JP2015071687A - Composite polyamide ester composition and lubricant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite polyamide ester composition which can exhibit excellent lubrication performance and has excellent dispersibility in a base oil.SOLUTION: Provided is a composite polyamide ester composition containing a polyamide ester which is obtained by condensing a dendrimer compound represented by the following general formula (1), a polybasic carboxylic acid, and a monohydric alcohol. In the general formula (1), Z represents a n-valent atomic group containing a nitrogen atom; Lrepresents a (m+1)-valent linking group; Xrepresents -CONH-, -COO-, -OCO-, or -NHCO-; Rrepresents a group having a terminal amino group or hydroxyl group; n is an integer of 2 to 6; m is an integer of 1 to 4; and n+m is 4 or more.

Description

  The present invention relates to composite polyamide ester compositions and lubricants. Specifically, the present invention relates to a composite polyamide ester composition containing a polyamide ester obtained by condensing a dendrimer compound, a polyvalent carboxylic acid and a monohydric alcohol, and a lubrication containing the composite polyamide ester composition. It relates to the agent.

  Lubricants generally include base oils and various additives. Base oils include mineral oils obtained from crude oils, chemically synthesized ester oils, fluorine oils, polyalphaolefin oils, and the like. Among these, ester oils are suitably used for jet aircraft, automobile engine oils, greases and the like because of their low pour point, high viscosity index, high flash point, good lubricating performance, biodegradability, and the like.

  As ester oil, monoester obtained from reaction of aliphatic monocarboxylic acid and monohydric alcohol; diester obtained from reaction of aliphatic dibasic acid and monohydric alcohol; polyhydric alcohol and aliphatic carboxylic acid; Various esters are disclosed (Patent Documents 1 to 5), such as esters obtained from the above reaction; and complex esters obtained from reaction with polyols, polybasic acids, and aliphatic monocarboxylic acids.

  Patent Documents 6 and 7 disclose polyester compositions synthesized using branched compounds. Patent Document 6 discloses a polyester composition obtained from the reaction of a polyhydric alcohol, a dimer acid, and a monohydric alcohol having a branched chain. Patent Document 7 discloses a polyhydric alcohol, a dimer acid, A polyester composition obtained from the reaction of a monovalent carboxylic acid having a branched chain is disclosed. Thus, it has been proposed to use a compound having a branched structure for the synthesis of polyester.

  Patent Documents 8 and 9 disclose polyamide ester compositions using a polyvalent amine. Patent Document 8 discloses a polyamide ester composition obtained from a reaction of an aliphatic dibasic acid such as dimer acid or trimer acid, diamine and methanol. Here, the obtained polyamide ester composition is used for an optical member such as a lens. Patent Document 9 discloses a polyamide ester composition obtained from the reaction of a polyvalent amine, an aliphatic dibasic acid and a polyhydric alcohol, and such a composition is used as a lubricating oil composition. ing.

JP 2002-097482 A JP 2005-154726 A JP 2005-232434 A JP 2005-213377 A JP 2005-232470 A Japanese Patent Laid-Open No. 1-311122 Special table 2009-533406 gazette Japanese Patent Laid-Open No. 9-12716 JP 2003-268395 A

  In recent years, with the diversification and sophistication of industrial fields, lubricants are required to have high lubrication performance. However, lubricants containing polyesters and polyamide esters described in conventional patent documents often have insufficient lubrication performance, and further improvements are required.

  In addition, the polyester and polyamide ester compositions obtained by the prior art may not be sufficiently dispersible in the base oil when used as a lubricant. That is, the conventional polyamide ester composition has a problem that it is difficult to achieve both lubrication performance and dispersibility. For this reason, there is a demand for a polyamide ester composition that exhibits excellent lubricating performance and is excellent in dispersibility in base oil.

  Therefore, in order to solve the problems of the prior art, the inventors of the present invention provide a polyamide ester composition that can exhibit excellent lubrication performance and has excellent dispersibility in a base oil. We proceeded with the study for the purpose of providing.

As a result of intensive studies to solve the above-mentioned problems, the present inventors obtained a composite polyamide ester composition by condensing a dendrimer compound, a polyvalent carboxylic acid, and a monohydric alcohol. It has been found that the lubricating performance and dispersibility of the polyamide ester composition in the base oil can be improved.
Specifically, the present invention has the following configuration.

（一般式（１）中、Ｚは窒素原子を含むｎ価の原子団を表し、Ｌ¹は（ｍ＋１）価の連結基を表し、Ｘ¹は−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨＣＯ−を表し、Ｒ¹は末端がアミノ基又はヒドロキシ基である基を表す。また、ｎは２〜６の整数であり、ｍは１〜４の整数であり、ｎ＋ｍは４以上である。）
［２］前記一般式（１）中、Ｒ¹はアミノアルキル基又はヒドロキシアルキル基である［１］に記載のポリアミドエステル組成物。
［３］前記一般式（１）中、Ｒ¹はアミノアルキル基である［１］又は［２］に記載のポリアミドエステル組成物。
［４］前記デンドリマー化合物は、下記一般式（２）で表される［１］に記載の複合ポリアミドエステル組成物。

（一般式（２）中、Ｚは窒素原子を含むｎ価の原子団を表し、Ｌ¹は（ｍ＋１）価の連結基を表し、Ｌ²は（ｐ＋１）価の連結基を表し、Ｘ¹及びＸ²はそれぞれ独立に、−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨＣＯ−を表し、Ｒ²は末端がアミノ基又はヒドロキシ基である基を表す。また、ｎは２〜６の整数であり、ｍは１〜４の整数であり、ｐは１〜４の整数であり、ｎ＋ｍは４以上、もしくはｎ＋ｐは４以上である。）
［５］前記一般式（２）中、Ｒ²はアミノアルキル基又はヒドロキシアルキル基である［４］に記載の複合ポリアミドエステル組成物。
［６］前記一般式（２）中、Ｒ²はアミノアルキル基である［４］又は［５］に記載の複合ポリアミドエステル組成物。
［７］前記デンドリマー化合物の末端官能基数は、３〜７６８である［１］〜［６］のいずれか１項に記載の複合ポリアミドエステル組成物。
［８］前記デンドリマー化合物の分子量は、３５０以上である［１］〜［７］のいずれか１項に記載の複合ポリアミドエステル組成物。
［９］前記多価カルボン酸の炭素数は１０以上である［１］〜［８］のいずれか１項に記載の複合ポリアミドエステル組成物。
［１０］前記多価カルボン酸の炭素数は２４〜４８である［１］〜［９］のいずれか１項に記載の複合ポリアミドエステル組成物。
［１１］前記多価カルボン酸は不飽和脂肪酸の二塩基酸又は三塩基酸である［１］〜［１０］のいずれか１項に記載の複合ポリアミドエステル組成物。
［１２］前記多価カルボン酸はダイマー酸、トリマー酸又はエルカ酸ダイマーである［１］〜［１１］のいずれか１項に記載の複合ポリアミドエステル組成物。
［１３］前記１価アルコールの炭素数は６以上である［１］〜［１２］のいずれか１項に記載の複合ポリアミドエステル組成物。
［１４］前記１価アルコールは少なくとも１つのオキシアルキレン基を有する［１］〜［１３］のいずれか１項に記載の複合ポリアミドエステル組成物。
［１５］前記１価アルコールは、下記一般式（３）で表される［１］〜［１４］のいずれか１項に記載の複合ポリアミドエステル組成物。

（一般式（３）中、Ｒ^aは置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基であり、Ｘ^a1及びＸ^a2はそれぞれ独立に水素原子、ハロゲン原子又はアルキル基を表す。また、ｎａ１は１〜４の整数を表し、ｎａ２は１〜１２の整数を表す。ｎａ１が２以上の場合、ｎａ１個のＸ^a1は同じであっても異なっていてもよく、ｎａ１個のＸ^a2は同じであっても異なっていてもよい。また、ｎａ２が２以上の場合、ｎａ２個の−（Ｏ（ＣＸ^a1Ｘ^a2）_na1−は同じであっても異なっていてもよい。）
［１６］有機モリブデン化合物及び有機亜鉛化合物の少なくとも１種の有機金属化合物をさらに含む［１］〜［１５］のいずれか１項に記載の複合ポリアミドエステル組成物。
［１７］前記有機金属化合物は、硫化オキシモリブデン−Ｎ,Ｎ−ジ−オクチルジチオカルバメート、硫化オキシモリブデン−Ｎ,Ｎ−ジ−トリデシルジチオカルバメート、ｎ−ブチル−ｎ−ペンチルジチオリン酸亜鉛、ジ−２−エチルヘキシルジチオリン酸亜鉛又はイソプロピル−１−エチルブチルジチオリン酸亜鉛である［１６］に記載の複合ポリアミドエステル組成物。
［１８］前記ポリアミドエステル、前記デンドリマー化合物に対して、前記多価カルボン酸の当量比が１〜２０となり、前記１価アルコールの当量比が０．５〜３０となるように混合され、縮合されることにより得られる［１］〜［１７］のいずれか１項に記載の複合ポリアミドエステル組成物。
［１９］前記ポリアミドエステルは、下記一般式（５）で表されるポリアミドエステル及び下記一般式（６）で表されるポリアミドエステルの少なくとも一方を含む［１］〜［１８］のいずれか１項に記載の複合ポリアミドエステル組成物。

（一般式（５）中、Ｚは窒素原子を含むｎ価の原子団を表し、Ｌは（ｍ＋１）価の連結基を表し、Ｘは−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨＣＯ−を表し、Ｙは２価の連結基を表す。Ｒ³は（ｐ＋１）価の鎖状もしくは環状の脂肪族連結基又は芳香族連結基を表し、Ｒ⁴は置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基を表す。また、ｎは２〜６の整数であり、ｍは１〜４の整数であり、ｐは１〜４の整数であり、ｎ＋ｍは４以上、もしくはｎ＋ｐは４以上である。なお、ｐが２以上の場合、ｐ個のＲ⁴は同じであっても異なっていてもよい。ｍが２以上の場合は、ｍ個の−Ｘ−Ｙ−ＮＨＣＯＲ³−（ＣＯＯＲ⁴）_pは同じであっても異なっていてもよい。また、ｎ個の−ＣＯＮＨ−Ｌ−｛Ｘ−Ｙ−ＮＨＣＯＲ³−（ＣＯＯＲ⁴）_p｝_mは同じであっても異なっていてもよい。）

