JP2004002747A - Friction regulating agent for lubricating oil and lubricating oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a friction regulating agent for lubricating oil exhibiting lowered shock in gear change and having improved torque transmission function. <P>SOLUTION: The friction regulating agent for a lubricating oil is composed of an oil-soluble copolymer having a weight-average molecular weight of ≥3,000 and containing a unit of at least one monomer (a) expressed by general formula (1), CH<SB>2</SB>=C(R<SP>1</SP>)-Q-(Z-A<SP>1</SP>)<SB>m</SB>-X and a unit of at least one monomer (b) expressed by general formula (2), CH<SB>2</SB>=C(R<SP>3</SP>)-CO-(O-A<SP>2</SP>)<SB>n</SB>-OR<SP>4</SP>(X is PH<SB>2</SB>, NH<SB>2</SB>or (O)<SB>a</SB>-P(=O)<SB>b</SB>(OR<SP>2</SP>)<SB>2</SB>; one of (a) and (b) is 1 and the other is 0 or 1; R<SP>2</SP>is H, an alkyl or the like; R<SP>1</SP>and R<SP>3</SP>are each H or methyl; Z is O or NH; A<SP>1</SP>and A<SP>2</SP>are each an alkylene; (m) is an integer of 0-50; Q is CO or a hydrocarbon group; (n) is an integer of 0-30; and R<SP>4</SP>is an alkyl or the like). <P>COPYRIGHT: (C)2004,JPO

Description

【００２１】
式中、Ｒ^１、Ｑ、Ｚ、Ａ^１およびｍは一般式（１）におけると同じであり、好ましいものも同様である。Ｒ^５およびＲ^６は、同一又は異なる、ＨもしくはＣ１〜８のアルキル基であるか又はＲ^５とＲ^６が相互に結合して炭素数３〜１１のアルキレン基となり隣り合った炭素原子と一緒になって環を形成する。Ｒ^５およびＲ^６のうちで好ましいのはＣ１〜４、のアルキル基、さらに好ましいのはメチル、エチルおよびｉｓｏ−ブチル基である。
（ａ_０１）の例としては、式（３）において、Ｒ^１およびＲ^５がメチル基、Ｒ^６がｉｓｏ−ブチル基、Ｑが−ＣＯ−、Ｚが−Ｏ−、Ａ^１がエチレン基、ｍが１である単量体（以下、ＭＩＢＫＭＡと略記する）が挙げられる。
（ａ_０１）の単位を含有する（Ａ_０）はＮ＝Ｃ結合を加水分解することにより−ＮＨ_２基に変換できる。加水分解は、水、アルカリ性水溶液もしくは酸性水溶液で４０〜１２０℃で１〜２０時間加熱撹拌することで行われる。
アルカリ性水溶液としては、前記アルカリ金属もしくはアルカリ土類金属の水酸化物、アンモニアまたは前記脂肪族アミンの水溶液（濃度：１０重量％以下）が使用できる。酸性水溶液としては無機酸またはＣ１〜４の有機酸の水溶液（濃度：１０％以下）が使用できる。無機酸としては炭酸、硫酸、塩酸、硝酸、ホウ酸および燐酸など、有機酸としてはＣ１〜４のカルボン酸（例えば蟻酸、酢酸、プロピオン酸および酪酸）が使用できる。
加水分解したのち、−ＮＨ_２が酸の塩を形成している場合は、酸をイオン交換樹脂などにより除去することによって−ＮＨ_２に変換することができる。−ＮＨ_２基であることにより、塩のままである共重合体に比べて基油との親和性が良好になる。加水分解方法のうち好ましいのは生成する共重合体が塩を形成しないので製造工程が簡略であるという観点から、水もしくはアルカリ水溶液で加水分解する方法であり、さらに好ましいのは水で加水分解する方法である。
（ａ_０１）は、例えばＱが−ＣＯ−の場合は、（メタ）アクリル酸またはそのエステルもしくはアミド形成性誘導体（Ｃ１〜６のアルキルエステル、酸ハライドおよび酸無水物が含まれる）と、下記一般式（４）で示されるシッフ塩基から得られる。
【００２２】
【化３】

