JP2004352946A - Pour point depressant and hydrocarbon oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pour point depressant for hydrocarbon oils having improved pour point depressing capability, and a hydrocarbon oil composition comprising the agent. <P>SOLUTION: This pour point depressant comprises one or more types of oil-soluble polymers having a crosslinked structure such as a polymer having, as indispensable constituent monomers, a cross-linkable monomer having two or more vinyl groups, and an alkyl (meth)acrylate having an 8-32C alkyl group. The oil-soluble polymer or polymers satisfy formula (1): 5×ä(aMn)/(AMn)}≤Y≤200×ä(aMn)/(AMn)} (wherein Y is the amount of the crosslinkable monomer in wt.% per the weight of the polymer or polymers; (aMn) is the molecular weight of the crosslinkable monomer; and (AMn) is the number average molecular weight of the polymer or polymers). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００４７】
Ｙの好ましい範囲は上記式（２）で示される範囲であるが、更に好ましい範囲は０．１〜８０％、特に好ましい範囲は０．２〜５０％、最も好ましい範囲は０．４〜３０％である。
【００４８】
（Ａ１）の重量に基づく（ａ１）の割合は、好ましくは０．１〜８０％、さらに好ましくは０．２〜５０％、特に好ましくは０．４〜３０％である。
また、（ａ１）／（ｂ）は、好ましくは０．００１〜０．５、さらに好ましくは０．００５〜０．３である。
必要により使用できる（ｄ）は、（Ａ１）の重量に基づいて好ましくは０〜２０％、さらに好ましくは０〜１０％である。
【００４９】
本発明における重合体（Ａ２）の必須構成単量体である（ｃ１）としては、前述の（ｄ１１−１）および（ｄ１２）が挙げられる。
【００５０】
（Ａ２）の必須構成単量体である（ｂ）としては前述の（ｂ）が挙げられ、好ましいものも同様であり、必要により少量の（ｄ）および／または（ａ１）を併用することもできる。 （ｄ）および／または（ａ１）を併用する場合の（ｂ）の重量に基づく（ｄ）＋（ａ１）の重量割合は、好ましくは０〜１０％である。
【００５１】
架橋剤（ａ２）は、活性水素原子含有基と反応可能な官能基を２つ以上含有する化合物であり、例えば下記の有機ポリイソシアネート（ａ２−１）および下記のポリエポキシド化合物（ａ２−２）が挙げられる。（ａ２）は１種でも２種以上の併用でもよい。
【００５２】
（ａ２−１）；有機ポリイソシアネート
炭素数（ＮＣＯ基中の炭素を除く、以下同様）６〜２０の芳香族ポリイソシアネート、炭素数２〜１８の脂肪族ポリイソシアネート、炭素数４〜１５の脂環式ポリイソシアネート、炭素数８〜１５の芳香脂肪族ポリイソシアネートおよびこれらのポリイソシアネートの変性物（ウレタン基、カルボジイミド基、アロファネート基、ウレア基、ビューレット基、ウレトジオン基、ウレトイミン基、イソシアヌレート基、オキサゾリドン基含有変性物など）およびこれらの２種以上の混合物が含まれる。
【００５３】
上記芳香族ポリイソシアネートの具体例としては、１，３−および／または１，４−フェニレンジイソシアネート、２，４−および／または２，６−トリレンジイソシアネート（ＴＤＩ）、粗製ＴＤＩ、２，４’−および／または４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）、４，４’−ジイソシアナトビフェニル、３，３’−ジメチル−４，４’−ジイソシアナトビフェニル、３，３’−ジメチル−４，４’−ジイソシアナトジフェニルメタン、粗製ＭＤＩ［粗製ジアミノフェニルメタン〔ホルムアルデヒドと芳香族アミン（アニリン）またはその混合物との縮合生成物；ジアミノジフェニルメタンと少量（たとえば５〜２０重量％）の３官能以上のポリアミンとの混合物〕のホスゲン化物：ポリアリルポリイソシアネート（ＰＡＰＩ）］、１，５−ナフチレンジイソシアネート、４，４’，４”−トリフェニルメタントリイソシアネート、ｍ−およびｐ−イソシアナトフェニルスルホニルイソシアネートが挙げられる。
【００５４】
上記脂肪族ポリイソシアネートの具体例としては、エチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＤＩ）、ドデカメチレンジイソシアネート、１，６，１１−ウンデカントリイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２，６−ジイソシアナトメチルカプロエート、ビス（２−イソシアナトエチル）フマレート、ビス（２−イソシアナトエチル）カーボネート、２−イソシアナトエチル−２，６−ジイソシアナトヘキサノエートなどの脂肪族ポリイソシアネートが挙げられる。
【００５５】
上記脂環式ポリイソシアネートの具体例としては、イソホロンジイソシアネート（ＩＰＤＩ）、ジシクロヘキシルメタン−４，４’−ジイソシアネート（水添ＭＤＩ）、シクロヘキシレンジイソシアネート、メチルシクロヘキシレンジイソシアネート（水添ＴＤＩ）、ビス（２−イソシアナトエチル）−４−シクロヘキセン−１，２−ジカルボキシレート、２，５−および／または２，６−ノルボルナンジイソシアネートが挙げられる。
【００５６】
上記芳香脂肪族ポリイソシアネートの具体例としては、ｍ−および／またはｐ−キシリレンジイソシアネート（ＸＤＩ）、α，α，α’，α’−テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）が挙げられる。
【００５７】
また、上記ポリイソシアネートの変性物には、変性ＭＤＩ（ウレタン変性ＭＤＩ、カルボジイミド変性ＭＤＩ、トリヒドロカルビルホスフェート変性ＭＤＩ）、ウレタン変性ＴＤＩ、ビウレット変性ＨＤＩ、イソシアヌレート変性ＨＤＩ、イソシアヌレート変性ＩＰＤＩなどのポリイソシアネートの変性物およびこれらの２種以上の混合物［たとえば変性ＭＤＩとウレタン変性ＴＤＩ（イソシアネート含有プレポリマー）との併用］が含まれる。該ウレタン変性ポリイソシアネート［過剰のポリイソシアネート（ＴＤＩ、ＭＤＩなど）とポリオールとを反応させて得られる遊離イソシアネート含有プレポリマー］の製造に用いるポリオールとしては、当量が３０〜２００のポリオールたとえばエチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコールなどのグリコール；トリメチロールプロパン、グリセリンなどのトリオール；ペンタエリスリトール、ソルビトールなどの高官能ポリオール；およびこれらのアルキレンオキサイド（エチレンオキサイドおよび／またはプロピレンオキサイド）付加物が挙げられる。これらのうちで好ましいものは官能基数２〜３のものである。
上記変性ポリイソシアネートおよびプレポリマーの遊離イソシアネート基含量は通常８〜３３％、好ましくは１０〜３０％、とくに好ましくは１２〜２９％のものである。
【００５８】
これらのうちで好ましいものは芳香族ジイソシアネートであり、とくに好ましいものは２，４−および２，６−ＴＤＩおよびこれらの異性体の混合物、粗製ＴＤＩ、４，４’−および２，４’−ＭＤＩおよびこれらの異性体の混合物、粗製ＭＤＩ（ＰＡＰＩ）、およびこれらのポリイソシアネート類より誘導されるウレタン基、カルボジイミド基、アロファネート基、ウレア基、ビューレット基、イソシアヌレート基を含有する変性ポリイソシアネート類であり、最も好ましいのは変性ＭＤＩ［たとえばコロネートＣ−１０５９，Ｃ−１０５０（日本ポリウレタン製）、アイソネ―ト１６０Ｌ，１８１（化成アップジョン製）、スミジュールＰＣ，ＰＦ（住友バイエルウレタン製）］である。
【００５９】
（ａ２−２）；ポリエポキシド化合物
ポリエポキシド化合物には１分子中に２個もしくは３個以上、好ましくは２個のエポキシ基を有する脂肪族系、脂環族系、複素環系および芳香族系ポリエポキシドが含まれる。
【００６０】
芳香族系ポリエポキシドとしては、多価フェノールのグリシジルエーテル体およびグリシジル芳香族ポリアミンが挙げられる。
多価フェノールのグリシジルエーテル体としては、ビスフェノールＦジグリシジルエーテル、ビスフェノールＡジグリシジルエーテル、ビスフェノールＢジグリシジルエーテル、ビスフェノールＡＤジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、ハロゲン化ビスフェノールＡジグリシジル、テトラクロロビスフェノールＡジグリシジルエーテル、カテキンジグリシジルエーテル、レゾルシノールジグリシジルエーテル、ハイドロキノンジグリシジルエーテル、ピロガロールトリグリシジルエーテル、１，５−ジヒドロキシナフタリンジグリシジルエーテル、ジヒドロキシビフェニルジグリシジルエーテル、オクタクロロ−４，４’−ジヒドロキシビフェニルジグリシジルエーテル、フェノールまたはクレゾールノボラック樹脂のグリシジルエーテル体、ビスフェノールＡ２モルとエピクロロヒドリン３モルの反応から得られるジグリシジルエーテル体、フェノールとグリオキザール、グルタールアルデヒド、またはホルムアルデヒドの縮合反応によって得られるポリフェノールのポリグリシジルエーテル体、およびレゾルシンとアセトンの縮合反応によって得られるポリフェノールのポリグリシジルエーテル体が挙げられる。
グリシジル芳香族ポリアミンとしては、Ｎ，Ｎ−ジグリシジルアニリンおよびＮ，Ｎ，Ｎ’，Ｎ’−テトラグリシジルジフェニルメタンジアミンが挙げられる。
さらに、芳香族系ポリエポキシドには、トリレンジイソシアネートまたはジフェニルメタンジイソシアネートとグリシドールの付加反応によって得られるジグリシジルウレタン化合物、前記２反応物にポリオールも反応させて得られるグリシジル基含有ポリウレタン（プレ）ポリマーおよびビスフェノールＡのアルキレンオキシド（エチレンオキシドまたはプロピレンオキシド）付加物のジグリシジルエーテル体も含まれる。
【００６１】
複素環系ポリエポキシドとしては、トリスグリシジルメラミンが挙げられる。
【００６２】
脂環族系ポリエポキシドとしては、ビニルシクロヘキセンジオキシド、リモネンジオキシド、ジシクロペンタジエンジオキシド、ビス（２，３−エポキシシクロペンチル）エーテル、エチレングリコールビスエポキシジシクロペンチルエール、３，４−エポキシ−６−メチルシクロヘキシルメチル−３’，４’−エポキシ−６’−メチルシクロヘキサンカルボキシレート、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）アジペート、およびビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）ブチルアミンが挙げられる。また、脂環族系ポリエポキシドには前記芳香族系ポリエポキシドの核水添化物も含む。
【００６３】
脂肪族系ポリエポキシドとしては、多価脂肪族アルコールのポリグリシジルエーテル体、多価脂肪酸のポリグリシジルエステル体、およびグリシジル脂肪族アミンが挙げられる。
多価脂肪族アルコールのポリグリシジルエーテル体としては、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、テトラメチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、およびソルビトールポリグリシジルエーテルが挙げられる。
多価脂肪酸のポリグリシジルエステル体としては、ジグリシジルアジペートが挙げられる。
グリシジル脂肪族アミンとしては、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジルヘキサメチレンジアミンが挙げられる。
また、脂肪族系ポリエポキシドにはグリシジル（メタ）アクリレートの（共）重合体も含まれる。
【００６４】
（Ａ２）における、（ｃ１）と（ａ２）とのモル比（ｃ１）／（ａ２）は１〜２、好ましくは１．０〜１．５であり、（Ａ２）の重量に基づく（ａ２）の割合Ｙ％は、前述の（Ａ１）と同様に上記式（１）を満たすような割合である。
この場合は、先に（ｃ１）と（ｂ）および必要により（ｄ）からなる重合体のＭｎを測定しておき、（Ａ１）と同様にしてＹを決定する。
