JP6231367B2 - Organic degradation product remover - Google Patents

Description

  The present invention is added to a lubricant to disperse and remove insoluble organic degradation products such as degradation products and insolubles caused by oxidation or alteration of organic materials in a lubricant containing a resin liquid and a plasticizer. The present invention relates to an organic degradation product remover used in the manufacturing process.

  When a lubricant containing a resin liquid or a plasticizer is partially exposed to high temperature or high pressure, organic substances constituting the lubricant are often deteriorated to generate soot-like carbon residue or sludge. Carbon debris is a deteriorated product caused by thermal, mechanical, chemical alteration and oxidation of a lubricant composed of organic matter. Sludge is an aggregate of the deteriorated product and foreign substances in the lubricant. It is an insoluble material that adheres to and accumulates on the lubricated part. Such a deteriorated product or an organic deteriorated product that is an insoluble material aggregates, precipitates, or accumulates in the lubricant, thereby impairing the function of the lubricant and causing deterioration in quality and performance.

  In order to improve such a problem, for example, Patent Document 1 discloses a lubricating oil additive for diesel engines made of amino alcohol. This improves the cleanliness of the lubricating oil for land and marine diesel engines, thereby extending the life of the lubricating oil. Patent Document 2 discloses a lubricating oil composition based on mineral oil that improves the cleanliness of a piston in an internal combustion engine. A succinimide derivative or the like is used as a dispersant contained in this lubricating oil composition, and it retains solid and liquid contaminants resulting from oxidation in the suspension, and condenses and precipitates or deposits sludge on metal parts. Can be prevented.

  Such conventional lubricants with improved cleanliness do not provide sufficient removal performance for carbon debris and sludge required in the market, so the unnecessary components in various lubricants are sufficiently dispersed and stabilized. What can be removed is desired.

JP 09-1000048 A1 JP 2005-054193 A

The present invention has been made in order to solve the above-mentioned problems, such as heat treatment, pressure treatment, contamination by foreign substances, atmospheric gas oxygen, SO ₃ , NO _{X and the} like in a lubricant containing a resin liquid and a plasticizer. Low cost that can improve the adsorptivity, dispersibility and stability to carbon debris and sludge generated by oxidation, etc., remove these insoluble organic degradation products, have versatility and can be easily manufactured An object of the present invention is to provide an organic degradation product remover.

In order to achieve the above object, the organic degradation product removing agent according to claim 1 is at least one nitrogen selected from an amino group, an ammonium group, and a nitrogen-containing heterocyclic group. At least one of a nitrogen-containing polymer obtained by polymerizing a nitrogen-containing monomer having a containing group and an unsaturated group, and a nitrogen-containing polymer obtained by polymerizing an imine monomer and having an imino group as a nitrogen-containing group. A polymer having a weight average molecular weight of 300 to 100,000, and the following chemical formula (1)
R ¹ R ² R ³ N (1)
Wherein R ¹ is an alkyl group having 8 to 22 carbon atoms, R ² is a hydrogen atom or an alkyl group having 4 to 22 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 4 to 22 carbon atoms, provided that R . except when both ² and R ³ are hydrogen atoms) contains a nitrogen-containing substance consisting of an amine compound represented by the weight ratio of the amine compound and the polymer 2-8: 8-2 characterized by a.

  The organic degradation product removing agent according to claim 2 is the one described in claim 1, wherein the nitrogen-containing monomer is an amino group-containing (meth) acrylate monomer or an ammonium group-containing (meth). It is at least one selected from an acrylate monomer and a monomer having a nitrogen-containing heterocyclic group.

  The organic degradation product removing agent according to claim 3 is the one according to any one of claims 1 to 2, wherein the polymer is composed of the nitrogen-containing monomer and the nitrogen-free monomer. It is a copolymer.

  The organic degradation product removing agent according to claim 4 is the one described in claim 3, wherein the nitrogen-free monomer is saturated or unsaturated, unsubstituted or hydroxy-substituted, or a glycol group or polyglycol. It is at least one selected from a group-substituted (meth) acrylate monomer and a macromonomer.

  The organic degradation product removing agent according to claim 5 is the one described in any one of claims 1 to 3, wherein the polymer is saturated with 10 to 60 parts by weight of the nitrogen-containing monomer. Or a copolymer of 10 to 85 parts by weight of an unsaturated, unsubstituted or hydroxy-substituted or glycol or polyglycol group-substituted (meth) acrylate monomer and 5 to 30 parts by weight of a macromonomer. Features.

（式中、Ｒ^４は水素原子又はメチル基、Ｒ^５及びＲ^６はそれぞれ独立して同一又は異なり水素原子又は炭素数１〜６のアルキル基、ｎは２〜８の正数である）で表されるアミノ基含有（メタ）アクリレート単量体、下記化学式（３）

（式中、Ｒ^４は水素原子又はメチル基、Ｒ^７、Ｒ^８及びＲ^９はそれぞれ独立して異なり、炭素数１〜６のアルキル基、炭素数２〜６のヒドロキシアルキル基、炭素数１〜４のアルコキシアルキル基、シクロアルキル基、アラルキル基、フェニル基、他の原子が置換したフェニル基、Ｘ⁻はハロゲン化物イオン又は酸の陰イオン残基、ｍは２〜８の正数である）で表されるアンモニウム基含有（メタ）アクリレート単量体、又は、下記化学式（４）

若しくは、下記化学式（５）

で表される窒素含有複素環基を有する単量体であることを特徴とする。 The organic degradation product removing agent according to claim 6 is the one according to any one of claims 1 to 5, wherein the nitrogen-containing monomer has the following chemical formula (2):

(Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ and R ⁶ are each independently the same or different, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is a positive number of 2 to 8). Amino group-containing (meth) acrylate monomer represented by the following chemical formula (3)

(Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁷ , R ⁸ and R ⁹ are each independently different, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, and 1 carbon atom) to 4 alkoxyalkyl group, a cycloalkyl group, an aralkyl group, a phenyl group, the other phenyl group atom-substituted, X ^- is an anion residue of halide ions or acid, m is a positive number of 2 to 8 ) -Containing ammonium group-containing (meth) acrylate monomer or the following chemical formula (4)

Or the following chemical formula (5)

It is a monomer which has a nitrogen-containing heterocyclic group represented by these.

  The organic degradation product removing agent according to claim 7 is described in any one of claims 1 to 6, wherein the polymer is an amino group-containing (meth) acrylate monomer and / or an ammonium group. The (meth) acrylate monomer contained, a saturated or unsaturated, unsubstituted or hydroxy-substituted, or glycol or polyglycol group-substituted (meth) acrylate monomer and a macromonomer are copolymerized to give a weight average molecular weight of 4 , 100,000 to 100,000.

  The organic degradation product removing agent according to claim 8 is the organic degradation product removing agent according to any one of claims 1 to 7, wherein the polymer includes a monomer having a nitrogen-containing heterocyclic group and a saturated or non-saturated monomer. A saturated, unsubstituted or hydroxy-substituted, or glycol or polyglycol group-substituted (meth) acrylate monomer is copolymerized with a macromonomer to give a weight average molecular weight of 4,000 to 100,000. It is characterized by that.