【００２３】
式中、Ｒ^５、Ｒ^６、Ｚ、Ａ^１およびｍは一般式（３）におけると同じである。
（ａ_０２）の単位を含有する（Ａ_０）はイオン交換樹脂などで酸成分を除去することにより−ＮＨ２基を有する共重合体に変換することができる。
−ＮＨ_２基を有する（Ａ）のうち、好ましいのは（ａ_０１）を用いた前駆体から得られる（Ａ）である。
【００２４】
（ａ）のうち好ましいのは、摩擦調整効果の観点から、（ａ２）、（ａ５）および特に（ａ１）である。（ａ１）のうち、好ましいのは（ａ１１）、（ａ１３）および（ａ１１）と（ａ１３）の併用、とりわけＥＰＭＡ、ＤＥＰＭＡ、ＰＥＰＭＡおよびこれらの併用である。併用の場合、好ましいのは５０％以上、特に６０〜９５％の（ａ１１）と（ａ１３）との併用である。上記および以下において、％は特に限定しない限り重量％を表す。
【００２５】
一般式（２）において、Ｒ^３は水素原子またはメチル基であり、メチル基が好ましい。Ａ^２はＣ２〜１８のアルキレン基であり、例えば上記のＡ^１と同様の基が挙げられ、好ましいものも同様である。ｎは、好ましくは０または１〜１０、さらに好ましくは０または１である。
【００２６】
Ｒ^４の炭素数１〜３２の脂肪族炭化水素基としては、Ｃ１〜３２の直鎖もしくは分岐のアルキル基、Ｃ２〜３２の直鎖もしくは分岐のアルケニル基が挙げられる。
アルキル基としては前述のアルキル基の他にヘキサコシル、オクタコシル（２−ドデシルヘキサデシルなど）、トリアコシル並びにドトリアコシル基（２−テトラデシルオクタデシル基など）；アルケニル基としては、ビニル、（メタ）アリル、イソプロペニル、ブテニル、オクテニル、デセニル、ドデセニル、ペンタデセニル、オクタデセニル、ドコセニル、テトラコセニル、オクタコセニルおよびトリアコセニル基；が挙げられる。
Ｒ^４のＣ５〜７の脂環族炭化水素基としては、シクロペンチル、シクロヘキシルおよびシクロヘプチル基など、Ｃ７〜３２のアラルキル基（アルキル基は直鎖もしくは分岐の基）としては、ベンジル、フェニルエチル、フェニルブチル、フェニルノニルおよびフェニルドデシル基などが挙げられる。
Ａ^２がＣ２〜３の場合は、（Ａ）の油溶性の観点から、ｎは好ましくは０もしくは１〜１０の整数、さらに好ましくは０もしくは１特に０である。
【００２７】
一般式（２）で示される（ｂ）の例には、以下のものが含まれる。
（ｂ１）Ｃ１〜７（好ましくはＣ１〜６、さらに好ましくはＣ１〜４とくにＣ１）のアルキル基、Ｃ２〜７（好ましくはＣ２〜３）のアルケニル基、Ｃ５〜７（好ましくはＣ６）のシクロアルキル基またはＣ７〜８のアラルキル基を有する（メタ）アクリル酸エステル：例えばメチルアクリレート、メチルメタクリレート（以下、ＭＭＡと略記）、エチル、ブチルおよびヘキシル（メタ）アクリレート；アリルおよびイソプロペニル（メタ）アクリレート；シクロペンチル（メタ）アクリレート、シクロヘキシルアクリレートおよびシクロヘキシルメタクリレート（以下、ＭＡ−ＣＨと略記）；ベンジルおよびフェニルエチル（メタ）アクリレート。
【００２８】
（ｂ２）Ｃ８〜３２（好ましくはＣ８〜２４、さらに好ましくはＣ１２〜２４）のアルキル基またはアルケニル基、またはＣ９〜３２（好ましくはＣ９〜１８）のアラルキル基を有する（メタ）アクリル酸エステル：例えば、
ドデシルメタクリレート（以下、ＭＡ−１２と略記）、テトラデシルメタクリレート（以下、ＭＡ−１４と略記）、ヘキサデシルメタクリレート（以下、ＭＡ−１６と略記）、オクタデシルメタクリレート（以下、ＭＡ−１８と略記）、
２−デシルテトラデシルメタクリレート（以下、ＭＡ−２４と略記）、ドデシル、テトラデシル、ヘキサデシル、オクタデシルおよび２−デシルテトラデシルアクリレート、２−エチルヘキシル、ｎ−オクチル、デシル、イソデシル、トリデシル、エイコシルおよびテトラコシル（メタ）アクリレート；オクテニル、デセニル、ドデセニルおよびオクタデセニル（メタ）アクリレートなど。
【００２９】
（ｂ３）（ポリ）アルキレン（Ｃ２〜１８）グリコールモノアルキル（Ｃ１〜３２、好ましくはＣ１〜８）、アルケニル（Ｃ２〜３２、好ましくはＣ２〜３）もしくはアラルキル（Ｃ７〜３２、好ましくはＣ７〜８）エーテルのモノ（メタ）アクリル酸エステル：アルキレン基、アルキル基、アルケニル基およびアラルキル基としては、前述と同様の基、アルキレングリコールの重合度は、好ましくは１〜２０、さらに好ましくは１〜１０である。
例えば、（ポリ）エチレングリコール（重合度１〜９）モノメチルエーテル、（ポリ）プロピレングリコール（重合度１〜５）モノエチルエーテル、エチレングリコールモノ−２−エチルヘキシルエーテルおよびポリプロピレングリコール（重合度２〜４）モノブチルエーテル　モノ（メタ）アクリレートなど。
（ｂ）のうち、好ましいのは（ｂ１）〜（ｂ３）のうちの２種以上の併用であり、さらに好ましいのは（ｂ１）のうちの１〜２種と、（ｂ２）のうちの２種以上特に２〜４種の併用である。
併用の場合の（ｂ１）／（ｂ２）の重量比は、好ましくは５０／５０〜２／９８、特に３５／６５〜３／９７である。（ｂ２）が５０以上であれば（Ａ）が油溶性になりやすく、９８以下であれば摩擦調整効果が特に良好に発揮できる。また、（ｂ）中の［（ｂ１）＋（ｂ２）］の量は、（ｂ）の重量に基づいて好ましくは８０〜１００％、さらに好ましくは１００％である。
なお、単量体（ｂ）が、一般式（２）で示され、式中のｎが０または１であり、Ｒ^４が炭素数１〜７のアルキル基、炭素数２〜７のアルケニル基、炭素数５〜７のシクロアルキル基または炭素数７〜８のアラルキル基である単量体（ｂ１）２〜５０重量％と、一般式（２）で示され、式中のｎが０または１であり、Ｒ^４が炭素数８〜３２のアルキル基もしくはアルケニル基または炭素数９〜３２のアラルキル基である単量体（ｂ２）５０〜９８重量％からなるものが好ましい。
【００３０】
（Ａ）の重量に基づく（ａ）の含量は、好ましくは０．０１〜５０％、さらに好ましくは０．０５〜４０％、特に０．１〜１５％、最も好ましくは０．２〜５％である。（ａ）が０．０１％以上であれば摩擦調整効果に優れている点で好ましく、５０％以下であれば油溶性になりやすいとい観点で好ましい。
（Ａ）の重量に基づく（ｂ）の含量は、好ましくは５０〜９９．９９％、さらに好ましくは６０〜９９．９５％、特に８０〜９９．９％、最も好ましくは９０〜９９．８％である。
【００３１】
（Ａ）は、（ａ）および（ｂ）以外に、必要によりその他の単量体（ｃ）から誘導される構成単位を含有していてもよい。（ｃ）としては以下の疎水性単量体（ｃ１）および親水性単量体（ｃ２）が挙げられる。
【００３２】
（ｃ１）疎水性単量体
（ｃ１１）芳香族ビニル系炭化水素；
スチレン、置換スチレン（置換基の炭素数１〜１８）［例えばアルキル置換スチレン（α−メチルスチレン、ビニルトルエン、２，４−ジメチルスチレン、ｐ−エチルスチレン、ｐ−イソプロピルスチレンおよびｐ−ブチルスチレン）、シクロアルキル置換スチレン（ｐ−シクロヘキシルスチレン）、フェニル置換スチレン（ｐ−フェニルスチレン）、アラルキル置換スチレン（ｐ−ベンジルスチレン）、アシル基置換スチレン（ｐ−アセトキシスチレン）、フェノキシ基置換スチレン（ｐ−フェノキシスチレン）］、ジビニル置換芳香族炭化水素［例えばジビニルベンゼン、ジビニルトルエンおよびジビニルキシレン］並びにビニルナフタレンなど。
（ｃ１２）脂肪族ビニル系炭化水素；
Ｃ２〜３０の鎖式アルケン［例えばエチレン、プロピレン、１−ブテン、イソブチレン、１−ペンテン、１−ヘプテン、４−メチルペンテン−１、１−ヘキセン、ジイソブチレン、１−オクテン、１−ドデセン、１−オクタデセンおよびその他のα−オレフィン］、Ｃ４〜１８、好ましくは４〜５の鎖式アルカジエン［例えばブタジエン、イソプレン、１，４−ペンタジエン、１，６−ヘキサジエンおよび１，７−オクタジエン］、およびＣ６〜３０の脂環式ビニル系炭化水素［例えば（ジ）シクロペンタジエン、（ビニル）シクロヘキセン、エチリデンビシクロヘプテン、ピネン、リモネンおよびインデン］。
（ｃ１３）アルキルアルケニルエーテル；
Ｃ１〜３０の直鎖または分岐アルキル基とＣ２〜４のアルケニル基とのエーテル、例えばアルキルビニルエーテル［例えばメチル、エチルおよびｎ−ブチル　ビニルエーテル］、アルキル（メタ）アリルエーテル［例えばメチル、エチルおよびｎ−ブチル　アリルエーテル］、アルキル（イソ）プロペニルエーテルが挙げられる。これらのうちで好ましいものは、メチルおよびエチル　ビニルエーテル、並びにメチルおよびエチル　アリルエーテルである。
（ｃ１４）（メタ）アクリル酸以外の不飽和カルボン酸の単量体（ｂ）に相当するエステル；
不飽和モノカルボン酸［（イソ）クロトン酸など］の前記Ｒ^４に相当するエステル、ならびに不飽和ジカルボン酸［マレイン、フマルおよびイタコン酸など］アルキル（Ｃ１〜２４）ジエステル［ジメチル、ジエチルおよびジオクチルマレエート並びにフマル酸ジメチルなど］。
（ｃ１５）脂肪族カルボン酸アルケニルエステル；
Ｃ１〜３０、好ましくは２〜１８の直鎖状、分岐状または環状の飽和もしくは不飽和脂肪族モノカルボン酸（例えば、酢酸、プロピオン酸、酪酸、ヘキサン酸、ヘプタン酸、２−エチルヘキサン酸およびｎ−オクタン酸などの直鎖もしくは分岐飽和脂肪族カルボン酸、シクロヘキサン酸、シクロオクタン酸、デカヒドロナフチル酸などの環状飽和脂肪族カルボン酸、並びにオレイン酸、リノール酸およびリノレン酸などの直鎖不飽和脂肪族カルボン酸）のビニル、（メタ）アリルおよび（イソ）プロペニルエステル。
（ｃ１６）ビニルケトン類；
Ｃ１〜８のアルキルもしくはＣ６〜１８の芳香環含有炭化水素基とビニル基から構成されるケトン［例えばメチルビニルケトン、エチルビニルケトンおよびフェニルビニルケトン］。
（ｃ１７）ハロゲン含有ビニル単量体：
塩化ビニル、臭化ビニル、塩化ビニリデン、塩化（メタ）アリルおよびハロゲン化スチレン（モノおよびジクロルスチレン、テトラフルオロスチレンおよび塩化アリルなど）。
【００３３】
（ｃ２）親水性単量体
（ｃ２１）ヒドロキシル基含有ビニル単量体；
（ポリ）アルキレングリコール（重合度１〜２０）モノ（メタ）アクリレート［ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート（以下、ＭＡ−ＨＥと略記）およびジエチレングリコールモノ（メタ）アクリレートなど］、ビニルアルコール（酢酸ビニル単位の加水分解により形成される）、Ｃ３〜１２のアルケノール［（メタ）アリルアルコール、（イソ）クロチルアルコール、１−オクテノールおよび１−ウンデセノールなど］、Ｃ４〜１２のアルケンジオール［１−ブテン−３−オール、２−ブテン−１−オールおよび２−ブテン−１，４−ジオールなど］、ヒドロキシアルキル（Ｃ１〜６）アルケニル（Ｃ３〜１０）エーテル［２−ヒドロキシエチルプロペニルエーテルなど］並びにヒドロキシル基含有芳香族ビニル単量体［ｐ−ヒドロキシスチレンなど］。
（ｃ２２）アニオン性単量体：
（ｃ２２−１）カルボキシル基含有ビニル単量体：
不飽和モノカルボン酸［例えば（メタ）アクリル酸、α−メチル（メタ）アクリル酸、クロトン酸および桂皮酸］、不飽和ジカルボン酸［例えばマレイン酸、フマル酸およびイタコン酸］、不飽和ジカルボン酸のモノアルキル（Ｃ１〜２４）エステル［例えばマレイン酸モノメチル、フマル酸モノメチル、イタコン酸モノエチルおよびマレイン酸モノオクチル］。
（ｃ２２−２）スルホン酸基含有ビニル単量体：
Ｃ２〜６のアルケンスルホン酸［ビニルスルホン酸および（メタ）アリルスルホン酸など］、Ｃ６〜１２のビニル基含有芳香族スルホン酸［α−メチルスチレンスルホン酸など］、スルホン酸基含有（メタ）アクリルエステル系単量体［スルホプロピル（メタ）アクリレートおよびスルホエチル（メタ）アクリレートなど］、スルホン酸基含有（メタ）アクリルアミド系単量体［２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸など］、スルホン酸基と水酸基を含有するビニル単量体［３−（メタ）アクリルアミド−２−ヒドロキシプロパンスルホン酸、３−（メタ）アリロキシ−２−ヒドロキシプロパンスルホン酸、３−（メタ）アクリロイルオキシ−２−ヒドロキシプロパンスルホン酸など］、アルキル（Ｃ３〜１８）（メタ）アリルスルホコハク酸エステル［ドデシルアリルスルホコハク酸エステルなど］など。
（ｃ２３）窒素原子含有単量体；
（ｃ２３−１）アミド基含有ビニル単量体：
（メタ）アクリルアミド、モノアルキル（Ｃ１〜４）置換（メタ）アクリルアミド、［Ｎ−メチル、Ｎ−エチル、Ｎ−ｉｓｏ−プロピルおよびＮ−ｎ−ブチル（メタ）アクリルアミド］、ジアルキル（Ｃ１〜４）置換（メタ）アクリルアミド［Ｎ，Ｎ−ジメチル、Ｎ，Ｎ−ジエチルおよびＮ，Ｎ−ジｎ−ブチル　（メタ）アクリルアミド］、およびＮ−ビニルカルボン酸アミド［Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニル−ｎ−およびｉ−プロピオニルアミド］など。
（ｃ２３−２）２〜３級アミノ基含有ビニル単量体：
２級アミノ基含有ビニル単量体、例えば、アルキル（Ｃ１〜６）アミノアルキル（Ｃ２〜６）（メタ）アクリレート［ｔ−ブチルアミノエチルメタクリレート、メチルアミノエチル（メタ）アクリレートなど］、Ｃ６〜１２のジアルケニルアミン［ジ（メタ）アリルアミンなど］、３級アミノ基含有ビニル単量体、例えば、ジアルキル（Ｃ１〜４）アミノアルキル（Ｃ２〜６）（メタ）アクリレート［ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレートなど、ジアルキル（Ｃ１〜４）アミノアルキル（Ｃ２〜６）（メタ）アクリルアミド［ジメチルアミノエチル（メタ）アクリルアミド、ジエチルアミノエチル（メタ）アクリルアミドなど］、３級アミノ基含有芳香族ビニル系単量体［Ｎ，Ｎ−ジメチルアミノスチレンなど］、含窒素複素環含有ビニル系単量体［モルホリノエチル（メタ）アクリレート、４−ビニルピリジン、２−ビニルピリジン、Ｎ−ビニルピロール、Ｎ−ビニルピロリドン、Ｎ−ビニルチオピロリドンなど］。