なお、（Ａ２）における他の単量体として（ａ１）を併用する場合は、式（１）におけるＹは、（ａ２）の重量として（ａ１）の重量も加えたものを用いて計算され、式（１）における（ａＭｎ）は（ａ２）と（ａ１）の合計の数平均分子量である。
Ｙが下限未満であれば流動点降下効果に劣り、上限を超える場合は基油への溶解性に劣る。
（Ａ２）においても、式（１）における（ａＭｎ）は、好ましくは７０〜２，０００、さらに好ましくは７０〜５００であり、（ＡＭｎ）は、好ましくは１，０００〜５００，０００、さらに好ましくは３，０００〜３０，０００である。
【００６５】
本発明における重合体（Ａ３）の必須構成単量体である（ｃ２）としては、下記のものが挙げられる。
【００６６】
（ｃ２−１）；エポキシ基含有モノビニル単量体
例えば、グルシジル（メタ）アクリレートおよび（メタ）アリルグリシジルエーテルが挙げられる。
【００６７】
（ｃ２−２）；イソシアネート基含有モノビニル単量体
例えばイソシアナトエチル（メタ）アクリレート、ｍ−イソプロペニル−α，α−ジメチルメチルベンジルイソシアネートが挙げられる。
【００６８】
（Ａ３）の必須構成単量体である（ｂ）としては前述の（ｂ）が挙げられ、好ましいものも同様であり、必要により少量の（ｄ）および／または（ａ１）を併用することもできる。 （ｄ）および／または（ａ１）を併用する場合の（ｂ）の重量に基づく（ｄ）＋（ａ１）の重量割合は、好ましくは０〜１０％である。
【００６９】
架橋剤（ａ３）は、活性水素原子含有基を２個以上含有する化合物であり、例えば下記の多価アルコール（ａ３−１）、多価フェノール（ａ３−２）、アンモニアおよび１級もしくは２級アミン（ａ３−３）、ポリカルボン酸（ａ３−４）、リン酸類（ａ３−５）、並びにポリチオール（ａ３−６）が挙げられる。（ａ３）は１種でも２種以上の併用でもよい。
【００７０】
（ａ３−１）；多価アルコール
例えば、エチレングリコール、プロピレングリコール、１，３−ブチレングリコ−ル、１，４−ブタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール、ビス（ヒドロキシメチル）シクロヘキサン、ビス（ヒドロキシエチル）ベンゼンなどの２価アルコール；グリセリン、トリメチロールプロパン、ペンタエリスリトール、ジグリセリン、α−メチルグルコシド、ソルビトール、キシリット、マンニット、ジペンタエリスリトール、グルコース、フルクトース、ショ糖などの３〜８価の多価アルコールが挙げられる。
【００７１】
（ａ３−２）；多価フェノール類
例えば、ピロガロール、カテコール、ヒドロキノンなどの多価フェノール；ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳなどのビスフェノール類が挙げられる。
【００７２】
（ａ３−３）；アンモニアおよび１級もしくは２級アミン類
例えば、アンモニア、炭素数１〜２０のアルキルアミン類（ブチルアミンなど）、アニリンなどのモノアミン類；エチレンジアミン、トリメチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミンなどの脂肪族ポリアミン；ピペラジン、Ｎ−アミノエチルピペラジンおよびその他特公昭５５−２１０４４号公報記載の複素環式ポリアミン類；ジシクロヘキシルメタンジアミン、イソホロンジアミンなどの脂環式ポリアミン；フェニレンジアミン、トリレンジアミン、ジエチルトリレンジアミン、キシリレンジアミン、ジフェニルメタンジアミン、ジフェニルエーテルジアミン、ポリフェニルメタンポリアミンなどの芳香族ポリアミン；および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、トリイソプロパノールアミンなどのアルカノールアミン類が挙げられる。
【００７３】
（ａ３−４）；ポリカルボン酸
例えば、コハク酸、アジピン酸などの脂肪族ポリカルボン酸、フタル酸、テレフタル酸、トリメリット酸などの芳香族ポリカルボン酸があげられる。
【００７４】
（ａ３−５）；リン酸類
例えば、燐酸、亜燐酸、ホスホン酸が挙げられる。
【００７５】
（ａ３−６）；ポリチオール
例えば、グリシジル基含有化合物と硫化水素との反応で得られる多価ポリチオール化合物が挙げられる。
【００７６】
重合体（Ａ３）における、（ｃ２）と（ａ３）とのモル比（ｃ２）／（ａ３）は１〜２、好ましくは１．０〜１．５であり、（Ａ３）の重量に基づく（ａ３）の割合Ｙ％は、前述の（Ａ１）と同様に上記式（１）を満たすような割合である。なお、（Ａ３）における他の単量体として（ａ１）を併用する場合は、式（１）におけるＹは、架橋剤（ａ３）の重量として（ａ１）の重量も加えたものを用いて計算され、式（１）における（ａＭｎ）は（ａ３）と（ａ１）の合計の数平均分子量である。
Ｙが下限未満であれば流動点降下効果に劣り、上限を超える場合は基油への溶解性に劣る。
（Ａ３）においても、式（１）における（ａＭｎ）は、好ましくは７０〜２，０００、さらに好ましくは７０〜５００であり、（ＡＭｎ）は、好ましくは１，０００〜５００，０００、さらに好ましくは３，０００〜３００，０００である。
【００７７】
本発明における結晶化温度（以下Ｔｃと略記する）は、ＰＥＲＫＩＮ−ＥＬＭＥＲ社製 示差走査熱量計（ＵＮＩＸ−ＤＳＣ７：ＵＮＩＸは登録商標）を使用し、試料５ｍｇを１４０℃から−８０℃まで１０℃／分の等温速度で冷却したときに観測される結晶化による吸熱ピーク温度（℃）である。
【００７８】
（Ａ１）、（Ａ２）および（Ａ３）のＴｃは、好ましくは−５０℃〜１０℃、さらに好ましくは−４５℃〜０℃、特に好ましくは−４０℃〜−１０℃である。Ｔｃが−５０℃以上および１０℃以下では、流動点降下能に優れている点で好ましい。
【００７９】
（Ａ１）または架橋剤で架橋する前の重合体を製造する方法は、従来から知られているラジカル重合方法でよく、例えば溶液重合法、乳化重合法、懸濁重合法、逆相懸濁重合法、薄膜重合法、噴霧重合法等が挙げられる。これらのうち、好ましいのは溶液重合法であり、通常、溶剤中で、開始剤存在下で単量体をラジカル重合させる方法である。
溶剤には、鉱物油［溶剤精製油、水素化改質油、イソパラフィンを含有するおよび／または水素化分解による粘度指数１００〜１６０の高粘度指数油、ナフテン系オイル］並びに合成潤滑油［炭化水素系合成潤滑油（ポリα−オレフィン系合成潤滑油など）およびエステル系合成潤滑油］などの高引火点溶剤（引火点１３０℃以上）；その他の溶剤［脂肪族炭化水素（ペンタン、ヘキサン等）、芳香族炭化水素（トルエン、キシレン等）、アルコール系溶剤［イソプロピルアルコール（以下、ＩＰＡと略記）、オクタノール、ブタノール等］、ケトン系溶媒（メチルイソブチルケトン、メチルエチルケトン等）、アミド系溶媒（Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン等）、スルホキシド系溶媒（ジメチルスルホキシド等）］およびこれらの２種以上の併用が含まれる。好ましいのは、高引火点溶剤および芳香族炭化水素である。
開始剤には、アゾ系開始剤、過酸化物系開始剤およびレドックス系開始剤が含まれる。
アゾ系開始剤としては、２，２’−アゾビス（２，４−ジメチルバレロニトリル）（以下、ＡＶＮと略記）、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）、アゾビスシアノ吉草酸およびその塩（例えば塩酸塩など）、２，２′−アゾビス（２−アミジノプロパン）ハイドロクロライド、２，２′−アゾビス（２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミドなどが挙げられる。
過酸化物系開始剤には、無機過酸化物［例えば、過酸化水素、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウムなど］および有機過酸化物［例えば、ベンゾイルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、クメンヒドロパーオキサイド、コハク酸パーオキサイド、ジ（２−エトキシエチル）パーオキシジカーボネート、ｔ−ブチルパーオキシピバレート、ｔ−ヘキシルパーオキシピバレート、ｔ−ブチルパーオキシネオヘプタノエート、ｔ−ブチルパーオキシネオデカノエート、ｔ−ブチルパーオキシ２−エチルヘキサノエート、ｔ−ブチルパーオキシイソブチレート、ｔ−アミルパーオキシ２−エチルヘキサノエート、１，１，３，３−テトラメチルブチルパーオキシ２−エチルヘキサノエート、ジブチルパーオキシトリメチルアジペート、ラウリルパーオキシドなど］が含まれる。
レドックス系触媒には、アルカリ金属の亜硫酸塩および重亜硫酸塩（例えば、亜硫酸アンモニウム、重亜硫酸アンモニウムなど）、塩化第一鉄、硫酸第一鉄、アスコルビン酸などの還元剤とアルカリ金属の過硫酸塩、過硫酸アンモニウム、過酸化水素、有機過酸化物などの酸化剤との組合せよりなるものが含まれる。
開始剤の使用量は、モノマーの合計重量に基づいて、好ましくは０．０５〜２％、さらに好ましくは０．１〜１％である。
連鎖移動剤を使用してもよく、例えばメルカプタン類［ｎ−ラウリルメルカプタン（以下、ＬＳＨと略記する）、メルカプトエタノールおよびメルカプトプロパノールなど］、チオカルボン酸類（チオグリコール酸およびチオリンゴ酸など）、２級アルコール類（イソプロパノ−ルなど）、アミン類（ジブチルアミンなど）および次亜燐酸塩類（次亜燐酸ナトリウなど）が挙げられる。連鎖移動剤の使用量はモノマーの合計重量に基づいて、好ましくは０〜７％、さらに好ましくは０．０５〜５％である。
【００８０】
重合温度は、好ましくは３０〜１４０℃、さらに好ましくは５０〜１３０℃、特に７０〜１２０℃である。重合温度は断熱重合法または温度制御重合法によって制御できる。
また、熱による重合開始の方法の他に、放射線、電子線、紫外線などを照射して重合を開始させる方法を採ることもできる。好ましいものは温度制御した溶液重合法である。
共重合の様式は、ランダム付加重合または交互共重合のいずれでもよく、またグラフト共重合またはブロック共重合のいずれでもよい。
【００８１】
（Ａ２）は、上記の方法で重合体を得た後、（ａ２）を用いて架橋反応させることで得られる。
【００８２】
架橋反応の方法は、断熱法、温度制御法が挙げられる。反応温度としては、好ましくは３０〜１４０℃、さらに好ましくは５０〜１３０℃、特に好ましくは７０〜１２０℃である。また、必要により触媒を添加することができる。
【００８３】
重合体中の活性水素原子含有基と（ａ２）との反応を促進するための触媒としては、金属触媒たとえば錫系触媒［トリメチルチンラウレート、トリメチルチンヒドロキサイド、ジメチルチンジラウレート、ジブチルチンジアセテート、ジブチルチンジラウレート、スタナスオクトエート、ジブチルチンマレエートなど］、鉛系触媒［オレイン酸鉛、２−エチルヘキサン酸鉛、ナフテン酸鉛、オクテン酸鉛など］、その他の金属触媒［ナフテン酸コバルトなどのナフテン酸金属塩、フェニル水銀プロピオン酸塩など］；およびアミン系触媒たとえばトリエチレンジアミン、テトラメチルエチレンジアミン、テトラメチルヘキシレンジアミン、ジアザビシクロアルケン類［１，８−ジアザビシクロ［５，４，０］ウンデセン−７｛ＤＢＵ（サンアプロ製、登録商標）｝など］；ジアルキルアミノアルキルアミン類［ジメチルアミノエチルアミン、ジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン、ジブチルアミノエチルアミン、ジメチルアミノオクチルアミン、ジプロピルアミノプロピルアミンなど］または複素環式アミノアルキルアミン類［２−（１−アジリジニル）エチルアミン、４−（１−ピペリジニル）−２−ヘキシルアミンなど］の炭酸塩および有機酸塩（ギ酸塩など）等；Ｎ−メチルモルホリン、Ｎ−エチルモルホリン、トリエチルアミン、ジエチルエタノールアミン、ジメチルエタノールアミン等；およびこれらの２種以上の併用系が挙げられる。
【００８４】
（Ａ３）は、上記の方法で重合体を得た後、（ａ３）を用いて架橋反応させるることで得られる。
【００８５】
架橋反応の方法は、断熱法、温度制御法が挙げられる。好ましい反応温度は上記（Ａ２）における架橋反応の場合と同様である。また、必要により前述の触媒を添加することができる。
【００８６】
なお、上記の製造法で得られる（Ａ１）、（Ａ２）または（Ａ３）の分子には、それぞれ（ａ１）、（ａ２）または（ａ３）を含有しない分子も副生することがあっても、本発明においては、これらも含めて（Ａ１）、（Ａ２）または（Ａ３）とする。
【００８７】
（Ａ１）の具体例としては、例えば、
（１）：エチレングリコールジメタクリレート（Ｍｎ＝１９８）（１．３％）／ＭＡ−１６（３０％）／ＭＡ−１４（３０％）／ＭＡ−１２（３８．７％）からなる重合体（Ｍｎ＝・２０，０００）、Ｙ＝１．３、式（１）の左辺の値＝０．０５０、式（１）の右辺の値＝１．９８、
（２）：ペンタエリスリトールテトラアクリレート１．０％（Ｍｎ＝３５２）／ＭＡ−１６（２５％）／ＭＡ−１８（１０％）／ＭＡ−１２（６４％）からなる重合体、（Ｍｎ＝２０，０００）、Ｙ＝１．０、式（１）の左辺の値＝０．０８８、式（１）の右辺の値＝３．５２、
（Ａ２）の具体例としては、例えば