（式中、Ｒ^１０は炭素数１〜４のアルキル鎖）で表される繰返単位Ｓと、下記化学式（６ｂ）

（式中、Ｒ^１０は前記と同じ、Ｑは該繰返単位ごとに同一又は異なり下記化学式（７）

（式中、Ｒ^１１は炭素数７〜１７のアルキル鎖、Ｒ^１２は炭素数２〜５のアルキレン鎖、ｕ＝５〜１５である）で表される側鎖基又は水素原子とし、その全繰返単位のうち少なくとも一つを該側鎖基とする）で表される繰返単位Ｔとを、規則的又は不規則的に結合し、前記繰返単位Ｓ：前記繰返単位Ｔ＝１：１〜２：１で前記繰返単位Ｓ及び前記繰返単位Ｔを夫々１０〜５００含むものであることを特徴とする。 The organic degradation product removing agent according to claim 9 is the one described in claim 1, wherein the polymer is a nitrogen-containing polymer in which the imine monomer is polymerized and the imino group is a nitrogen-containing group. And a side chain formed of a polyester oligomer having a weight average molecular weight derived from ε-caprolactone of 500 to 4,000 and a main chain formed of a polyimine having a weight average molecular weight of 300 to 40,000. The composition weight ratio of the side chain to the main chain is 80:20 to 97: 3, and the following chemical formula (6a)

(Wherein R ¹⁰ is an alkyl chain having 1 to 4 carbon atoms) and the following chemical formula (6b)

(Wherein R ¹⁰ is the same as described above, Q is the same or different for each repeating unit, and the following chemical formula (7)

(Wherein R ¹¹ is an alkyl chain having 7 to 17 carbon atoms, R ¹² is an alkylene chain having 2 to 5 carbon atoms, and u = 5 to 15) or a hydrogen atom, A repeating unit T represented by (at least one of the repeating units is the side chain group), and the repeating unit S: the repeating unit T = 1. : 1 to 2: 1 and includes 10 to 500 of the repeating unit S and the repeating unit T, respectively.

  The organic degradation product removing agent according to claim 10 is described in any one of claims 1 to 8, wherein the polymer is the nitrogen-containing monomer and an alkyl having 1 to 18 carbon atoms. Alkyl (meth) acrylates containing a group, alkenyl (meth) acrylates containing an alkenyl group having 2 to 18 carbon atoms, hydroxyalkyl (meth) acrylates containing an alkyl group having 2 to 4 carbon atoms, carbon number Alkyl monoalkylene glycol (meth) acrylates containing 1 to 18 alkyl groups and / or alkyl polyalkylene glycol (meth) acrylates, alkenyl monoalkylene glycol (meth) acrylates containing alkenyl groups having 1 to 18 carbon atoms And / or alkenyl polyalkylene glycol (meth) acrylates, and carbon number At least any saturated or unsaturated, unsubstituted or hydroxy substituted selected from alkyl alkenyl monoalkylene glycol (meth) acrylates and / or alkylalkenyl polyalkylene glycol (meth) acrylates containing -18 alkylalkenyl groups or It is a copolymer with a glycol group or polyglycol group-substituted (meth) acrylate monomer.

  The organic degradation product removing agent according to claim 11 is described in any one of claims 1 to 8, wherein the polymer contains the nitrogen-containing monomer and a terminal (meth) acryloyl group. Selected from polyalkyl (meth) acrylate macromonomer, terminal (meth) acryloyl group-containing polyalkenyl (meth) acrylate macromonomer, terminal (meth) acryloyl group-containing polyester macromonomer, and terminal (meth) acryloyl group-containing polystyrene macromonomer It is a copolymer with at least one of the macromonomers.

  The organic degradation product removing agent according to claim 12 is the agent according to any one of claims 1 to 11, wherein the nitrogen-containing substance contains at least the amine compound, and the amine value of the amine compound is 30. It is characterized by being -450 mgKOH / g.

Organic deterioration removal agent This prior Symbol nitrogen-containing substance, the polymer and consists of a said amine compound and the weight ratio of 2-8: characterized by a 8-2.

A lubricant according to a thirteenth aspect includes the organic degradation product removing agent according to any one of the first to twelfth aspects and a lubricating component.
The lubricant according to claim 14 is the lubricant according to claim 13, wherein 2 to 20 parts by weight of the organic degradation product remover, and 80 to 98 of the lubricant component selected from polyolefin and fatty acid ester are used. And containing parts by weight.

  The organic degradation product removing agent of the present invention can be selectively adsorbed and dispersed in carbon debris and sludge generated in the lubricant when used together with the lubricant, without impairing the function of the lubricant. Performance can be maintained and quality deterioration of the lubricant can be prevented. Also, by dispersing and stabilizing insoluble component particles that are insoluble organic degradation products that aggregate, precipitate or deposit in the lubricant, it is possible to remove unnecessary components that cause a decrease in the performance of the lubricant from the lubricated part. it can.

  Moreover, this organic deterioration thing removal agent is excellent in the removability of an organic deterioration thing, can be manufactured cheaply and simply, and can be used by adding to various lubricants. The lubricant containing the organic degradation product remover disperses degradation products generated by thermal, mechanical, chemical alteration and oxidation, and does not cause aggregation, precipitation, or deposition in the lubricant.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  The organic degradation product removing agent of the present invention comprises a nitrogen-containing polymer obtained by polymerizing a nitrogen-containing monomer having at least any nitrogen-containing group and unsaturated group selected from an amino group, an ammonium group, and a nitrogen-containing heterocyclic group. It includes a polymer and at least one of a polymer containing an imine monomer and a nitrogen-containing polymer having an imino group as a nitrogen-containing group, and / or a nitrogen-containing substance which is an amine compound. The organic degradation product remover is used by being added to the lubricant, and the nitrogen-containing material is selectively adsorbed on the organic degradation product that is a degradation product or an insoluble product generated in the lubricant and disperses them. Thus, an unnecessary component in the lubricant can be removed from the lubricated portion.

  The polymer contained in the organic degradation product remover is a copolymer or a homopolymer, and has a weight average molecular weight (Mw) of 300 to 100,000.

  Examples of the nitrogen-containing monomer to be a polymer include amino group-containing (meth) acrylate monomers, ammonium group-containing (meth) acrylate monomers, and monomers having nitrogen-containing heterocyclic groups. These nitrogen-containing monomers may be used alone or in combination of two or more.

  The polymer may be a copolymer of the nitrogen-containing monomer and another monomer different from the nitrogen-containing monomer, for example, a nitrogen-free monomer. Specific examples of the nitrogen-free monomer include saturated or unsaturated (meth) acrylate monomers and macromonomers which are unsubstituted or substituted with hydroxy or substituted with glycol or polyglycol groups. These nitrogen-free monomers may be used alone or as a mixture of two or more.

  Preferred examples of the polymer contained in the organic degradation product remover of the present invention are shown in (A) to (E).