（ｃ２３−３）第４級アンモニウム塩基含有ビニル単量体：
前述の（ｃ７−２）に記載した３級アミノ基含有ビニル単量体を、４級化剤（Ｃ１から１２のアルキルクロライド、ジアルキル硫酸、ジアルキルカーボネート、およびベンジルクロライド等）を用いて４級化したものなどが挙げられる。具体的には、（メタ）アクリロイルオキシアルキル第４級アンモニウム塩、例えば、（メタ）アクリロイルオキシエチルトリメチルアンモニウムクロライド、（メタ）アクリロイルオキシエチルトリエチルアンモニウムクロライド、（メタ）アクリロイルオキシエチルジメチルベンジルアンモニウムクロライド、（メタ）アクリロイルオキシエチルメチルモルホリニウムクロライドなど；（メタ）アクリルアミドアルキル第４級アンモニウム塩、例えば、（メタ）アクリルアミドエチルトリメチルアンモニウムクロライド、（メタ）アクリルアミドエチルトリエチルアンモニウムクロライド、（メタ）アクリルアミドエチルジメチルベンジルアンモニウムクロライドなど；その他の第４級アンモニウム塩基含有ビニル系単量体、例えば、ジメチルジアリルアンモニウムメチルサルフェート、トリメチルビニルフェニルアンモニウムクロライドなど。
（ｃ２３−４）ニトリル基含有単量体：
（メタ）アクリロニトリルなど。
【００３４】
（ｃ）のうち、摩擦調整効果の観点から、好ましいのは（ｃ２）、さらに好ましいのは（ｃ２１）、（ｃ２２−１）および（ｃ２３−２）、特に好ましいのは（ｃ２１）である。
また、（Ａ）の油溶性を向上させるという観点からは、好ましいのは（ｃ１）であり、（ａ）および（ｂ）のみからなる共重合体が油溶性でない場合は、疎水性である（ｃ１）を使用することが好ましい。
（Ａ）の重量に基づく（ｃ）の重量割合は、摩擦調整効果の観点から好ましくは０〜２０％、さらに好ましくは０．５〜１０％、特に好ましくは１〜８％である。
【００３５】
（Ａ）は、従来から知られているラジカル重合方法、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、好ましくは溶液重合法により製造することができる。通常、溶剤中で、開始剤および必要により連鎖移動剤の存在下で（ａ）、（ｂ）および必要により（ｃ）をラジカル重合させることにより（Ａ）を製造できる。
溶剤には、鉱物油［溶剤精製油、水素化改質油（例えば粘度指数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、芳香族炭化水素およびアルコール系溶剤、特にＩＰＡ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。
過酸化物系開始剤としては無機過酸化物［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］、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］が挙げられる。
レドックス系開始剤には、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。連鎖移動剤には、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）、メルカプトエタノール、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、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）、次亜燐酸塩類（次亜燐酸ナトリウなど）などが含まれる。
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される。
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。
さらに、共重合としては、ランダム付加重合および交互共重合のいずれでもよく、またグラフト共重合およびブロック共重合のいずれでもよい。
【００３６】
本発明における摩擦調整剤組成物は、本発明の摩擦調整剤および希釈剤および／または他の添加剤からなるものである。
摩擦調整剤を希釈剤で溶解・希釈することことにより基油への溶解が容易になる。
【００３７】
希釈剤としては、前述の（Ａ）の製造法において挙げた溶剤が使用でき、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。希釈剤のうち、好ましいのは前述の鉱物油、特に水素化改質油である。
摩擦調整剤の希釈剤への溶解は、必要により加熱（好ましくは４０〜１５０℃）下に行われる。
希釈剤を使用する場合の摩擦調整剤組成物中の（Ａ）の含量は好ましくは１％以上、さらに好ましくは２０〜９０％、特に３０〜８０％であり、希釈剤の含量は好ましくは９９％以下、さらに好ましくは１０〜８０％、特に２０〜７０％である。
【００３８】
摩擦調整剤組成物における他の添加剤としては共重合体（Ｂ）が挙げられる。
（Ｂ）は前述の（ｂ）の単位および必要により前述の（ｃ）の単位を含有し、（ａ）の単位を含まない共重合体である。
（ｂ）のうち好ましいのは（ｂ１）、（ｂ２）およびこれらの併用であり、
さらに好ましいのは（ｂ２）、および（ｂ１）と（ｂ２）の併用であり、特に好ましいのは（ｂ２）のうちの２種以上の併用、およびＭＭＡと（ｂ２）の併用である。
（ｂ１）を含まず（ｂ２）からなる（Ｂ）は後述の潤滑油組成物において流動点降下作用を発揮できるという観点で好ましく、（ｂ１）と（ｂ２）からなる（Ｂ）は後述の潤滑油組成物の粘度指数向上効果を発揮できるという観点で好ましい。
（ｂ１）と（ｂ２）の併用の場合の好ましい重量比率は２〜５０％／５０〜９８％、さらに好ましくは１０〜３５％／６５〜９０％である。
必要により含有することのできる（ｃ）として好ましいのは（ｃ１）のうちの（ｃ１１）、（ｃ１２）、（ｃ１４）および（ｃ１５）、並びに（ｃ２）のうちの（ｃ２１）および（ｃ２３）であり、さらに好ましいのは（ｃ２１）および（ｃ２３−２）である。
（Ｂ）の重量に基づく（ｃ）の割合は通常０〜２０％、好ましくは１〜１０％である。
（Ｂ）のＭｗは通常５，０００〜３００，０００、好ましくは２０，０００〜１００，０００であり、（ｂ１）を含まず（ｂ２）からなる（Ｂ）のさらに好ましいＭｗは５０，０００〜７０，０００である。
（Ａ）の重量に基づく（Ｂ）の割合は、通常０〜５０％、好ましくは０〜２０％である。
【００３９】
摩擦調整剤組成物における他の添加剤には、さらにその他の任意成分、例えば清浄剤［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塩およい炭酸カルシウム］、分散剤［コハク酸イミド系（例えばビスタイプ、モノタイプ、ボレートタイプ、マンニッヒ縮合物系など）］、抗酸化剤［ジンクジチオフォスフェート、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、チオリン酸亜鉛およびトリアルキルフェノールなど）、従来から公知の摩擦調整剤［長鎖脂肪酸（例えばオレイン酸）、長鎖脂肪酸エステル（例えばオレイン酸エステル）、長鎖アミン系（例えばオレイルアミン）、長鎖アミド（例えばオレアミド）］、耐摩耗剤［例えば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］、極圧剤［例えば硫黄リン系、硫黄系、リン系およびクロル系］、消泡剤［例えばシリコーン油、金属石けん、脂肪酸エステルおよびリン酸エステル］、抗乳化剤［例えば４級アンモニウム塩、硫酸化油およびリン酸エステル］および腐食防止剤［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］が含まれる。
これらの添加量は、摩擦調整剤組成物の重量に基づいて清浄剤は通常０〜４０％、好ましくは０．１〜３０％、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０．１〜３％、耐摩耗剤および極圧剤は通常０〜４０％、好ましくは０．１〜３０％、消泡剤は通常０〜１０，０００ｐｐｍ、好ましくは１０〜４，０００ｐｐｍ、抗乳化剤は通常０〜１５％、好ましくは０〜１％、並びに腐食防止剤は通常０〜３％、好ましくは０〜２％である。
摩擦調整剤組成物中のその他の添加剤の合計量は、通常０〜６０％、好ましくは０．１〜４０％である。
その他の添加剤は、摩擦調整剤組成物として配合された後に基油と配合してもよいが、それぞれを別にして基油に配合してもよく、その場合の配合の順序は特に限定されない。
【００４０】
本発明の摩擦調整剤は、摩擦調整効果のみでなく、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も発揮することできる。
【００４１】
本発明の摩擦調整剤の用途は、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、トラクション油およびグリースなどに幅広く好適に用いることができるが、好ましくは変速機油、さらに好ましくは自動変速機油、特に好ましくは、自動車用ギア油、自動スリップ制御機構を有する自動変速機用のオ−トマチックトランスミッション油およびベルトＣＶＴ油への使用であり、省燃費性に優れ、シャダー性にも悪影響を及ぼさず、快適性においても効果的である。
【００４２】
本発明の潤滑油組成物に用いることのできる基油としては特に限定はなく、例えば前述の鉱物油および合成潤滑油などが挙げられ、好ましいのは粘度指数１００〜１６０の高粘度指数の鉱物油、炭化水素系合成潤滑油およびエステル系合成潤滑油である。また、基油の好ましい曇点（ＪＩＳ　Ｋ２２６９）は−５℃以下、さらに好ましくは−１５℃〜−７０℃である。曇点がこの範囲であるとワックスの析出量が少なく低温粘度が良好である。また、基油の動粘度は１００℃において好ましくは１〜１４ｍｍ^２／ｓである。
【００４３】
本発明の潤滑油組成物において、基油の重量に基づく（Ａ）の含量は、通常０．０１〜４０％、好ましくは０．０３〜３０％である。
なお、潤滑油組成物がエンジン油として使用される場合には基油の重量に基づく（Ａ）の含量は０．１〜１５％、ギヤ油として使用される場合には０．１〜１５％、自動変速機油（オートマチックトランスミッション油、ベルトＣＶＴ油など）および作動油の場合は０．１〜２０％、トラクション油の場合は０．１〜２０％であることが好ましい。
また、基油の重量に基づく（Ａ）＋（Ｂ）の含量は、通常０．０１〜４０％、好ましくは０．０３〜３０％である。
【００４４】
実施例
以下に、実施例において本発明を説明するがこれに限定するものではない。なお、以下において部は重量部を表す。
［ＧＰＣによるＭｗ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％のテトラヒドロフラン溶液
溶液注入量　：　２００μｌ
検出装置　　：　屈折率検出器
標準　　　　：　ポリスチレン
［摩擦係数および変速ショック低減性能の測定法］
ＪＡＳＯ　Ｍ３４８−９５の方法で行い、摩擦係数として５００サイクル目のμｄ（１，８００ｒｐｍ）、変速ショックの低減性能として５００サイクル目のμ０（３，６００ｒｐｍ）／μｄ（１，８００ｒｐｍ）を測定する。
μ０／μｄが１．０に近い方が変速ショックの低減効果があり、μｄが大きい方が摩擦係数が大である。
ＪＡＳＯ　Ｍ３４８−９５の方法で行い、摩擦係数として５００サイクル目のμｄ（１，８００ｒｐｍ）、変速ショックの指標として５００サイクル目のμ０／μｄを測定する。μ０／μｄが１．０に近い方が変速ショックが少なく、μｄが大きい方が摩擦係数が大である。
［耐摩耗性の測定法］
ＳＲＶを用い、ボールオンディスクでボールの摩耗痕径を測定する。
摩耗痕経：ボールの摩耗痕の縦と横の直径の平均値
装置：オプチモール　ＳＲＶ試験機（日本パーカライジング株）
ボール：直径１０ｍｍ
ディスク：直径２４ｍｍ×厚さ７．９ｍｍ
荷重：２００Ｎ
ストローク幅：２ｍｍ
振動数：５０Ｈｚ
試験時間：１０分間
【００４５】
実施例１〜１２
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ＩＰＡ２，５００部を仕込み、反応容器の気相部の窒素置換を行った後に密閉下７５〜８５℃で環流させながら、滴下ロートから表１または表２に記載の組成の単量体−開始剤溶液を等速度で３時間かけて滴下し、さらに１時間同温度で熟成した。得られたポリマー溶液を１２０℃に加熱し、溶媒を減圧下に除去して、表１に記載のＭｗを有する共重合体（Ａ−１）〜（Ａ−１２）１０，０００部を得た。（Ａ−１）〜（Ａ−１２）からなる本発明の摩擦調整剤５，２００部に、鉱物油（水素化改質油：１００℃の動粘度は２．３ｍｍ^２／ｓ、粘度指数８３）４，８００部を加えて１２０℃で均一に溶解して希釈し、本発明の摩擦調整剤組成物（Ｖ−１）〜（Ｖ−１２）を得た。さらに表１または表２に記載の量の摩擦調整剤組成物と高粘度指数油［「ＹＵＢＡＳＥ３」（ＳＫ　Ｃｏｒｐ．製、粘度指数＝１０７）］を混合して本発明の潤滑油組成物（Ｆ−１）〜（Ｆ−１２）を得た。
【００４６】
【表１】