（１）：エチレングリコールモノメタクリレート０．８％／ＭＡ−１８（２０％）／ＭＡ−１２（８０％）からなる重合体をヘキサメチレンジイソシアネート（Ｍｎ＝１６８）１％で架橋反応した重合体、（Ｍｎ＝２０，０００）、Ｙ＝１．０、式（１）の左辺の値＝０．０４２、式（１）の右辺の値＝１．６８、が挙げられる。
【００８８】
本発明の流動点降下剤組成物は、（Ａ）、並びに希釈剤および／または他の添加剤からなり、希釈剤で溶解・希釈することにより基油への溶解が容易になる点で好ましい。希釈剤としては、前述の（Ａ）の製造法において挙げた溶剤と同様のものが使用でき、（Ａ）の重合工程で使用した溶剤を除去せずにそのまま残しておいてもよい。希釈剤として好ましいのは高引火点溶剤および芳香族炭化水素である。
（Ａ）が希釈剤に溶解しにくい場合は、加熱（好ましくは４０〜１５０℃）して溶解することが好ましい。
流動点降下剤組成物が（Ａ）と希釈剤のみからなる場合の、（Ａ）と希釈剤の割合は、通常（Ａ）が１％以上で希釈剤が９９％以下、好ましくは（Ａ）が１０〜９０％で希釈剤が１０〜９０％、さらに好ましくは（Ａ）が２０〜９０％で希釈剤が１０〜８０％である。
【００８９】
流動点降下剤組成物中の他の添加剤としては、前述の（ｂ）、（ｃ１）、（ｃ２）および（ｄ）からなる群から選ばれる１種以上の単量体から構成される非架橋型ビニル重合体（Ｂ）が例示される。
【００９０】
（Ｂ）を構成する単量体のうち、好ましいのは（ｂ）、（ｄ１）〜（ｄ７）、および（ｄ１０）〜（ｄ１２）からなる群から選ばれる少なくとも１種、並びにそれと他のモノマーの少なくとも１種との併用（共重合重量比は少なくとも５０／５０、好ましくは少なくとも９５／５）であり、さらに好ましいのは（ｂ）、並びに（ｂ）と（ｄ１）のうちの少なくとも１種との併用（共重合重量比は少なくとも５０／５０、好ましくは少なくとも９５／５）である。
【００９１】
（Ｂ）を構成する（ｂ）のうち、特に好ましいのは炭素数８〜２４さらに好ましくは炭素数１２〜１８の直鎖もしくは分岐のアルキル基を有する（メタ）アクリル酸エステルである。
（Ｂ）のＭｗは通常５，０００〜１，０００，０００、好ましくは２０，０００〜４００，０００である。
【００９２】
（Ｂ）の具体例としては、例えば、ＭＡ−１２（３０〜８０％）／ＭＡ−１８（２０〜７０％）からなる共重合体、およびメチルメタクリレート（０〜３０％）／ＭＡ−１２（１０〜４０％）／ＭＡ−１４（１０〜４０％）／ＭＡ−１６（０〜２０％）共重合体などが挙げられる。
【００９３】
（Ｂ）／（Ａ）の重量比は、好ましくは０〜１０／１、さらに好ましくは０．０１〜３／１である。
（Ｂ）の添加の目的は粘度指数の改善（向上）と低温粘度の改善（低下）である。
【００９４】
本発明の流動点降下剤組成物における他の添加剤としては、（Ｂ）以外にさらに以下のものが例示できる。
清浄剤［スルフォネート系、サリシレート系、フェネート系、ナフテネート系などのＣａやＭｇ塩および炭酸カルシウムなど］、分散剤［コハク酸イミド系（ビスタイプ、モノタイプ、ボレートタイプおよびマンニッヒ縮合物系など）］、抗酸化剤［アミン系（ジフェニルアミンなど）、ヒンダードフェノール系（トリアルキルフェノールなど）およびジンクジチオフォスフェートなど］、公知の摩擦調整剤［長鎖脂肪酸（オレイン酸など）、長鎖脂肪酸エステル（オレイン酸エステルなど）、長鎖アミン系（オレイルアミンなど）、長鎖アミド（オレアミドなど）］、耐摩耗剤［モリブデンジチオフォスフェート、モリブデンジチオカーバメイトおよびジンクジアルキルジチオフォスフェートなど］、極圧剤［硫黄系（ジアルキルジスルフィド）、リン系（リン酸エステル、亜リン酸エステル）およびハロゲン系（塩素化炭化水素）など］、消泡剤［シリコーン油および金属石けんなど］、抗乳化剤［４級アンモニウム塩、硫酸化油およびリン酸エステルなど］並びに腐食防止剤［ベンゾトリアゾールおよび１，３，４−チオジアゾリル−２，５−ビスジアルキルジチオカルバメートなど］。
【００９５】
（Ｂ）以外の添加剤の流動点降下剤組成物における添加量は、後述の炭化水素油組成物の重量に基づくこれらの添加剤の含有量が以下のようになる添加量である。
清浄剤は通常０〜２０％、好ましくは０．１〜１０％、分散剤は通常０〜２０％、好ましくは０．２〜１０％、抗酸化剤は通常０〜５％、好ましくは０．１〜３％、公知の摩擦調整剤は通常０〜５％、好ましくは０．１〜１％、耐摩耗剤は通常０〜１０％、好ましくは０．１〜３％、極圧剤は通常０〜２０％、好ましくは０．１〜１０％、消泡剤は通常２〜１，０００ｐｐｍ、好ましくは１０〜７００ｐｐｍ、抗乳化剤は通常０〜３％、好ましくは０〜１％、および腐食防止剤は通常０〜３％、好ましくは０〜２％である。
【００９６】
流動点降下剤組成物の全重量に基づく、（Ｂ）も含めた他の添加剤の合計量は、通常０〜７０％、好ましくは０〜３０％、さらに好ましくは０〜１５％である。
また、流動点降下剤組成物が、（Ａ）、（Ｂ）も含めた他の添加剤、および希釈剤からなる場合の流動点降下剤組成物の重量に基づく希釈剤の割合は、通常希釈剤が９９％以下、好ましくは１０〜９０％、さらに好ましくは１０〜８０％である。
【００９７】
本発明の炭化水素油組成物は、基油と流動点降下剤および必要により他の添加剤、または基油と流動点降下剤組成物からなるものであるが、他の添加剤は流動点降下剤組成物の中に配合してから基油に配合してもよく、それぞれを別にして基油に配合してもよい。その場合の配合の順序は特に限定されない。
【００９８】
本発明の炭化水素油組成物には炭化水素系燃料油組成物および炭化水素系潤滑油組成物が含まれる。
本発明の炭化水素油系燃料油組成物に用いることのできる炭化水素油系燃料油としては、例えばＪＩＳ １号軽油、ＪＩＳ ２号軽油、ＪＩＳ ３号軽油、ＪＩＳ 特３号軽油、ＪＩＳ Ａ重油、ＪＩＳ Ｂ重油、ＪＩＳ Ｃ重油などの原油を原料とする燃料油が挙げられ、硫黄含量が０．０５重量％以下の低硫黄燃料油に対しても有効である。低硫黄燃料油の具体例としては、低硫黄原油（たとえば、ミナス原油等南方系の原油）の通常の蒸留で得られるＪＩＳ１号軽油、ＪＩＳ２号軽油、ＪＩＳ３号軽油、ＪＩＳ特３号軽油；通常の原油から水素化脱硫処理工程を経て製造される脱硫軽油；この脱硫軽油と直留軽油（水素化脱硫工程前の軽油）をブレンドして得られる軽油留分から製造されるＪＩＳ１号軽油、ＪＩＳ２号軽油、ＪＩＳ３号軽油、ＪＩＳ特３号軽油が挙げられる。
なお、本発明において炭化水素油系燃料油には、上記炭化水素油とその他の燃料油との混合物も含まれる。その他の燃料油としては、植物油、動物油および合成エステル油などが挙げられる。混合物の場合の混合物中のその他の燃料油の割合は通常６０％以下、好ましくは４０％以下である。
【００９９】
本発明の炭化水素油系潤滑油組成物に用いることのできる炭化水素油系潤滑油としては、炭素数が少なくとも１８〜２７のワックスを含有し、１００℃における動粘度が１〜５０ｍｍ^２／ｓかつ流動点が１５℃以下であるものが好ましい。具体的には、溶剤精製油、イソパラフィンを含有するおよび／または水素化分解による粘度指数１００〜１６０の高粘度指数油、炭化水素系合成潤滑油（ポリα−オレフィン系合成潤滑油など）、ナフテン油並びにこれら２種以上の混合油などが挙げられる。なお、本発明において炭化水素油系潤滑油には、上記炭化水素油とエステル系合成潤滑油との混合物も含まれる。混合物の場合の混合物中のエステル系合成潤滑油の割合は通常６０％以下、好ましくは４０％以下である。
【０１００】
本発明の炭化水素油組成物中の（Ａ）の含有量は、好ましくは炭化水素油組成物の重量に基づいて０．００１〜３０％、さらに好ましくは０．００５〜１０％、特に好ましくは０．０１〜２％である。
【０１０１】
本発明の流動点降下剤を潤滑油に添加した場合は、流動点降下効果だけでなく、摩擦調整効果、摩耗防止効果、分散効果、酸化防止効果および粘度指数向上効果などを発揮することもできる。従って、対象となる潤滑油は、エンジン油（ガソリン用、ディーゼル用など）、変速機油［ギア油（工業用、自動車用）、自動変速機油（オートマチックトランスミッション油、トロイダルＣＶＴ油、ベルトＣＶＴ油）］、パワーステアリング油、ショックアブソーバー油、トラクション油、グリースなどに幅広く好適に用いることができ、低温流動性に優れる。
【０１０２】
【実施例】
以下に、実施例において試験例を説明するがこれに限定するものではない。なお、実施例および比較例中の部は重量部を表す。
【０１０３】
（ＧＰＣによる数平均分子量の測定法）
装置 ： 東洋曹達製 ＨＬＣ−８０２Ａ
カラム ： ＴＳＫ ｇｅｌ ＧＭＨ６ ２本
測定温度 ： ４０℃
試料溶液 ： ０．５質量％のＴＨＦ溶液
溶液注入量 ： ２００μｌ
検出装置 ： 屈折率検出器
標準 ： ポリスチレン
【０１０４】
（流動点の測定法）
ＪＩＳ Ｋ−２２６９の方法で測定した。
【０１０５】
実施例１〜３、比較例１〜２
撹拌装置、加熱冷却装置、温度計、滴下ロート、および窒素吹き込み管を備えた反応容器に、重合溶剤としてトルエン２，０００部を仕込んだ。別のガラス製ビーカーに、表１記載の化合物を表１記載の部数仕込んで２０℃で混合・溶解して単量体溶液を調製した。
単量体溶液を滴下ロートに仕込み、反応容器の気相部の窒素置換を行った後に、密閉下７５〜８５℃で滴下ロート中の単量体溶液を４時間かけて等速度で全量滴下し、重合反応を行った。その後、トルエンを１００℃、減圧下で除去することによって表１記載の重合体を得た。これらの重合体１０，０００部に、さらに鉱物油を５，０００部加え、１２０℃で均一に溶解し、流動点降下剤組成物とした。流動点降下剤組成物のうちの２部を、鉱物油［１００℃動粘度：５．２、粘度指数：１１０、流動点：−１７．５℃］９９８部に添加することにより炭化水素系潤滑油油組成物を得た。
【０１０６】
使用した（ａ１）の略号は以下の通りである。
ＥＧ；エチレングリコールジメタクリレート（「ライトエステルＥＧ」：共栄社化学株式会社製）、
ＰＥ−４Ａ；ペンタエリスリトールテトラアクリレート（「ライトアクリレートＰＥ−４Ａ」：共栄社化学株式会社製）、
ＢＰ−４ＥＡ；ビスフェノールＡエチレンオキサイド付加物のジアクリレート「ライトアクリレートＢＰ−４ＥＡ」（共栄社化学株式会社製）。
【０１０７】
【表１】

【０１０８】
表２には、得られた重合体のＭｎ、ＴｃおよびＹなどを示し、表３には炭化水素油組成物の流動点を示す。
【０１０９】
【表２】

【０１１０】
【表３】

【０１１１】
表３からわかるように、本発明の炭化水素油組成物は、比較例と比べて流動点が低くなっている。
【０１１２】
【発明の効果】
本発明の流動点降下剤は、従来の流動点降下剤に比べ流動点降下能に優れるため、自動車等の潤滑油および燃料油に使用した際には始動性および省燃費化に効果的である。また、該流動点降下剤は粘度指数向上剤、摩耗防止剤、分散剤、酸化防止剤としても有効に作用することから駆動系潤滑油（マニュアルトランスミッション油、デファレンシャルギヤ油、オートマチックトランスミッション油、ベルトＣＶＴ油など）、作動油（機械の作動油、パワーステアリング油、ショックアブソーバー油など）、エンジン油（ガソリン用、ディーゼル用等）、トラクション油、グリース等に好適に用いることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a pour point depressant and a hydrocarbon oil composition containing the same, and more particularly, to a hydrocarbon oil-based fuel oil composition and a hydrocarbon oil-based lubricating oil composition.
[0002]
[Prior art]
Hydrocarbon fuel oils and lubricating oils have a problem in that their fluidity may decrease when exposed to low temperatures in winter or in cold regions. For example, in a fuel oil composed of a middle petroleum distillate (for example, diesel fuel oil and heavy fuel oil A), wax contained therein precipitates and clogs a filter in a piping system or solidifies in a piping system. In addition, wax is precipitated even in lubricating oil, and a combustion device such as an engine or a drive system device does not start or stops. Several proposals have been made as means for solving these problems. For fuel oil, for example, a method of adding a vinyl ester copolymer of ethylene-saturated carboxylic acid to fuel oil (see Patent Documents 1 to 3) has been proposed, and for lubricating oil, poly (meth) acrylate has been added. (See Patent Documents 4 and 5).