  (A) Amino group-containing (meth) acrylate monomer and / or ammonium group-containing (meth) acrylate monomer as nitrogen-containing monomer and saturated or unsaturated, unsubstituted or hydroxy as nitrogen-free monomer Examples thereof include a copolymer in which a polymerization component including a substituted or glycol group- or polyglycol group-substituted (meth) acrylate monomer and a macromonomer are copolymerized.

  The amino group-containing (meth) acrylate monomer is represented by the chemical formula (2), specifically, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meta) ) Acrylate, Nt-butylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N-propylaminoethyl (meth) acrylate, N -Butylaminoethyl (meth) acrylate is mentioned.

The ammonium group-containing (meth) acrylate monomer is represented by the chemical formula (3) and has one quaternary ammonium group and one (meth) acryloyl group in one molecule. Specifically, 2-hydroxy-3 (meth) acryloyloxypropyltrimethylammonium chloride, 2-hydroxy-3 (meth) acryloyloxypropyltriethanolammonium chloride, 2-hydroxy-3 (meth) acryloyloxypropyldimethylbenzylammonium Examples include chloride, 2-hydroxy-3 (meth) acryloyloxypropyldimethylphenylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, and (meth) acrylamidopropyltrimethylammonium chloride. In the above list, the counter ion X ⁻ in the chemical formula (3) is exemplified as Cl ⁻ , but the counter ion is Br ⁻ , I ⁻ , F ⁻ , HSO ₄ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , It may be another ion such as PO ₄ ³⁻ , HPO ₄ ³⁻ , H ₂ PO ₄ ⁻ , C ₆ H ₅ SO ₃ ⁻ , and OH ⁻ .

  Examples of saturated or unsaturated, unsubstituted or hydroxy-substituted or glycol or polyglycol group-substituted (meth) acrylate monomers include, for example, alkyl (meth) acrylates or carbons containing an alkyl group having 1 to 18 carbon atoms. Alkenyl (meth) acrylates containing alkenyl groups of 2 to 18, more specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n -Butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate , Benzyl (meth) acrylate, isobornyl (meth) acrylate, unsaturated derivatives thereof; hydroxyalkyl (meth) acrylates containing an alkyl group having 2 to 4 carbon atoms, more specifically 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; alkyl monoalkylene glycol (meth) acrylates containing alkyl groups having 1 to 18 carbon atoms and alkyl polyalkylene glycols (meta ) Acrylates, alkenyl monoalkylene glycol (meth) acrylates or alkenyl polyalkylene glycol (meth) acrylates containing an alkenyl group having 1 to 18 carbon atoms, alky containing an alkyl alkenyl group having 1 to 18 carbon atoms Rualkenyl monoalkylene glycol (meth) acrylates and alkylalkenyl polyalkylene glycol (meth) acrylates, more specifically, methoxydiethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, and n-butoxyethylene Examples include glycol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, and trioxyethylene nonylphenol (meth) acrylate. These (meth) acrylate monomers may be used individually by 1 type, and may be used in mixture of multiple types.

  The macromonomer is a macromonomer having a (meth) acryloyl group at the terminal, for example, a terminal (meth) acryloyl group-containing polyalkyl (meth) acrylate macromonomer, a terminal (meth) acryloyl group-containing polyalkenyl (meth) Examples thereof include acrylate macromonomers, terminal (meth) acryloyl group-containing polyester macromonomers, and terminal (meth) acryloyl group-containing polystyrene macromonomers. More specifically, macromonomer AA-6 (terminal group: methacryloyl group, segment: methyl methacrylate, number average molecular weight: 6000; trade name manufactured by Toagosei Co., Ltd.), macromonomer AW-6S (terminal group: Methacryloyl group, segment: isobutyl methacrylate, number average molecular weight: 6000; trade name of Toagosei Chemical Co., Ltd., macromonomer AB-6 (terminal group: methacryloyl group, segment: butyl acrylate number, average molecular weight: 6000; Synthetic Chemical Industry Co., Ltd. trade name), macromonomer AS-6 (terminal group: methacryloyl group, segment: styrene-equivalent number average molecular weight: 6000; Toagosei Chemical Industry Co., Ltd. trade name). These terminal (meth) acryloyl group-containing macromonomers may be used singly or in combination.

  The number average molecular weight of the (meth) acrylic copolymer that is a copolymer obtained from these polymerization components is preferably 4,000 to 100,000. When the molecular weight is lower than 4,000, it selectively adsorbs to the deteriorated product generated in the lubricant or the organic deteriorated product which is insoluble, and disperses them to remove unnecessary components in the lubricant to be lubricated. The ability to remove from may decrease. If it is higher than 100,000, the viscosity of the organic degradation product remover may become too high, making it difficult to handle. The number average molecular weight of the (meth) acrylic copolymer is particularly preferably 6,000 to 50,000. The molecular weight can be appropriately adjusted by adding a polymerization regulator such as an alkyl mercaptan and copolymerizing it.

  This (meth) acrylic copolymer is preferably produced by solution polymerization. Specifically, 10 to 60 parts by weight of the nitrogen-containing monomer, 10 to 85 parts by weight of the (meth) acrylate monomer, and 5 to 30 parts by weight of the macromonomer are present in the presence of the polymerization initiator. Then, polymerization is carried out in a suitable inert solvent to produce a (meth) acrylic copolymer. The reaction temperature is 70 to 150 ° C, preferably 80 to 130 ° C. The reaction time is 1 to 15 hours, preferably 4 to 8 hours.

  Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile and dimethylazobisisobutyrate, and organic peroxides such as lauroyl peroxide and diisopropylbenzene hydroperoxide.

  The inert solvent is preferably one that can dissolve the resulting (meth) acrylic copolymer and is miscible with the lubricant. Specifically, aromatic solvents such as xylene, Solvesso 100, Solvesso 150; ketone solvents such as methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; cellosolv solvents such as butyl cellosolve and ethyl cellosolve; propylene Examples include propylene glycol solvents such as glycol monomethyl ether; cellosolve acetate solvents such as ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ether acetate solvents such as propylene glycol monomethyl ether acetate. Further, water, a solvent miscible with water, an alcohol solvent such as ethanol or isopropanol, or the like can be used. These inert solvents may be used alone or in combination.

  (B) As another polymer, vinyl pyridine which is a monomer having a nitrogen-containing heterocyclic group represented by the chemical formula (4) as a nitrogen-containing monomer, and saturated or non-nitrogen-containing monomer Examples thereof include a copolymer in which a polymerization component containing an unsaturated, unsubstituted, hydroxy-substituted, or glycol group or polyglycol group-substituted (meth) acrylate monomer, and a macromonomer is copolymerized.

  As vinylpyridine, 2-vinylpyridine may be sufficient, 4-vinylpyridine may be sufficient, and these may be used together.

  (C) As another polymer, 1-vinylimidazole which is a monomer having a nitrogen-containing heterocyclic group represented by the chemical formula (5) as a nitrogen-containing monomer, and a nitrogen-free monomer Examples thereof include a copolymer in which a polymerization component containing a saturated or unsaturated, unsubstituted or hydroxy-substituted or glycol or polyglycol group-substituted (meth) acrylate monomer, and a macromonomer is copolymerized.

