JPS63162789A - Grease composition - Google Patents
Grease compositionInfo
- Publication number
- JPS63162789A JPS63162789A JP30890486A JP30890486A JPS63162789A JP S63162789 A JPS63162789 A JP S63162789A JP 30890486 A JP30890486 A JP 30890486A JP 30890486 A JP30890486 A JP 30890486A JP S63162789 A JPS63162789 A JP S63162789A
- Authority
- JP
- Japan
- Prior art keywords
- grease
- type
- micelles
- present
- lubricating oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004519 grease Substances 0.000 title claims abstract description 88
- 239000000203 mixture Substances 0.000 title claims description 34
- 239000000693 micelle Substances 0.000 claims abstract description 64
- 239000002562 thickening agent Substances 0.000 claims abstract description 30
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- -1 diurea compound Chemical class 0.000 claims abstract description 12
- 239000010687 lubricating oil Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 230000009466 transformation Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000001050 lubricating effect Effects 0.000 abstract description 6
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 abstract description 6
- XMKLTEGSALONPH-UHFFFAOYSA-N 1,2,4,5-tetrazinane-3,6-dione Chemical compound O=C1NNC(=O)NN1 XMKLTEGSALONPH-UHFFFAOYSA-N 0.000 abstract description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000003405 preventing effect Effects 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 22
- 238000005461 lubrication Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- 238000010008 shearing Methods 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 7
- 235000010446 mineral oil Nutrition 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、まったく新しい概念に基づく新規なグリース
組成物に関するもので、更に特に今までにない新しい存
効な機能を有し、かつ優れた潤滑特性を有するグリース
組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel grease composition based on a completely new concept, and more particularly, it has unprecedented new and effective functions and excellent The present invention relates to a grease composition having lubricating properties.
本発明のグリース組成物は潤滑剤として、今まで不満足
ながら止むを得ず使用されている箇所でも基本的に優れ
た潤滑を行ないうる、省資源、省エネルギー、省力化が
可能な新しい型の有用なグリース組成物である。The grease composition of the present invention is a new type of useful lubricant that can basically provide excellent lubrication even in places where it has been used unsatisfactorily but unavoidably, and can save resources, energy, and labor. It is a grease composition.
（従来の技術）
従来、潤滑に使用されるグリース組成物としては、数多
くの種類のものが実用化されている。グリースは半固体
であるため、潤滑油による潤滑（油潤滑）に較べ多くの
利点があり、軸受をはじめ多くの産業機械や装置の潤滑
に使用されている。(Prior Art) Conventionally, many types of grease compositions used for lubrication have been put into practical use. Since grease is a semi-solid, it has many advantages over lubrication with lubricating oil (oil lubrication), and is used to lubricate many industrial machines and devices including bearings.
グリースによる潤滑（グリース潤滑）が油潤滑に較べ、
最も有利な点は半固体であることから、潤滑している箇
所やその周辺によく付着し、飛散することがなく、シー
ルの機構が簡単で良いことであり、また、外部からの異
物の混入を防ぐことも有利な点である。かように、グリ
ースは半固体であることが不可欠であるが、従来より使
用されているグリースは、潤滑部の剪断により、グリー
ス中の増ちょう剤ミセルは徐々に切断されて、増ちょう
能力が低下し、軟化、さらには液状化してしまう。従来
のグリースは、この潤滑部での剪断による切断に対する
抵抗力を向上させることで対処して来た。また、金属石
けんを増ちょう剤としたグリースには、基油の劣化に対
して触媒作用があり、化学劣化による軟化、液状化の問
題もある。かように、グリースの軟化、液状化を防止す
ることには限度があり、最近の産業機械や装置における
めざましい技術革新に伴うグリースへの要求性能に対応
することは難しく、新しい型のグリースの開発が切望さ
れて来た。Lubrication with grease (grease lubrication) is more effective than oil lubrication.