（一般式（６）中、Ｚは窒素原子を含むｎ価の原子団を表し、Ｌは（ｍ＋１）価の連結基を表し、Ｘは−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨＣＯ−を表し、Ｙは２価の連結基を表す。Ｒ⁵は（ｐ＋１）価の鎖状もしくは環状の脂肪族連結基又は芳香族連結基を表し、Ｒ⁶は置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基を表す。また、ｎは２〜６の整数であり、ｍは１〜４の整数であり、ｐは１〜４の整数であり、ｎ＋ｍは４以上、もしくはｎ＋ｐは４以上である。なお、ｐが２以上の場合、ｐ個のＲ⁶は同じであっても異なっていてもよい。ｍが２以上の場合は、ｍ個の−Ｘ−Ｙ−ＯＣＯＲ⁵−（ＣＯＯＲ⁶）_pは同じであっても異なっていてもよい。また、ｎ個の−ＣＯＮＨ−Ｌ−｛Ｘ−Ｙ−ＯＣＯＲ⁵−（ＣＯＯＲ⁶）_p｝_mは同じであっても異なっていてもよい。）
［２０］前記一般式（５）及び（６）において、Ｒ³及びＲ⁵はそれぞれ独立に、ダイマー酸残基、トリマー酸残基又はエルカ酸ダイマー残基である［１９］に記載の複合ポリアミドエステル組成物。
［２１］前記一般式（５）及び（６）において、Ｒ⁴及びＲ⁶はそれぞれ独立に、オキシアルキレン構造を有する基である［１９］又は［２０］に記載の複合ポリアミドエステル組成物。
［２２］４０℃における粘度が５０〜１６５０ｍＰａｓである［１］〜［２１］のいずれか１項に記載の複合ポリアミドエステル組成物。
［２３］［１］〜［２２］のいずれか１項に記載の複合ポリアミドエステル組成物と、摩耗防止剤、粘度指数向上剤、酸化防止剤、清浄剤、分散剤，流動、硬化剤、腐食防止剤、シール適合剤、消泡剤、錆防止剤、腐食防止剤、摩擦調整剤、及び増ちょう剤から選択される１種又は２種以上の添加剤とを含有する組成物。
［２４］［１］〜［２２］のいずれか１項に記載の複合ポリアミドエステル組成物、又は［２３］に記載の組成物と、鉱物油、油脂化合物、ポリオレフィン油、シリコーン油、パーフルオロポリエーテル油、芳香族エステル油、及びポリオールエステル潤滑油から選択される１種又は２種以上の媒体とを少なくとも含有する組成物。
［２５］［１］〜［２２］のいずれか１項に記載の複合ポリアミドエステル組成物、又は［２３］又は［２４］に記載の組成物を含む潤滑剤。
［２６］グリース用潤滑油、離型剤、内燃機関用エンジンオイル、金属加工用（切削用）オイル、軸受け用オイル、燃焼機関用燃料、車両エンジン油、ギヤ油、自動車用作動油、船舶・航空機用潤滑油、マシン油，タービン油、軸受用オイル、油圧作動油、圧縮機・真空ポンプ油、冷凍機油、金属加工用潤滑油剤、磁気記録媒体用潤滑剤、マイクロマシン用潤滑剤、人工骨用潤滑剤、ショックアブソーバ油又は圧延油として用いられる［２５］に記載の潤滑剤。 [1] A composite polyamide ester composition comprising a polyamide ester obtained by condensing a dendrimer compound represented by the following general formula (1), a polyvalent carboxylic acid, and a monohydric alcohol.

(In General Formula (1), Z represents an n-valent atomic group containing a nitrogen atom, L ¹ represents a (m + 1) -valent linking group, and X ¹ represents —CONH—, —COO—, —OCO—, or -NHCO-, R ¹ represents a group whose terminal is an amino group or a hydroxy group, n is an integer of 2 to 6, m is an integer of 1 to 4, and n + m is 4 or more. .)
[2] The polyamide ester composition according to [1], wherein R ¹ in the general formula (1) is an aminoalkyl group or a hydroxyalkyl group.
[3] The polyamide ester composition according to [1] or [2], wherein R ¹ is an aminoalkyl group in the general formula (1).
[4] The composite polyamide ester composition according to [1], wherein the dendrimer compound is represented by the following general formula (2).

(In General Formula (2), Z represents an n-valent atomic group containing a nitrogen atom, L ¹ represents a (m + 1) -valent linking group, L ² represents a (p + 1) -valent linking group, and X ¹ And X ² each independently represents —CONH—, —COO—, —OCO— or —NHCO—, R ² represents a group whose terminal is an amino group or a hydroxy group, and n represents 2 to 6 (It is an integer, m is an integer of 1 to 4, p is an integer of 1 to 4, n + m is 4 or more, or n + p is 4 or more.)
[5] The composite polyamide ester composition according to [4], wherein in the general formula (2), R ² is an aminoalkyl group or a hydroxyalkyl group.
[6] The composite polyamide ester composition according to [4] or [5], wherein R ² is an aminoalkyl group in the general formula (2).
[7] The composite polyamide ester composition according to any one of [1] to [6], wherein the number of terminal functional groups of the dendrimer compound is 3 to 768.
[8] The composite polyamide ester composition according to any one of [1] to [7], wherein the dendrimer compound has a molecular weight of 350 or more.
[9] The composite polyamide ester composition according to any one of [1] to [8], wherein the polyvalent carboxylic acid has 10 or more carbon atoms.
[10] The composite polyamide ester composition according to any one of [1] to [9], wherein the polyvalent carboxylic acid has 24 to 48 carbon atoms.
[11] The composite polyamide ester composition according to any one of [1] to [10], wherein the polyvalent carboxylic acid is a dibasic acid or a tribasic acid of an unsaturated fatty acid.
[12] The composite polyamide ester composition according to any one of [1] to [11], wherein the polyvalent carboxylic acid is dimer acid, trimer acid, or erucic acid dimer.
[13] The composite polyamide ester composition according to any one of [1] to [12], wherein the monohydric alcohol has 6 or more carbon atoms.
[14] The composite polyamide ester composition according to any one of [1] to [13], wherein the monohydric alcohol has at least one oxyalkylene group.
[15] The composite polyamide ester composition according to any one of [1] to [14], wherein the monohydric alcohol is represented by the following general formula (3).

(In General Formula (3), R ^a has an alkyl group which may have ^a substituent, ^a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An aryl group which may be substituted or a heteroaryl group which may have a substituent, wherein X ^a1 and X ^a2 each independently represents a hydrogen atom, a halogen atom or an alkyl group, and na 1 represents an integer of 1 to 4. Na2 represents an integer of 1 to 12. When na1 is 2 or more, the na1 X ^a1 may be the same or different, and the na1 X ^a2 may be the same or different. In addition, when na2 is 2 or more, na2 — (O (CX ^a1 X ^a2 ) _na1 — may be the same or different).
[16] The composite polyamide ester composition according to any one of [1] to [15], further including at least one organometallic compound of an organomolybdenum compound and an organozinc compound.
[17] The organometallic compound includes sulfurized oxymolybdenum-N, N-di-octyldithiocarbamate, sulfurized oxymolybdenum-N, N-di-tridecyldithiocarbamate, zinc n-butyl-n-pentyldithiophosphate, di- The composite polyamide ester composition according to [16], which is zinc 2-ethylhexyldithiophosphate or zinc isopropyl-1-ethylbutyldithiophosphate.
[18] The polyamide ester and the dendrimer compound are mixed and condensed so that the equivalent ratio of the polyvalent carboxylic acid is 1 to 20 and the equivalent ratio of the monohydric alcohol is 0.5 to 30. The composite polyamide ester composition according to any one of [1] to [17].
[19] Any one of [1] to [18], wherein the polyamide ester includes at least one of a polyamide ester represented by the following general formula (5) and a polyamide ester represented by the following general formula (6). The composite polyamide ester composition described in 1.

(In General Formula (5), Z represents an n-valent atomic group containing a nitrogen atom, L represents an (m + 1) -valent linking group, and X represents —CONH—, —COO—, —OCO—, or —NHCO. Y represents a divalent linking group, R ³ represents a (p + 1) valent chain or cyclic aliphatic linking group or an aromatic linking group, and R ⁴ may have a substituent. Represents an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group; N is an integer of 2 to 6, m is an integer of 1 to 4, p is an integer of 1 to 4, n + m is 4 or more, or n + p is 4 or more, where p is if more, if p number of R ⁴ is optionally different than the same .m is 2 or more, m-number of -X-Y- ^{HCOR 3 -. (COOR 4)} p may be different even in the same addition, n pieces of -CONH-L- {X-Y- NHCOR 3 - (COOR 4) p} m be the same May be different.)

(In General Formula (6), Z represents an n-valent atomic group containing a nitrogen atom, L represents an (m + 1) -valent linking group, and X represents —CONH—, —COO—, —OCO—, or —NHCO. Y represents a divalent linking group, R ⁵ represents a (p + 1) valent chain or cyclic aliphatic linking group or an aromatic linking group, and R ⁶ may have a substituent. Represents an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group; N is an integer of 2 to 6, m is an integer of 1 to 4, p is an integer of 1 to 4, n + m is 4 or more, or n + p is 4 or more, where p is if more, if p number of R ⁶ is optionally different even in the same .m is 2 or more, m-number of -X-Y- ^{COR 5 -. (COOR 6)} p may be different even in the same addition, n pieces of -CONH-L- {X-Y- OCOR 5 - (COOR 6) p} m be the same May be different.)
[20] The composite polyamide according to [19], wherein in the general formulas (5) and (6), R ³ and R ⁵ are each independently a dimer acid residue, a trimer acid residue or an erucic acid dimer residue. Ester composition.
[21] The composite polyamide ester composition according to [19] or [20], wherein in the general formulas (5) and (6), R ⁴ and R ⁶ are each independently a group having an oxyalkylene structure.
[22] The composite polyamide ester composition according to any one of [1] to [21], wherein the viscosity at 40 ° C. is 50 to 1650 mPas.
[23] The composite polyamide ester composition according to any one of [1] to [22], an antiwear agent, a viscosity index improver, an antioxidant, a detergent, a dispersant, a flow, a curing agent, and corrosion. A composition comprising one or more additives selected from an inhibitor, a seal compatibilizer, an antifoaming agent, a rust inhibitor, a corrosion inhibitor, a friction modifier, and a thickener.
[24] The composite polyamide ester composition according to any one of [1] to [22], or the composition according to [23], a mineral oil, a fat compound, a polyolefin oil, a silicone oil, a perfluoropoly A composition comprising at least one medium selected from ether oils, aromatic ester oils, and polyol ester lubricating oils.
[25] A lubricant comprising the composite polyamide ester composition according to any one of [1] to [22], or the composition according to [23] or [24].
[26] Grease lubricating oil, release agent, engine oil for internal combustion engine, metal working (cutting) oil, bearing oil, combustion engine fuel, vehicle engine oil, gear oil, automotive hydraulic oil, Aircraft lubricant, machine oil, turbine oil, bearing oil, hydraulic fluid, compressor / vacuum pump oil, refrigeration oil, metalworking lubricant, magnetic recording medium lubricant, micromachine lubricant, artificial bone The lubricant according to [25], which is used as a lubricant, shock absorber oil or rolling oil.

  According to the present invention, a composite polyamide ester composition capable of exhibiting excellent lubricating performance can be obtained. Furthermore, the composite polyamide ester composition of the present invention has a low viscosity of the composition itself and can exhibit excellent dispersibility with respect to the base oil. Thus, the composite polyamide ester composition of the present invention has high lubricating performance and dispersibility.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

(Composite polyamide ester composition)
The present invention relates to a composite polyamide ester composition comprising a polyamide ester obtained by condensing a dendrimer compound, a polyvalent carboxylic acid and a monohydric alcohol. In addition, a dendrimer compound is represented by following General formula (1) mentioned later.