  The (meth) acrylate monomer and macromonomer contained in the polymerization component that is the raw material of the (meth) acryl / vinyl copolymer that is the copolymer exemplified in (B) and (C), respectively, The thing similar to what was illustrated by (A) can be used. The (meth) acryl / vinyl copolymer can be polymerized by the same method and weight ratio as described above, and the number average molecular weight is preferably 4,000 to 100,000.

  (D) Another polymer includes a nitrogen-containing polymer in which an imine monomer is polymerized, a polyimine chain having an imino group as a nitrogen-containing group as a main chain, and a polyester chain as a side chain. . This polymer has a weight average molecular weight of 500 to 4,000 and a polyester bonded as a side chain to a main chain made of polyimine having a weight average molecular weight of 300 to 40,000. The composition weight ratio of the side chain and the main chain is 80:20 to 97: 3.

The repeating units constituting the polymer are shown in the following chemical formulas (6a) and (6b).

In the chemical formulas (6a) and (6b), R ¹⁰ is an alkyl chain having 1 to 4 carbon atoms.

  The repeating unit S (hereinafter, abbreviated as S) represented by the chemical formula (6a) and the repeating unit T (hereinafter, abbreviated as T) represented by the chemical formula (6b) In the polymer, 10 to 500 are contained respectively. The composition ratio is S: T = 1: 1 to 2: 1. S and T are bonded regularly or irregularly to form a polymer. As a coupling example, for example, S and T may be coupled alternately and repeatedly as "-S-T-", and "-S-S-T-" is repeated as one block. It may be bonded. Further, S and T may be randomly and repeatedly combined, and blocks such as “-S-T-” and “-S-S-T-” may be randomly and repeatedly combined.

  In the chemical formula (6b), Q is the same or different for each repeating unit, and is a side chain group represented by the following chemical formula (7) obtained from the polyester oligomer. Moreover, some Qs in this repeating unit may be hydrogen atoms.

In the formula, R ¹¹ is an alkyl chain having 7 to 17 carbon atoms, R ¹² is an alkylene chain having 2 to 5 carbon atoms, and u = 5 to 15. The side chain group is a group obtained from a polyester oligomer.

  The polyester oligomer contained in the polymerization component that is the raw material of this copolymer is derived from ε-caprolactone. For example, a polyester that can be obtained by polymerizing ε-caprolactone and a saturated fatty acid. Moreover, the polyester chain which is a side chain may have a carboxyl group at the terminal.

  (E) As another polymer, each amino group-containing (meth) acrylate monomer, ammonium group-containing (meth) acrylate monomer, and nitrogen exemplified in the copolymers (A) to (C). A homopolymer obtained by polymerizing any nitrogen-containing monomer among the monomers having a containing heterocyclic group is exemplified.

  In the organic degradation product removing agent of the present invention, these polymers may be used alone or in combination.

The amine compound contained in the organic degradation product removing agent of the present invention is a secondary amine compound or a tertiary amine compound represented by the following chemical formula (1).
R ¹ R ² R ³ N (1)

R ¹ is a linear, branched, or cyclic alkyl group having 8 to 22 carbon atoms. R ² is a hydrogen atom or a linear, branched, or cyclic alkyl group having 4 to 22 carbon atoms. R ³ is a hydrogen atom or a linear, branched, or cyclic alkyl group having 4 to 22 carbon atoms. R ^{1 to} R ³ may be the same or different. However, if both of R ² and R ³ as primary amine compound is a hydrogen atom is removed, if one in R ² and R ³ is a hydrogen atom and the other is an alkyl group.

The alkyl group of R ¹ and R ^{2 to} R ³ may have a substituent as long as it has an alkyl group having 8 to 22 carbon atoms and 4 to 22 carbon atoms, specifically, carbon residue. It may have a non-adsorptive substituent other than the adsorptive substituent such as a carboxyl group contained in. Examples of non-adsorbing substituents include hydrocarbon groups such as linear, branched, or cyclic alkyl groups, phenyl groups, acyl groups, alkyloxy groups, benzoyl groups, polyoxyalkylene alkyl ether groups, Examples include a heterocyclic group, a hydroxyl group, a silanol group, a perfluoroalkyl group, and a halogen atom such as a fluorine atom. These substituents are not included in the above carbon number.

  Examples of amine compounds include distearylamine, trioctylamine, N-pentyldioctylamine, dioctylamine, dibutyl-2-ethyl-hexylamine, triisooctylamine, tri (2-ethylhexyl) amine, didecylamine, didodecyl. Examples thereof include alkylamines such as amine, ditetradecylamine, dihexadecylamine, and dioleylamine.

  These secondary amine compounds or tertiary amine compounds have large steric hindrance unlike primary amine compounds, so that organic degradation products such as carbon debris adsorbed by amine groups are encased in these organic degradation products. A thing can be pulled apart and can be stably dispersed. In addition, the long chain alkyl group possessed by these amine compounds increases steric hindrance, so that the amine compound can be dispersed more stably. Since such amine compounds are small molecules, they easily adsorb organic degradation products, and also have long-chain alkyl groups, so they separate organic degradation products that have been adsorbed in the same manner as polymers that are low in molecular weight. While being stably dispersed.

  In the organic degradation product removing agent of the present invention, these amine compounds may be used alone or in combination. The amine compound contained in the organic degradation product remover preferably has an amine value of 30 to 450 mgKOH / g.

The method for measuring the amine value is as follows. The amine value refers to a value obtained by converting the amount of hydrochloric acid required to neutralize the total amount of primary, secondary and tertiary amines in 1 g of a sample into mg of caustic potash. First, a sample was weighed in a 100 ml Erlenmeyer flask, and a neutral mixed solvent, for example, a mixed solution of xylene / isopropyl alcohol = 8/2 (volume ratio) was used immediately before use with phenolphthalein as an indicator, and 0.1 mol / dm ³ Perform neutralization titration with ethanol potassium hydroxide solution and dissolve using neutralized neutral solvent. Next, bromcresol green is used as an indicator, titrated with 0.2 mol / dm ³ ethanolic hydrochloric acid, neutralized titration, and the point where the color changes from green to yellow is the end point. From the 0.2 mol / dm ³ ethanolic hydrochloric acid titration amount required for neutralization, the amine value is calculated using the following formula.

Amine number = (11.22 × A × f) / S
A: 0.2 mol / dm ³ ethanolic hydrochloric acid use amount (ml)
f: 0.2 mol / dm factor of ³ ethanolic hydrochloric acid S: sampling amount (g)

  The organic degradation product removing agent of the present invention may be composed only of a nitrogen-containing substance that is a polymer or an amine compound, and may contain other nitrogen-containing organic compounds or additives. The organic degradation product removing agent may consist of only a polymer or an amine compound, or may consist only of a mixture of a polymer and an amine compound. The weight ratio of the polymer to the amine compound in the nitrogen-containing material is preferably 2-8: 8-2. The organic degradation product removing agent is a small molecule having a low molecular weight of less than 1 μm with respect to an organic degradation product that could not adsorb a polymer having a high molecular weight and a macromolecule by including a polymer and an amine compound. Since the amine compound is adsorbed, the adsorptivity, dispersibility, and stability can be further improved by a synergistic effect.

