下させることとなるので、溶剤の量は出来るだけ少なくするのが望ましく、油類又は油類組成物の全量に対して約０．５質量％以下で使用するのが好ましい。
As a solvent used for preparing the dilute solution of dimethylpolysiloxane, kerosene, toluene, cyclohexanone, methyl isobutyl ketone (MIBK) and the like can be used. Especially, any solvent that can easily dissolve or disperse a desired dialkylpolysiloxane. It is not limited and various things can be used.
In addition, when a solvent having a low flash point is used as this solvent, the flash point is lowered if the amount of the diluted solvent is excessively increased. Therefore, it is desirable to reduce the amount of the solvent as much as possible. It is preferably used in an amount of about 0.5% by mass or less based on the total amount of the composition.
上記したジアルキルポリシロキサンは、引火点を向上させようとする油類又は油類組成物の全量に対して１〜１００質量ｐｐｍの範囲で使用することができ、好ましくは１〜７０質量ｐｐｍの範囲、より好ましくは１〜３０質量ｐｐｍの範囲、更に好ましくは１〜１０質量ｐｐｍの範囲で使用するとよい。
ジアルキルポリシロキサンの濃度が低すぎると引火点を向上させる効果が期待できない虞があり、高すぎると良好な溶解、分散状態を維持することが困難となって、分離・沈降が起り、引火点向上効果が持続されない虞がある。
The above-mentioned dialkylpolysiloxane can be used in the range of 1 to 100 ppm by mass, preferably in the range of 1 to 70 ppm by mass, based on the total amount of oil or oil composition to be improved in flash point. More preferably, it is good to use in the range of 1-30 mass ppm, More preferably, it is 1-10 mass ppm.
If the dialkylpolysiloxane concentration is too low, the effect of improving the flash point may not be expected. If it is too high, it will be difficult to maintain a good dissolved and dispersed state, causing separation / sedimentation and improving the flash point. The effect may not be sustained.
以下に、本発明の方法及び引火点が向上された油性組成物について実施例および比較例によって具体的に説明するが、本発明はこれらによって何ら限定されるものではない。
実施例及び比較例を作製するために、下記のものを用意した。
The oily composition with improved flash point according to the method of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
The following were prepared in order to produce Examples and Comparative Examples.
（油類及び油類組成物）
油類１：米国石油協会（ＡＰＩ）潤滑油基油カテゴリーのグループ３に該当する高粘度指数の水素化精製基油〔性状等：密度が０.８４ｇ／ｍｌ（１５℃）、引火点（ＣＯＣ）が２３０℃、４０℃動粘度が３６ｍｍ２／ｓ、粘度指数が１３０、流動点が−１５℃、硫黄分が１質量ｐｐｍ、窒素分が１質量ｐｐｍ〕
油類組成物１：上記油類１に工業用添加剤パッケージ（IRGALUBE 2030A、BASF社製）を添加したものである。実施例・比較例のものでは、上記油類１の９９．５７質量％に対し、当該添加剤パッケージを０．４３質量％添加している。この工業用添加剤パッケージには、N-1-ナフチルアニリン、N,N-ビス(2-エチルヘキシル)-(4又は5)-メチル-1H-ベンゾトリアゾール-1-メチルアミン、(4-ノニルフェノキシ)酢酸、アルキル化ジフェニルアミン、立体障害ヒンダードフェノール、アシルサルコシン酸が含まれている。
(Oil and oil composition)
Oils 1: Hydrorefined base oil with high viscosity index corresponding to Group 3 of the American Petroleum Institute (API) lubricant base oil category [Properties, etc .: density is 0.84 g / ml (15 ° C), flash point (COC) ) 230 ° C., 40 ° C. kinematic viscosity 36 mm 2 / s, viscosity index 130, pour point −15 ° C., sulfur content 1 mass ppm, nitrogen content 1 mass ppm]
Oil composition 1: A product obtained by adding an industrial additive package (IRGALUBE 2030A, manufactured by BASF) to the oil 1 described above. In the examples and comparative examples, 0.43% by mass of the additive package is added to 99.57% by mass of the oils 1 described above. This industrial additive package includes N-1-naphthylaniline, N, N-bis (2-ethylhexyl)-(4 or 5) -methyl-1H-benzotriazol-1-methylamine, (4-nonylphenoxy) ) Acetic acid, alkylated diphenylamine, sterically hindered hindered phenol, acyl sarcosine acid.