  In the present invention, a composite polyamide ester composition capable of exhibiting high lubricating performance can be obtained by including the specific polyamide ester as described above. Furthermore, the composite polyamide ester composition of the present invention can keep the viscosity of the composite polyamide ester composition low even when a dendrimer compound is used. This is presumed that when the dendrimer compound is in the core, the linking chains can be positioned radially, and the entanglement of the linking chains causing thickening can be reduced, so that the composite polyamide ester composition viscosity can be reduced. The For the same reason, it is presumed that the molecules of the dendrimer core improve the dispersibility of the composite polyamide ester composition because the molecular chains are not entangled and spread.

<Dendrimer compound>
The dendrimer compound used for the condensation of the polyamide ester is represented by the following general formula (1).

In General Formula (1), Z represents an n-valent atomic group containing a nitrogen atom, L ¹ represents an (m + 1) -valent linking group, and X ¹ represents —CONH—, —COO—, —OCO—, or — NHCO- is represented, and R ¹ represents a group whose terminal is an amino group or a hydroxy group. N is an integer of 2 to 6, m is an integer of 1 to 4, and n + m is 4 or more.

  In general formula (1), Z represents an n-valent atomic group containing a nitrogen atom. The number of nitrogen atoms contained in the atomic group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. In addition, when two or more nitrogen atoms are contained in an atomic group, it is preferable that the nitrogen atoms are connected by a divalent or higher valent aliphatic hydrocarbon or aromatic hydrocarbon. Especially, it is preferable that the nitrogen atom is connected with the aliphatic hydrocarbon more than bivalence, and it is more preferable that it is connected with the saturated aliphatic hydrocarbon more than bivalence. Further, when the atom group contains one nitrogen atom, the nitrogen atom preferably has three aliphatic hydrocarbon linking groups or aromatic hydrocarbon linking groups.

  Z is preferably an atomic group in which a divalent or higher aliphatic hydrocarbon or aromatic hydrocarbon is linked to a nitrogen atom of a polyvalent amine. Specifically, Z is an atomic group in which a divalent or higher valent aliphatic hydrocarbon or aromatic hydrocarbon is linked to a nitrogen atom of a polyvalent amine such as ammonia, ethylenediamine, propylenediamine, or tris (2-aminoethyl) amine. Preferably, it is an atomic group in which divalent or higher valent aliphatic hydrocarbons are linked, more preferably an atomic group in which divalent or higher valent saturated aliphatic hydrocarbons are linked. Among these, Z is particularly preferably an atomic group in which an alkenyl group is linked to a nitrogen atom of ammonia or ethylenediamine.

  Z is an atomic group that forms the core of the dendrimer compound. The core part preferably has a branched structure, and the nitrogen atom contained in Z is preferably a branched group. That is, in the core part of a dendrimer compound, a nitrogen atom becomes a starting point of a branched structure, and a connecting group will connect from there in dendritic form.

  In General formula (1), n should just be an integer of 2-6, it is preferable that it is an integer of 2-4, and it is more preferable that it is an integer of 3 or 4. That is, Z is more preferably a trivalent or tetravalent atomic group.

In the general formula (1), L ¹ represents an (m + 1) -valent linking group. L ¹ is preferably a (m + 1) -valent linking group containing a nitrogen atom. The number of nitrogen atoms contained in the linking group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. When the linking group contains two or more nitrogen atoms, the nitrogen atoms are preferably linked by a divalent or higher valent aliphatic hydrocarbon or aromatic hydrocarbon. Especially, it is preferable that the nitrogen atom is connected with the aliphatic hydrocarbon more than bivalence, and it is more preferable that it is connected with the saturated aliphatic hydrocarbon more than bivalence.

L ¹ is preferably a linking group in which a divalent or higher aliphatic hydrocarbon or aromatic hydrocarbon is linked to the nitrogen atom of the polyvalent amine. Specifically, L ¹ is a linkage in which a divalent or higher aliphatic hydrocarbon or aromatic hydrocarbon is linked to the nitrogen atom of a polyvalent amine such as ammonia, ethylenediamine, propylenediamine, or tris (2-aminoethyl) amine. It is preferably a group, more preferably a linking group in which a divalent or higher valent aliphatic hydrocarbon is linked, and even more preferably a linking group in which a divalent or higher valent saturated aliphatic hydrocarbon is linked. Among these, L ¹ is particularly preferably a linking group in which an alkenyl group is linked to a nitrogen atom of ammonia or ethylenediamine.

In General formula (1), m should just be an integer of 1-4, and it is preferable that it is an integer of 1-3. That is, L ¹ is preferably a divalent to tetravalent linking group. Note that the nitrogen atom contained in L ¹ is preferably a branched group. That is, the dendrimer compound preferably has a branched structure in the linking group represented by L ¹ in addition to the branched structure of the core portion.
In the general formula (1), n + m is 4 or more, more preferably 5 or more, and further preferably 6 or more.

In the general formula (1), X ¹ represents —CONH—, —COO—, —OCO— or —NHCO—. Among these, X ¹ is more preferably —CONH— or —NHCO—.

In the general formula (1), R ¹ represents a group whose terminal is an amino group or a hydroxy group. That is, the group present on the surface of the dendrimer compound is an amino group or a hydroxy group. The amino group or hydroxy group present at the terminal is preferably linked to X ¹ via a divalent or higher valent linking group. The divalent or higher valent linking group may be a repeating unit as described later, or may be an aliphatic hydrocarbon or an aromatic hydrocarbon.

R ¹ may be (-L ^a -X ^a -R ^a ), and R ^a may be (-L ^b -X ^b -R ^b ). L ^a and L ^b represent an (m + 1) -valent linking group as in L ¹ described above, and X ^a and X ^b represent —CONH—, —COO—, —OCO— as in X ¹ described above. Or -NHCO- is represented. That is, R ¹ may have a repeating structure represented by (—L ¹ —X ¹ —R ¹ ). In addition, when R ¹ has a repeating structure represented by (—L ¹ -X ¹ -R ¹ ), the final terminal is an amino group or a hydroxy group.

In the general formula (1), R ¹ may be an aminoalkyl group or a hydroxyalkyl group. As described above, when R ¹ does not further have a structure represented by (-L ¹ -X ¹ -R ¹ ), the dendrimer compound represented by the general formula (1) is a first generation dendrimer. It can be called a compound. That is, the dendrimer compound used in the present invention is a first generation or higher dendrimer compound.
When R ¹ is (-L ^a -X ^a -R ^a ) and R ^a is an aminoalkyl group or a hydroxyalkyl group, the dendrimer compound represented by the general formula (1) is It can be said that it is a second generation dendrimer compound. Further, when R ¹ is (—L ^a —X ^a —R ^a ), R ^a is (—L ^b —X ^b —R ^b ), and R ^b is an aminoalkyl group or hydroxy When it is an alkyl group, the dendrimer compound represented by the general formula (1) can be referred to as a third generation dendrimer compound. The dendrimer compound used in the present invention is preferably a first generation to fourth generation dendrimer compound, more preferably a first generation to third generation dendrimer compound, and a first generation or second generation dendrimer compound. More preferably.

  The second generation or higher dendrimer compound can also be represented by the following general formula (2).

In General Formula (2), Z represents an n-valent atomic group containing a nitrogen atom, L ¹ represents a (m + 1) -valent linking group, L ² represents a (p + 1) -valent linking group, and X ¹ and X ² independently represents —CONH—, —COO—, —OCO— or —NHCO—, and R ² represents a group whose terminal is an amino group or a hydroxy group. Moreover, n is an integer of 2-6, m is an integer of 1-4, p is an integer of 1-4, n + m is 4 or more, or n + p is 4 or more.

In the general formula (2), a preferred range of Z is the same as Z in the general formula (1), the preferred range of L ¹ and L ² are the same as L ¹ in the general formula (1), X ¹ And the preferred range of X ² is the same as X ¹ in the general formula (1).
Moreover, n should just be an integer of 2-6, it is preferable that it is an integer of 2-4, and it is more preferable that it is an integer of 3 or 4. m should just be an integer of 1-4, and it is preferable that it is an integer of 1-3. p should just be an integer of 1-4, and it is preferable that it is an integer of 1-3.

  In the general formula (2), n + m is 4 or more, more preferably 5 or more, and further preferably 6 or more. N + p is 4 or more, more preferably 5 or more, and further preferably 6 or more. Furthermore, n + m + p is preferably 6 or more, and more preferably 7 or more.

When the dendrimer compound represented by the general formula (2) is a third generation compound, R ² is (-L ^a -X ^a -R ^a ), and when it is a fourth generation compound, R ^a is Furthermore, (−L ^b −X ^b −R ^b ) is obtained. On the other hand, when the dendrimer compound represented by the general formula (2) is a second generation compound, R ² is preferably an aminoalkyl group or a hydroxyalkyl group.

The terminal functional group of the dendrimer compound is more preferably an amino group. That is, the R ¹ of the general formula (1), R ² are each independently of the general formula (2), and more preferably an amino group. By making R ¹ and R ² an aminoalkyl group, the lubricating performance and the dispersibility in the base oil can be further improved.

The number of terminal functional groups of the dendrimer compound is preferably 3 to 768, more preferably 4 to 243, and still more preferably 6 to 81.
The molecular weight of the dendrimer compound is preferably 350 or more, more preferably 750 or more, and further preferably 1000 or more. In the present invention, even when a dendrimer compound having a large number of terminal functional groups or a dendrimer compound having a large molecular weight is used, it is possible to keep the viscosity of the composite polyamide ester composition low. Thereby, it becomes possible to improve the dispersibility to a base oil, and the outstanding lubrication performance can be exhibited.

  The dendrimer compound used in the present invention may be a dendrimer compound having a so-called “chip”. A dendrimer compound having “missing” refers to a compound in which a linking group linked to a nitrogen atom of an atomic group or a linking group is partially lost. Specifically, it means a dendrimer compound containing a secondary amino group in an atomic group or a linking group. In addition, the “chip” of the dendrimer compound may include those in which the linking group is not linked to the atomic group represented by Z in the general formulas (1) and (2).

  Specific examples of the dendrimer compound that can be used in the present invention are shown below, but the present invention is not limited thereto.

<Polyvalent carboxylic acid>
The polyvalent carboxylic acid used for the condensation of the polyamide ester is a compound containing at least two carboxyl groups. It is preferable that 2-4 carboxyl groups are contained in one molecule, and it is more preferable that 2 or 3 carboxyl groups are contained in one molecule. As the polyvalent carboxylic acid used in the present invention, any one of divalent to tetravalent polyvalent carboxylic acids may be used, or a plurality of types may be used. For example, a mixture of a divalent carboxylic acid and a trivalent carboxylic acid may be used, or a mixture of a divalent carboxylic acid, a trivalent carboxylic acid, and a tetravalent carboxylic acid may be used, A mixture of a trivalent carboxylic acid and a tetravalent carboxylic acid may be used.