  The organic degradation product removing agent may be a mixture containing an activator, a resin, and the like in addition to a nitrogen-containing substance that is a polymer or an amine compound. Further, the organic degradation product removing agent may be in the form of a solution dissolved in an inert solvent. The organic degradation product removing agent may be diluted at an arbitrary concentration, and is preferably diluted at a concentration of 10% to 90%.

  The inert solvent is an organic solvent miscible with the lubricant. Specific examples of the organic solvent include aromatic solvents such as xylene, Solvesso 100 and Solvesso 150; ketone solvents such as methyl isobutyl ketone; ethyl acetate Ester solvents such as butyl acetate; cellosolv solvents such as butyl cellosolve and ethyl cellosolve; propylene glycol solvents such as propylene glycol monomethyl ether; cellosolve acetate solvents such as ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether acetate and the like Examples include propylene glycol monoalkyl ether acetate solvents. Further, water, a solvent miscible with water, or an alcohol solvent such as ethanol or isopropanol can be used. These inert solvents may be used alone or in combination.

  The lubricant of the present invention comprises 2 to 20 parts by weight of an organic degradation product removing agent, 80 to 98 parts by weight of a lubricating component exemplified by polyolefin and fatty acid ester, and an antioxidant and an antifoaming agent as necessary. 1 to 5 parts by weight of such a third component is contained.

  This lubricant is exposed to harsh physical environment of high temperature and high pressure, exposed to harsh mechanical environment such as rotation, agitation, vibration, etc., or exposed to harsh chemical environment that contacts chemical substances. Even so, it is possible to disperse in the lubricant, such as carbon debris and sludge generated by thermal, mechanical and chemical alteration and oxidation. Therefore, the lubricant does not cause aggregation, precipitation, and accumulation of these deteriorated products in the lubricant, so that the life of the lubricant can be extended. As a result, it is possible to reduce the replacement frequency of the lubricant and reduce the consumption of the mechanical device using the lubricant and its components.

  The organic degradation product removing agent to which the present invention is applied is shown in Examples 1 to 15, and the comparative removing agent that is not applied to the present invention is shown in Comparative Examples 1 to 7.

Example 1
50 parts by weight of xylene was put in an apparatus equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, and the liquid temperature was kept at 100 ° C. Under nitrogen atmosphere, 20 parts by weight of ethyl acrylate, 10 parts by weight of macromonomer AA-6 (methyl methacrylate macromonomer, manufactured by Toa Gosei Chemical Co., Ltd.), light ester DM (dimethylaminoethyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) 20 A mixed solution of parts by weight, 0.5 parts by weight of dodecyl mercaptan and 1 part by weight of azobisisobutyronitrile was added dropwise to xylene over about 3 hours. After completion of the dropwise addition, 0.5 parts by weight of azobisisobutyronitrile was further added and reacted at 100 ° C. for 2 hours to synthesize a methacrylic copolymer.

  About the obtained copolymer, the gel permeation chromatography which can isolate | separate the molecule | numerator of a different molecular weight was eluted for every molecular weight on the following conditions, and the molecular weight distribution was calculated | required. The column was manufactured by Showa Denko KK and used by connecting two product names SB-806HQ and one SB-802.5HQ. The elution solvent was used by dissolving 10 mM LiBr in N, N-dimethylformamide (DMF). A calibration curve was previously obtained from a polyethylene glycol standard substance having a known molecular weight, and the weight average molecular weight of the copolymer was determined by comparison with the molecular weight distribution of the copolymer. As a result, an organic degradation product removing agent having a weight average molecular weight (Mw) of 43,000 in terms of polyethylene glycol was obtained. The amine value was 71 mg KOH / g.

(Example 2)
The composition of the mixed solution dropped into xylene is 20 parts by weight of 2-ethylhexyl methacrylate, 10 parts by weight of methoxydiethylene glycol methacrylate, 10 parts by weight of macromonomer AB-6 (butyl acrylate macromonomer, manufactured by Toagosei Co., Ltd.), light ester DM (Dimethylaminoethyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) 10 parts by weight, dodecyl mercaptan 1 part by weight, azobisisobutyronitrile 1 part by weight, and the other conditions were the same as in Example 1 to obtain a methacrylic copolymer. Synthesized. As a result of measuring the weight average molecular weight in the same manner as in Example 1, an organic degradation product remover having a methacrylic copolymer having a weight average molecular weight of 21,000 was obtained. The amine value was 36 mgKOH / g.

(Example 3)
The composition of the mixed solution dropped into xylene is 10 parts by weight of butyl methacrylate, 10 parts by weight of macromonomer AA-6 (methyl methacrylate macromonomer, manufactured by Toa Gosei Chemical Co., Ltd.), light ester DM (dimethylaminoethyl methacrylate, Kyoeisha Chemical Co., Ltd.) 10 parts by weight (made by company), 20 parts by weight dimethylaminoethyl methacrylate, 2.5 parts by weight dodecyl mercaptan, and 1 part by weight azobisisobutyronitrile. Was synthesized. As a result of measuring the weight average molecular weight in the same manner as in Example 1, an organic degradation product remover having a weight average molecular weight of 14,000 of the methacrylic copolymer was obtained. The amine value was 36 mgKOH / g.

Example 4
An apparatus equipped with a reflux condenser, a thermometer, and a stirrer is charged with 60 parts by weight of lauric acid, 500 parts by weight of ε-caprolactone (manufactured by Daicel Chemical Industries, Ltd .: Plaxel M), and 0.2 parts by weight of tetrabutyl titanate. The polyester oligomer was synthesized by reacting at 180 ° C. for 8 hours in a nitrogen atmosphere. To this, 56 parts by weight of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd .: SP-006) was added as polyimine, and reacted at 180 ° C. By reacting for 8 hours, a yellow wax-like organic degradation product remover was obtained. As a result of measuring the weight average molecular weight in the same manner as in Example 1, an organic degradation product removing agent having a polymer weight average molecular weight of 25,000 was obtained. The amine value was 65 mgKOH / g.

(Example 5)
An apparatus equipped with a reflux condenser, a thermometer, and a stirrer is charged with 90 parts by weight of stearic acid, 500 parts by weight of ε-caprolactone (Daicel Chemical Industries, Ltd .: Plaxel M), and 0.2 parts by weight of tetrabutyl titanate. The polyester oligomer was synthesized by reacting at 180 ° C. for 8 hours in a nitrogen atmosphere. To this, 59 parts by weight of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd .: SP-006) was added as polyimine and reacted at 180 ° C. By reacting for 8 hours, a yellow wax-like organic degradation product remover was obtained. As a result of measuring the weight average molecular weight in the same manner as in Example 1, an organic degradation product removing agent having a polymer weight average molecular weight of 23,000 was obtained. The amine value was 64 mg KOH / g.