【００４７】
【表２】

【００４８】
実施例１３および１４
実施例１と同様の反応容器に、表３記載の重合溶剤を仕込み、反応容器の気相部の窒素置換を行った後に密閉下８５℃に昇温し、滴下ロートから表３記載の組成の単量体−開始剤溶液を等速度で２時間かけて滴下し、さらに２時間同温度で熟成した。その後、水９２４部を加えて８５℃で２時間加熱撹拌し加水分解した。つぎに、１２０℃に昇温し、減圧下で水およびトルエンを留去し、得られた共重合体をメタノールで再沈殿し、メタノール８，７００部で２回洗浄後、１００℃で４時間減圧乾燥して表３記載の量およびＭｗの共重合体（Ａ−１３）および（Ａ−１４）を得た。
（Ａ−１３）または（Ａ−１４）からなる本発明の摩擦調整剤に同量の実施例１と同様の鉱物油を加えて１２０℃で均一に溶解して希釈し、本発明の摩擦調整剤組成物（Ｖ−１３）および（Ｖ−１４）を得た。さらに表３記載の量のこれらと高粘度指数油（「ＹＵＢＡＳＥ３」）を混合して本発明の潤滑油組成物（Ｆ−１３）および（Ｆ−１４）を得た。
【００４９】
比較例１および２
表３記載の組成の単量体−開始剤溶液および重合溶剤を用い、重合温度を８５℃にし、溶媒を除去しなかった以外は実施例１と同様にして重合を行って共重合体（Ｂ−１）および（Ｂ−２）の「ＹＵＢＡＳＡ３」溶液を得た。これらの溶液を表３に示す共重合体／希釈剤の比率になるように水素化改質油で希釈して比較例の摩擦調整剤組成物（Ｙ−１）および（Ｙ−２）を得た。なお、表３における共重合体／希釈剤の希釈剤には、希釈に用いた水素化改質油と重合に用いたＹＵＢＡＳＥ３が含まれる。さらに実施例１と同様にしてこれらと高粘度指数油（「ＹＵＢＡＳＥ３」）を表３記載の割合で混合して比較例の潤滑油組成物（Ｚ−１）および（Ｚ−２）を得た。
【００５０】
比較例３
（Ｚ−１）９９５部に、オレイルアミンを５部添加して比較例３の潤滑油組成物（Ｚ−３）を得た。
【００５１】
【表３】

【００５２】
これらの潤滑油組成物についてμｄ、μ０／μｄおよび摩耗痕径を測定した。その結果を表４に示す。
【００５３】
【表４】

【００５４】
【発明の効果】
本発明の摩擦調整剤、摩擦調整剤組成物および潤滑油組成物は摩擦調整効果に優れており、変速ショックを軽減することができる上、動力伝達に必要な摩擦係数が高い。さらに本発明の摩擦調整剤は、摩擦調整効果のみでなく、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も発揮することもできる。
従って、本発明の摩擦調整剤は、エンジン油、変速機油、パワーステアリング油、ショックアブソーバー油、トラクション油およびグリースなどに幅広く好適に用いることができ、省燃費性に優れ、シャダー性にも悪影響を及ぼさず、快適性においても効果的である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a friction modifier for lubricating oil and a lubricating oil composition.
More specifically, the present invention relates to a friction modifier, a friction modifier composition, and a lubricating oil composition for adjusting a friction coefficient of an automotive lubricant.
[0002]
[Prior art]
Conventionally, oleylamine, a fatty acid amide of diethanolamine, or a fatty acid ester (see Patent Document 1) has been added to a lubricating oil for automobiles as a friction modifier for reducing a shock due to friction during shifting.
However, these friction modifiers can reduce the shock caused by friction during gear shifting, but on the other hand, there is a problem in that the torque transmission function from the engine is reduced due to a decrease in the friction coefficient, leading to deterioration in fuel efficiency. Was.
[0003]
[Patent Document-1] Japanese Patent Publication No. 61-21517
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a friction modifier capable of exhibiting an improved torque transmission function while reducing a shock during a gear shift, and to provide a lubricating oil composition containing the same.
[0005]
[Means for Solving the Problems]
Means for Solving the Problems As a result of intensive studies, the present inventors have found a friction modifier with improved torque transmission function and a lubricating oil composition containing the same, and have achieved the present invention.
That is, the present invention comprises a unit of at least one monomer (a) represented by the general formula (1) and a unit of at least one monomer (b) represented by the general formula (2), A friction modifier for lubricating oil comprising an oil-soluble copolymer (A) having a weight average molecular weight of 3,000 or more; 1 selected from the group consisting of the copolymer (A), a diluent and other additives Friction modifier composition comprising at least one kind: and a base oil and the friction modifier or the friction modifier composition, wherein the copolymer (A) is present in an amount of 0.01 to 40% by weight based on the weight of the base oil. % Lubricating oil composition.
CH₂= C (R¹) -Q- (ZA¹) MX (1)
CH₂= C (R³) -CO- (OA²) N-OR⁴(2)
Where X is the formula -PH₂, -NH₂Or-(O)_a-P (= O)_b(OR²)₂One of a and b is 1 and the other is 0 or 1;²Are the same or different, H, an alkyl group having 1 to 24 carbon atoms, and a formula-(A¹-Z)_m-QC (R¹) = CH₂Or a group represented by the formula M_{1 / f}Is a cation of f valency (monovalent or divalent); R¹Is H or a methyl group; Z is -O- or -NH-;¹Is an alkylene group having 2 to 18 carbon atoms; m is 0 or an integer of 1 or 2 to 50; Q is -CO- or a divalent hydrocarbon group having 1 to 22 carbon atoms; R is a divalent hydrocarbon group having 1 to 22 carbon atoms;³Is H or a methyl group; n is 0 or an integer from 1 to 30;²Is an alkylene group having 2 to 18 carbon atoms;⁴Is an aliphatic hydrocarbon group having 1 to 32 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, or an aralkyl group having 7 to 32 carbon atoms;¹, Z, Q, R¹, M and A²May be the same or different.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The copolymer (A) in the present invention is usually from 3,000 to 500,000 or more, preferably from 5,000 to 300,000, particularly preferably from 8,000 to 100,000, most preferably from 10,000 to 500,000. It has a weight average molecular weight of 35,000 (hereinafter abbreviated as Mw). Mw in the present invention is measured by gel permeation chromatography (GPC) as a molecular weight in terms of polystyrene.
Further, the copolymer (A) is oil-soluble, and in the present invention, the oil-soluble is defined as a mineral oil (kinematic viscosity at 100 ° C of 2.3 mm at 40 ° C).²/ S, 100 g of mineral oil having a viscosity index of 83), at least 1 g is uniformly dissolved. It is preferable to dissolve 5 g or more.
[0007]
In the formula (1), X is-(O)_a-P (= O)_b(OR²)₂R if²Among them, alkyl groups having 1 to 24 carbon atoms (hereinafter abbreviated as C) include, for example, methyl, ethyl, n- and isopropyl, n-, iso-, sec- and tert-butyl, n- , Iso-, sec- and neopentyl, hexyl, heptyl, n- and iso-octyl, 2-ethylhexyl, n- and iso-nonyl, n- and iso-decyl, n- and iso-dodecyl, n- and iso- Tridecyl, n- and iso-tetradecyl, n- and iso-pentadecyl, n- and iso-hexadecyl, n- and iso-octadecyl, n-eicosyl, 2-ethyloctadecyl, 2-hexyltetradecyl, 2-octyldodecyl, Docosyl, n-tetracosyl and 2-decyltetradecyl groups It is. Preferred from the viewpoint of the friction adjusting effect of (A) are C1-4 alkyl groups, especially methyl and ethyl groups.
[0008]
The cation M having f value (f is 1 or 2) includes H (proton), alkali metal cation, alkaline earth metal cation, NH₄, Organic amine cations, quaternary ammonium cations, and combinations of two or more of these.
Lithium, sodium and potassium are included in the alkali metal constituting the cation; calcium and magnesium are included in the alkaline earth metal;
Organic amines include primary, secondary and tertiary aliphatic amines (amines having a C1-20 alkyl group and / or a C2-4 hydroxyalkyl group: diethylamine, triethylamine, monoethanolamine, monopropanolamine, etc.) Alicyclic amines (such as cyclohexylamine and dicyclohexylamine), aromatic amines (such as aniline and toluidine), aromatic heterocyclic amines (such as pyridine and quinoline), and heterocyclic amines (such as morpholine, N-methylmorpholine and piperazine); And N-position C2-4 hydroxyalkyl substituents of these cyclic amines (such as N-hydroxyethylmorpholine); quaternary ammoniums include aliphatic and alicyclic quaternary ammoniums such as tetra (cyclo) alkylammonium [C1 12 alkyl groups ( Chill, ethyl, propyl, butyl, hexyl, octyl, having a dodecyl group) and / or cycloalkyl groups (cyclohexyl group); four (cyclo) alkyl groups may be the same or different. ]; The (cyclo) alkyl group represents an alkyl group and / or a cycloalkyl group, and the same expression is used hereinafter.
Preferred among the cations are organic amine cations, particularly aliphatic amine cations, from the viewpoint of the oil solubility of (A).
[0009]
R²Is-(A¹-Z)_m-QC (R¹) = CH₂Q, Z and A when¹The following are mentioned.
[0010]
The divalent hydrocarbon group having 1 to 22 carbon atoms of Q includes a linear or branched aliphatic hydrocarbon group (for example, methylene, ethylene, 1,2-propylene, 1,3-propylene, 1,2- Butylene, 1,3-butylene, 1,4-butylene, 1,2-hexylene, 1,6-hexylene and 1,2-dodecylene group), alicyclic hydrocarbon group (for example, cyclohexylene, cyclohexylmethylene) , Cyclohexylethylene and cyclooctylhexylene groups) and aromatic hydrocarbon groups (eg, phenylene, phenylmethylene, phenylethylene, phenylhexylene, phenylbismethylene and phenylbisethylene groups). Among these hydrocarbon groups, preferred are those having C1 to 10, particularly C1 to C2.
Among Q's, preferred are aliphatic hydrocarbon groups (particularly methylene groups) and especially -CO- from the viewpoint of easy production of a copolymer having the target Mw.
Z is preferably -O- from the viewpoint of easy production of the monomer.
[0011]
A¹Include C2-18 alkylene groups among the divalent aliphatic hydrocarbon groups for Q. A C2-4 alkylene group is preferable from the viewpoint of easy production of the monomer.
− (ZA¹) M- represents m oxyalkylene groups or aminoalkylene groups. When Q is -CO-, m is preferably 1 or 2 to 20, more preferably 1 or 2 to 6, particularly 1. When Q is a hydrocarbon group having 1 to 22 carbon atoms, m may be 0, preferably 0 or 1.
[0012]
CH in the formula (1)₂= C (R¹) -Q- (ZA¹) M-Q, Z and A¹And the same are the same as described above, and preferred ones are also the same.
[0013]
Formula of X-(O)_a-P (= O)_b(OR²)₂The polar groups represented by include phosphoric acid groups, phosphonic acid groups, phosphite groups and their esters and salts. Preferred are those in which b is 1, especially those in which a and b are both 1.
In (a), X is-(O)_a-P (= O)_b(OR²)₂Examples of the monomer represented by are (a1) to (a3) below.
[0014]
(A1) a monomer wherein a = 1 and b = 1;
(A11) R²Are all H:
Monoalkenyl (C3-12) phosphates [e.g., mono (meth) allyl, mono (iso) propenyl, monobutenyl, monopentenyl, monooctenyl, monodecenyl and monododecenyl phosphate], mono (meth) acryloyloxyalkyl (C2-12) 12) phosphates [for example, monomethacryloyloxyethyl phosphate (hereinafter abbreviated as EPMA), monoacryloyloxyethyl phosphate, and mono (meth) acryloyloxyisopropyl phosphate], and monomethacryloylpoly (degree of polymerization of 2 to 20) ) Oxyethylene phosphate (hereinafter abbreviated as PEPMA) and the like. Commercially available products include "Light Ester P-1M" manufactured by Kyoeisha Chemical Co., Ltd. (composition: EPMA) and "Phosmer @ PE" manufactured by Uni Chemical Co., Ltd. (PEPMA having a polymerization degree of 4 to 5).
(A12) R²Wherein at least one of the alkyl groups is:
Monoalkenyl (C3-12) monoalkyl (C1-24) phosphate [eg allyl monomethyl and allyl monoethyl phosphate], monoalkenyl (C3-12) dialkyl (C1-24) phosphate [eg allyl dimethyl and allyl diethyl phosphate], And mono (meth) acryloyloxyalkyl (C2-12) monoalkyl (C1-24) phosphates [for example, mono (meth) acryloyloxyethyl monomethyl phosphate].
(A13) R²At least one of which is-(A¹-Z) m-QC (R¹) = CH₂Things;
Di (meth) acryloyloxyalkyl (C2-12) phosphate [for example, dimethacryloyloxyethyl phosphate (hereinafter abbreviated as DEPMA), diacryloyloxyethyl and di (meth) acryloyloxyisopropyl phosphate]. Commercially available products include Kyoeisha Chemical Co., Ltd.'s "Light Ester P-2M" (composition is DEPMA).
[0015]
(A2) a monomer wherein a = 0 and b = 1;
(A21) R²Are all H:
Alkene (C3-12) phosphonic acid [e.g. 2-propene-1-, 1-propene, decene and dodecenephosphonic acid], mono (meth) acryloyloxyalkane (C2-12) phosphonic acid [e.g. mono (meth) Acryloyloxyethane and mono (meth) acryloyloxyisopropanephosphonic acid], and mono (meth) acryloylpoly (degree of polymerization 2 to 20) oxyethylene phosphonic acid.
(A22) R²Wherein at least one of the alkyl groups is:
Monoalkyl (C1-24) monoalkene (C3-12) phosphonates [e.g. monomethyl and monoethyl 2-propene-1-phosphonate], dialkyl (C1-24) alkene (C3-12) phosphonates [e.g. dimethyl and diethyl 2-propene] -1-phosphonates], and monoalkyl (C1-24) mono (meth) acryloyloxyalkanes (C2-12) phosphonates [e.g., monomethyl mono (meth) acryloyloxyethane phosphonate].
(A23) R²At least one of which is-(A¹-Z) m-QC (R¹) = CH₂Things;
(Meth) acryloyloxyalkyl (C2-12) (meth) acryloyloxyalkane (C2-12) phosphonate [for example, (meth) acryloyloxyethyl (meth) acryloyloxyethane and (meth) acryloyloxypropyl ( (Meth) acryloyloxypropane phosphonate].
[0016]
(A3) a monomer wherein a = 1 and b = 0;
(A31) R²Are all H:
Monoalkenyl (C3-12) phosphites [e.g., monoallyl, monopropenyl, monodecenyl and monododecenyl phosphites], mono (meth) acryloyloxyalkyl (C2-12) phosphites [e.g. mono (meth) acryloy Loxyethyl and mono (meth) acryloyloxyisopropyl phosphite], and mono (meth) acryloyl poly (degree of polymerization 2 to 20) oxyethylene phosphite.
(A32) R²Wherein at least one of the alkyl groups is:
Monoalkenyl (C3-12) monoalkyl (C1-24) phosphites [eg allyl monomethyl and allyl monoethyl phosphite], monoalkenyl (C3-12) dialkyl (C1-24) phosphites [eg allyl dimethyl and allyl diethyl Phosphite], as well as mono (meth) acryloyloxyalkyl (C2-12) monoalkyl (C1-24) phosphite [eg, mono (meth) acryloyloxyalkylethyl monomethyl phosphite].
(A33) R²At least one of them is-(A¹-Z) m-QC (R¹) = CH₂Things;
Di (meth) acryloyloxyalkyl (C2-12) phosphites [eg di (meth) acryloyloxyethyl and di (meth) acryloyloxyisopropyl phosphite].
[0017]
In (a), X is -PH₂As the monomer (a4),
Monoalkenyl (C3-12) phosphines [e.g., monoallyl, monopropenyl, monodecenyl and monododecenylphosphine], mono (meth) acryloyloxyalkyl (C2-12) phosphines [e.g. mono (meth) acryloyloxyethyl and Mono (meth) acryloyloxyisopropylphosphine], and mono (meth) acryloylpoly (degree of polymerization 2 to 20) oxyethylene phosphine.
[0018]
In (a), X is -NH₂As the monomer (a5),
Monoalkenyl (C3-12) amines [e.g. monoallyl, monopropenyl, monodecenyl and monododecenylamine], mono (meth) acryloyloxyalkyl (C2-12) amines [e.g. mono (meth) acryloyloxyethyl and mono (Meth) acryloyloxyisopropylamine] and mono (meth) acryloylpoly (polymerization degree 2 to 20) oxyethyleneamine.
[0019]
Among (A) in the present invention, the copolymer containing the monomer (a5) may be prepared by a method of polymerizing a monomer mixture containing the (a5) or a precursor (a5) of the (a5).₀(A) is obtained by polymerizing a monomer mixture containing₀) And then (a)₀) Can be produced by a method of converting the unit into the unit (a5).
(A₀) Includes a monomer (a) represented by the general formula (3)₀₁) And a salt of the monomer (a5) (a₀₂) Is included.
[0020]
Embedded image