[0003]
[Patent Document 1] Japanese Patent Publication No. 39-200692
[Patent Document-2] Japanese Patent Publication No. 48-23165
[Patent Document 3] JP-A-59-136391
[Patent Document-4] JP-A-54-70305
[Patent Document-5] JP-A-2001-122925
[0004]
[Problems to be solved by the invention]
However, the effects of the conventionally proposed additives are still inadequate, and there is a need for an additive having excellent pour point lowering ability.
[0005]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found a pour point depressant having improved pour point depressing ability as compared with the prior art, and have reached the present invention.
That is, the present invention comprises at least one oil-soluble vinyl polymer (A) selected from the group consisting of the following polymers (A1), (A2) and (A3) having a crosslinked structure, and comprises (A1) to (A3) ) Are a pour point depressant for a hydrocarbon oil satisfying the following formula (1), a pour point depressant composition containing the pour point depressant, and a hydrocarbon oil composition.
(A1); a polymer comprising, as essential constituent monomers, a crosslinkable monomer (a1) having two or more vinyl groups and an alkyl (meth) acrylate (b) having an alkyl group having 8 to 32 carbon atoms. ,
(A2); a polymer comprising, as essential constituent monomers, a monovinyl monomer (c1) having an active hydrogen atom-containing group and an alkyl (meth) acrylate (b) having an alkyl group having 8 to 32 carbon atoms. A polymer obtained by performing a crosslinking reaction with a crosslinking agent (a2) having two or more functional groups capable of reacting with the active hydrogen atom-containing group,
(A3): a monovinyl monomer (c2) having a functional group capable of reacting with an active hydrogen atom-containing group and a (meth) acrylic acid alkyl ester (b) having an alkyl group having 8 to 32 carbon atoms are essential constituent monomers A polymer obtained by subjecting a polymer to be crosslinked with a crosslinking agent (a3) having two or more active hydrogen atom-containing groups.
5 × {(aMn) / (AMn)} ≦ Y ≦ 200 × {(aMn) / (AMn)} (1)
Wherein Y is% by weight of (a1), (a2) or (a3) based on the respective weight of (A1), (A2) or (A3), and (aMn) is (a1), (a2) or (aMn). The molecular weight of a3) (the number average molecular weight in the case of two or more types) and (AMn) are the number average molecular weights of (A1), (A2) and (A3).
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The polymer (A) in the present invention comprises one or more selected from the group consisting of (A1), (A2) and (A3), and (A1), (A2) and (A3) are each A crosslinked structure is formed by using (a1), (a2) or (a3).
The weight percentage of (a1), (a2) or (a3) based on the weight of (A1), (A2) or (A3) is within the specific range represented by the above formula (1). , (A) are oil-soluble and exhibit a good pour point lowering effect.
[0007]
The following are mentioned as (a1) which is an essential constituent monomer of (A1).
[0008]
(A1-1); a polyfunctional (meth) acrylate,
(A1-1-1) (poly) alkylene glycol di (meth) acrylate represented by the general formula (2):
R ¹ -O- (XO) p-R ² (2)
Where R ¹ And R ² Is a (meth) acryloyl group. X is an alkylene group having 2 to 27, preferably 2 to 4 carbon atoms [eg, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, a 1,4-butylene group], p represents an integer of 1 to 250, preferably 1 to 12, and more preferably 1 to 4. When p is 2 or more, X may be the same or different, and the (XO) p portion may be randomly added or block-added.
Specific examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and diethylene glycol di (meth) acrylate.
(A1-1-2) Poly (meth) acrylate of trivalent or higher polyol:
Tri, tetra, penta or hexa (e.g., trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, or an alkylene (carbon number 2 to 4) oxide adduct thereof (total number of moles of 1 to 30 moles) such as polyols] (Meth) acrylate and the like.
[0009]
(A1-2); (poly) (total number of added moles 1 to 20) alkylene (2 to 4 carbon atoms) glycol poly (2 to 6 valent) (meth) allyl ether,
Examples include ethylene glycol di (meth) allyl ether, propylene glycol di (meth) allyl ether, diethylene glycol di (meth) allyl ether, and pentaerythritol triallyl ether.
[0010]
(A1-3); bis (meth) acrylamide,
For example, N, N-alkylene (1-6 carbon atoms) bis (meth) acrylamide (such as N, N-methylene-bisacrylamide) is exemplified.
[0011]
(A1-4); an aromatic hydrocarbon having two or more vinyl groups,
Examples thereof include divinyl aromatic hydrocarbons having 10 to 24 carbon atoms (e.g., divinylbenzene, divinyltoluene, and divinylxylene) and trivinyl aromatic hydrocarbons having 12 to 36 carbon atoms (such as trivinylbenzene).
[0012]
(A1-5) a ketone having 5 to 18 carbon atoms having two or more vinyl groups and an ether having 4 to 12 carbon atoms,
Examples include divinyl ketone and divinyl ether.
[0013]
(A1-6); poly (2-4 tetravalent) allyl ester of poly (2-4 tetravalent) carboxylic acid,
Diallyl esters of aliphatic polycarboxylic acids (such as diallyl adipate and diallyl sebacate) and diallyl esters of aromatic polycarboxylic acids (such as diallyl phthalate).
[0014]
(A1-7); an alkenyl (meth) acrylate having an alkenyl group having 2 to 6 carbon atoms,
Examples include vinyl (meth) acrylate, (meth) allyl (meth) acrylate and (iso) propenyl (meth) acrylate.
[0015]
Among (a1), from the viewpoint of polymerizability, (a1-1), (a1-2), (a1-3) and (a1-4) are preferable, and (a1-1) is more preferable. ) And (a1-2), particularly preferred are (a1-1), especially (a1-1-1).