  The number of carbon atoms of the polyvalent carboxylic acid is preferably 7 or more, more preferably 10 or more, preferably 12 or more, more preferably 18 or more, and further preferably 24 or more. preferable. Further, the carbon number of the polyvalent carboxylic acid is preferably 66 or less, more preferably 60 or less, and further preferably 48 or less. Especially, it is especially preferable that carbon number of polyvalent carboxylic acid is 24-48. In the present invention, the carbon number of the polyvalent carboxylic acid represents the number of carbon atoms including the carbon atom constituting the carboxyl group. Thus, the lubricity performance of a composite polyamide-ester composition can be improved more by making carbon number of polyhydric carboxylic acid into the said range.

  The carboxyl groups in the molecule are linked by a chain or cyclic divalent or higher aliphatic hydrocarbon or aromatic hydrocarbon. One or more carbon atoms not adjacent to each other of the carbon atoms of the aliphatic hydrocarbon or aromatic hydrocarbon linking group may be substituted with oxygen atoms. Especially, in this invention, it is preferable that the group which connects the carboxyl group in a molecule | numerator is a C20-C46 aliphatic hydrocarbon.

  The aliphatic hydrocarbon that connects the carboxyl groups in the molecule of the polyvalent carboxylic acid preferably contains an unsaturated bond. That is, the polyvalent carboxylic acid is preferably an unsaturated fatty acid, more preferably a dibasic acid or a tribasic acid of an unsaturated fatty acid.

  Examples of the polyvalent carboxylic acid that can be used in the present invention include terephthalic acid, phthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and trimellitic acid. , Dimer acid, trimer acid, erucic acid dimer, and the like. Of these, dimer acid, trimer acid, and erucic acid dimer are preferably used. The dimer acid, trimer acid, and erucic acid dimer may be hydrogenated.

Here, the dimer acid is an aliphatic or alicyclic dicarboxylic acid produced by dimerization of an unsaturated fatty acid (usually 18 carbon atoms) by polymerization or Diels-Alder reaction (in addition to most dimers, Many of them contain trimers, monomers and the like of several mol%), and among them, those whose main components are trimers are defined as trimer acids.
As specific examples of dimer acid or trimer acid, Tsunodim (registered trademark) 205, 216, 228, and 395 manufactured by Tsukino Food Industry Co., Ltd. can be exemplified as dimer acid, and tunodim 345 and the like can be exemplified as trimer acid. Other products manufactured by Cognis and Unikema are also included.

  The erucic acid dimer is a dicarboxylic acid having 44 carbon atoms obtained by dimerizing an unsaturated fatty acid (erucic acid) having 22 carbon atoms. Examples of erucic acid preferably used for dimerization of erucic acid dimer include compounds such as CAS No. 112-86-7. Further, as a typical erucic acid dimer, there is a trade name Pripol 1004 (manufactured by Croda).

  In the present invention, polyhydric carboxylic acid anhydrides can be used in place of polycarboxylic acids. The polyhydric carboxylic acid anhydride is a product obtained by intramolecular or intermolecular dehydration condensation of two COOHs of the above polycarboxylic acid. The preferred form is the same as above. Examples of the anhydrides include succinic anhydride, glutaric anhydride, adipic anhydride, maleic anhydride, phthalic anhydride, nadoic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride and mixed polybasic anhydride Things are included.

  Specific examples of the polyvalent carboxylic acid that can be used in the present invention are shown below, but the present invention is not limited thereto.

<Monohydric alcohol>
The monohydric alcohol used for the condensation of the polyamide ester is a compound containing one hydroxyl group in one molecule. A monohydric alcohol is represented by R (OH). R is a monovalent aliphatic, alicyclic or aromatic ring group. R preferably has 3 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more. By setting the carbon number of the monohydric alcohol within the above range, the monohydric alcohol can be prevented from evaporating during the condensation reaction, and the condensation reaction of the polyamide ester can be advanced efficiently.

  The monohydric alcohol preferably has at least one oxyalkylene group. An oxyalkylene group refers to a structure in which an oxygen atom is introduced into an alkylene chain. The alkylene chain may be linear, branched or cyclic. Moreover, 1-10 are preferable, as for carbon number of an alkylene chain, 2-8 are more preferable, and 2-4 are more preferable. Moreover, 1-10 are preferable, as for the oxygen number introduce | transduced, 1-6 are preferable, and 1-4 are more preferable.

  The monohydric alcohol used in the present invention is preferably one represented by the following general formula (3).

Here, in the general formula (3), Ra represents an alkyl group which may have ^a substituent, ^a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An aryl group which may have or a heteroaryl group which may have a substituent, and X ^a1 and X ^a2 each independently represent a hydrogen atom, a halogen atom or an alkyl group; Na1 represents an integer of 1 to 4, and na2 represents an integer of 1 to 12. When na1 is 2 or more, na1 X ^a1 may be the same or different, and na1 X ^a2 may be the same or different. When na2 is 2 or more, na2-(O (CX ^a1 X ^a2 ) _na1 -may be the same or different.

That the number of carbon atoms of the alkyl moiety of the alkyl group which may have a substituent represented by R ^a is preferably 3 to 17, more preferably from 4 to 13, 5 to 9 Is more preferable. The alkyl group represented by R ^a may be linear or branched. R ^a may be a cycloalkyl group.

The number of carbon atoms of the alkenyl group moiety alkenyl group which may have a substituent represented by R ^a is preferably 3 to 17, more preferably from 4 to 13, 5 to 9 Is more preferable. The alkyl group represented by R ^a may be linear, branched or cyclic.

The number of carbon atoms of the aryl moiety of the aryl group or heteroaryl group which may have a substituent represented by R ^a is preferably 6 to 17, and more preferably 6-12. Examples of the aryl group represented by ^Ra include a phenyl group and a naphthyl group, and among them, a phenyl group is particularly preferable. Examples of the heteroaryl group represented by ^Ra include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, indolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl Can be illustrated. The hetero atom contained in the heteroaryl group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably an oxygen atom.

Especially, in General formula (3), it is more preferable that ^Ra is an alkyl group which may have ^a substituent. Here, the alkyl group may be a branched alkyl group. More preferably, X ^a1 and X ^a2 are each independently a hydrogen atom or an alkyl group.

  In general (3), na1 is more preferably an integer of 1 to 3, and further preferably 1 or 2. Na2 is more preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.

  The number of carbon atoms of the monohydric alcohol represented by general formula (3) is preferably 3 or more, more preferably 6 or more, and even more preferably 8 or more. By using such a monohydric alcohol, it is possible to prevent the monohydric alcohol from being volatilized during the condensation reaction, and it is possible to efficiently advance the condensation reaction of the polyamide ester.

Examples of the substituent that R ^a may have include a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms (for example, methyl, ethyl, which are both linear or branched propyl, butyl, Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, or tetracosyl); alkenyl having 2 to 35 carbon atoms Groups (eg, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl); cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl) Cycloheptyl); an aromatic ring group having 6 to 30 carbon atoms (for example, phenyl, naphthyl, biphenyl, phenanthryl, anthracenyl), a heterocyclic group (nitrogen atom, oxygen atom, and sulfur atom) Preferably a heterocyclic residue containing an atom, for example pyridyl, pyrimidyl, triazinyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, imidazolyl, oxazolyl, thiadialyl, oxadiazolyl, quinolyl, isoquinolyl); A group consisting of a combination thereof is represented. If possible, these substituents may further have one or more substituents. Examples of the substituents include alkoxy groups, alkoxycarbonyl groups, halogen atoms, ether groups, alkylcarbonyl groups, cyano groups. Group, thioether group, sulfoxide group, sulfonyl group, amide group and the like.

  Specific examples of the monohydric alcohol that can be used in the present invention are shown below, but the present invention is not limited thereto.

(Organic metal compound)
The composite polyamide ester composition of the present invention may further contain at least one organometallic compound of an organomolybdenum compound and an organozinc compound in addition to the polyamide ester obtained by reacting and condensing each compound described above. .

  Examples of the organic molybdenum compound used in the present invention include sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate (sometimes referred to as MoDTP) and molybdenum dithiocarbamate (sometimes referred to as MoDTC); inorganic molybdenum compounds (for example, Molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, orthomolybdic acid, paramolybdic acid, molybdic acid such as (poly) sulfurized molybdic acid, metal salts of these molybdic acids, molybdate such as ammonium salts, molybdenum disulfide, Molybdenum sulfide such as molybdenum trisulfide, molybdenum pentasulfide, and polysulfide molybdenum, molybdenum sulfides, metal salts of molybdenum sulfides or amine salts, molybdenum halides such as molybdenum chloride, and the like; sulfur-containing organic compounds (eg, alkyl (Thio) xanthate, thiadiazole, mercaptothiadiazole, thiocarbonate, tetrahydrocarbyl thiuram disulfide, bis (di (thio) hydrocarbyl dithiophosphonate) disulfide, organic (poly) sulfide, sulfide ester, etc.) or other organic compounds A complex with molybdenum, or a complex of a sulfur-containing molybdenum compound such as molybdenum sulfide or sulfurized molybdic acid with an alkenyl succinimide can be used.

  As the organic molybdenum compound, an organic molybdenum compound that does not contain sulfur as a constituent element can be used. Specific examples of organic molybdenum compounds that do not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.

As a method for producing the MoDTP, for example, the methods described in JP-A Nos. 61-87690 and 61-106687 are preferably used. That is, it can be obtained by reacting molybdenum trioxide or molybdate with alkali sulfide or alkali hydrosulfide, and then adding P ₂ S ₅ and secondary alcohol and reacting them at an appropriate temperature. As a method for producing MoDTC, for example, the method described in Japanese Patent Publication No. 56-12638 is preferably used. That is, it can be obtained by reacting molybdenum trioxide or molybdate with alkali sulfide or alkali hydrosulfide, then adding carbon disulfide and secondary amine and reacting them at an appropriate temperature.

  Zinc dithiophosphate (ZDTP), which is an organozinc compound used in the present invention, is represented by the general formula (4).

In the general formula (4), Q ¹ , Q ² , Q ³ and Q ⁴ may be the same or different, and are each independently isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, hexyl. An alkyl group having 4 to 20 carbon atoms such as a group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, mistyl group, palmityl group, stearyl group, etc. It is preferable to represent.

The organometallic compound may comprise a metal salt or a metal-ligand complex. Here, the metal is preferably molybdenum or zinc. Ligand includes alcohol, polyol, glycerol, partial ester glycerol, thiol, carboxylate, carbamate, thiocarbamate, dithiocarbamate, phosphate, thiophosphate, dithiophosphate, amide, imide, amine, thiazole, thiadiazole, dithiazole, diazole , Hydrocarbyl derivatives of triazole, and other polar molecular functional groups containing effective amounts of O, N, S or P individually or in combination. For example, sulfurized oxymolybdenum -N, N-di - octyl dithiocarbamate _{(C 8 -Mo (DTC))} , sulfurized oxymolybdenum -N, N-di - tridecyl dithiocarbamate _{(C 16 -Mo (DTC))} , n - butyl -n- pentyl zinc dithiophosphate _{(C 4 / C 5 ZnDTP)} , with di-2-ethylhexyl dithiophosphate, zinc (C ₈ ZnDTP) or isopropyl-1-ethyl butyl zinc dithiophosphate (C ₃ / C ₆ ZnDTP) Preferably there is. Other examples include Mo-containing compounds such as Mo-dithiophosphate [Mo (DTP)], Mo-amine [Mo (Am)], Mo-alcolate, and Mo-alcohol-amide.