The most advantageous point is that since it is semi-solid, it adheres well to the lubricated area and its surroundings, does not scatter, has a simple sealing mechanism, and prevents foreign matter from entering from the outside. It is also advantageous to prevent As described above, it is essential that grease be semi-solid, but in the case of conventionally used greases, the thickener micelles in the grease are gradually cut off due to shearing of the lubricating part, resulting in a loss of thickening ability. It will drop, soften, and even liquefy. Conventional greases have addressed this problem by increasing their resistance to shear cuts in the lubricated zone. Furthermore, greases that use metal soap as a thickener have a catalytic effect on the deterioration of the base oil, and there is also the problem of softening and liquefaction due to chemical deterioration. As described above, there is a limit to the ability to prevent grease from softening and liquefying, and it is difficult to meet the performance requirements for grease that come with recent remarkable technological innovations in industrial machinery and equipment, so it is difficult to develop new types of grease. has been desperately needed.
（発明が解決しようとする問題点）
かかる要求性能を満足するものとして提案された新しい
タイプのグリースとしては、本出願人らが既に特公昭５
１−９６５号公報に開示した「グリース組成物」などの
新しい増ちょう剤を含有するものや、同特開昭５７−４
８０６９８号公報の「潤滑用グリース組成物」の様に新
しい機能を有するグリース及びその製造法等がある。こ
の様な優れたグリースにおいても、先に述べた最近のグ
リースへの厳しい要求に対して、必ずしも十分とは言え
ない。従って、より優れた潤滑特性を有する新しい型の
グリースの出現が望まれている。(Problems to be Solved by the Invention) As a new type of grease that has been proposed as one that satisfies such required performance, the present applicants have already reported
Products containing new thickeners such as the "grease composition" disclosed in Japanese Patent Publication No. 1-965,
There are greases with new functions and methods for producing the same, such as the "lubricating grease composition" disclosed in Japanese Patent No. 80698. Even with such excellent grease, it cannot be said that it is necessarily sufficient to meet the recent strict requirements for grease mentioned above. Therefore, it is desirable to develop a new type of grease with better lubrication properties.
本発明は新しい機能をもち、その優れた潤滑特性により
、厳しい潤滑条件下で、長寿命、摩耗防止゛の特徴を有
するあらゆる潤滑箇所に適用し得るグリース組成物を提
供することを目的とする。The object of the present invention is to provide a grease composition which has new functions and can be applied to all lubrication points under severe lubrication conditions, has long service life and anti-wear characteristics due to its excellent lubrication properties.
（問題点を解決するための手段）
上記目的を満足する本発明のグリース組成物は、潤滑油
と、２つのウレア結合が直線上に配置する化学構造を有
するジウレア化合物増ちょう剤からなり、潤滑油中での
増ちょう剤ミセルが２種の安定な構造を形成し得るよう
に、かつこの２種のミセルの変態がグリース中で物理条
件によって可逆的に起るように成らしめた上記増ちょう
剤を１〜３０重量％含有したことを特徴とする。(Means for Solving the Problems) The grease composition of the present invention, which satisfies the above objects, is composed of a lubricating oil and a diurea compound thickener having a chemical structure in which two urea bonds are arranged in a straight line. The above-mentioned thickener is made such that the thickener micelles in the oil can form two types of stable structures, and the transformation of the two types of micelles occurs reversibly depending on the physical conditions in the grease. It is characterized by containing 1 to 30% by weight of the agent.