[0016]
The alkyl group having 8 to 32 carbon atoms constituting (b) which is an essential constituent monomer of (A1) may be a linear or branched octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group. , Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octacosyl and triacosyl. Of these, straight-chain alkyl groups having 10 to 24 carbon atoms, particularly 12 to 18 carbon atoms, are preferred.
(B) may be used in combination of two or more kinds, and preferably 2 to 4 kinds are used in combination. The weight ratio in the case of combined use is not particularly limited, but the average carbon number (average by weight fraction) of the alkyl group in the case of combined use is preferably 10 to 18, and more preferably 12 to 17.
[0017]
Examples of (b) include n-dodecyl methacrylate (hereinafter abbreviated as MA-12), n-tetradecyl methacrylate, n-hexadecyl methacrylate (hereinafter abbreviated as MA-16), n-octadecyl methacrylate ( Hereinafter, abbreviated as MA-18), and n-octadecyl methacrylate.
[0018]
(A1) may be further composed of another monomer (d) if necessary.
Examples of (d) include the following monovinyl monomers. In addition, (d) may be used alone or in combination of two or more.
[0019]
(D1) an alkyl (meth) acrylate having an alkyl group having 1 to 7 carbon atoms;
Alkyl groups include methyl, ethyl, and linear or branched propyl, butyl, pentyl, hexyl, and heptyl groups, with methyl and ethyl groups being preferred, especially methyl.
[0020]
(D2) a mono (meth) acrylate of a (poly) alkylene glycol monoalkyl ether;
As the alkylene group constituting the (poly) alkylene glycol monoalkyl ether, an alkylene group having 2 to 20, preferably 2 to 6 carbon atoms, for example, an ethylene group, a propylene group, a butylene group, a 2-butylene group and an isobutylene group are exemplified. No.
Examples of the alkyl group constituting the monoalkyl ether include the linear or branched alkyl groups having 1 to 20, preferably 1 to 18 carbon atoms described in (b) and (d1) above.
The number of alkylene glycol units in the (poly) alkylene glycol is preferably 1 to 50, more preferably 1 to 20.
Examples of (d2) include polyethylene glycol (the number of units of ethylene glycol is 6) monomethyl ether mono (meth) acrylate, ethylene glycol mono-2-ethylhexyl ether mono (meth) acrylate, and polypropylene glycol (the number of units of propylene glycol is 3) Monobutyl ether mono (meth) acrylate is exemplified.
[0021]
(D3) (meth) acrylate having an alicyclic group having 6 to 24 carbon atoms
Examples of the alicyclic group include a cyclohexyl group, a decahydronaphthyl group, a cyclohexylethyl group, a cyclohexylmethyl group and a cycloheptylethyl group.
[0022]
(D4) hydrocarbyl esters of unsaturated carboxylic acids other than (meth) acrylic acid;
Unsaturated monocarboxylic acid having an alkyl group mentioned in the above (d2), an alicyclic group mentioned in the above (d3), or an aralkyl group having 7 to 18 carbon atoms (such as a benzyl group and a phenylethyl group) [crotonic acid and the like; And unsaturated dicarboxylic acids [such as maleic acid, fumaric acid and itaconic acid] esters (eg, diesters such as dimethyl maleate, dimethyl fumarate, diethyl maleate and dioctyl maleate).
[0023]
(D5); aliphatic hydrocarbon-based vinyl monomer:
For example, an alkene having 2 to 30 carbon atoms [ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-heptene, 4-methylpentene-1, 1-hexene, diisobutylene, 1-octene, 1-dodecene, 1-octadecene and other α-olefins and the like].
[0024]
(D6); alkyl alkenyl ether:
Alkyl vinyl ethers having a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms [eg methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether], alkyl (meth) allyl ethers [methyl allyl ether, ethyl Allyl ether, n-butyl allyl ether, etc.], alkyl propenyl ether and alkyl isopropenyl ether. Preferred among these are methyl vinyl ether, ethyl vinyl ether, methyl allyl ether and ethyl allyl ether.
[0025]
(D7); monocarboxylic acid vinyl ester
Examples of the monocarboxylic acid include saturated aliphatic, alicyclic and aromatic monocarboxylic acids having 2 to 30 carbon atoms, preferably 1 to 18 carbon atoms. Examples of aliphatic monocarboxylic acids include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, vinyl 2-ethylhexanoate, and vinyl n-octanoate. Examples of alicyclic monocarboxylic acids include vinyl cyclohexanoate. And aromatic monocarboxylic acids such as vinyl cyclooctanoate include vinyl benzoate.
[0026]
(D8); vinyl ketones:
Alkyl or aryl vinyl ketones having 1 to 8 carbon atoms such as methyl vinyl ketone, ethyl vinyl ketone, and phenyl vinyl ketone.
[0027]
(D9); alicyclic hydrocarbon-based vinyl monomer:
Examples thereof include cyclohexene, pinene, limonene, and indene having an alicyclic group having 5 to 24 carbon atoms.
[0028]
(D10); an aromatic hydrocarbon-based vinyl monomer:
Styrene, substituted styrene (substituent having 1 to 18 carbon atoms) [alkyl-substituted styrene (α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, etc.), cycloalkyl-substituted styrene ( Such as cyclohexylstyrene), aryl-substituted styrene (such as phenylstyrene), aralkyl-substituted styrene (such as benzylstyrene)], and vinylnaphthalene.
[0029]
(D11); a nitrogen atom-containing monomer:
(D11-1); primary or secondary amino group-containing vinyl monomer
Aminoalkyl (C1-8) (meth) acrylate or (meth) acrylamide [such as aminoethyl (meth) acrylate, aminopropyl (meth) acrylate and N-aminoethyl (meth) acrylamide] and monoalkyl (carbon) Formulas 1 to 6) Substitutes [monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, etc.], heterocyclic amino group-containing vinyl monomer [morpholinoethyl (meth) acrylate, 4 -Vinylpyridine, 2-vinylpyridine, vinylimidazole and N-vinylpyrrole] and monoallylamine.
[0030]
(D11-2); tertiary amino group-containing vinyl monomer
Examples thereof include dialkyl (C1-6) -substituted aminoalkyl (C1-8) (meth) acrylate or (meth) acrylamide [dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.].
[0031]
(D11-3); quaternary nitrogen atom-containing vinyl monomer
Dialkyl (C 1-4) aminoalkyl (C 2-8) (meth) acrylate or quaternary (meth) acrylamide [dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl ( Quaternary compounds such as meth) acrylamide and diethylaminoethyl (meth) acrylamide] and quaternary compounds of monoallylamine. As the quaternizing agent, a compound having an alkyl or aralkyl group having 1 to 12 carbon atoms such as methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate or an alkylene oxide (2 to 4 carbon atoms) is used. Is exemplified.
[0032]
(D11-4); amide group-containing vinyl monomer
Unsubstituted or monoalkyl (C 1-4) substituted (meth) acrylamide, [(meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Ni-propyl (meth) acrylamide, Nn- and i-butyl (meth) acrylamide, etc.), dialkyl (C 1-4) substituted (meth) acrylamide [N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N , N-di-n-butyl (meth) acrylamide], N-vinylcarboxylic acid amide [N-vinylformamide, N-vinylacetamide, N-vinyl-n- and i-propionylamide, N-vinylhydroxyacetamide] and heterogeneous Ring (thio) amide group-containing vinyl monomer [N-vinylpyrrolidone, N Vinylthioether pyrrolidone] and the like.
[0033]
(D11-5); a nitrile group-containing monomer
(Meth) acrylonitrile and cyanostyrene.
[0034]
(D11-6); nitro group-containing monomer
4-nitrostyrene and the like.
[0035]
(D12); a hydroxyl group-containing vinyl monomer
(D12-1) Hydroxyl group-containing aromatic vinyl monomer
p-hydroxystyrene and the like.
(D12-2) Hydroxyl group-containing aliphatic monomer
Vinyl alcohol (formed by hydrolysis of vinyl acetate unit), alkenol having 3 to 12 carbon atoms (such as (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-octenol and 1-undecenol), and carbon number 4 to 12 alkene diols [such as 1-buten-3-ol, 2-buten-1-ol and 2-buten-1,4-diol], and hydroxyalkyl (C1-6) alkenyl (C3-C3) 10) Ether [such as 2-hydroxyethylpropenyl ether] and mono (meth) acrylate of (poly) alkylene glycol [oxyalkylene groups constituting (poly) alkylene glycol include those described above, and p is preferable. The same applies to the range. Examples thereof include (meth) acrylic acid hydroxyethyl ester, polyethylene glycol (p = 9) mono (meth) acrylate, and polypropylene glycol (p = 3) mono (meth) acrylate.
[0036]
(D13); a halogen atom-containing vinyl monomer
Examples include vinyl chloride, vinyl bromide, vinylidene chloride, (meth) allyl chloride, halogenated styrene (mono- and dichlorostyrene, and tetrafluorostyrene).
[0037]
(D14); anionic monomer
(D14-1); carboxyl group-containing vinyl monomer
Unsaturated monocarboxylic acid [(meth) acrylic acid, α-methyl (meth) acrylic acid, crotonic acid, cinnamic acid, etc.], monoalkyl (1 to 24 carbon atoms) ester of unsaturated dicarboxylic acid [monoalkyl maleate Monoalkyl esters of fumaric acid and monoalkyl itaconic acid], unsaturated dicarboxylic acids [such as maleic acid, fumaric acid, itaconic acid, citraconic acid and aconitic acid] and unsaturated dicarboxylic anhydrides [maleic anhydride and itaconic anhydride] Etc.].
[0038]
(D14-2); a sulfo group-containing vinyl monomer
Alkenesulfonic acid having 2 to 6 carbon atoms [such as vinylsulfonic acid and (meth) allylsulfonic acid], aromatic vinyl group-containing sulfonic acid having 8 to 12 carbon atoms [such as styrenesulfonic acid and α-methylstyrenesulfonic acid], Sulfoalkyl (C2 to C6) (meth) acrylate [such as sulfoethyl (meth) acrylate and sulfopropyl (meth) acrylate], (meth) acrylamide alkane (C2 to C8) sulfonic acid [2- (meth) acrylamide -2-methylpropanesulfonic acid, etc.], a vinyl monomer having a sulfo group and a hydroxyl group [3- (meth) acrylamide-2-hydroxypropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid and 3- (meth) Acryloyloxy-2-hydroxypropanesulfo Acid, etc.] and an alkyl (having 3 to 18 carbon atoms) (meth) allyl sulfosuccinate [dodecyl (meth) allyl sulfosuccinate] and the like.
[0039]
(D14-3); a vinyl monomer containing a sulfate group
Poly (p = 2-30) oxyalkylene (carbon number 2-4: ethylene, propylene and butylene, etc .: any of single addition, random addition and block addition) sulfate of mono (meth) acrylate of glycol; And poly (p = 2 to 30) oxyalkylene (alkylene is the same as described above). Sulfuric acid ester of bisphenol A mono (meth) acrylate.
[0040]
(D14-4); a phosphoric acid group-containing vinyl monomer
(Meth) acryloyloxyalkyl (C2-6) phosphoric acid monoester [(meth) acryloyloxyethyl phosphate etc.], (meth) acryloyloxyalkane (C2-4) phosphonic acid [2-acryloyloxyethanephosphonic acid Etc.].