  In the composite polyamide ester composition of the present invention, when an organic molybdenum compound is used, the content thereof is preferably 10 to 1000 ppm, and preferably 50 to 800 ppm, with respect to the total mass of the composition. More preferably, it is more preferably 100 to 600 ppm. Moreover, when using an organic zinc compound, it is preferable that the content is contained 0.01-5 mass% with respect to the composition total mass, and it is more contained 0.05-3 mass%. Preferably, 0.08 to 1% by mass is contained. By setting the content of the organometallic compound within the above range, the stability of the composite polyamide ester composition can be increased, and more excellent lubricating performance can be exhibited.

(Other compounds)
In the present invention, in addition to the dendrimer compound represented by the general formula (1), the polyvalent carboxylic acid and the monohydric alcohol, other components may be used for the condensation reaction, and the composite polyamide ester composition containing the resulting polyamide ester A thing is also preferably used. In addition to the above-described organometallic compound, another compound may be mixed.

(Polyamide ester)
The composite polyamide ester composition of the present invention includes a polyamide ester obtained by mixing a dendrimer compound as described above, a polyvalent carboxylic acid, and a monohydric alcohol and condensing the mixture. The composite polyamide ester composition preferably includes at least one of a polyamide ester represented by the following general formula (5) and a polyamide ester represented by the following general formula (6).

In General Formula (5), Z represents an n-valent atomic group containing a nitrogen atom, L represents an (m + 1) -valent linking group, and X represents —CONH—, —COO—, —OCO—, or —NHCO—. Y represents a divalent linking group. R ³ represents a (p + 1) -valent chain-like or cyclic aliphatic linking group or aromatic linking group, and R ⁴ represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent. Represents an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Moreover, n is an integer of 2-6, m is an integer of 1-4, p is an integer of 1-4, n + m is 4 or more, or n + p is 4 or more. When p is 2 or more, p R ^{4 s} may be the same or different. When m is 2 or more, m pieces of —X—Y—NHCOR ³ — (COOR ⁴ ) _p may be the same or different. Moreover, n pieces of —CONH-L- {XY—NHCOR ³ — (COOR ⁴ ) _p } _m may be the same or different.

In General Formula (6), Z represents an n-valent atomic group containing a nitrogen atom, L represents an (m + 1) -valent linking group, and X represents —CONH—, —COO—, —OCO—, or —NHCO—. Y represents a divalent linking group. R ⁵ represents a (p + 1) -valent chain-like or cyclic aliphatic linking group or aromatic linking group, and R ⁶ represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent. Represents an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Moreover, n is an integer of 2-6, m is an integer of 1-4, p is an integer of 1-4, n + m is 4 or more, or n + p is 4 or more. When p is 2 or more, p R ^{6 s} may be the same or different. When m is 2 or more, m pieces of —X—Y—OCOR ⁵ — (COOR ⁶ ) _p may be the same or different. Further, n pieces of —CONH-L- {XY—OCOR ⁵ — (COOR ⁶ ) _p } _m may be the same or different.

Z in the general formulas (5) and (6) is the same as Z in the general formula (1). Further, L is in the general formula (5) and (6) is the same as L ¹ in the general formula (1), X in the general formula (5) and (6), and X ¹ in the general formula (1) It is the same.

  Y in the general formulas (5) and (6) represents a divalent linking group. When the dendrimer compound used for the polyamide ester is a first generation dendrimer compound, Y is preferably a divalent aliphatic hydrocarbon linking group or an aromatic hydrocarbon linking group, and a divalent aliphatic hydrocarbon linking group. It is more preferably a group, and further preferably an alkylene group. When the dendrimer compound used for the polyamide ester is a second-generation dendrimer compound, Y represents the above linking group containing a nitrogen atom in the chain and —CONH—, —COO—, —OCO— or —NHCO—. The linking group is preferably a linking group in which an alkylene group containing a nitrogen atom in the chain and -CONH-, -COO-, -OCO-, or -NHCO- are combined.

In the general formulas (5) and (6), R ³ and R ⁵ each independently represent a residue of a polyvalent carboxylic acid. Here, the residue of the polyvalent carboxylic acid refers to a group constituting a part obtained by removing the carboxyl group from the polyvalent carboxylic acid. In particular, R ³ and R ⁵ are preferably each independently a dimer acid residue, a trimer acid residue or an erucic acid dimer residue.

R ³ and R ⁵ preferably have 7 or more carbon atoms, more preferably 14 or more, and still more preferably 20 or more. The number of carbon atoms of R ¹ and R ³ is preferably 64 or less, more preferably 58 or less, and even more preferably 46 or less. Of these, the carbon number of the carbon atoms of R ¹ and R ³ is preferably 20 to 46.

In the general formulas (5) and (6), R ⁴ and R ⁶ may each independently have an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or a substituent. A good alkenyl group, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent are represented. Specific examples of the group that R ⁴ and R ⁶ can take include the group represented by ^Ra in the general formula (3). In addition, the substituent of each group that R ⁴ and R ⁵ may have is not particularly limited. As the substituent, the above substituents can be exemplified similarly.

R ⁴ and R ⁶ are preferably each independently a group having an oxyalkylene structure. That is, R ⁴ and R ⁶ are preferably a branched alkyl group or an alkyl group containing an ether bond in the chain. R ⁴ and R ⁶ preferably have 3 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

  In general formula (5) and (6), n should just be an integer of 2-6, it is preferable that it is an integer of 2-4, and it is more preferable that it is an integer of 3 or 4. m should just be an integer of 1-4, and it is preferable that it is an integer of 1-3. p should just be an integer of 1-4, and it is preferable that it is an integer of 1-3. N + m is 4 or more, more preferably 5 or more, and further preferably 6 or more. N + p is 4 or more, more preferably 5 or more, and further preferably 6 or more. Furthermore, n + m + p is preferably 6 or more, and more preferably 7 or more.

  When mixing a dendrimer compound, a polyhydric carboxylic acid and a monohydric alcohol compound, the polyhydric alcohol or polyhydric amine has an equivalent ratio of mixing the polyhydric carboxylic acid of 1 to 30, and the polyhydric alcohol On the other hand, the equivalent ratio of mixing the monohydric alcohol is preferably 0.5 to 35. That is, the mixing ratio is preferably polyhydric alcohol: polyhydric carboxylic acid: monohydric alcohol = 1: 1 to 30: 0.5 to 35. The mixing ratio is more preferably 1: 2 to 25: 1 to 30, and more preferably 1: 3 to 20: 2 to 25. In particular, since the side chain of the polyamide ester is preferably end-capped, the total equivalent of the polyhydric alcohol and the monohydric alcohol is preferably the same or larger than the equivalent of the dendrimer compound.

  The viscosity of the composite polyamide ester composition of the present invention at 40 ° C. is preferably 50 to 1650 mPas. The viscosity at 40 ° C. of the composite polyamide ester composition is preferably 50 mPas or more, more preferably 70 mPas or more, and further preferably 100 mPas or more. Further, the viscosity at 40 ° C. of the composite polyamide ester composition is preferably 1650 mPas or less, more preferably 1200 mPas or less, and further preferably 1000 mPas or less. By setting the viscosity of the composite polyamide ester composition within the above range, the coefficient of friction of the composite polyamide ester composition can be kept low, thereby improving the lubricating performance.

The composite polyamide ester composition of the present invention also has an excellent feature that the increase in the coefficient of friction is small from the normal fluid lubrication or elastohydrodynamic lubrication region to the extreme pressure region. Such an excellent effect is considered to be obtained when the polyamide ester obtained in the present invention has a three-dimensional structure in which side chains are radially arranged with a dendrimer compound as a core. The polyamide ester obtained in the present invention comprises a dendrimer compound capable of radially arranging a side chain, a polyvalent carboxylic acid connected to the dendrimer compound, and a monohydric alcohol serving as a terminal linking group of the polyvalent carboxylic acid. It is a composed compound. In the present invention, a large free volume can be ensured by the three-dimensional structure by arranging the dendrimer compound as a central atomic group and arranging the side chains evenly. Thereby, an increase in viscosity and friction coefficient can be suppressed even under high pressure.
Moreover, although the composite polyamide ester composition of the present invention has a dendrimer compound having a large molecular weight and a large number of terminal functional groups in the central atomic group, the viscosity of the composition itself can be kept low. Thereby, the handleability of a composite polyamide-ester composition can be improved, and the dispersibility to a base oil can be improved.

  In the present invention, in addition to the predetermined polyamide ester, a light component may be further included. Here, the light component refers to a component having a low molecular weight, and refers to an ester obtained by reacting all carboxyl groups of a polyvalent carboxylic acid with a monohydric alcohol and a compound having a smaller molecular weight. The viscosity of the composite polyamide ester composition can be further reduced by allowing a liquid having a lower viscosity, such as a light component, to coexist. Thereby, high lubrication performance can be exhibited under all conditions.

In the composite polyamide ester composition of the present invention, the ratio between the predetermined polyamide ester and the light component is not particularly limited. In the aspect utilized for the use of the lubricant, the content of the light component is preferably 50% by mass or less, more preferably 45% by mass or less, and 40% by mass or less with respect to the predetermined polyamide ester. More preferably it is. In addition, although there is no restriction | limiting in particular about a lower limit, it is preferable that it is 15 mass% or more.
The ratio between the predetermined polyamide ester and the light component can be achieved by controlling the charging ratio of the three raw materials in the production method described later. Moreover, it can also adjust to a preferable range by isolate | separating a light part by distillation etc. and mixing with the remaining polyamide ester in arbitrary ratios.
The composition ratio between the predetermined polyamide ester and the light component containing dimer diol can be calculated by measuring gel permeation chromatography (GPC). The light component is easy to distinguish because the peak of GPC analysis appears sharply and its intensity is large.

  In the present invention, unreacted COOH in the polycarboxylic acid may remain in the side chain of the polyamide ester contained in the composite polyamide ester composition, and unreacted OH in the monohydric alcohol may remain. Although it may exist, when OH and COOH remain, the hydroxyl value and the acid value increase, and depending on the use (for example, the use of a lubricant), it may not be preferable. In such a case, OH and COOH in the polyamide ester can be eliminated by a separate acylation and / or esterification treatment, and the hydroxyl value and the acid value can be reduced.

In order to eliminate OH in the polyamide ester, after once obtaining a polyamide ester in which OH remains in the side chain, a treatment of acylating at least a part thereof can be performed. In the acylation treatment, monobasic acid (R ¹ COOH) or monobasic acid anhydride ((R ¹ CO) ₂ O) is added to the polyamide ester in which OH remains and heated to convert the remaining OH to OCOR. ^This is a process of converting to ¹ . When the hydroxyl value is reduced by the acylation treatment, mixing with other oil-based media is preferable in terms of easy mixing.
Moreover, you may perform the process which lose | disappears COOH in a polyamide ester. For example, it can be esterified by treatment with diazomethane or the like.