（作 用）
グリース潤滑において、グリースは潤滑箇所への供給過
程、潤滑部やその周辺部での剪断や流動、それぞれの箇
所や過程での熱などいろいろな条件下にさらされる。こ
れらの条件は、著しく広範囲であり、特定の一つの状態
だけを呈するグリースで賄うことには無理がある。本発
明のグリースは、上記のグリースがさらされる広範囲な
条件で満足させるために、グリースに二つの安定な状態
を持たせ、かつ、その二つの状態が、グリースの使用条
件内で可逆的に変化し得る様にしたことで対処しようと
するものであり、この様な機能を有するグリースは今ま
でになく、本発明によって初めて提供されるものである
。本発明は、増ちょう剤の作用、ミセルの生成機構を鋭
意検討した結果、初めて成し得たものである。従来のグ
リースにおいて、製造工程では相転移やミセル形成など
が変化することは知られているが、最終の製品ではいず
れも一定の状態にすることに注意が払われており、変化
することは製品の品質がバラツクため好ましくないとさ
れて来た。しかし、本発明は先にも述べた様に、この変
化を積極的に有効利用するために、種々の増ちょう剤に
ついて、その増ちょう作用、ミセルの生成機構を詳細に
調べ、特定の化学構造を有し、特定のミセル状態のグリ
ースが、グリースの使用条件により可逆性の二つのグリ
ース状態を形成し得ることを明らかにしたことにより成
し得たものである。この可逆の変化は本発明の組成物に
特有のもので、従来のグリース組成物では、もし二つの
グリース状態が存在したとしても、いずれかの状態は不
安定か、非常に狭い条件でしか存在しないし、可逆性を
有することはない。(Function) During grease lubrication, grease is exposed to various conditions such as the process of supplying it to the lubricated area, shearing and flow in and around the lubricated area, and heat at each location and process. These conditions are extremely wide-ranging, and it is impossible to meet them with a grease that exhibits only one specific condition. In order to satisfy the wide range of conditions to which the grease is exposed, the grease of the present invention has two stable states, and these two states change reversibly within the conditions of use of the grease. The present invention is the first grease to have such a function. The present invention was achieved for the first time as a result of intensive study of the action of thickeners and the mechanism of micelle formation. It is known that in conventional greases, things such as phase transition and micelle formation change during the manufacturing process, but care is taken to maintain a constant state in the final product; It has been considered undesirable because of its variable quality. However, as mentioned earlier, in order to actively and effectively utilize this change, the present invention has investigated in detail the thickening action and micelle formation mechanism of various thickeners, and This was achieved by revealing that grease in a specific micellar state can form two reversible grease states depending on the conditions in which the grease is used. This reversible change is unique to the composition of the present invention; in conventional grease compositions, even if two grease states exist, one of the states is unstable or exists only under very narrow conditions. It is not reversible and is not reversible.
ウレア系のグリースとしては多くのものが知られており
、一部実用化されている。ウレア化合物はイソシアネー
ト基とアミノ基の重付加反応で合成され、イソシアネー
ト化合物とアミノ化合物（特にアミン）の組み合せによ
り、及びウレア基の数により多種多様のものが得られる
。グリースの増ちょう剤としては、イソシアネート類と
して、トリレンジイソシアネート、ジフェニルメタンジ
イソシアネート、トリジンジイソシアネート、ナフチレ
ンジイソシアネート等のジイソシアネート類、アミノ化
合物としては炭素数４〜■８のアルキルアミンやアニリ
ン、トルイジン等の芳香族アミン、シクロヘキシルアミ
ン等の脂環アミン、それらの誘導体等の第一級アミンか
らのジウレア化合物あるいは各種ジアミンを併用したテ
トラウレアやポリウレアが一般に用いられる。ウレア結
合が３つのトリウレア化合物やウレタン基を一部含有す
るウレア化合物なども使用されている。グリースの増ち
ょう剤としてはうレア基を一つもつモノウレア化合物が
使用されることはない。Many urea-based greases are known, and some are in practical use. Urea compounds are synthesized by polyaddition reaction of isocyanate groups and amino groups, and a wide variety of compounds can be obtained depending on the combination of isocyanate compounds and amino compounds (especially amines) and the number of urea groups. As thickeners for grease, diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, toridine diisocyanate, and naphthylene diisocyanate are used as thickeners for grease, and aromatic amino compounds such as alkylamines having 4 to 8 carbon atoms, aniline, toluidine, etc. Diurea compounds derived from primary amines such as group amines, alicyclic amines such as cyclohexylamine, and derivatives thereof, or tetraureas and polyureas in combination with various diamines are generally used. Triurea compounds having three urea bonds and urea compounds partially containing urethane groups are also used. Monourea compounds having one rea group are never used as thickeners for grease.