[0041]
Among (d), preferred are at least one selected from the group consisting of (d1) to (d4), (d10) and (d11), and at least one of other monomers of (d) and (d). (Copolymerization weight ratio is at least 50/50, preferably at least 95/5), and more preferably at least one of (d1) to (d4), and at least one of other monomers thereof and (d) (Copolymerization weight ratio is at least 50/50, preferably at least 95/5), and particularly preferred are (d1), at least one of (d1), and (d1) It is a combination of two or more.
[0042]
The proportion of (a1) in (A1) is such that the weight percentage Y [%] of (a1) based on the weight of (A1) satisfies the following formula (1). It is within the range that satisfies.
5 × {(aMn) / (AMn)} ≦ Y ≦ 200 × {(aMn) / (AMn)} (1)
20 × {(aMn) / (AMn)} ≦ Y ≦ 120 × {(aMn) / (AMn)} (2)
In the formula, (aMn) is the molecular weight of (a1) (in the case of two or more, the number average molecular weight), and (AMn) is the number average molecular weight of (A1). In addition, Y does not exceed 100% (% represents weight% unless otherwise specified).
[0043]
(AMn) is preferably from 70 to 2,000, and more preferably from 70 to 500.
(AMn) is preferably from 1,000 to 500,000, and more preferably from 3,000 to 300,000.
In the present invention, the number average molecular weight is measured by GPC (gel permeation chromatography) as a molecular weight in terms of polystyrene.
[0044]
If Y is less than the lower limit, the pour point lowering effect is poor, and if it exceeds the upper limit, the solubility in the base oil is poor.
[0045]
Y for setting the charged amount of (a1) is the target number average molecular weight (AMn ′) of (A1) and the number average molecular weight (AMn) of the polymer synthesized without using only (a1). ₀ ), The number m of functional groups of (a1), and (aMn). Specifically, first, the polymer (A1) was used without using only (a1). ₀ ), And the number average molecular weight (AMn) ₀ ) Is measured. Then, Y is calculated from m and (aMn) by the following equation (3).
[0046]
(Equation 1)

[0047]
The preferred range of Y is the range represented by the above formula (2), a more preferred range is 0.1 to 80%, a particularly preferred range is 0.2 to 50%, and a most preferred range is 0.4 to 30%. It is.
[0048]
The proportion of (a1) based on the weight of (A1) is preferably from 0.1 to 80%, more preferably from 0.2 to 50%, particularly preferably from 0.4 to 30%.
(A1) / (b) is preferably 0.001 to 0.5, more preferably 0.005 to 0.3.
(D) which can be used if necessary is preferably 0 to 20%, more preferably 0 to 10%, based on the weight of (A1).
[0049]
(C1), which is an essential constituent monomer of the polymer (A2) in the present invention, includes (d11-1) and (d12) described above.
[0050]
The above-mentioned (b) is mentioned as (b) which is an essential constituent monomer of (A2), and preferable examples are also the same. If necessary, a small amount of (d) and / or (a1) may be used in combination. it can. When (d) and / or (a1) are used in combination, the weight ratio of (d) + (a1) based on the weight of (b) is preferably 0 to 10%.
[0051]
The crosslinking agent (a2) is a compound containing two or more functional groups capable of reacting with an active hydrogen atom-containing group. For example, the following organic polyisocyanate (a2-1) and the following polyepoxide compound (a2-2) are used. No. (A2) may be used alone or in combination of two or more.
[0052]
(A2-1); Organic polyisocyanate
Aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), aliphatic polyisocyanate having 2 to 18 carbon atoms, alicyclic polyisocyanate having 4 to 15 carbon atoms, and 8 to 9 carbon atoms 15 aromatic aliphatic polyisocyanates and modified products of these polyisocyanates (such as urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified products) and A mixture of two or more of these is included.
[0053]
Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′ -And / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4 4,4′-diisocyanatodiphenylmethane, crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; triamino or higher trifunctional or more in a small amount (eg, 5 to 20% by weight)] With polyamine]: polyallyl polyisocyanate (PAPI) ], 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate.
[0054]
Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate And other aliphatic polyisocyanates.
[0055]
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.
[0056]
Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).
[0057]
Examples of the modified polyisocyanate include polyisocyanates such as modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI. And a mixture of two or more of these [for example, a combination of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)]. Examples of the polyol used for producing the urethane-modified polyisocyanate [free isocyanate-containing prepolymer obtained by reacting an excess of polyisocyanate (TDI, MDI, etc.) with a polyol] include polyols having an equivalent weight of 30 to 200, such as ethylene glycol. Glycols such as propylene glycol, diethylene glycol and dipropylene glycol; triols such as trimethylolpropane and glycerin; highly functional polyols such as pentaerythritol and sorbitol; and alkylene oxide (ethylene oxide and / or propylene oxide) adducts thereof. . Of these, those having 2 to 3 functional groups are preferred.
The free isocyanate group content of the modified polyisocyanate and prepolymer is usually from 8 to 33%, preferably from 10 to 30%, particularly preferably from 12 to 29%.
[0058]
Preferred among these are aromatic diisocyanates, particularly preferred are 2,4- and 2,6-TDI and mixtures of isomers thereof, crude TDI, 4,4'- and 2,4'-MDI And a mixture of isomers thereof, crude MDI (PAPI), and modified polyisocyanates containing urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, and isocyanurate groups derived from these polyisocyanates The most preferred is a modified MDI [for example, Coronate C-1059, C-1050 (manufactured by Nippon Polyurethane), Isonate 160L, 181 (manufactured by Kasei Upjohn), Sumidur PC, PF (manufactured by Sumitomo Bayer Urethane)]. It is.
[0059]
(A2-2); a polyepoxide compound
The polyepoxide compounds include aliphatic, alicyclic, heterocyclic and aromatic polyepoxides having two or more, preferably two, epoxy groups in one molecule.
[0060]
Examples of the aromatic polyepoxide include a glycidyl ether of a polyhydric phenol and a glycidyl aromatic polyamine.
Examples of the glycidyl ether of polyhydric phenol include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, phenol or cresol novolak Glycidyl ether of fat, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A with 3 mol of epichlorohydrin, polyglycidyl ether of polyphenol obtained by condensation reaction of phenol and glyoxal, glutaraldehyde or formaldehyde, and Polyglycidyl ethers of polyphenols obtained by the condensation reaction of resorcinol and acetone are mentioned.
Glycidyl aromatic polyamines include N, N-diglycidylaniline and N, N, N ', N'-tetraglycidyldiphenylmethanediamine.
Further, a diglycidyl urethane compound obtained by an addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate with glycidol, a glycidyl group-containing polyurethane (pre) polymer obtained by reacting a polyol with the two reactants, and bisphenol A diglycidyl ether of an alkylene oxide (ethylene oxide or propylene oxide) adduct of A is also included.
[0061]
Heterocyclic polyepoxides include trisglycidylmelamine.
[0062]
Examples of the alicyclic polyepoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ale, and 3,4-epoxy-6. Methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) ) Butylamine. Further, the alicyclic polyepoxide also includes a nuclei hydrogenated product of the aromatic polyepoxide.
[0063]
Examples of the aliphatic polyepoxide include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines.
Examples of polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether. , Pentaerythritol tetraglycidyl ether, and sorbitol polyglycidyl ether.
Examples of the polyglycidyl ester of polyhydric fatty acid include diglycidyl adipate.
Glycidyl aliphatic amines include N, N, N ', N'-tetraglycidylhexamethylenediamine.
The aliphatic polyepoxide also includes a (co) polymer of glycidyl (meth) acrylate.
[0064]
The molar ratio (c1) / (a2) between (c1) and (a2) in (A2) is 1-2, preferably 1.0-1.5, and is based on the weight of (A2). Is a ratio that satisfies the expression (1) as in the case of the above (A1).
In this case, the Mn of the polymer composed of (c1) and (b) and, if necessary, (d) is measured first, and Y is determined in the same manner as in (A1).
When (a1) is used as the other monomer in (A2), Y in the formula (1) is calculated using the weight of (a2) and the weight of (a1), (AMn) in the formula (1) is the total number average molecular weight of (a2) and (a1).
If Y is less than the lower limit, the pour point lowering effect is poor, and if it exceeds the upper limit, the solubility in the base oil is poor.
Also in (A2), (aMn) in the formula (1) is preferably from 70 to 2,000, more preferably from 70 to 500, and (AMn) is preferably from 1,000 to 500,000, more preferably. Is 3,000 to 30,000.
[0065]
(C2) which is an essential constituent monomer of the polymer (A3) in the present invention includes the following.
[0066]
(C2-1); an epoxy group-containing monovinyl monomer
Examples include glycidyl (meth) acrylate and (meth) allyl glycidyl ether.
[0067]
(C2-2); isocyanate group-containing monovinyl monomer
Examples include isocyanatoethyl (meth) acrylate and m-isopropenyl-α, α-dimethylmethylbenzyl isocyanate.
[0068]
The above-mentioned (b) is mentioned as (b) which is an essential constituent monomer of (A3), and preferable examples are also the same. If necessary, a small amount of (d) and / or (a1) may be used in combination. it can. When (d) and / or (a1) are used in combination, the weight ratio of (d) + (a1) based on the weight of (b) is preferably 0 to 10%.
[0069]
The cross-linking agent (a3) is a compound containing two or more active hydrogen atom-containing groups. For example, the following polyhydric alcohol (a3-1), polyhydric phenol (a3-2), ammonia and primary or secondary Examples include amines (a3-3), polycarboxylic acids (a3-4), phosphoric acids (a3-5), and polythiols (a3-6). (A3) may be used alone or in combination of two or more.
[0070]
(A3-1); polyhydric alcohol
For example, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene Dihydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose, etc. Is mentioned.
[0071]
(A3-2); polyhydric phenols
Examples include polyhydric phenols such as pyrogallol, catechol, and hydroquinone; and bisphenols such as bisphenol A, bisphenol F, and bisphenol S.
[0072]
(A3-3); ammonia and primary or secondary amines
For example, monoamines such as ammonia, alkylamines having 1 to 20 carbon atoms (such as butylamine) and aniline; aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, and diethylenetriamine; piperazine, N-aminoethylpiperazine and others Heterocyclic polyamines described in JP-B-55-21044; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine; Aromatic polyamines such as polyphenylmethane polyamine; and monoethanolamine, diethanolamine, triethanolamine, triisopropano Alkanolamines such as triethanolamine and the like.
[0073]
(A3-4); polycarboxylic acid
Examples include aliphatic polycarboxylic acids such as succinic acid and adipic acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid.
[0074]
(A3-5); phosphoric acids
Examples include phosphoric acid, phosphorous acid, and phosphonic acid.
[0075]
(A3-6); polythiol
For example, a polyvalent polythiol compound obtained by reacting a glycidyl group-containing compound with hydrogen sulfide is exemplified.
[0076]
The molar ratio (c2) / (a3) between (c2) and (a3) in the polymer (A3) is 1-2, preferably 1.0-1.5, based on the weight of (A3) ( The ratio Y% of a3) is a ratio that satisfies the above formula (1) as in (A1) described above. When (a1) is used as the other monomer in (A3), Y in the formula (1) is calculated using the weight of the crosslinking agent (a3) plus the weight of (a1). (AMn) in the equation (1) is the total number average molecular weight of (a3) and (a1).
If Y is less than the lower limit, the pour point lowering effect is poor, and if it exceeds the upper limit, the solubility in the base oil is poor.