（添加剤）
添加剤Ａ：ジメチルポリシロキサン（信越化学工業（株）製 KF96-1000CS）〔性状等：２５℃動粘度が１０００ｍｍ２／ｓ、２５℃比重が０.９７０、粘度温度係数V.T.Cが０.６０、２５℃屈折率が１.４０３〕
添加剤Ｂ：ジメチルポリシロキサン（信越化学工業（株）製 KF96-500CS）〔性状等：２５℃動粘度が５００ｍｍ２／ｓ、２５℃比重が０.９７０、粘度温度係数V.T.Cが０.６０、２５℃屈折率が１.４０３〕
添加剤Ｃ：ジメチルポリシロキサン（信越化学工業（株）製 KF96-200CS）〔性状等：２５℃動粘度が２００ｍｍ２／ｓ、２５℃比重が０.９７０、粘度温度係数V.T.Cが０.６０、２５℃屈折率が１.４０３〕
添加剤Ｄ：ジメチルポリシロキサン（信越化学工業（株）製 KF96-50CS）〔性状等：２５℃動粘度が５０ｍｍ２／ｓ、２５℃比重が０.９６０、粘度温度係数V.T.Cが０.５９、２５℃屈折率が１.４０２〕
添加剤Ｅ：ジメチルポリシロキサン（信越化学工業（株）製 KF96-30CS）〔性状等：２５℃動粘度が３０ｍｍ２／ｓ、２５℃比重が０.９５５、粘度温度係数V.T.Cが０.５８、２５℃屈折率が１.４０１〕
(Additive)
Additive A: Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd. KF96-1000CS) [Properties, etc .: 25 ° C. kinematic viscosity 1000 mm 2 / s, 25 ° C. specific gravity 0.970, viscosity temperature coefficient VTC 0.60, The refractive index at 25 ° C. is 1.403]
Additive B: Dimethylpolysiloxane (KF96-500CS, manufactured by Shin-Etsu Chemical Co., Ltd.) [Properties, etc .: 25 ° C. kinematic viscosity 500 mm 2 / s, 25 ° C. specific gravity 0.970, viscosity temperature coefficient VTC 0.60, The refractive index at 25 ° C. is 1.403]
Additive C: Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd. KF96-200CS) [Properties, etc .: 25 ° C. kinematic viscosity 200 mm 2 / s, 25 ° C. specific gravity 0.970, viscosity temperature coefficient VTC 0.60, The refractive index at 25 ° C. is 1.403]
Additive D: Dimethylpolysiloxane (KF96-50CS manufactured by Shin-Etsu Chemical Co., Ltd.) [Properties, etc .: 25 ° C. kinematic viscosity 50 mm 2 / s, 25 ° C. specific gravity 0.960, viscosity temperature coefficient VTC 0.59, The refractive index at 25 ° C. is 1.402]
Additive E: Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd. KF96-30CS) [Properties, etc .: 25 ° C. kinematic viscosity 30 mm 2 / s, 25 ° C. specific gravity 0.955, viscosity temperature coefficient VTC 0.58, Refractive index at 25 ° C. is 1.401]
（実施例１〜３）
上記添加剤Ａ〜Ｃについて灯油を溶媒として１０００倍の希釈液を作成し、これを表１に示す配合（表中の数値は質量％を示す）に基づいて油類１に添加剤Ａ〜Ｃ希釈液を加え、よく撹拌して、添加剤Ａ〜Ｃが最終的に５質量ｐｐｍの濃度となるようにし、実施例１〜３の油性組成物とした。
(Examples 1-3)
With respect to the additives A to C, a 1000-fold dilution was prepared using kerosene as a solvent, and the additives A to C were added to the oils 1 based on the formulation shown in Table 1 (the numerical values in the table indicate mass%). Diluent was added and stirred well so that the additives A to C finally had a concentration of 5 ppm by mass, whereby the oil compositions of Examples 1 to 3 were obtained.
（比較例１）
表１に示す配合に基づいて油類１に溶媒の灯油を加え、よく撹拌して油性組成物としたものである。
（比較例２、３）
上記添加剤Ｄ、Ｅについて灯油を溶媒として１０００倍の希釈液を作成し、これを表１に示す配合（表中の数値は質量％を示す）に基づいて油類１に添加剤Ｄ、Ｅ希釈液を加え、よく撹拌して、添加剤Ｄ、Ｅが最終的に５質量ｐｐｍの濃度となるようにし、比較例２、３とした。
(Comparative Example 1)
Based on the formulation shown in Table 1, kerosene as a solvent is added to the oils 1 and stirred well to obtain an oily composition.