(Example 6)
An apparatus equipped with a reflux condenser, a thermometer, and a stirrer is charged with 90 parts by weight of lauric acid, 700 parts by weight of ε-caprolactone (manufactured by Daicel Chemical Industries, Ltd .: Plaxel M), and 0.2 parts by weight of tetrabutyl titanate. The polyester oligomer was synthesized by reacting at 180 ° C. for 8 hours in a nitrogen atmosphere. 79 parts by weight of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd .: SP-018) was added as polyimine and reacted at 180 ° C. By reacting for 8 hours, a yellow wax-like organic degradation product remover was obtained. As a result of measuring the weight average molecular weight in the same manner as in Example 1, an organic degradation product remover having a polymer weight average molecular weight of 32,000 was obtained. The amine value was 78 mgKOH / g.

(Example 7)
50 parts by weight of xylene was put in an apparatus equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, and the liquid temperature was kept at 100 ° C. Under nitrogen atmosphere, 20 parts by weight of ethyl acrylate, 10 parts by weight of macromonomer AA-6 (methyl methacrylate macromonomer, manufactured by Toa Gosei Chemical Co., Ltd.), 20 parts by weight of 2-vinylpyridine (manufactured by Organic Synthetic Chemical Industry Co., Ltd.) A mixed solution of 0.5 parts by weight of dodecyl mercaptan and 1 part by weight of azobisisobutyronitrile was dropped into xylene over about 3 hours. After completion of the dropwise addition, 0.5 part by weight of azobisisobutyronitrile was further added and reacted at 100 ° C. for 2 hours to synthesize a methacryl / vinyl copolymer. As a result of measuring the weight average molecular weight in the same manner as in Example 1, an organic degradation product removing agent having a weight average molecular weight of 27,000 of the methacryl / vinyl copolymer was obtained. The amine value was 107 mgKOH / g.

(Example 8)
The composition of the mixed solution dropped into xylene is 20 parts by weight of 2-ethylhexyl methacrylate, 10 parts by weight of methoxydiethylene glycol methacrylate, 10 parts by weight of macromonomer AB-6 (butyl acrylate macromonomer, manufactured by Toagosei Co., Ltd.), 2-vinyl A methacryl / vinyl copolymer was prepared in the same manner as in Example 7 except that 10 parts by weight of pyridine (manufactured by Organic Synthetic Chemical Industry Co., Ltd.), 1 part by weight of dodecyl mercaptan and 1 part by weight of azobisisobutyronitrile were used. Synthesized. As a result of measuring the weight average molecular weight in the same manner as in Example 1, an organic degradation product removing agent having a weight average molecular weight of 23,000 of the methacryl / vinyl copolymer was obtained. The amine value was 53 mg KOH / g.

Example 9
50 parts by weight of xylene was put in an apparatus equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, and the liquid temperature was kept at 100 ° C. Under a nitrogen atmosphere, ethyl acrylate 20 parts by weight, macromonomer AA-6 (methyl methacrylate macromonomer, manufactured by Toa Gosei Chemical Co., Ltd.) 10 parts by weight, 1-vinylimidazole (manufactured by BASF Japan Ltd.) 20 parts by weight, dodecyl A mixed solution of 0.5 part by weight of mercaptan and 1 part by weight of azobisisobutyronitrile was added dropwise to xylene over about 3 hours. After completion of the dropwise addition, 0.5 part by weight of azobisisobutyronitrile was further added and reacted at 100 ° C. for 2 hours to synthesize a methacryl / vinyl copolymer. As a result of measuring the weight average molecular weight in the same manner as in Example 1, an organic degradation product remover having a weight average molecular weight of 25,000 of the methacryl / vinyl copolymer was obtained. The amine value was 120 mgKOH / g or less.

(Example 10)
The composition of the mixed solution dropped into xylene is 20 parts by weight of 2-ethylhexyl methacrylate, 10 parts by weight of methoxydiethylene glycol methacrylate, 10 parts by weight of macromonomer AB-6 (butyl acrylate macromonomer, manufactured by Toagosei Co., Ltd.), 1-vinyl A methacryl / vinyl copolymer was synthesized in the same manner as in Example 9 except that 10 parts by weight of imidazole (BASF Japan Ltd.), 1 part by weight of dodecyl mercaptan and 1 part by weight of azobisisobutyronitrile were used. . As a result of measuring the weight average molecular weight in the same manner as in Example 1, an organic degradation product remover having a weight average molecular weight of 24,000 for the methacryl / vinyl copolymer was obtained. The amine value was 58 mgKOH / g.

(Example 11)
Weigh out 50 parts by weight of distearylamine and 50 parts by weight of mineral spirit, and stir and mix in a flask equipped with a reflux tube, a stirring motor, a stirring blade, and a heater for 3 hours at 60 ° C. to remove organic degradation products Got. The amine value was 57 mgKOH / g.

Example 12
Weigh 20 parts by weight of trioctylamine, 30 parts by weight of dioleylamine, and 50 parts by weight of mineral spirit, and stir and mix in a flask equipped with a reflux tube, a stirring motor, stirring blades and a heater for 3 hours at 60 ° C. And an organic degradation product remover was obtained. The amine value was 65 mgKOH / g.

(Example 13)
In a flask equipped with a reflux tube, a stirring motor, a stirring blade, and a heater, weighed 30 parts by weight of the organic degradation product removing agent obtained in Example 1, 20 parts by weight of dioctylamine, and 50 parts by weight of mineral spirit. The mixture was stirred and mixed at 60 ° C. for 3 hours to obtain an organic degradation product remover. The amine value was 68 mgKOH / g.

(Example 14)
Weigh out 20 parts by weight of the organic degradation product remover obtained in Example 2, 30 parts by weight of distearylamine and 50 parts by weight of mineral spirit, and in a flask equipped with a reflux tube, a stirring motor, stirring blades, and a heater. The mixture was stirred and mixed at 60 ° C. for 3 hours to obtain an organic degradation product remover. The amine value was 42 mgKOH / g.

(Example 15)
Weigh out 30 parts by weight of the organic degradation product remover obtained in Example 4, 20 parts by weight of distearylamine and 50 parts by weight of mineral spirit, and in a flask equipped with a reflux tube, a stirring motor, a stirring blade, and a heater. The mixture was stirred and mixed at 60 ° C. for 3 hours to obtain an organic degradation product remover. The amine value was 42 mgKOH / g.

(Comparative Example 1)
The composition of the mixed solution dropped into xylene is 25 parts by weight of butyl methacrylate, 10 parts by weight of light ester DQ-100 (quaternized dimethylaminoethyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.), 15 parts by weight of dimethylaminoethyl methacrylate, dodecyl mercaptan 2 The copolymer was synthesized in the same manner as in Example 1 except that 0.5 part by weight and 1 part by weight of azobisisobutyronitrile were used, and a comparative remover was obtained. The weight average molecular weight of the copolymer was 18,000. The amine value was 1 mgKOH / g or less.