The proportion of unreacted OH in the polyamide ester is determined by measuring ¹³ C-NMR. In the use of the lubricant, the residual ratio of OH in the polyamide ester is preferably 0 to 40%, more preferably 0 to 35%, and further preferably 0 to 30%. In the same application, the acid value of the polyamide ester (mg number of KOH required to neutralize 1 g of the sample) is preferably 0 to 50, more preferably 0 to 40, and 0 to 30. More preferably. However, it is not limited to this range.

(Production method of composite polyamide ester composition)
The composite polyamide ester composition of the present invention can be obtained by charging at least three raw materials of the above-described dendrimer compound, polyvalent carboxylic acid and monohydric alcohol, followed by dehydration condensation. That is, the method for producing a composite polyamide ester composition of the present invention comprises a step of mixing a dendrimer compound having a specific structure, a polyvalent carboxylic acid and a monohydric alcohol to obtain a mixture, and dehydrating and condensing the mixture to form a polyamide ester. The process of obtaining. In the production process, two raw materials (for example, a dendrimer compound and a polyvalent carboxylic acid, or a polyvalent carboxylic acid and a monohydric alcohol) may be reacted first, and then the remaining raw materials may be reacted.

The charging ratio (mixing ratio) of the dendrimer compound, polyvalent carboxylic acid and monohydric alcohol is determined by an equivalent amount. The equivalent here means the chemical equivalent of COOH, OH or NH _{2 in} the reaction. If the number of NH ₂ or OH in one molecule of the dendrimer compound is n and the number of moles is M1, the equivalent of the dendrimer compound is defined as n × M1. Similarly, when the number of COOH in one molecule of the polycarboxylic acid is m and the number of moles is M2, the equivalent of the polyvalent carboxylic acid is defined as m × M2. Since monohydric alcohol has one OH in one molecule, M3 is defined as M3. The above ratio is a ratio of these n × M1, m × M2, and M3.

  In the present invention, the mixing ratio is preferably polyhydric alcohol or polyhydric amine: polyhydric carboxylic acid: monohydric alcohol = 1: 1 to 30: 0.5 to 35. The mixing ratio is more preferably 1: 2 to 25: 1 to 30, and more preferably 1: 3 to 20: 2 to 25. In particular, since the side chain of the polyamide ester is preferably end-capped, the total equivalent of the polyhydric alcohol and the monohydric alcohol is preferably the same or larger than the equivalent of the dendrimer compound.

  The composite polyamide ester composition of the present invention can be obtained by subjecting the mixture prepared as described above to a dehydration condensation reaction in the presence or absence of a catalyst.

  In the dehydration condensation, it is desirable to heat or to make an appropriate amount of a solvent azeotropic with water exist. Thereby, dehydration proceeds smoothly without coloring the product. This solvent is preferably a hydrocarbon solvent having a boiling point of 100 to 200 ° C, more preferably a hydrocarbon solvent having a boiling point of 100 to 170 ° C, and most preferably a hydrocarbon solvent having a boiling point of 110 to 160 ° C. Examples of these solvents include toluene, xylene, mesitylene and the like. If the amount to be added is too large, the liquid temperature will be in the vicinity of the solvent, and dehydration condensation will not proceed easily. On the other hand, if the amount is too small, azeotropy does not go smoothly. Therefore, the addition amount is preferably 1 to 25 mass%, more preferably 2 to 20 mass%, particularly preferably 3 to 15 mass%, based on the total amount of the dendrimer compound, polyvalent carboxylic acid and monohydric alcohol. 12% by mass is also preferable.

  Although the reaction is accelerated by using the catalyst, it is desirable not to use it because the post-treatment of removing the catalyst is complicated and causes coloring of the product. However, when used, normal conditions and procedures are used with normal catalysts. In this regard, reference can be made to Japanese Patent Publication Nos. 2001-501989, 2001-500499, 2001-507334, and 2002-509563.

  After completion of the preparation, the reaction is performed at a liquid temperature of 120 to 250 ° C, preferably 130 to 230 ° C, more preferably 130 to 220 ° C, and particularly preferably 140 to 220 ° C. As a result, a solvent containing water is azeotroped, cooled at a cooling site such as Dean Stark, and becomes a liquid to separate water and the solvent. This water may be removed.

  As for the reaction time, since the theoretically generated water amount is calculated from the number of moles charged, it is preferable to carry out the reaction until the water amount is obtained, but it is difficult to complete the reaction completely. Even when the reaction is terminated when the theoretical water generation amount is 60 to 90%, the lubricity of the composite polyamide ester composition is good. The reaction time is 1 to 24 hours, preferably 3 to 18 hours, more preferably 5 to 18 hours, and most preferably 6 to 15 hours.

After dehydration condensation and removal of volatile matter, the remaining OH may be acylated. When acylating, a suitable amount of monobasic acid (R ¹ COOH) or monobasic acid anhydride ((R ¹ CO) ₂ O), preferably monobasic acid anhydride ((R ¹ CO) ₂ O) is added Preferably, at least a part, preferably almost all of the remaining OH can be converted to OCOR ¹ by heating at 100 ° C. or higher, more preferably 120 ° C. or higher, particularly 150 ° C. or higher. It is preferable to remove the by-product volatile matter by distillation described later. R ¹ is an alkyl group or aryl group having 1 to 10 carbon atoms, preferably an alkyl group or aryl group having 1 to 6 carbon atoms, and is a methyl group, ethyl group, butyl group, or phenyl group. Are more preferable, a methyl group or a phenyl group is preferable, and a methyl group is particularly preferable.

  Further, after dehydration condensation and removal of volatile matter, an esterification treatment may be performed in order to eliminate the remaining COOH. The esterification treatment can be performed, for example, by adding diazomethane, and at least a part, preferably almost all of COOH can be converted into a methyl ester.

  By this reaction, a composite polyamide ester composition containing a predetermined polyamide ester and a soft component containing at least the ester produced as described above is obtained. After the dehydration-condensation reaction, if desired, after performing acylation treatment and / or esterification treatment, the obtained composite polyamide ester composition can be used as it is for various uses, for example, as a lubricant. Various processes may be performed depending on the application.

  After completion of the reaction and the treatment after the reaction, it is preferable to perform filtration to remove dust and the like. When the composite polyamide ester becomes solid, it can be melted out or taken out as a powder by reprecipitation.

(Composition)
The present invention may relate to a composition containing at least a composite polyamide ester composition. For example, the composite polyamide ester composition of the present invention and various additives and / or media can be added to the composition.
Examples of additives include antiwear agents, viscosity index improvers, antioxidants, detergents, dispersants, flow agents, curing agents, corrosion inhibitors, seal conformers, antifoaming agents, rust inhibitors, and corrosion inhibitors. , One or more selected from friction modifiers and thickeners.
By adding such an additive, a preferable function as a lubricant such as wear suppression can be imparted. Regarding the lubricant that can be used in the present invention, the description in paragraphs [0098] to [0165] of JP2011-89106A can be referred to.

Examples of the medium include one or more selected from mineral oils, fat compounds, polyolefin oils, silicone oils, perfluoropolyether oils, aromatic ester oils, and polyol ester lubricating oils.
In the present invention, the “medium” means all the media generally called “fluid liquids”. However, it is not necessary to be liquid at room temperature or the temperature used, and any form of material such as solid and gel can be used in addition to liquid. There is no restriction | limiting in particular about the medium utilized in this invention, According to a use, it can select from various liquids. Regarding the medium that can be used in the present invention, the description in paragraphs [0067] to [0096] of JP-A-2011-89106 can be referred to.

  As a medium, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, and sulfuric acid washing. It is also preferable to use a hydrocarbon base oil that has been refined by combining one or more of the refining treatments such as white clay treatment alone or in combination of two or more. As the hydrocarbon base oil, the ratio (CA / CB) of the ratio (CA) of components having 24 or less carbon atoms and the ratio (CB) of components having 25 or more carbon atoms in the carbon number distribution obtained by gas chromatographic distillation is 2. It is preferred that a base oil of 0.0 or more is used. CA / CB is preferably 2.5 or more, more preferably 3 or more, and most preferably 5 or more. By setting CA / CB within the above range, a sufficiently low high temperature high shear (HTHS) viscosity at 80 ° C. can be obtained.

  Hydrocarbon base oil having a ratio CC / CD of 0.3 or less of the ratio (CC) of components having 18 or less carbon atoms and the ratio (CD) of components having 19 or more carbon atoms obtained by gas chromatographic distillation. It is preferable that Preferably, CC / CD is 0.25 or less, more preferably 0.2 or less, and most preferably 0.1 or less. By setting CC / CD within the above range, the consumption of lubricating oil can be suppressed even in the generator engine.

The gas chromatographic distillation here was carried out under the following conditions.
Model: GC-2010 manufactured by Shimadzu Corporation
Column: Ultra Alloy-1HT (30mm x 0.25mmΦ)
Carrier gas: Helium 200kPa
Detector: FID
Det. Temp. : 350 ° C
Oven Temp. : 80 ° C. to 320 ° C. (5 min)
Temp. Rate: 5 ° C / min
Inj. Vol: 1 μL toluene solution

As a medium, the following base oils (1) to (8) are used as raw materials, and the raw oil and / or a lubricating oil fraction recovered from the raw oil is refined by a predetermined refining method, A mineral oil base oil obtained by recovering the fraction can also be used.
(1) Distilled oil by atmospheric distillation of paraffinic crude oil and / or mixed base crude oil (2) Distilled oil by vacuum distillation of atmospheric distillation residue of paraffinic crude oil and / or mixed base crude oil ( WVGO)
(3) Wax (slack wax, etc.) obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-to-liquid (GTL) process, etc.
(4) One or two or more mixed oils selected from base oils (1) to (3) and / or mild hydrocracked oils of the mixed oils (5) selected from base oils (1) to (4) 2 or more kinds of mixed oils (6) Base oil (1), (2), (3), (4) or (5) debris oil (DAO)
(7) Mild hydrocracking treatment oil (MHC) of base oil (6)
(8) Two or more mixed oils selected from base oils (1) to (7).

  The above-mentioned predetermined purification methods include hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay White clay refining; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning are preferred. In the present invention, one of these purification methods may be performed alone, or two or more may be combined. Moreover, when combining 2 or more types of purification methods, the order in particular is not restrict | limited, It can select suitably.

Furthermore, as the medium, the following base oil (9) or the following base oil (9) obtained by performing a predetermined treatment on the base oil selected from the base oils (1) to (8) or the lubricating oil fraction recovered from the base oil (10) is particularly preferred.
(9) The base oil selected from the base oils (1) to (8) or the lubricating oil fraction recovered from the base oil is hydrocracked and recovered from the product or the product by distillation or the like. Hydrocracked mineral oil obtained by performing dewaxing treatment such as solvent dewaxing or catalytic dewaxing on the lubricating oil fraction, or distillation after the dewaxing treatment (10) The above base oils (1) to (8) ) Or a lubricating oil fraction recovered from the base oil is hydroisomerized, and the product or the lubricating oil fraction recovered from the product by distillation or the like is subjected to solvent dewaxing or catalytic dewaxing. Hydroisomerized mineral oil obtained by performing a dewaxing process such as or by distillation after the dewaxing process.