(Comparative Examples 2 and 3)
With respect to the additives D and E, a 1000-fold dilution was prepared using kerosene as a solvent, and the additives D and E were added to the oils 1 based on the formulation shown in Table 1 (the values in the table indicate mass%). Diluents were added and stirred well so that the additives D and E finally had a concentration of 5 ppm by mass.
（実施例４〜６）
上記添加剤Ａ〜Ｃについて灯油を溶媒として１０００倍の希釈液を作成し、これを表２に示す配合（表中の数値は質量％を示す）に基づいて上記油類組成物１に添加剤Ａ〜Ｃ希釈液を加え、よく撹拌して、添加剤Ａ〜Ｃが最終的に５質量ｐｐｍの濃度となるようにし、実施例４〜６の油性組成物とした。
(Examples 4 to 6)
A 1000-fold dilution is prepared for the additives A to C using kerosene as a solvent, and the additive is added to the oil composition 1 based on the formulation shown in Table 2 (the numerical values in the table indicate mass%). The diluents A to C were added and stirred well so that the additives A to C finally had a concentration of 5 ppm by mass, whereby oil compositions of Examples 4 to 6 were obtained.
（比較例４）
表２に示す配合に基づいて油類組成物１に溶媒の灯油を加え、よく撹拌して油性組成物としたものである。
（比較例５、６）
上記添加剤Ｄ、Ｅについて灯油を溶媒として１０００倍の希釈液を作成し、これを表２に示す配合（表中の数値は質量％を示す）に基づいて油類組成物１に添加剤Ｄ、Ｅ希釈液を加え、よく撹拌して、添加剤Ｄ、Ｅが最終的に５質量ｐｐｍの濃度となるようにし、比較例５、６とした。
(Comparative Example 4)
Based on the formulation shown in Table 2, kerosene as a solvent is added to the oil composition 1 and stirred well to obtain an oily composition.
(Comparative Examples 5 and 6)
With respect to the additives D and E, a 1000-fold dilution was prepared using kerosene as a solvent, and this was added to the oil composition 1 based on the formulation shown in Table 2 (the values in the table indicate mass%). Comparative Examples 5 and 6 were prepared by adding E diluent and stirring well so that the additives D and E finally had a concentration of 5 ppm by mass.
（引火点の測定）
引火点は、ＪＩＳ Ｋ２２６５−４によるクリーブランド開放式自動引火点測定装置によって実施例と比較例の各試料について測定を行い、小数点以下１桁の四捨五入により求めた。
(Measure flash point)
The flash point was measured for each sample of the example and the comparative example with a Cleveland open type automatic flash point measuring device according to JIS K2265-4, and obtained by rounding off to one decimal place.
（引火点の測定結果）
引火点測定の結果を表１、表２に示す。
(Measurement result of flash point)
Tables 1 and 2 show the results of flash point measurement.
（引火点についての評価）
表１に示すように、実施例１〜３のものにおいては、比較例１の添加剤を添加しないものに対して引火点を８〜１６℃向上させることができることが判る。また、比較例２では添加剤Ｄを加えても引火点を上昇させることができないし、比較例３の添加剤Ｅを加えたものではむしろ引火点を８℃も降下させていることが判る。
また、表２に示すように、実施例４〜６のものにおいては、比較例４の添加剤を添加しないものに対して引火点を６〜１３℃向上させることができることが判る。また、比較例５では添加剤Ｄを加えても引火点を上昇させることができないし、比較例６の添加剤Ｅを加えたものではむしろ引火点を１０℃も降下させていることが判る。
(Evaluation of flash point)
As shown in Table 1, it can be seen that in Examples 1 to 3, the flash point can be improved by 8 to 16 ° C. relative to those in which the additive of Comparative Example 1 is not added. In addition, it can be seen that in Comparative Example 2, the flash point cannot be increased even if the additive D is added, and that in which the additive E of Comparative Example 3 is added, the flash point is rather lowered by 8 ° C.
Moreover, as shown in Table 2, in Examples 4-6, it turns out that a flash point can be improved 6-13 degreeC with respect to what does not add the additive of Comparative Example 4. FIG. In addition, it can be seen that in Comparative Example 5, the flash point cannot be raised even when the additive D is added, and the flash point is lowered by 10 ° C. rather than the additive E of Comparative Example 6.
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