[0021]
Where R¹, Q, Z, A¹And m are the same as those in the general formula (1), and preferred ones are also the same. R⁵And R⁶Are the same or different, H or a C1-8 alkyl group or R⁵And R⁶Are bonded to each other to form an alkylene group having 3 to 11 carbon atoms, and form a ring together with adjacent carbon atoms. R⁵And R⁶Among them, preferred are a C1-4 alkyl group, and more preferred are a methyl, ethyl and iso-butyl group.
(A₀₁As an example of), in the formula (3), R¹And R⁵Is a methyl group, R⁶Is an iso-butyl group, Q is -CO-, Z is -O-, A¹Is an ethylene group and m is 1 (hereinafter abbreviated as MIBKMA).
(A₀₁) (A)₀) Is -NH by hydrolyzing the N = C bond.₂Can be converted to a base. The hydrolysis is performed by heating and stirring with water, an alkaline aqueous solution or an acidic aqueous solution at 40 to 120 ° C. for 1 to 20 hours.
As the alkaline aqueous solution, an aqueous solution (concentration: 10% by weight or less) of the alkali metal or alkaline earth metal hydroxide, ammonia or the aliphatic amine can be used. As the acidic aqueous solution, an aqueous solution of an inorganic acid or an organic acid of C1-4 (concentration: 10% or less) can be used. As the inorganic acid, carbonic acid, sulfuric acid, hydrochloric acid, nitric acid, boric acid and phosphoric acid can be used, and as the organic acid, a C1-4 carboxylic acid (for example, formic acid, acetic acid, propionic acid and butyric acid) can be used.
After hydrolysis, -NH₂Form an acid salt, the acid is removed with an ion-exchange resin or the like to give -NH₂Can be converted to -NH₂By being a group, the affinity with the base oil becomes better than that of a copolymer which remains as a salt. Among the hydrolysis methods, preferred is a method of hydrolysis with water or an aqueous alkali solution, from the viewpoint that the produced copolymer does not form a salt, so that the production process is simplified, and more preferred is hydrolysis with water. Is the way.
(A₀₁) Is, for example, when Q is —CO—, a (meth) acrylic acid or an ester or amide-forming derivative thereof (including a C1-6 alkyl ester, an acid halide and an acid anhydride), and the following general formula ( It is obtained from the Schiff base shown in 4).
[0022]
Embedded image