ウレア系のグリースは、増ちょう剤中に金属を含有せず
、石けんグリースで見られる金属の触媒作用による劣化
がなく、また、汎用的に使用されているリチウムグリー
スよりも高い滴点を有し、耐熱長寿命グリースとして、
一部ではリチウムグリース、アルミコンプレックスグリ
ースやカルシウムコンプレックスグリースに代って使用
されている。今後、より広く使用されて来るグリースの
一つと思われる。Urea-based grease does not contain metals in its thickener, does not deteriorate due to the catalytic action of metals that occurs in soap greases, and has a higher dropping point than the commonly used lithium grease. , as a heat-resistant, long-life grease.
In some cases, it is used in place of lithium grease, aluminum complex grease, and calcium complex grease. It is thought that this is one of the greases that will become more widely used in the future.
ウレア系グリースの全てが、本発明の特性を有するもの
ではなく、前述の潤滑油中での増ちょう剤ミセルが２種
の安定な構造を形成し得るように、かつこの２種のミセ
ルの変態がグリース中での物理条件によって可逆的に起
るという特性、機能をもつためには、２つのウレア結合
が直線に配置する化学構造であるジウレアグリースであ
ることが必須条件である。この条件は、ウレア系をはじ
め石けん系、非石けん系の多種の増ちょう剤の増ちょう
作用機構、ミセル生成機構を詳細に検討した結果、得ら
れたものであり、他のウレア系増ちょう剤、石けん系増
ちょう剤、非石けん系増ちょう剤では、この様な特性、
機能は認められないし、従来、本発明の様な観点から検
討されたものはなく、容易に類推することは出来なかっ
た。本発明のグリース組成物が、かような特性、機能を
もつ理由としては、まだ十分には解明されたとは言えな
いが、おおむね次の通りであると思われる。Not all urea-based greases have the characteristics of the present invention, and the above-mentioned thickener micelles in the lubricating oil can form two types of stable structures, and the transformation of these two types of micelles is necessary. In order to have the property and function that this occurs reversibly depending on the physical conditions in the grease, it is essential that the diurea grease has a chemical structure in which two urea bonds are arranged in a straight line. These conditions were obtained as a result of a detailed study of the thickening action mechanism and micelle formation mechanism of various types of thickeners, including urea-based and soap-based and non-soap-based thickeners. , soap-based thickeners, and non-soap-based thickeners have these characteristics,
No function has been recognized, and nothing has been studied from the perspective of the present invention so far, and it has not been possible to easily make an analogy. Although the reason why the grease composition of the present invention has such characteristics and functions has not yet been fully elucidated, it is believed to be roughly as follows.
本発明のグリース組成物中の増ちょう剤ミセルには、多
形現象が存在し、２つの安定状態があり、その２つの安
定度の差が非常に小さく、かつその２つの安定状態間の
遷移エネルギーも小さいと考えられる。２つの安定状態
をそれぞれ■型と■型として従来のグリース（１）、
（２）と比較すると第１図の様になると考える。The thickener micelles in the grease composition of the present invention exhibit polymorphism, have two stable states, the difference in stability between the two is very small, and the transition between the two stable states. The energy is also considered to be small. Conventional grease (1) with two stable states as ■ type and ■ type, respectively.
If we compare it with (2), we think that it will look like Figure 1.