(Comparative Example 2)
The composition of the mixed solution dropped into xylene is 25 parts by weight of butyl methacrylate, 10 parts by weight of 2-vinylpyridine, 15 parts by weight of dimethylaminoethyl methacrylate, 2.5 parts by weight of dodecyl mercaptan, and 1 part by weight of azobisisobutyronitrile. A copolymer was synthesized under the same conditions as in Example 1 to obtain a comparative remover. The weight average molecular weight of the copolymer was 19,000. The amine value was 52 mgKOH / g.

(Comparative Example 3)
The composition of the mixed solution dropped into xylene is 25 parts by weight of butyl methacrylate, 10 parts by weight of 1-vinylimidazole, 15 parts by weight of dimethylaminoethyl methacrylate, 2.5 parts by weight of dodecyl mercaptan, and 1 part by weight of azobisisobutyronitrile. A copolymer was synthesized under the same conditions as in Example 1 to obtain a comparative remover. The weight average molecular weight of the copolymer was 20,000. The amine value was 120 mgKOH / g.

(Comparative Example 4)
Polyester oligomer is charged with 800 parts by weight of hydroxystearic acid and 0.2 parts by weight of tetrabutyl titanate in an apparatus equipped with a reflux condenser, a thermometer, and a stirrer, and subjected to a dehydration condensation reaction at 180 ° C. for 8 hours in a nitrogen atmosphere. Was synthesized. To this, 75 parts by weight of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd .: SP-012) was added as polyimine, and reacted at 180 ° C. A yellow soft wax-like comparative removal agent was obtained by reacting for 8 hours. As a result of measuring the weight average molecular weight in the same manner as in Example 1, a comparative removal agent having a weight average molecular weight of 21,000 was obtained. The amine value was 75 mgKOH / g.

(Comparative Example 5)
Monoisopropanolamine was used as an amino alcohol and used as a comparative removal agent.

(Comparative Example 6)
As a succinimide derivative, alkenisuccin monoimide (Nippon Lubrizol Corporation: Lubrizol 6406) was used as a comparative removal agent.

(Comparative Example 7)
Weigh out 50 parts by weight of 1,6-diaminohexane and 50 parts by weight of mineral spirit, and stir and mix in a flask equipped with a reflux tube, a stirring motor, stirring blades, and a heater for 3 hours at 60 ° C. for comparative removal. An agent was obtained. The amine value was 484 mgKOH / g.

  The performance test of each removal agent obtained in the Examples and Comparative Examples was performed.

(Adjustment of lubricant composition)
500 parts by weight of DOS (dioctyl sebacate (2-ethylhexyl)) and 500 parts by weight of polyolefin (Idemitsu Kosan Co., Ltd .: Linearlen PAO V-50) were weighed into a 2 L beaker, and using a disper with a blade diameter of 8 cm at 1500 rpm, Stir for 30 minutes. The obtained mixture was used as a lubricant composition (lubricant component).

(Carbon debris (carbon black) removal test)
Carbon debris, which is an oxidized deterioration product generated by oxidation of a lubricant exposed to high temperature under an atmospheric gas, or a model material of a compound generated under incomplete combustion of organic matter, carbon debris removal test Carried out. In a 140 ml glass bottle, 80 parts by weight of the lubricant composition, 12 parts by weight of normal hexane, 5 parts by weight of carbon black (Mitsubishi Chemical Co., Ltd .: # 25), 3 parts by weight of each remover of Examples and Comparative Examples are weighed. A carbon black dispersion test sample was prepared by mixing for 10 minutes at 3000 rpm with a blade diameter 4 cm disper. The dispersion sample was allowed to stand at room temperature for 7 days and then visually evaluated based on the following evaluation criteria for the presence or absence of carbon black sedimentation.
A: No sediment (removability is very good)
○: Sediment is very small (removability is good)
Δ: Precipitate is present (removability is slightly poor)
×: Many precipitates (poor removability)

(Carbon waste (resin oxidation degradation product) removability test)
As a carbon debris model substance of oxidation degradation products generated by oxidizing the lubricant with atmospheric gas, a resin oxidation degradation product in which methacrylic (MMA) resin is maintained at a high temperature in a nitrogen atmosphere is substituted, and a resin oxidation degradation product removal test is performed. Carried out. An MMA resin (manufactured by Mitsubishi Chemical Corporation: ACRYPET VH) was held at 350 ° C. for 3 hours in a nitrogen atmosphere to obtain an oxidized and deteriorated resin that is an organic substance that was oxidized and deteriorated. Into a 50 ml glass bottle, 0.1 g of the above-mentioned resin oxidative degradation product, 20 g of mineral spirits, and 0.05 g of each removing agent of Examples and Comparative Examples were added to obtain an oxidative degradation product dispersion test sample. The dispersion sample was stirred for 10 minutes using a paint shaker, allowed to stand at room temperature for 7 days, and then visually evaluated based on the following evaluation criteria for the presence or absence of oxidation degradation products.
A: No sediment (removability is very good)
○: Sediment is very small (removability is good)
Δ: Precipitate is present (removability is slightly poor)
×: Many precipitates (poor removability)

(Sludge removal test)
As a model material for sludge, which is an insoluble matter generated by thermal decomposition products and foreign matter contamination of lubricant components, heavy oil containing residual impurities obtained from crude oil distillate with high viscosity and various impurities was used. A sludge dispersion test sample was prepared by adding 0.1 g of heavy oil, 20 g of mineral spirit, and 0.05 g of each removing agent of Examples and Comparative Examples to a 50 ml glass bottle. The dispersion sample was stirred for 10 minutes using a paint shaker, allowed to stand at room temperature for 7 days, and then visually evaluated for the presence or absence of sludge sedimentation based on the following evaluation criteria.
A: No sediment (removability is very good)
○: Sediment is very small (removability is good)
Δ: Precipitate is present (removability is slightly poor)
×: Many precipitates (poor removability)

(Evaluation results)
Examples of the organic degradation product removing examples 1 to 15 to which the present invention is applied, and carbon black, resin oxidation degradation products, and sludge to which the comparative removal agents 1 to 7 of the comparative removal agent not applied to the present invention are added Table 1 shows the test results of the removal test.

  From Table 1, it can be seen that the organic degradation product removing agents of Examples 1 to 15 to which the present invention is applied have good evaluation of carbon black, resin oxidation degradation product, and sludge removability test and do not cause sedimentation of the removal target. It became clear. In particular, the organic degradation product removing agents of Examples 13 to 15 including the polymer and the amine compound exhibit extremely good removability with respect to all organic degradation products of carbon black, resin oxidation degradation product, and sludge, It became clear that it had excellent removability with respect to various organic degradation products. On the other hand, the organic deterioration product removing agents of Comparative Examples 1 to 7 to which the present invention is not applied are defective or slightly defective in all the removability of carbon black, resin oxidation deterioration products, and sludge, and precipitates to be removed. Many were detected. The organic degradation product removing agent of the present invention can remove various organic degradation products. For example, even if a plurality of organic degradation products having different sizes, types, properties, etc. are mixed, adsorbability, dispersibility It can show excellent removability without impairing stability and can be used for general purposes.