[0023]
Where R⁵, R⁶, Z, A¹And m are the same as in the general formula (3).
(A₀₂) (A)₀) Can be converted to a copolymer having an —NH 2 group by removing an acid component with an ion exchange resin or the like.
-NH₂Of (A) having a group, preferred is (a)₀₁(A) obtained from the precursor using (A).
[0024]
Among (a), (a2) and (a5) and particularly (a1) are preferable from the viewpoint of the friction adjustment effect. Among (a1), preferred are (a11), (a13) and a combination of (a11) and (a13), especially EPMA, DEPMA, PEPMA and a combination thereof. In the case of combined use, the combination of (a11) and (a13) is preferably 50% or more, particularly 60 to 95%. Above and below,% represents% by weight unless otherwise specified.
[0025]
In the general formula (2), R³Is a hydrogen atom or a methyl group, preferably a methyl group. A²Is a C2-18 alkylene group, for example, A¹And the same groups are preferred, and preferred ones are also the same. n is preferably 0 or 1 to 10, more preferably 0 or 1.
[0026]
R⁴Examples of the aliphatic hydrocarbon group having 1 to 32 carbon atoms include a C1 to 32 linear or branched alkyl group and a C2 to 32 linear or branched alkenyl group.
Examples of the alkyl group include hexacosyl, octacosyl (such as 2-dodecylhexadecyl), triacosyl and dotriacosyl group (such as a 2-tetradecyloctadecyl group) in addition to the above-described alkyl group; and examples of the alkenyl group include vinyl, (meth) allyl, Propenyl, butenyl, octenyl, decenyl, dodecenyl, pentadecenyl, octadecenyl, docosenyl, tetracosenyl, octacocenyl and triacocenyl groups.
R⁴Examples of the C5-7 alicyclic hydrocarbon group include cyclopentyl, cyclohexyl, and cycloheptyl groups. Examples of the C7-32 aralkyl group (where the alkyl group is a linear or branched group) include benzyl, phenylethyl, and phenylbutyl. Phenylnonyl and phenyldodecyl groups.
A²Is preferably C2 to C3, n is preferably 0 or an integer of 1 to 10, more preferably 0 or 1, particularly 0 from the viewpoint of the oil solubility of (A).
[0027]
Examples of (b) represented by the general formula (2) include the following.
(B1) C1-7 (preferably C1-6, more preferably C1-4, particularly C1) alkyl group, C2-7 (preferably C2-3) alkenyl group, C5-7 (preferably C6) cycloalkyl group (Meth) acrylic acid ester having an alkyl group or a C7-8 aralkyl group: for example, methyl acrylate, methyl methacrylate (hereinafter abbreviated as MMA), ethyl, butyl and hexyl (meth) acrylate; allyl and isopropenyl (meth) acrylate Cyclopentyl (meth) acrylate, cyclohexyl acrylate and cyclohexyl methacrylate (hereinafter abbreviated as MA-CH); benzyl and phenylethyl (meth) acrylate.
[0028]
(B2) a (meth) acrylate having a C8-32 (preferably C8-24, more preferably C12-24) alkyl or alkenyl group, or a C9-32 (preferably C9-18) aralkyl group: For example,
Dodecyl methacrylate (hereinafter abbreviated as MA-12), tetradecyl methacrylate (hereinafter abbreviated as MA-14), hexadecyl methacrylate (hereinafter abbreviated as MA-16), octadecyl methacrylate (hereinafter abbreviated as MA-18),
2-decyltetradecyl methacrylate (hereinafter abbreviated as MA-24), dodecyl, tetradecyl, hexadecyl, octadecyl and 2-decyltetradecyl acrylate, 2-ethylhexyl, n-octyl, decyl, isodecyl, tridecyl, eicosyl and tetracosyl ( A) acrylates; octenyl, decenyl, dodecenyl and octadecenyl (meth) acrylate and the like.
[0029]
(B3) (poly) alkylene (C2-18) glycol monoalkyl (C1-32, preferably C1-8), alkenyl (C2-32, preferably C2-3) or aralkyl (C7-32, preferably C7- 8) Mono (meth) acrylate of ether: As the alkylene group, alkyl group, alkenyl group and aralkyl group, the same groups as described above, and the polymerization degree of alkylene glycol are preferably 1 to 20, more preferably 1 to 20. It is 10.
For example, (poly) ethylene glycol (degree of polymerization 1 to 9) monomethyl ether, (poly) propylene glycol (degree of polymerization 1 to 5) monoethyl ether, ethylene glycol mono-2-ethylhexyl ether and polypropylene glycol (degree of polymerization 2 to 4) ) Monobutyl ether mono (meth) acrylate and the like.
Among (b), a combination of two or more of (b1) to (b3) is preferable, and one or two of (b1) and two of (b2) are more preferable. More than one kind, especially two to four kinds in combination.
When used in combination, the weight ratio of (b1) / (b2) is preferably 50/50 to 2/98, particularly preferably 35/65 to 3/97. If (b2) is 50 or more, (A) tends to be oil-soluble, and if it is 98 or less, the friction adjusting effect can be exhibited particularly favorably. Further, the amount of [(b1) + (b2)] in (b) is preferably 80 to 100%, more preferably 100%, based on the weight of (b).
The monomer (b) is represented by the general formula (2), wherein n is 0 or 1, and R⁴Is an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms or an aralkyl group having 7 to 8 carbon atoms, 2 to 50% by weight And n is 0 or 1 in the general formula (2);⁴Is an alkyl or alkenyl group having 8 to 32 carbon atoms or an aralkyl group having 9 to 32 carbon atoms, and is preferably composed of 50 to 98% by weight.
[0030]
The content of (a) based on the weight of (A) is preferably 0.01 to 50%, more preferably 0.05 to 40%, especially 0.1 to 15%, most preferably 0.2 to 5%. It is. When (a) is 0.01% or more, it is preferable in that the friction adjusting effect is excellent, and when it is 50% or less, it is preferable from the viewpoint that oil solubility is easily obtained.
The content of (b) based on the weight of (A) is preferably from 50 to 99.99%, more preferably from 60 to 99.95%, especially from 80 to 99.9%, most preferably from 90 to 99.8%. It is.
[0031]
(A) may contain a structural unit derived from another monomer (c), if necessary, in addition to (a) and (b). (C) includes the following hydrophobic monomers (c1) and hydrophilic monomers (c2).
[0032]
(C1) hydrophobic monomer
(C11) an aromatic vinyl hydrocarbon;
Styrene, substituted styrene (substituent having 1 to 18 carbon atoms) [for example, alkyl-substituted styrene (α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, p-ethylstyrene, p-isopropylstyrene and p-butylstyrene)] , Cycloalkyl-substituted styrene (p-cyclohexylstyrene), phenyl-substituted styrene (p-phenylstyrene), aralkyl-substituted styrene (p-benzylstyrene), acyl-substituted styrene (p-acetoxystyrene), phenoxy-substituted styrene (p- Phenoxystyrene)], divinyl-substituted aromatic hydrocarbons [eg, divinylbenzene, divinyltoluene and divinylxylene], and vinylnaphthalene.
(C12) an aliphatic vinyl hydrocarbon;
C2-30 chain alkene [e.g., ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-heptene, 4-methylpentene-1, 1-hexene, diisobutylene, 1-octene, 1-dodecene, -Octadecene and other [alpha] -olefins], C4-18, preferably 4-5, linear alkadienes [e.g. butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene and 1,7-octadiene], and C6. ~ 30 alicyclic vinyl hydrocarbons [e.g. (di) cyclopentadiene, (vinyl) cyclohexene, ethylidenebicycloheptene, pinene, limonene and indene].
(C13) alkyl alkenyl ether;
Ethers of C1-30 linear or branched alkyl groups and C2-4 alkenyl groups, such as alkyl vinyl ethers [eg, methyl, ethyl and n-butyl @ vinyl ether], alkyl (meth) allyl ethers [eg, methyl, ethyl and n- Butyl diallyl ether] and alkyl (iso) propenyl ether. Of these, methyl and ethyl vinyl ether, and methyl and ethyl diallyl ether are preferred.
(C14) an ester corresponding to the monomer (b) of an unsaturated carboxylic acid other than (meth) acrylic acid;
R of the unsaturated monocarboxylic acid [(iso) crotonic acid or the like]⁴And unsaturated dicarboxylic acids [such as maleic, fumaric and itaconic acid] alkyl (C1-24) diesters [such as dimethyl, diethyl and dioctyl maleate and dimethyl fumarate].
(C15) alkenyl aliphatic carboxylic acid ester;
C1-30, preferably 2-18 linear, branched or cyclic, saturated or unsaturated aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic acid and Linear or branched saturated aliphatic carboxylic acids such as n-octanoic acid, cyclic saturated aliphatic carboxylic acids such as cyclohexanoic acid, cyclooctanoic acid, and decahydronaphthylic acid, and linear unsaturated carboxylic acids such as oleic acid, linoleic acid and linolenic acid. Vinyl, (meth) allyl and (iso) propenyl esters of saturated aliphatic carboxylic acids).
(C16) vinyl ketones;
Ketones composed of C1-8 alkyl or C6-18 aromatic ring-containing hydrocarbon groups and vinyl groups [eg, methyl vinyl ketone, ethyl vinyl ketone and phenyl vinyl ketone].
(C17) Halogen-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, (meth) allyl chloride and halogenated styrenes (such as mono- and dichlorostyrene, tetrafluorostyrene and allyl chloride).
[0033]
(C2) hydrophilic monomer
(C21) a hydroxyl group-containing vinyl monomer;
(Poly) alkylene glycol (degree of polymerization 1 to 20) mono (meth) acrylate [hydroxyethyl acrylate, hydroxyethyl methacrylate (hereinafter abbreviated as MA-HE) and diethylene glycol mono (meth) acrylate, etc.], vinyl alcohol (vinyl acetate unit) Formed by hydrolysis of C3 to C12) alkenols (such as (meth) allyl alcohol, (iso) crotyl alcohol, 1-octenol and 1-undecenol), and C4 to C12 alkenediols [1-butene-3]. -Ol, 2-buten-1-ol and 2-butene-1,4-diol, etc.], hydroxyalkyl (C1-6) alkenyl (C3-10) ether [such as 2-hydroxyethylpropenyl ether] and hydroxyl group-containing Aromatic vinyl Monomer [p- hydroxystyrene, etc.].
(C22) anionic monomer:
(C22-1) Carboxyl group-containing vinyl monomer:
Unsaturated monocarboxylic acids [eg (meth) acrylic acid, α-methyl (meth) acrylic acid, crotonic acid and cinnamic acid], unsaturated dicarboxylic acids [eg maleic acid, fumaric acid and itaconic acid], unsaturated dicarboxylic acids Monoalkyl (C1-24) esters [e.g. monomethyl maleate, monomethyl fumarate, monoethyl itaconate and monooctyl maleate].
(C22-2) Sulfonic acid group-containing vinyl monomer:
C2-6 alkenesulfonic acid [such as vinylsulfonic acid and (meth) allylsulfonic acid], C6-12 vinyl group-containing aromatic sulfonic acid [such as α-methylstyrenesulfonic acid], and sulfonic acid group-containing (meth) acrylic acid Ester monomers [such as sulfopropyl (meth) acrylate and sulfoethyl (meth) acrylate], sulfonic acid group-containing (meth) acrylamide monomers [such as 2- (meth) acrylamide-2-methylpropanesulfonic acid], Vinyl monomer containing sulfonic acid group and hydroxyl group [3- (meth) acrylamide-2-hydroxypropanesulfonic acid, 3- (meth) allyloxy-2-hydroxypropanesulfonic acid, 3- (meth) acryloyloxy-2 -Hydroxypropanesulfonic acid, etc.], alkyl (C3-18) (meth ) Allyl sulfosuccinate [dodecyl allyl sulfosuccinate] like.
(C23) a nitrogen atom-containing monomer;
(C23-1) Amide group-containing vinyl monomer:
(Meth) acrylamide, monoalkyl (C1-4) substituted (meth) acrylamide, [N-methyl, N-ethyl, N-iso-propyl and Nn-butyl (meth) acrylamide], dialkyl (C1-4) Substituted (meth) acrylamides [N, N-dimethyl, N, N-diethyl and N, N-di-n-butyl} (meth) acrylamide], and N-vinylcarboxylic acid amides [N-vinylformamide, N-vinylacetamide; N-vinyl-n- and i-propionylamide] and the like.
(C23-2) Secondary or tertiary amino group-containing vinyl monomer:
Secondary amino group-containing vinyl monomer, for example, alkyl (C1-6) aminoalkyl (C2-6) (meth) acrylate [t-butylaminoethyl methacrylate, methylaminoethyl (meth) acrylate, etc.], C6-12 Dialkenylamines [such as di (meth) allylamine] and tertiary amino group-containing vinyl monomers such as dialkyl (C1-4) aminoalkyl (C2-6) (meth) acrylate [dimethylaminoethyl (meth) acrylate Dialkyl (C1-4) aminoalkyl (C2-6) (meth) acrylamide [dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide etc.] such as diethylaminoethyl (meth) acrylate Group vinyl monomer [N, N-dimethyl Aminostyrene, etc.], nitrogen-containing heterocyclic-containing vinyl monomer [morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, N-vinylpyrrole, N-vinylpyrrolidone, N-vinylthiopyrrolidone, etc.] .
(C23-3) Quaternary ammonium base-containing vinyl monomer:
The tertiary amino group-containing vinyl monomer described in the above (c7-2) is quaternized using a quaternizing agent (C1 to C12 alkyl chloride, dialkyl sulfate, dialkyl carbonate, benzyl chloride, etc.). And the like. Specifically, (meth) acryloyloxyalkyl quaternary ammonium salts, for example, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (Meth) acryloyloxyethylmethylmorpholinium chloride and the like; (meth) acrylamidoalkyl quaternary ammonium salts, for example, (meth) acrylamidoethyltrimethylammonium chloride, (meth) acrylamidoethyltriethylammonium chloride, (meth) acrylamidoethyldimethyl Benzyl ammonium chloride and the like; other quaternary ammonium base-containing vinyl monomers such as dimethyl Luzia Lil ammonium methylsulfate, tri-methyl-vinylphenyl chloride.
(C23-4) Nitrile group-containing monomer:
(Meth) acrylonitrile and the like.
[0034]