  Further, when obtaining the medium of the above (9) or (10), a solvent purification treatment and / or a hydrofinishing treatment step may be further provided as necessary at an advantageous step.

The kinematic viscosity at 100 ° C. of the mineral base oil is preferably 4.5 mm ² / s or less, more preferably 4 mm ² / s or less, still more preferably 3.5 mm ² / s or less, and most preferably 3 mm ² / s. s or less. On the other hand, the kinematic viscosity at 100 ° C. is preferably 1 mm ² / s or more, more preferably 1.5 mm ² / s or more, still more preferably 2 mm ² / s or more, and most preferably 2.3 mm ² / s or more. It is.
The kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.

As the medium, it is preferable to use a mineral oil base oil having a kinematic viscosity at 100 ° C. within the following range by distillation or the like. It is possible to use a mixture of (I) and (II), but it is preferable to use (I) alone.
(I) Mineral oil base oil (II) 100 having a kinematic viscosity at 100 ° C. of 1 mm ² / s or more, preferably 2.3 mm ² / s or more and less than 3 mm ² / s, preferably 2.9 mm ² / s or less. Mineral base oil having a kinematic viscosity at 3 ° C. of 3 mm ² / s or more, preferably 3.5 mm ² / s or more, 4.5 mm ² / s or less, preferably 4.0 mm ² / s or less

The mineral oil base oil preferably has a viscosity index of 90 or more, more preferably 105 or more, and still more preferably 110 or more. Moreover, it is preferable that it is 160 or less. Further, the viscosity index of the mineral oil base oil (I) is preferably 90 or more, more preferably 105 or more, still more preferably 110 or more, and most preferably 120 or more. Moreover, 160 or less is preferable. Further, the viscosity index of the mineral oil base oil (II) is preferably 110 or more, more preferably 120 or more, still more preferably 130 or more, and most preferably 140 or more. Moreover, 160 or less is preferable. By setting the viscosity index of the mineral base oil within the above range, the degree-temperature characteristics, heat / oxidation stability, and volatilization prevention properties are improved, and wear prevention properties are improved.
In addition, the viscosity index as used in the field of this invention means the viscosity index measured based on JISK2283-1993.

Further, the density (ρ ₁₅ ) of the mineral base oil at 15 ° C. depends on the viscosity grade of the lubricating base oil component, but is not more than the value of ρ represented by the following formula, that is, ρ ₁₅ ≦ ρ. Is preferred.
ρ = 0.0025 × kv100 + 0.816
In the formula, kv100 represents the kinematic viscosity (mm ² / s) of the lubricating base oil component at 100 ° C.

By setting the density (ρ ₁₅ ) of the mineral oil base oil at 15 ° C. within the above range, the viscosity-temperature characteristics and thermal / oxidation stability, as well as the volatilization prevention and low-temperature viscosity characteristics can be improved. Can save fuel.

Specifically, the density (ρ ₁₅ ) at 15 ° C. of the mineral oil base oil is preferably 0.835 or less, more preferably 0.828 or less, still more preferably 0.822 or less, and particularly preferably 0.815 or less. Most preferably, it is 0.805 or less, and preferably 0.785 or more. In addition, the density in 15 degreeC said by this invention means the density measured in 15 degreeC based on JISK2249-1995.

(Property of composition)
The composition of the present invention preferably has a viscosity at 40 ° C. of 1650 mPa · s or less, more preferably 1200 mPa · s or less, and even more preferably 1000 mPa · s or less. Viscosity needs to be adjusted to an appropriate viscosity depending on the usage environment.

In the composition of the present invention, the constituent elements are preferably composed of carbon, hydrogen, oxygen and silicon. Even if the composition of this invention does not contain phosphorus and sulfur, it can exhibit the same or better performance. The oil used as the oily medium is also preferably composed of carbon, hydrogen, oxygen and silicon.
The current lubricating oil usually contains phosphorus, sulfur and heavy metals. Lubricating oil used in a two-stroke engine that also burns lubricating oil together with fuel does not include phosphorus and heavy metals in consideration of environmental impact, but sulfur is included in about half of the lubricating oil used in a four-stroke engine. Yes. In other words, with the current lubrication technology, it is inferred that the formation of a boundary lubrication film with a sulfur content is indispensable. However, since it contains elemental sulfur, the load on the catalyst for exhaust gas purification is extremely high. large. Platinum and nickel are used for the exhaust gas purification catalyst, but the poisoning action of phosphorus and sulfur is a serious problem. From this point of view, the merit that the elements constituting the lubricating oil composition do not contain phosphorus or sulfur is very large. Furthermore, the absence of phosphorus and sulfur is optimal for industrial machinery other than engine oil, especially for lubricating oil in food production equipment. In the current technology, the elemental composition is taken into consideration for the environment at the expense of the friction coefficient. This is also a very preferable technique for metal cutting and machining lubricants that require a large amount of water for cooling.

(Method for preparing composition)
The composition of the present invention can be prepared by adding the composite polyamide ester composition in an oily medium or an aqueous medium, and dissolving and / or dispersing it. Dissolution and / or dispersion may be performed under heating. The amount of the composite polyamide ester composition added is preferably 10% by mass or more with respect to the mass of the oily medium. However, it is not limited to this range, and may be outside the above range as long as the compound is an amount sufficient to exhibit a friction reducing action.

(Use of composition)
The composition of the present invention is useful as a lubricant. That is, the present invention also relates to a lubricant including the above-described composite polyamide ester composition or the above-described composition.
The lubricant of the present invention is supplied, for example, between two sliding surfaces, and can be used to reduce friction. The composition of the present invention can form a film on the sliding surface. As for the material of the sliding surface, in steel, specifically, carbon steel for machine structure, alloy steel for structural machinery such as nickel chrome steel, nickel chrome molybdenum steel, chrome steel, chrome molybdenum steel, aluminum chrome molybdenum steel, Examples include stainless steel and multi-aged steel.

As the material of the sliding surface, various metals other than steel, or inorganic or organic materials other than metals are widely used. Examples of inorganic or organic materials other than metals include various plastics, ceramics, carbon, etc., and mixtures thereof. More specifically, examples of the metal material other than steel include cast iron, copper / copper-lead / aluminum alloy, castings thereof, and white metal.
In addition, about the material of a sliding surface, description of Paragraph [0168]-[0175] of Unexamined-Japanese-Patent No. 2011-89106 can be referred.

  The lubricant of the present invention can be used for various applications. For example, lubricating oil for grease, release agent, engine oil for internal combustion engine, oil for metal processing (cutting), oil for bearing, fuel for combustion engine, vehicle engine oil, gear oil, hydraulic oil for automobile, ship / aircraft Lubricant, machine oil, turbine oil, bearing oil, hydraulic fluid, compressor / vacuum pump oil, refrigerator oil, metalworking lubricant, magnetic recording medium lubricant, micromachine lubricant, artificial bone lubricant It can be used as an agent, shock absorber oil or rolling oil. It is also used for air conditioners and refrigerators with reciprocating and rotary hermetic compressors, automotive air conditioners and dehumidifiers, freezers, refrigerated warehouses, vending machines, showcases, chemical plant and other cooling devices. .

As a lubricant for metal processing that does not contain chlorine compounds, for example, when hot rolling metal materials such as steel materials and Al alloys, or when performing processing such as cutting, cold rolling oil of aluminum, cutting oil, As metal processing oil such as grinding oil, drawing oil, press processing oil and plastic processing oil of metal, especially as a deterrent for wear, breakage and surface roughness during high speed and high load processing, as well as broaching and gun drilling It is also useful as a metal working oil composition that can be applied to low speed and heavy cutting.
Further, it can be used for various grease lubricants, magnetic recording medium lubricants, micromachine lubricants, artificial bone lubricants, and the like. In addition, since the elemental composition of the composition can be a carbohydrate, for example, polyoxyethylene ether widely used in cake mix, salad dressing, shortening oil, chocolate, etc. as an emulsifying, dispersing or solubilizing agent is used. By using the composition of the sorbitan fatty acid ester containing edible oil as the base oil as the lubricating oil, a high-performance lubricating oil that is completely harmless to the human body can be used for lubrication of food production line manufacturing equipment and medical equipment members.
Furthermore, the composition of the present invention can be used as cutting oil or rolling oil by emulsifying and dispersing it in an aqueous system or by dispersing it in a polar solvent or a resin medium.

Moreover, the composition of this invention can be utilized for various uses also as a mold release agent. For example, polycarbonate resin, flame retardant polycarbonate resin, crystalline polyamide ester resin, which is the main component of image forming toner used in electrophotographic apparatus and electrostatic recording apparatus, various molding thermoplastic resin compositions, and semiconductor encapsulation It is used as a release agent for epoxy resin compositions for cutting. One embodiment of the release agent is an embodiment containing 0.01 to 10 parts by mass (preferably 0.1 to 5 parts by mass) of the composite polyamide ester composition with respect to 100 parts by mass of a resin such as a polycarbonate resin.
Moreover, it can also be used as an antifouling agent for preventing the soiling of the textile product by kneading or applying to the textile product such as clothing in advance to promote the removal of the soiling attached to the textile product.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

(Examples 1-130)
<Synthesis of polyamide ester>
Component A, Component B, and Component C described in Table 1 were charged into a reaction vessel equipped with a Dean-Stark dehydrator so as to have a molar equivalent ratio described in Table 1. Then, it stirred at liquid temperature 160-200 degreeC for 12 hours. Water generated during stirring was removed. After cooling to room temperature, a polyamide ester composition (Chemical Formulas 1 to 130) was obtained as a yellow to transparent liquid. In addition, in component A, component B, and component C shown in Table 1, CA-26 is Tsunodai 395 manufactured by Tsukino Foods Co., Ltd., CA-27 is Tsunodim 346 manufactured by Tsukuno Foods Co., Ltd. The other raw materials were those manufactured by Wako Pure Chemical Industries.

(Comparative Examples 1 and 2)
<Synthesis of polyamide ester>
According to the methods described in JP-A-01-311122 and JP-T 2009-533406, Ratio-1 and Ratio-2 were respectively synthesized.

<Preparation 1 of composite polyamide ester composition>
Each polyamide ester composition obtained in Examples 1-132 (Chemical Formulas 1-130 and Ratios-1, 2) and mineral oil (100 neutral oil, viscosity at 100 ° C., 4.4 mm / s ² ), The lubricant was adjusted by mixing at an arbitrary ratio.

<Evaluation 1: Dispersion performance>
When adjusting 100 parts by mass of the two types of lubricant so that the mixing ratio of the polyamide ester composition and mineral oil is 1/99 and 30/70, the time until the liquid is uniformly mixed is visually evaluated. It was.
If the dispersibility of the polyamide ester composition in the base oil is high, the polyamide ester composition can be mixed and uniformly dispersed in any amount. That is, even when the mixing ratio of the mineral oil to the polyamide ester is small or large, both can be uniformly dispersed in the same mixing time without separation. Therefore, when adjusting the lubricant so that the mixing ratio of the polyamide ester composition and the mineral oil was 1/99 or 30/70, the time difference until the visual mixing confirmation was measured. The evaluation criteria are as follows. In addition, the thing of evaluation more than B rank was set as the pass. The results are shown in Table 1 below.
Rank A: Time difference until visual mixing confirmation is less than 10 seconds Rank B: Time difference until visual mixing confirmation is 10 seconds or more and less than 30 seconds C Rank: Time difference until visual mixing confirmation is 30 seconds or more and less than 1 minute D Rank: Visual mixing Time difference until confirmation is 1 minute or more

<Preparation 2 of composite polyamide ester composition>
Each polyamide ester composition obtained in Examples 1-132 (Chemical Formulas 1-130 and Ratios-1, 2) and mineral oil (100 neutral oil, viscosity at 100 ° C., 4.4 mm / s ² ), The lubricant was adjusted by mixing at a mass ratio of 25/75.