Also in (A3), (aMn) in the formula (1) is preferably from 70 to 2,000, more preferably from 70 to 500, and (AMn) is preferably from 1,000 to 500,000, more preferably. Is 3,000 to 300,000.
[0077]
The crystallization temperature (hereinafter abbreviated as Tc) in the present invention was determined by using a differential scanning calorimeter (UNIX-DSC7: UNIX is a registered trademark) manufactured by PERKIN-ELMER and measuring 5 mg of a sample at 10 ° C from 140 ° C to -80 ° C. Endothermic peak temperature (° C.) due to crystallization observed when cooling at an isothermal rate of / min.
[0078]
The Tc of (A1), (A2) and (A3) is preferably -50C to 10C, more preferably -45C to 0C, and particularly preferably -40C to -10C. When Tc is −50 ° C. or more and 10 ° C. or less, it is preferable because the pour point lowering ability is excellent.
[0079]
The method for producing the polymer before crosslinking with (A1) or the crosslinking agent may be a conventionally known radical polymerization method, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a reversed-phase suspension weight. Synthetic method, thin film polymerization method, spray polymerization method and the like can be mentioned. Among these, a solution polymerization method is preferable, and a method is generally used in which a monomer is radically polymerized in a solvent in the presence of an initiator.
Solvents include mineral oils (solvent refined oils, hydrogenated reformed oils, high viscosity index oils containing isoparaffin and / or having a viscosity index of 100 to 160 by hydrocracking, naphthenic oils) and synthetic lubricating oils [hydrocarbons] High flash point solvents (flash point of 130 ° C or more) such as synthetic synthetic lubricating oils (poly-α-olefin synthetic lubricating oils, etc.) and ester synthetic lubricating oils; other solvents [aliphatic hydrocarbons (pentane, hexane, etc.)] , Aromatic hydrocarbons (toluene, xylene, etc.), alcohol solvents [isopropyl alcohol (hereinafter abbreviated as IPA), octanol, butanol, etc.], ketone solvents (methyl isobutyl ketone, methyl ethyl ketone, etc.), amide solvents (N, N-dimethylformamide, N-methylpyrrolidone, etc.), sulfoxide-based solvents (dimethylsulfoxide, etc.)] And it includes combinations of two or more of these. Preferred are high flash point solvents and aromatic hydrocarbons.
The initiator includes an azo initiator, a peroxide initiator, and a redox initiator.
Examples of the azo initiator include 2,2′-azobis (2,4-dimethylvaleronitrile) (hereinafter abbreviated as AVN), 2,2′-azobisisobutyronitrile, and 2,2′-azobis (2 -Methylbutyronitrile), azobiscyanovaleric acid and its salts (eg, hydrochloride), 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-methyl-N- (2 -Hydroxyethyl) propionamide and the like.
Peroxide-based initiators include inorganic peroxides (eg, hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.) and organic peroxides (eg, benzoyl peroxide, di-t-butyl peroxide). Oxide, cumene hydroperoxide, succinic peroxide, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxypivalate, t-hexylperoxypivalate, t-butylperoxyneoheptanoate, t-butyl peroxy neodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxyisobutyrate, t-amyl peroxy 2-ethyl hexanoate, 1,1,3,3 -Tetramethylbutylperoxy 2-ethylhexanoate, dibutylperoxytrime Ruajipeto include lauryl peroxide, etc.].
Redox catalysts include reducing agents such as alkali metal sulfites and bisulfites (eg, ammonium sulfite, ammonium bisulfite, etc.), ferrous chloride, ferrous sulfate, and ascorbic acid, and alkali metal persulfates. , Ammonium persulfate, hydrogen peroxide, organic peroxides and other oxidizing agents.
The amount of the initiator used is preferably 0.05 to 2%, more preferably 0.1 to 1%, based on the total weight of the monomers.
Chain transfer agents may be used, for example, mercaptans [n-laurylmercaptan (hereinafter abbreviated as LSH), mercaptoethanol and mercaptopropanol, etc.], thiocarboxylic acids (such as thioglycolic acid and thiomalic acid), and secondary alcohols (Such as isopropanol), amines (such as dibutylamine) and hypophosphites (such as sodium hypophosphite). The amount of the chain transfer agent to be used is preferably 0 to 7%, more preferably 0.05 to 5%, based on the total weight of the monomers.
[0080]
The polymerization temperature is preferably from 30 to 140C, more preferably from 50 to 130C, especially from 70 to 120C. The polymerization temperature can be controlled by an adiabatic polymerization method or a temperature-controlled polymerization method.
In addition to the method of initiating polymerization by heat, a method of initiating polymerization by irradiating radiation, an electron beam, ultraviolet light, or the like may be employed. Preferred is a temperature-controlled solution polymerization method.
The mode of copolymerization may be either random addition polymerization or alternating copolymerization, and may be either graft copolymerization or block copolymerization.
[0081]
(A2) is obtained by obtaining a polymer by the above method, and then subjecting it to a crosslinking reaction using (a2).
[0082]
Examples of the method of the crosslinking reaction include an adiabatic method and a temperature control method. The reaction temperature is preferably 30 to 140 ° C, more preferably 50 to 130 ° C, and particularly preferably 70 to 120 ° C. Further, a catalyst can be added if necessary.
[0083]
Examples of the catalyst for promoting the reaction between the group containing an active hydrogen atom in the polymer and (a2) include a metal catalyst such as a tin catalyst [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, Dibutyltin dilaurate, stannas octoate, dibutyltin maleate, etc.], lead catalysts [lead oleate, 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], and other metal catalysts [cobalt naphthenate, etc.] Metal salts of naphthenic acid, phenylmercury propionate, etc.]; and amine catalysts such as triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] Undecene-7 @ DBU (Sana Dialkylaminoalkylamines [dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine, etc.] or heterocyclic amino Carbonates and organic acid salts (such as formate) of alkylamines [such as 2- (1-aziridinyl) ethylamine and 4- (1-piperidinyl) -2-hexylamine]; N-methylmorpholine, N-ethylmorpholine , Triethylamine, diethylethanolamine, dimethylethanolamine, and the like; and a combination of two or more of these.
[0084]
(A3) is obtained by obtaining a polymer by the above method, and then subjecting it to a crosslinking reaction using (a3).
[0085]
Examples of the method of the crosslinking reaction include an adiabatic method and a temperature control method. Preferred reaction temperatures are the same as those for the crosslinking reaction in (A2) above. If necessary, the above-mentioned catalyst can be added.
[0086]
It should be noted that, although the molecules of (A1), (A2) or (A3) obtained by the above-mentioned production method may also by-produce molecules not containing (a1), (a2) or (a3), respectively. In the present invention, (A1), (A2), and (A3) are also included.
[0087]
As a specific example of (A1), for example,
(1): Polymer composed of ethylene glycol dimethacrylate (Mn = 198) (1.3%) / MA-16 (30%) / MA-14 (30%) / MA-12 (38.7%) Mn = · 20,000), Y = 1.3, the value on the left side of equation (1) = 0.050, the value on the right side of equation (1) = 1.98,
(2): A polymer composed of pentaerythritol tetraacrylate 1.0% (Mn = 352) / MA-16 (25%) / MA-18 (10%) / MA-12 (64%), (Mn = 20) , 000), Y = 1.0, the value on the left side of equation (1) = 0.0088, the value on the right side of equation (1) = 3.52,
As a specific example of (A2), for example,
(1): a polymer obtained by cross-linking a polymer composed of 0.8% ethylene glycol monomethacrylate / MA-18 (20%) / MA-12 (80%) with 1% hexamethylene diisocyanate (Mn = 168); (Mn = 20,000), Y = 1.0, the value on the left side of Expression (1) = 0.042, and the value on the right side of Expression (1) = 1.68.
[0088]
The pour point depressant composition of the present invention comprises (A) and a diluent and / or other additives, and is preferable in that dissolution and dilution with a diluent facilitates dissolution in a base oil. As the diluent, the same solvents as those mentioned in the above-mentioned production method (A) can be used, and the solvent used in the polymerization step (A) may be left without being removed. Preferred as diluents are high flash point solvents and aromatic hydrocarbons.
When (A) is difficult to dissolve in the diluent, it is preferable to dissolve by heating (preferably 40 to 150 ° C.).
When the pour point depressant composition comprises only (A) and a diluent, the ratio of (A) to the diluent is usually 1% or more and (D) 99% or less, preferably (A). Is 10 to 90% and the diluent is 10 to 90%, and more preferably (A) is 20 to 90% and the diluent is 10 to 80%.
[0089]
Other additives in the pour point depressant composition include a non-ionic additive composed of at least one monomer selected from the group consisting of (b), (c1), (c2) and (d) described above. A crosslinked vinyl polymer (B) is exemplified.
[0090]
Among the monomers constituting (B), preferred are at least one selected from the group consisting of (b), (d1) to (d7), and (d10) to (d12), and other monomers. (Copolymerization weight ratio is at least 50/50, preferably at least 95/5), and more preferably at least one of (b) and (b) and (d1) (Copolymerization weight ratio is at least 50/50, preferably at least 95/5).
[0091]
Among (b) constituting (B), particularly preferred are (meth) acrylates having a linear or branched alkyl group having 8 to 24 carbon atoms, more preferably 12 to 18 carbon atoms.
(B) Mw is usually 5,000 to 1,000,000, preferably 20,000 to 400,000.
[0092]
Specific examples of (B) include, for example, a copolymer composed of MA-12 (30 to 80%) / MA-18 (20 to 70%) and methyl methacrylate (0 to 30%) / MA-12 ( 10-40%) / MA-14 (10-40%) / MA-16 (0-20%) copolymer and the like.
[0093]
The weight ratio of (B) / (A) is preferably 0 to 10/1, and more preferably 0.01 to 3/1.
The purpose of adding (B) is to improve (improve) the viscosity index and to improve (decrease) the low-temperature viscosity.
[0094]
As the other additives in the pour point depressant composition of the present invention, the following can be further exemplified in addition to (B).
Detergent [sulfonate, salicylate, phenate, naphthenate and other Ca and Mg salts and calcium carbonate etc.], dispersant [succinimide (bis type, mono type, borate type and Mannich condensate type etc.)] , Antioxidants such as amines (such as diphenylamine), hindered phenols (such as trialkylphenol) and zinc dithiophosphate, and known friction modifiers such as long-chain fatty acids (such as oleic acid) and long-chain fatty acid esters (such as olein) Acid esters, etc.), long-chain amines (oleylamine, etc.), long-chain amides (oleamide, etc.), antiwear agents [molybdenum dithiophosphate, molybdenum dithiocarbamate and zinc dialkyl dithiophosphate, etc.], extreme pressure agents [sulfur-based ( Dialkyl disulf ), Phosphorus-based (phosphate ester, phosphite ester) and halogen-based (chlorinated hydrocarbon) etc.), defoamer [silicone oil and metal soap, etc.], demulsifier [quaternary ammonium salt, sulfated oil] And phosphoric acid esters] and corrosion inhibitors [benzotriazole and 1,3,4-thiodiazolyl-2,5-bisdialkyldithiocarbamate and the like].
[0095]
The amount of the additives other than (B) added in the pour point depressant composition is such that the content of these additives based on the weight of the hydrocarbon oil composition described below is as follows.