Among (c), from the viewpoint of the friction adjusting effect, (c2) is preferable, (c21), (c22-1), and (c23-2) are more preferable, and (c21) is particularly preferable.
Further, from the viewpoint of improving the oil solubility of (A), (c1) is preferable, and when the copolymer consisting of only (a) and (b) is not oil-soluble, it is hydrophobic ( It is preferred to use c1).
The weight ratio of (c) based on the weight of (A) is preferably 0 to 20%, more preferably 0.5 to 10%, and particularly preferably 1 to 8% from the viewpoint of the friction adjusting effect.
[0035]
(A) may be prepared by a conventionally known radical polymerization method, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, a thin film polymerization method, a spray polymerization method, preferably a solution polymerization method. Can be manufactured. Usually, (A) can be produced by radically polymerizing (a), (b) and optionally (c) in a solvent in the presence of an initiator and optionally a chain transfer agent.
Solvents include mineral oil [solvent refined oil, hydrogenated reforming oil (for example, high viscosity index oil having a viscosity index of 100 to 160), naphthenic oil] and synthetic lubricating oil [hydrocarbon synthetic lubricating oil (poly α-olefin). High-flash point solvents (flash points of 130 ° C. or higher), and other solvents [aliphatic hydrocarbons (pentane, hexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.) 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) ), Sulfoxide-based solvents (such as dimethyl sulfoxide)] and combinations of two or more of these. Preferred are high flash point solvents, aromatic hydrocarbons and alcoholic solvents, especially IPA.
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.
Examples of the peroxide-based initiator include inorganic peroxides [eg, hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.] and organic peroxides [eg, benzoyl peroxide, di-t-butyl peroxide] , 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 peroxy isobutyrate, t-amyl peroxy 2-ethyl hexanoate, 1,1,3,3- Tetramethylbutylperoxy 2-ethylhexanoate, dibutylperoxytrimethyl Adipate, lauryl peroxide] and the like.
Redox initiators include reducing agents such as alkali metal sulfites and bisulfites (eg, ammonium sulfite, ammonium bisulfite, etc.), ferrous chloride, ferrous sulfate, ascorbic acid, and alkali metal persulfate. Salts, combinations of oxidizing agents such as ammonium persulfate, hydrogen peroxide and organic peroxides are included. Examples of the chain transfer agent include mercaptans [n-lauryl mercaptan (hereinafter abbreviated as LSH), mercaptoethanol, mercaptopropanol, etc.], thiocarboxylic acids (thioglycolic acid, thiomalic acid, etc.), and secondary alcohols (isopropanol). ), Amines (such as dibutylamine), and hypophosphites (such as sodium hypophosphite).
The polymerization temperature is preferably from 30 to 140C, more preferably from 50 to 130C, especially from 70 to 120C. The polymerization temperature is 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.
Further, the copolymerization may be any of random addition polymerization and alternating copolymerization, and may be any of graft copolymerization and block copolymerization.
[0036]
The friction modifier composition of the present invention comprises the friction modifier of the present invention and a diluent and / or other additives.
Dissolving and diluting the friction modifier with the diluent facilitates dissolution in the base oil.
[0037]
As the diluent, the solvents mentioned in the above-mentioned production method (A) can be used, and the solvent used in the polymerization step may be left without being removed. Among the diluents, preferred are the mineral oils mentioned above, in particular hydrogenated reformates.
The dissolution of the friction modifier in the diluent is performed, if necessary, under heating (preferably at 40 to 150 ° C.).
When a diluent is used, the content of (A) in the friction modifier composition is preferably 1% or more, more preferably 20 to 90%, particularly 30 to 80%, and the content of the diluent is preferably 99%. %, More preferably 10 to 80%, particularly preferably 20 to 70%.
[0038]
Other additives in the friction modifier composition include a copolymer (B).
(B) is a copolymer containing the above-mentioned unit (b) and, if necessary, the above-mentioned unit (c), but not containing the unit (a).
Preferred among (b) are (b1), (b2) and combinations thereof,
More preferred are (b2), and a combination of (b1) and (b2), and particularly preferred are a combination of two or more of (b2) and a combination of MMA and (b2).
(B) comprising (b2) without (b1) is preferable from the viewpoint that a pour point depressing action can be exerted in a lubricating oil composition described below, and (B) comprising (b1) and (b2) is a lubricating oil composition described later. It is preferable from the viewpoint that the viscosity index of the oil composition can be improved.
The preferred weight ratio of the combination of (b1) and (b2) is 2 to 50% / 50 to 98%, more preferably 10 to 35% / 65 to 90%.
(C) which can be contained as necessary is preferably (c11), (c12), (c14) and (c15) of (c1), and (c21) and (c23) of (c2). And more preferred are (c21) and (c23-2).
The proportion of (c) based on the weight of (B) is usually 0 to 20%, preferably 1 to 10%.
The Mw of (B) is usually from 5,000 to 300,000, preferably from 20,000 to 100,000, and the more preferred Mw of (B) comprising (b2) without (b1) is from 50,000 to 70,000.
The proportion of (B) based on the weight of (A) is usually 0 to 50%, preferably 0 to 20%.
[0039]
Other additives in the friction modifier composition may further include other optional components such as detergents [Ca and Mg salts such as sulfonate, salicylate, phenate, and naphthenate and calcium carbonate, etc.], dispersants [succinate] Acid imides (for example, bis type, mono type, borate type, Mannich condensate type, etc.)], antioxidants [zinc dithiophosphate, amine type (eg, diphenylamine), hindered phenol type, zinc thiophosphate, trialkyl phenol, etc. ), Conventionally known friction modifiers [long-chain fatty acids (eg, oleic acid), long-chain fatty acid esters (eg, oleic acid ester), long-chain amines (eg, oleylamine), long-chain amides (eg, oleamide)], wear resistance Agents [eg molybdenum dithiophosphate, molybdenum di Ocabamate and zinc dialkyldithiophosphate], extreme pressure agents [eg sulfur-based, sulfur-based, phosphorus-based and chlorinated], defoamers [eg silicone oil, metal soaps, fatty acid esters and phosphate esters], demulsifiers [E.g. quaternary ammonium salts, sulfated oils and phosphate esters] and corrosion inhibitors [benzotriazole and 1,3,4-thiodiazolyl-2,5-bisdialkyldithiocarbamate].
The amount of these additives is usually 0 to 40%, preferably 0.1 to 30%, and the dispersant is usually 0 to 20%, preferably 0.2 to 10%, based on the weight of the friction modifier composition. %, The antioxidant is usually 0 to 5%, preferably 0.1 to 3%, the known friction modifier is usually 0 to 5%, preferably 0.1 to 3%, the antiwear agent and the extreme pressure agent are Usually 0 to 40%, preferably 0.1 to 30%, the defoamer is usually 0 to 10,000 ppm, preferably 10 to 4,000 ppm, the demulsifier is usually 0 to 15%, preferably 0 to 1%, The corrosion inhibitor is usually 0 to 3%, preferably 0 to 2%.
The total amount of other additives in the friction modifier composition is usually 0 to 60%, preferably 0.1 to 40%.
Other additives may be blended with the base oil after being blended as the friction modifier composition, but may be blended separately with the base oil, and the blending order in that case is not particularly limited. .
[0040]
The friction modifier of the present invention can exhibit not only a friction regulating effect but also a wear preventing effect, a dispersing effect, an antioxidant effect, a viscosity index improving effect, and the like.
[0041]
Uses of the friction modifier of the present invention include engine oil (for gasoline, diesel, etc.), transmission oil (gear oil (for industrial use, automobile use), automatic transmission oil (automatic transmission oil, toroidal CVT oil, belt CVT oil). ], Power steering oils, shock absorber oils, traction oils, greases, etc., but are preferably used for transmission oils, more preferably automatic transmission oils, particularly preferably gear oils for automobiles, and automatic slip control mechanisms. It is used in automatic transmission oils and belt CVT oils for automatic transmissions having excellent fuel economy, does not adversely affect shudder properties, and is effective in comfort.
[0042]
The base oil that can be used in the lubricating oil composition of the present invention is not particularly limited, and includes, for example, the above-described mineral oils and synthetic lubricating oils, and is preferably a mineral oil having a high viscosity index of 100 to 160. , Hydrocarbon synthetic lubricating oils and ester synthetic lubricating oils. Further, the preferred cloud point (JIS K2269) of the base oil is -5C or less, more preferably -15C to -70C. When the cloud point is within this range, the amount of wax deposited is small and the low-temperature viscosity is good. The kinematic viscosity of the base oil is preferably 1 to 14 mm at 100 ° C.²/ S.
[0043]
In the lubricating oil composition of the present invention, the content of (A) based on the weight of the base oil is usually 0.01 to 40%, preferably 0.03 to 30%.
The content of (A) based on the weight of the base oil is 0.1 to 15% when the lubricating oil composition is used as an engine oil, and 0.1 to 15% when it is used as a gear oil. In the case of automatic transmission oil (automatic transmission oil, belt CVT oil, etc.) and hydraulic oil, the content is preferably 0.1 to 20%, and in the case of traction oil, it is preferably 0.1 to 20%.
The content of (A) + (B) based on the weight of the base oil is usually 0.01 to 40%, preferably 0.03 to 30%.
[0044]
Example
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the following, parts represent parts by weight.
[Method for measuring Mw by GPC]
Equipment: {Toyo Soda} HLC-802A
Column I: 2 TSK gel gel GMH6
Measurement temperature: 40 ℃
Sample solution: 0.5% tetrahydrofuran solution
Solution injection volume: 200 µl
Detector: Refractive index detector
Standard: Polystyrene
[Method of measuring friction coefficient and shift shock reduction performance]
The friction coefficient is measured as μd (1,800 rpm) at the 500th cycle, and μ0 (3,600 rpm) / μd (1,800 rpm) at the 500th cycle as the performance to reduce shift shock.
When μ0 / μd is closer to 1.0, the shift shock is reduced, and when μd is large, the friction coefficient is large.
The measurement is performed according to the method of JASO M348-95, and the friction coefficient of μd (1,800 rpm) at the 500th cycle and μ0 / μd at the 500th cycle as an index of the shift shock are measured. The shift shock is smaller when μ0 / μd is closer to 1.0, and the friction coefficient is larger when μ0 / μd is larger.
[Method of measuring wear resistance]
The wear scar diameter of the ball is measured with a ball-on-disk using SRV.
Wear mark diameter: The average value of the vertical and horizontal diameters of the ball wear mark
Apparatus: Optimol @ SRV testing machine (Nippon Parkerizing Co., Ltd.)
Ball: 10mm diameter
Disk: 24mm diameter x 7.9mm thickness
Load: 200N
Stroke width: 2mm
Frequency: 50Hz
Test time: 10 minutes
[0045]
Examples 1 to 12
In a reaction vessel equipped with a stirrer, a heating / cooling apparatus, a thermometer, a dropping funnel, and a nitrogen blowing tube, 2,500 parts of IPA was charged as a polymerization solvent, and the gas phase of the reaction vessel was replaced with nitrogen. While refluxing at ~ 85 ° C, a monomer-initiator solution having the composition shown in Table 1 or Table 2 was dropped at a constant rate from the dropping funnel over 3 hours, and the mixture was further aged at the same temperature for 1 hour. The obtained polymer solution was heated to 120 ° C., and the solvent was removed under reduced pressure to obtain 10,000 parts of copolymers (A-1) to (A-12) having Mw shown in Table 1. . Mineral oil (hydrogenated reforming oil: kinematic viscosity at 100 ° C: 2.3 mm) was added to 5,200 parts of the friction modifier of the present invention composed of (A-1) to (A-12).²/ S, viscosity index 83) 4,800 parts were added and uniformly dissolved and diluted at 120 ° C to obtain friction modifier compositions (V-1) to (V-12) of the present invention. Further, the amount of the friction modifier composition shown in Table 1 or Table 2 and a high viscosity index oil [“YUBASE3” (manufactured by SK Corp., viscosity index = 107)] are mixed, and the lubricating oil composition (F) of the present invention is mixed. -1) to (F-12) were obtained.
[0046]
[Table 1]