<Evaluation 2: Lubrication performance>
Evaluation assuming extreme pressure conditions was performed using a vibration type frictional wear tester (manufactured by Optimol Instruments Prutechnik GmbH, trade name: SRV4), using a vibration frequency of 100 Hz, a vibration width of 2.0 mm, a load of 30 N, a temperature of 60 ° C., Test piece: The test was performed by measuring the coefficient of friction at a point contact (ball) and a test time of 30 minutes.
Generally, the friction coefficient obtained on the assumption of extreme pressure conditions is obtained as a value larger than the friction coefficient in a normal fluid lubrication region or elastohydrodynamic lubrication region. For this reason, those having a small coefficient of friction under extreme pressure conditions and good evaluation below naturally have a small coefficient of friction in a normal fluid lubrication region and elastohydrodynamic lubrication region, and the evaluation is good. In addition, the thing with evaluation more than D rank was set as the pass. Table 1 below shows the evaluation results of the coefficient of friction using an SRV4 testing machine assuming extreme pressure conditions.
Rank A: Friction coefficient <0.050
B rank: 0.050 ≦ coefficient of friction <0.055
C rank: 0.055 ≦ friction coefficient <0.060
D rank: 0.060 ≦ friction coefficient <0.070
E rank: Friction coefficient ≧ 0.070

As can be seen from Tables 1 and 2, the composite polyamide ester compositions of Examples 1 to 130 are excellent in dispersibility in the base oil and exhibit excellent lubricating performance.
On the other hand, it can be seen that the composite polyamide ester compositions of Comparative Examples 1 and 2 are not sufficiently dispersible in the base oil. Moreover, it turns out that lubrication performance is not fully demonstrated in addition to the dispersibility to base oil being bad.

(Examples 133-142)
<Preparation of composite polyamide ester composition>
A base oil (100 neutral oil, viscosity of 4.4 mm / s ^{2 at} 100 ° C.) was mixed with the polyamide ester composition shown in Table 2 and the organometallic compound in the ratio shown in Table 2 to prepare a lubricant. The dispersion performance and lubrication performance of the lubricant were measured by the following methods. The results are shown in Table 3.

  As can be seen from Table 3, the dispersibility and lubricity of the lubricants of Examples 133 to 142 are all good regardless of the type of the organometallic compound.

  According to the present invention, a composite polyamide ester composition capable of exhibiting excellent lubricating performance can be obtained. Furthermore, the composite polyamide ester composition of the present invention can exhibit excellent dispersibility with respect to the base oil. Thus, the composite polyamide ester composition of the present invention has high lubricating performance and dispersibility, and has high industrial applicability.

Claims (26)

A composite polyamide ester composition comprising a polyamide ester obtained by condensing a dendrimer compound represented by the following general formula (1), a polyvalent carboxylic acid, and a monohydric alcohol.

(In General Formula (1), Z represents an n-valent atomic group containing a nitrogen atom, L ¹ represents a (m + 1) -valent linking group, and X ¹ represents —CONH—, —COO—, —OCO—, or -NHCO-, R ¹ represents a group whose terminal is an amino group or a hydroxy group, n is an integer of 2 to 6, m is an integer of 1 to 4, and n + m is 4 or more. .) 2. The polyamide ester composition according to claim 1, wherein in the general formula (1), R ¹ is an aminoalkyl group or a hydroxyalkyl group. The polyamide ester composition according to claim 1 or 2, wherein R ¹ in the general formula (1) is an aminoalkyl group. The said dendrimer compound is a composite polyamide ester composition of Claim 1 represented by following General formula (2).

(In General Formula (2), Z represents an n-valent atomic group containing a nitrogen atom, L ¹ represents a (m + 1) -valent linking group, L ² represents a (p + 1) -valent linking group, and X ¹ And X ² each independently represents —CONH—, —COO—, —OCO— or —NHCO—, R ² represents a group whose terminal is an amino group or a hydroxy group, and n represents 2 to 6 (It is an integer, m is an integer of 1 to 4, p is an integer of 1 to 4, n + m is 4 or more, or n + p is 4 or more.) The composite polyamide ester composition according to claim 4, wherein R ² in the general formula (2) is an aminoalkyl group or a hydroxyalkyl group. The composite polyamide ester composition according to claim 4 or 5, wherein R ² in the general formula (2) is an aminoalkyl group.   The composite polyamide ester composition according to any one of claims 1 to 6, wherein the dendrimer compound has 3 to 768 terminal functional groups.   The composite polyamide ester composition according to any one of claims 1 to 7, wherein the molecular weight of the dendrimer compound is 350 or more.   The composite polyamide ester composition according to claim 1, wherein the polyvalent carboxylic acid has 10 or more carbon atoms.   The composite polyamide ester composition according to claim 1, wherein the polyvalent carboxylic acid has 24 to 48 carbon atoms.   The composite polyamide ester composition according to claim 1, wherein the polyvalent carboxylic acid is a dibasic acid or a tribasic acid of an unsaturated fatty acid.   The composite polyamide ester composition according to any one of claims 1 to 11, wherein the polyvalent carboxylic acid is dimer acid, trimer acid or erucic acid dimer.   The composite polyamide ester composition according to any one of claims 1 to 12, wherein the monohydric alcohol has 6 or more carbon atoms.   The composite polyamide ester composition according to any one of claims 1 to 13, wherein the monohydric alcohol has at least one oxyalkylene group. The said monohydric alcohol is a composite polyamide-ester composition of any one of Claims 1-14 represented by following General formula (3).

General formula (3)
(In General Formula (3), R ^a has an alkyl group which may have ^a substituent, ^a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An aryl group which may be substituted or a heteroaryl group which may have a substituent, wherein X ^a1 and X ^a2 each independently represents a hydrogen atom, a halogen atom or an alkyl group, and na 1 represents an integer of 1 to 4. Na2 represents an integer of 1 to 12. When na1 is 2 or more, the na1 X ^a1 may be the same or different, and the na1 X ^a2 may be the same or different. In addition, when na2 is 2 or more, na2 — (O (CX ^a1 X ^a2 ) _na1 — may be the same or different).   The composite polyamide ester composition according to any one of claims 1 to 15, further comprising at least one organometallic compound of an organomolybdenum compound and an organozinc compound.   The organometallic compound includes sulfurized oxymolybdenum-N, N-di-octyldithiocarbamate, sulfurized oxymolybdenum-N, N-di-tridecyldithiocarbamate, zinc n-butyl-n-pentyldithiophosphate, di-2- The composite polyamide ester composition according to claim 16, which is zinc ethylhexyl dithiophosphate or zinc isopropyl-1-ethylbutyldithiophosphate.   The dendrimer compound is obtained by mixing and condensing so that the equivalent ratio of the polyvalent carboxylic acid is 1 to 20 and the equivalent ratio of the monohydric alcohol is 0.5 to 30. The composite polyamide ester composition according to any one of 1 to 17. The composite polyamide according to any one of claims 1 to 18, wherein the polyamide ester includes at least one of a polyamide ester represented by the following general formula (5) and a polyamide ester represented by the following general formula (6). Ester composition.

(In General Formula (5), Z represents an n-valent atomic group containing a nitrogen atom, L represents an (m + 1) -valent linking group, and X represents —CONH—, —COO—, —OCO—, or —NHCO. Y represents a divalent linking group, R ³ represents a (p + 1) valent chain or cyclic aliphatic linking group or an aromatic linking group, and R ⁴ may have a substituent. Represents an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group; N is an integer of 2 to 6, m is an integer of 1 to 4, p is an integer of 1 to 4, n + m is 4 or more, or n + p is 4 or more, where p is if more, if p number of R ⁴ is optionally different than the same .m is 2 or more, m-number of -X-Y- ^{HCOR 3 -. (COOR 4)} p may be different even in the same addition, n pieces of -CONH-L- {X-Y- NHCOR 3 - (COOR 4) p} m be the same May be different.)

(In General Formula (6), Z represents an n-valent atomic group containing a nitrogen atom, L represents an (m + 1) -valent linking group, and X represents —CONH—, —COO—, —OCO—, or —NHCO. Y represents a divalent linking group, R ⁵ represents a (p + 1) valent chain or cyclic aliphatic linking group or an aromatic linking group, and R ⁶ may have a substituent. Represents an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group; N is an integer of 2 to 6, m is an integer of 1 to 4, p is an integer of 1 to 4, n + m is 4 or more, or n + p is 4 or more, where p is if more, if p number of R ⁶ is optionally different even in the same .m is 2 or more, m-number of -X-Y- ^{COR 5 -. (COOR 6)} p may be different even in the same addition, n pieces of -CONH-L- {X-Y- OCOR 5 - (COOR 6) p} m be the same May be different.) 20. The composite polyamide ester composition according to claim 19, wherein in the general formulas (5) and (6), R ³ and R ⁵ are each independently a dimer acid residue, a trimer acid residue or an erucic acid dimer residue. . 21. The composite polyamide ester composition according to claim 19 or 20, wherein in the general formulas (5) and (6), R ⁴ and R ⁶ are each independently a group having an oxyalkylene structure.   The composite polyamide ester composition according to any one of claims 1 to 21, which has a viscosity at 40 ° C of 50 to 1650 mPas.   The composite polyamide ester composition according to any one of claims 1 to 22, an antiwear agent, a viscosity index improver, an antioxidant, a detergent, a dispersant, a flow, a curing agent, a corrosion inhibitor, and a seal fit. A composition containing one or more additives selected from an agent, an antifoaming agent, a rust inhibitor, a corrosion inhibitor, a friction modifier, and a thickener.   The composite polyamide ester composition according to any one of claims 1 to 22, or the composition according to claim 23, a mineral oil, an oil and fat compound, a polyolefin oil, a silicone oil, a perfluoropolyether oil, an aromatic A composition comprising at least one ester oil and one or more media selected from polyol ester lubricating oils.   A lubricant comprising the composite polyamide ester composition according to any one of claims 1 to 22, or the composition according to claim 23 or 24.   Grease lubricants, mold release agents, engine oils for internal combustion engines, metal processing (cutting) oils, bearing oils, combustion engine fuels, vehicle engine oils, gear oils, automotive hydraulic oils, marine and aircraft lubricants Oil, machine oil, turbine oil, bearing oil, hydraulic oil, compressor / vacuum pump oil, refrigerator oil, metalworking lubricant, magnetic recording medium lubricant, micromachine lubricant, artificial bone lubricant, The lubricant according to claim 25, which is used as a shock absorber oil or a rolling oil.