  The organic degradation product removing agent of the present invention can be used by being added to various lubricants, and is widely used for removing organic degradation products such as degradation products and insolubles of lubricants composed of organic materials. . Further, the lubricant containing the organic degradation product removing agent is used for mechanical devices and parts thereof that rub against each other.

Claims (14)

A nitrogen-containing polymer obtained by polymerizing a nitrogen-containing monomer having at least one nitrogen-containing group and an unsaturated group selected from an amino group, an ammonium group, and a nitrogen-containing heterocyclic group, and an imine monomer are polymerized. A polymer having at least one of a nitrogen-containing polymer having an imino group as a nitrogen-containing group and having a weight average molecular weight of 300 to 100,000, and the following chemical formula (1)
R ¹ R ² R ³ N (1)
Wherein R ¹ is an alkyl group having 8 to 22 carbon atoms, R ² is a hydrogen atom or an alkyl group having 4 to 22 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 4 to 22 carbon atoms, provided that R Except when both ² and R ³ are hydrogen atoms.)
Amine compound represented by
An organic degradation product remover comprising: a nitrogen-containing material comprising : a weight ratio of the polymer to the amine compound of 2 to 8: 8 to 2 .   The nitrogen-containing monomer is at least one selected from an amino group-containing (meth) acrylate monomer, an ammonium group-containing (meth) acrylate monomer, and a monomer having a nitrogen-containing heterocyclic group. The organic deterioration removing agent according to claim 1, wherein:   The organic degradation product removing agent according to claim 1, wherein the polymer is a copolymer of the nitrogen-containing monomer and the nitrogen-free monomer.   The nitrogen-free monomer is at least one selected from a saturated or unsaturated, unsubstituted, hydroxy-substituted, or glycol or polyglycol group-substituted (meth) acrylate monomer, and a macromonomer. The organic degradation product remover according to claim 3.   10 to 60 parts by weight of the nitrogen-containing monomer, and 10 to 85 parts by weight of a saturated or unsaturated, unsubstituted or hydroxy-substituted or glycol or polyglycol group-substituted (meth) acrylate monomer. The organic degradation product removing agent according to any one of claims 1 to 3, which is a copolymer of 5 parts by weight and 5 to 30 parts by weight of a macromonomer. The nitrogen-containing monomer is
The following chemical formula (2)

(Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ and R ⁶ are each independently the same or different, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is a positive number of 2 to 8). An amino group-containing (meth) acrylate monomer represented,
The following chemical formula (3)

(Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁷ , R ⁸ and R ⁹ are each independently different, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, and 1 carbon atom) to 4 alkoxyalkyl group, a cycloalkyl group, an aralkyl group, a phenyl group, the other phenyl group atom-substituted, X ^- is an anion residue of halide ions or acid, m is a positive number of 2 to 8 ) Ammonium group-containing (meth) acrylate monomer represented by
Or
The following chemical formula (4)

Or the following chemical formula (5)

The organic degradation product removing agent according to claim 1, which is a monomer having a nitrogen-containing heterocyclic group represented by the formula:   The polymer is an amino group-containing (meth) acrylate monomer and / or an ammonium group-containing (meth) acrylate monomer, saturated or unsaturated, unsubstituted, hydroxy-substituted, or glycol group or polyglycol group-substituted ( The organic material according to any one of claims 1 to 6, which is a copolymer obtained by copolymerizing a meth) acrylate monomer and a macromonomer to have a weight average molecular weight of 4,000 to 100,000. Deteriorating agent remover.   In the polymer, a monomer having a nitrogen-containing heterocyclic group, a saturated or unsaturated, unsubstituted or hydroxy-substituted or glycol or polyglycol group-substituted (meth) acrylate monomer, and a macromonomer The organic degradation product removing agent according to any one of claims 1 to 7, which is a copolymer obtained by polymerization and having a weight average molecular weight of 4,000 to 100,000. The polymer is a nitrogen-containing polymer in which the imine monomer is polymerized and an imino group is a nitrogen-containing group, and is formed of a polyester oligomer having a weight average molecular weight derived from ε-caprolactone of 500 to 4,000. A side chain and a repeating unit comprising a main chain formed of polyimine having a weight average molecular weight of 300 to 40,000, and the composition weight ratio of the side chain to the main chain is 80:20 to 97: 3, the following chemical formula (6a)

(Wherein R ¹⁰ is an alkyl chain having 1 to 4 carbon atoms) and the following chemical formula (6b)

(Wherein R ¹⁰ is the same as described above, Q is the same or different for each repeating unit, and the following chemical formula (7)

(Wherein R ¹¹ is an alkyl chain having 7 to 17 carbon atoms, R ¹² is an alkylene chain having 2 to 5 carbon atoms, and u = 5 to 15) or a hydrogen atom, A repeating unit T represented by (at least one of the repeating units is the side chain group), and the repeating unit S: the repeating unit T = 1. The organic degradation product removing agent according to claim 1, wherein the repeating unit S and the repeating unit T are contained in an amount of 1 to 2: 1 and 10 to 500, respectively.   The polymer includes the nitrogen-containing monomer, an alkyl (meth) acrylate containing an alkyl group having 1 to 18 carbon atoms, an alkenyl (meth) acrylate containing an alkenyl group having 2 to 18 carbon atoms, carbon Hydroxyalkyl (meth) acrylates containing 2 to 4 alkyl groups, alkyl monoalkylene glycol (meth) acrylates and / or alkyl polyalkylene glycol (meth) acrylates containing alkyl groups of 1 to 18 carbon atoms , Alkenyl monoalkylene glycol (meth) acrylates and / or alkenyl polyalkylene glycol (meth) acrylates containing an alkenyl group having 1 to 18 carbon atoms, and alkyl alkenyl mono containing an alkyl alkenyl group having 1 to 18 carbon atoms Alkylene glycol ( (Ii) At least any saturated or unsaturated, unsubstituted or hydroxy-substituted or glycol or polyglycol group-substituted (meth) acrylate monomer selected from acrylates and / or alkylalkenyl polyalkylene glycol (meth) acrylates The organic degradation product removing agent according to any one of claims 1 to 8, wherein   The polymer includes the nitrogen-containing monomer, a terminal (meth) acryloyl group-containing polyalkyl (meth) acrylate macromonomer, a terminal (meth) acryloyl group-containing polyalkenyl (meth) acrylate macromonomer, and a terminal (meth) acryloyl. The organic material according to any one of claims 1 to 8, which is a copolymer with at least one macromonomer selected from a group-containing polyester macromonomer and a terminal (meth) acryloyl group-containing polystyrene macromonomer. Deteriorating agent remover. Organic deterioration removal agent according to any one of claims 1 to 11, characterized in that the amine value before Symbol amine compound 30~450mgKOH / g. A lubricant comprising the organic degradation product remover according to any one of claims 1 to 12 and a lubricating component. 14. The lubricant according to claim 13, comprising 2 to 20 parts by weight of the organic degradation product remover and 80 to 98 parts by weight of the lubricating component selected from polyolefin and fatty acid ester.