[0047]
[Table 2]

[0048]
Examples 13 and 14
The polymerization solvent shown in Table 3 was charged into the same reaction vessel as in Example 1, the gas phase of the reaction vessel was replaced with nitrogen, and then the temperature was raised to 85 ° C. in a sealed state. The monomer-initiator solution was added dropwise at a constant rate over 2 hours, and the mixture was aged at the same temperature for 2 hours. Thereafter, 924 parts of water was added, and the mixture was heated and stirred at 85 ° C. for 2 hours to hydrolyze. Next, the temperature was raised to 120 ° C., water and toluene were distilled off under reduced pressure, and the obtained copolymer was reprecipitated with methanol, washed twice with 8,700 parts of methanol and then at 100 ° C. for 4 hours. Drying under reduced pressure gave copolymers (A-13) and (A-14) having the amounts and Mw shown in Table 3.
The same amount of the same mineral oil as in Example 1 was added to the friction modifier of the present invention consisting of (A-13) or (A-14) and uniformly dissolved and diluted at 120 ° C. to prepare the friction modifier of the present invention. The agent compositions (V-13) and (V-14) were obtained. Further, these were mixed with high viscosity index oils ("YUBASE3") in the amounts shown in Table 3 to obtain lubricating oil compositions (F-13) and (F-14) of the present invention.
[0049]
Comparative Examples 1 and 2
Using a monomer-initiator solution having the composition shown in Table 3 and a polymerization solvent, the polymerization temperature was set to 85 ° C., and polymerization was carried out in the same manner as in Example 1 except that the solvent was not removed. "YUBASA3" solutions of (-1) and (B-2) were obtained. These solutions were diluted with a hydrogenated reforming oil so as to have a copolymer / diluent ratio shown in Table 3 to obtain friction modifier compositions (Y-1) and (Y-2) of Comparative Examples. Was. The diluent of the copolymer / diluent in Table 3 includes the hydrogenated reforming oil used for dilution and YUBASE3 used for polymerization. Further, in the same manner as in Example 1, these were mixed with a high viscosity index oil ("YUBASE3") at the ratio shown in Table 3 to obtain lubricating oil compositions (Z-1) and (Z-2) of Comparative Examples. .
[0050]
Comparative Example 3
5 parts of oleylamine were added to 995 parts of (Z-1) to obtain a lubricating oil composition (Z-3) of Comparative Example 3.
[0051]
[Table 3]

[0052]
For these lubricating oil compositions, μd, μ0 / μd and wear scar diameter were measured. Table 4 shows the results.
[0053]
[Table 4]

[0054]
【The invention's effect】
The friction modifier, the friction modifier composition and the lubricating oil composition of the present invention are excellent in friction regulation effect, can reduce shift shock, and have a high friction coefficient required for power transmission. Further, the friction modifier of the present invention can exert not only a friction regulating effect but also a wear preventing effect, a dispersing effect, an antioxidant effect, a viscosity index improving effect, and the like.
Therefore, the friction modifier of the present invention can be widely and suitably used in engine oils, transmission oils, power steering oils, shock absorber oils, traction oils, greases, and the like, is excellent in fuel economy, and has an adverse effect on shudder properties. It has no effect and is effective in comfort.

Claims (14)

It contains at least one unit of the monomer (a) represented by the general formula (1) and at least one unit of the monomer (b) represented by the general formula (2). A friction modifier for lubricating oils comprising the oil-soluble copolymer (A) having a weight average molecular weight.
_{^{CH 2 = C (R 1)}} -Q- (Z-A 1) m-X (1)
^{_{CH 2 = C (R 3)}} -CO- (O-A 2) n-OR 4 (2)
Wherein X is a polar group represented by the formula —PH ₂ , —NH ₂ or — (O) _a —P (＝ O) _b (OR ² ) ₂ ; one of a and b is 1, The other is 0 or 1; two R ² are the same or different, H, an alkyl group having 1 to 24 carbon atoms, and a group represented by the formula-(A ¹ -Z) _m -QC (R ¹ ) = CH ₂ . It is a cation of group or the formula _{M 1 / f} shown; M is (are f 1 or 2) f value be cation; ^{R 1} is H or methyl; Z is -O- or -NH- with A ¹ is an alkylene group having 2 to 18 carbon atoms; m is 0 or an integer of 1 or 2 to 50; Q is —CO— or a divalent hydrocarbon group having 1 to 22 carbon atoms. When m is 0, Q is a divalent hydrocarbon group having 1 to 22 carbon atoms; R ³ is H or a methyl group; n is 0 or 1 A ² is an alkylene group having 2 to 18 carbon atoms; R ⁴ is an aliphatic hydrocarbon group having 1 to 32 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms or carbon atom An aralkyl group of the formulas 7 to 32; when there are a plurality of groups, A ¹ , Z, Q, R ¹ , m and A ² may be the same or different. ] The regulator according to claim 1, wherein Q is -CO- and Z is -O-. X has the formula _{- (O) a -P (=} O) (OR 2) modifier according to claim 1, wherein represented by _2. Modifier according to any one of claims 1 to 3 X is -NH _2. The copolymer (A) according to claim 4, wherein the copolymer (A) is obtained by hydrolyzing a copolymer (A ₀ ) containing a unit derived from the monomer (a ₀₁ ) represented by the general formula (3). Conditioner.

[Wherein, R ¹ , Q, Z, A ¹ and m are the same as those in the general formula (1);
R ⁵ and R ⁶ are the same or different and are H or an alkyl group having 1 to 8 carbon atoms, or R ⁵ and R ⁶ are mutually bonded to form an alkylene group having 3 to 11 carbon atoms, and adjacent carbon atoms Together with to form a ring. ] The regulator according to claim 5, wherein the copolymer (A) is obtained by hydrolyzing the copolymer (A ₀ ) in the absence of an acid. The regulator according to any one of claims 1 to 6, wherein the copolymer (A) contains 0.01 to 50% by weight of a unit derived from the monomer (a). The monomer (b) is represented by the general formula (2), wherein n is 0 or 1, and R ⁴ is an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, 2 to 50% by weight of a monomer (b1) which is a cycloalkyl group having 5 to 7 carbon atoms or an aralkyl group having 7 to 8 carbon atoms, represented by the general formula (2), wherein n is 0 or 1 in and, ^{R 4} is according to any one of claims 1 to 7 comprising a monomer (b2) 50 to 98 wt% with an alkyl or alkenyl group or an aralkyl group having a carbon number of 9 to 32 8 to 32 carbon atoms Regulator. 9. The preparation according to claim 8, wherein n is 0. The modifier according to any one of claims 1 to 9, wherein (A) has a weight average molecular weight of 3,000 to 500,000. A friction modifier composition comprising the copolymer (A) according to claim 1 and one or more members selected from the group consisting of a diluent and other additives. The composition according to claim 11, comprising 20-90% by weight of (A) and 10-80% by weight of diluent. Lubrication comprising a base oil and the modifier or modifier composition according to any one of claims 1 to 12, and containing the copolymer (A) in an amount of 0.01 to 40% by weight based on the weight of the base oil. Oil composition. The composition according to claim 13, wherein the base oil is at least one selected from the group consisting of mineral oils having a high viscosity index of 100 to 160, hydrocarbon synthetic lubricating oils, and ester synthetic lubricating oils.