The detergent is usually 0 to 20%, preferably 0.1 to 10%, the dispersant is usually 0 to 20%, preferably 0.2 to 10%, and the antioxidant is usually 0 to 5%, preferably 0.1 to 10%. 1 to 3%, known friction modifiers are usually 0 to 5%, preferably 0.1 to 1%, antiwear agents are usually 0 to 10%, preferably 0.1 to 3%, and extreme pressure agents are usually 0-20%, preferably 0.1-10%, defoamer usually 2-1,000 ppm, preferably 10-700 ppm, demulsifier usually 0-3%, preferably 0-1%, and corrosion protection The amount of the agent is usually 0 to 3%, preferably 0 to 2%.
[0096]
The total amount of other additives, including (B), based on the total weight of the pour point depressant composition is usually 0-70%, preferably 0-30%, more preferably 0-15%.
When the pour point depressant composition is composed of other additives including (A) and (B), and a diluent, the ratio of the diluent based on the weight of the pour point depressant composition is usually a diluent. The content of the agent is 99% or less, preferably 10 to 90%, more preferably 10 to 80%.
[0097]
The hydrocarbon oil composition of the present invention comprises a base oil and a pour point depressant and, if necessary, other additives, or a base oil and a pour point depressant composition. It may be blended into the base oil after being blended into the agent composition, or may be blended separately into the base oil. In that case, the order of blending is not particularly limited.
[0098]
The hydrocarbon oil composition of the present invention includes a hydrocarbon fuel oil composition and a hydrocarbon lubricating oil composition.
Examples of the hydrocarbon oil-based fuel oil that can be used in the hydrocarbon oil-based fuel oil composition of the present invention include JIS No. 1 light oil, JIS No. 2 light oil, JIS No. 3 light oil, JIS special No. 3 light oil, and JIS A heavy oil. And JIS B heavy oil and JIS C heavy oil as fuels, and is effective for low sulfur fuel oil having a sulfur content of 0.05% by weight or less. Specific examples of the low sulfur fuel oil include JIS No. 1 gas oil, JIS No. 2 gas oil, JIS No. 3 gas oil, JIS No. 3 gas oil, and JIS special No. 3 gas oil obtained by ordinary distillation of low sulfur crude oil (for example, southern crude oil such as Minas crude oil); JIS No. 1 gas oil, JIS No. 2 manufactured from a gas oil fraction obtained by blending this desulfurized gas oil with a straight-run gas oil (gas oil before the hydrodesulfurization process) Light oil, JIS No. 3 light oil, and JIS special No. 3 light oil.
In the present invention, the hydrocarbon oil-based fuel oil also includes a mixture of the hydrocarbon oil and another fuel oil. Other fuel oils include vegetable oils, animal oils and synthetic ester oils. In the case of a mixture, the proportion of other fuel oils in the mixture is usually at most 60%, preferably at most 40%.
[0099]
The hydrocarbon oil-based lubricating oil that can be used in the hydrocarbon oil-based lubricating oil composition of the present invention contains a wax having at least 18 to 27 carbon atoms and has a kinematic viscosity at 100 ° C of 1 to 50 mm. ² / S and a pour point of 15 ° C or less are preferred. Specifically, a solvent refined oil, a high viscosity index oil containing isoparaffin and / or having a viscosity index of 100 to 160 by hydrocracking, a hydrocarbon-based synthetic lubricating oil (such as a poly-α-olefin-based synthetic lubricating oil), a naphthene And oils and mixed oils of two or more of these. In the present invention, the hydrocarbon oil-based lubricating oil also includes a mixture of the hydrocarbon oil and an ester-based synthetic lubricating oil. In the case of a mixture, the proportion of the ester-based synthetic lubricating oil in the mixture is usually 60% or less, preferably 40% or less.
[0100]
The content of (A) in the hydrocarbon oil composition of the present invention is preferably 0.001 to 30%, more preferably 0.005 to 10%, and particularly preferably 0.001 to 30%, based on the weight of the hydrocarbon oil composition. It is 0.01 to 2%.
[0101]
When the pour point depressant of the present invention is added to a lubricating oil, not only a pour point depressing effect but also a friction adjusting effect, an anti-abrasion effect, a dispersing effect, an anti-oxidation effect, a viscosity index improving effect and the like can be exhibited. . Therefore, the target lubricating oils are engine oil (for gasoline, diesel, etc.), transmission oil [gear oil (for industrial use, for automobiles), automatic transmission oil (automatic transmission oil, toroidal CVT oil, belt CVT oil)]. It can be widely and suitably used for power steering oil, shock absorber oil, traction oil, grease and the like, and has excellent low-temperature fluidity.
[0102]
【Example】
Hereinafter, test examples will be described in Examples, but the present invention is not limited thereto. Parts in Examples and Comparative Examples represent parts by weight.
[0103]
(Method for measuring number average molecular weight by GPC)
Equipment: HLC-802A manufactured by Toyo Soda
Column: 2 TSK gel GMH6
Measurement temperature: 40 ° C
Sample solution: 0.5% by mass of THF solution
Solution injection volume: 200 μl
Detector: Refractive index detector
Standard: polystyrene
[0104]
(Method of measuring pour point)
It was measured by the method of JIS K-2269.
[0105]
Examples 1-3, Comparative Examples 1-2
A reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a dropping funnel, and a nitrogen blowing tube was charged with 2,000 parts of toluene as a polymerization solvent. In a separate glass beaker, the compounds shown in Table 1 were charged in the number shown in Table 1 and mixed and dissolved at 20 ° C. to prepare a monomer solution.
After charging the monomer solution into the dropping funnel and performing nitrogen replacement of the gas phase part of the reaction vessel, the monomer solution in the dropping funnel is dropped at 75-85 ° C. at constant speed over 4 hours at 75-85 ° C. A polymerization reaction was performed. Then, the polymer shown in Table 1 was obtained by removing toluene at 100 ° C. under reduced pressure. To 10,000 parts of these polymers, 5,000 parts of mineral oil was further added and uniformly dissolved at 120 ° C. to obtain a pour point depressant composition. Hydrocarbon lubrication by adding 2 parts of the pour point depressant composition to 998 parts of mineral oil [100 ° C kinematic viscosity: 5.2, viscosity index: 110, pour point: -17.5 ° C] An oil-oil composition was obtained.
[0106]
Abbreviations of (a1) used are as follows.
EG: ethylene glycol dimethacrylate ("Light Ester EG": manufactured by Kyoeisha Chemical Co., Ltd.),
PE-4A; pentaerythritol tetraacrylate (“light acrylate PE-4A”: manufactured by Kyoeisha Chemical Co., Ltd.);
BP-4EA: diacrylate of bisphenol A ethylene oxide adduct “light acrylate BP-4EA” (manufactured by Kyoeisha Chemical Co., Ltd.).
[0107]
[Table 1]

[0108]
Table 2 shows Mn, Tc, Y and the like of the obtained polymer, and Table 3 shows the pour point of the hydrocarbon oil composition.
[0109]
[Table 2]

[0110]
[Table 3]

[0111]
As can be seen from Table 3, the pour point of the hydrocarbon oil composition of the present invention is lower than that of the comparative example.
[0112]
【The invention's effect】
Since the pour point depressant of the present invention is superior in pour point depressing ability as compared with conventional pour point depressants, it is effective for startability and fuel saving when used for lubricating oil and fuel oil of automobiles and the like. . Further, since the pour point depressant also effectively acts as a viscosity index improver, an antiwear agent, a dispersant, and an antioxidant, the drive system lubricating oil (manual transmission oil, differential gear oil, automatic transmission oil, belt CVT) Oil, etc.), hydraulic oil (machine hydraulic oil, power steering oil, shock absorber oil, etc.), engine oil (for gasoline, diesel, etc.), traction oil, grease and the like.

Claims (14)

It comprises at least one oil-soluble vinyl polymer (A) selected from the group consisting of the following polymers (A1), (A2) and (A3) having a crosslinked structure, wherein (A1) to (A3) are each represented by the following formula: A pour point depressant for hydrocarbon oils that satisfies (1).
(A1); a polymer comprising, as essential constituent monomers, a crosslinkable monomer (a1) having two or more vinyl groups and an alkyl (meth) acrylate (b) having an alkyl group having 8 to 32 carbon atoms. ,
(A2); a polymer comprising, as essential constituent monomers, a monovinyl monomer (c1) having an active hydrogen atom-containing group and an alkyl (meth) acrylate (b) having an alkyl group having 8 to 32 carbon atoms. A polymer obtained by performing a crosslinking reaction with a crosslinking agent (a2) having two or more functional groups capable of reacting with the active hydrogen atom-containing group,
(A3): a monovinyl monomer (c2) having a functional group capable of reacting with an active hydrogen atom-containing group and a (meth) acrylic acid alkyl ester (b) having an alkyl group having 8 to 32 carbon atoms are essential constituent monomers A polymer obtained by subjecting a polymer to be crosslinked with a crosslinking agent (a3) having two or more active hydrogen atom-containing groups.
5 × {(aMn) / (AMn)} ≦ Y ≦ 200 × {(aMn) / (AMn)} (1)
[Wherein, Y is the weight percentage of (a1), (a2) or (a3) based on the weight of each of (A1), (A2) or (A3), and (aMn) is (a1), (a2) or The molecular weight of (a3) (the number average molecular weight in the case of two or more types) and (AMn) are the number average molecular weights of (A1), (A2) and (A3). ] The pour point depressant according to claim 1, wherein (A) is (A1). 3. The pour point depressant according to claim 1, wherein (a1) constituting (A1) is a polyfunctional (meth) acrylate. The pour point depressant according to claim 3, wherein the polyfunctional (meth) acrylate is a (poly) alkylene glycol di (meth) acrylate represented by the following general formula (2).
R ¹ -O- (XO) p-R ² (2)
[Wherein, R ¹ and R ² represent a (meth) acryloyl group, X represents an alkylene group having 2 to 27 carbon atoms, and p represents an integer of 1 to 250. When p is 2 or more, X may be the same or different, and the (XO) p portion may be randomly added or block-added. ｝ The pour point depressant according to claim 1, wherein in (A2), (c1) is a monovinyl monomer having a hydroxyl group or a primary or secondary amino group, and (a2) is a polyisocyanate compound or a polyepoxy compound. In (A3), (c2) is a monovinyl monomer having an isocyanate group or an epoxy group, and (a3) is at least one selected from the group consisting of polyhydric alcohols, polycarboxylic acids and polythiols. A pour point depressant according to claim 1. The pour point depressant according to any one of claims 1 to 6, wherein the number average molecular weight of (A) is 1,000 to 500,000. The pour point depressant according to any one of claims 1 to 7, wherein the crystallization temperature measured by DSC in (A) is from 50C to -70C. A pour point depressant composition comprising (A) according to any one of claims 1 to 8, and a diluent and / or other additives. The pour point depressant composition according to claim 9, wherein at least one of the other additives is a non-crosslinked vinyl polymer (B). A hydrocarbon oil composition comprising a hydrocarbon oil-based fuel oil or a hydrocarbon oil-based lubricating oil and a pour point depressant according to any one of claims 1 to 8. The hydrocarbon oil composition according to claim 11, which contains 0.001 to 40% by weight of (A) based on the weight of the hydrocarbon oil composition. 13. The hydrocarbon oil composition according to claim 11, wherein the hydrocarbon oil-based fuel oil is a wax-containing hydrocarbon oil-based fuel oil. 13. The hydrocarbon oil composition according to claim 11, wherein the hydrocarbon oil-based lubricating oil is a wax-containing hydrocarbon-based lubricating oil.