第１図において曲線１は本発明のグリース組成物のエネ
ルギー準位、２はＩ型ミセル、３は■型ミセル、曲線４
．５は夫々、従来のグリース組成物（１）、 （２）の
エネルギー準位を示す。すなわち、従来のグリース組成
物（１）では曲線４の様にグリースとしての安定状態が
一つしかなく、または（２）では曲線５の様に二つの安
定なミセル状態はあっても遷移のエネルギーが極めて大
きく容易に一方のミセル状態から他方のミセル状態への
遷移が出来ない。しかし、本発明のグリース組成物では
、■型と■型のエネルギー準位に差が少な（、また遷移
するための遷移エネルギーも小さいために、■≠■の遷
移は容易に起ると考えられる。■型から■型、■型から
Ｉ型への遷移のメカニズムは明確ではないが、本発明の
グリース組成物において、■型から■型への遷移は熱、
■型からＩ型への遷移は機械的剪断であり水分、湿気に
よって加速されることが明らかになっている。増ちょう
剤として４．４′ −ジフェニルメタンジイソシアネー
トとｎ−オクチルアミンより合成したジウレア化合物と
、鉱物油（粘度１３０ｃｓ ｔ■４０°Ｃ）から調整し
たグリース中における、該増ちょう剤のＩ型ミセルと■
型ミセルの電子顕微鏡写真（倍率６０００）を第２図に
示す。第２図において（ａ）は■型ミセルの形状を示し
、（ｂ）は水によって遷移した■型ミセルの形状であり
、（Ｃ）は水及び機械的剪断により遷移したｒ型ミセル
の形状である。さらに（ｂ）、 （Ｃ）の■型ミセルに
熱を加えることにより（ｄ）の■型ミセルに遷移する。In FIG. 1, curve 1 is the energy level of the grease composition of the present invention, 2 is the I-type micelle, 3 is the ■-type micelle, and curve 4 is the energy level of the grease composition of the present invention.
．． 5 indicates the energy level of conventional grease compositions (1) and (2), respectively. In other words, in the conventional grease composition (1), there is only one stable state as a grease as shown in curve 4, or in (2) there are two stable micelle states as shown in curve 5, but the transition energy is low. is extremely large and cannot easily transition from one micelle state to the other. However, in the grease composition of the present invention, there is little difference between the energy levels of the ■ type and the ■ type (and the transition energy for the transition is also small, so it is thought that the ■≠■ transition occurs easily. Although the mechanism of the transition from ■ type to ■ type and from ■ type to I type is not clear, in the grease composition of the present invention, the transition from ■ type to ■ type is caused by heat,
It has been revealed that the transition from type ① to type I is caused by mechanical shearing and is accelerated by water and moisture. A diurea compound synthesized from 4.4'-diphenylmethane diisocyanate and n-octylamine as a thickener, and type I micelles of the thickener in a grease prepared from mineral oil (viscosity 130 cs t ■ 40 ° C). ■
An electron micrograph (magnification: 6000) of the type micelles is shown in FIG. In Figure 2, (a) shows the shape of a ■-type micelle, (b) shows the shape of a ■-type micelle transitioned by water, and (C) shows the shape of an r-type micelle transitioned by water and mechanical shearing. be. Furthermore, by applying heat to the ■-type micelles in (b) and (C), they transition to the ■-type micelles in (d).
この■型ミセルと■型ミセルの遷移は可逆性を持つこと
が確認されている。この増ちょう剤の１型、■型とも、
ウレア結合による水素結合により配列したミセル構造を
有しており、■型ミセルは単斜晶系に属し、■型ミセル
は斜方晶系に属することを本発明者らは明らかにした。It has been confirmed that this transition between ■-type micelles and ■-type micelles is reversible. Both type 1 and type ■ of this thickener,
The present inventors have clarified that the micelles have a micelle structure arranged by hydrogen bonds formed by urea bonds, and the ■-type micelles belong to the monoclinic system, and the ■-type micelles belong to the orthorhombic system.
■型と■型のエネルギー準位の差は小さく、また、遷移
するに要するエネルギーも余り大きくないと予想出来る
。本発明の２つのウレア結合が直線上に配置する化学構
造を有するジウレア化合物であることが必要であり、そ
の原理を見い出したことで本発明を完成することが出来
た。本発明で用いるジウレア化合物を得るためには、２
つのウレア結合が直線上に配置することが必要であり、
ジイソシアネートの化学構造が重要である。本発明に使
用出来るジイソシアネートとしては、４．４′−ジフェ
ニルメタンジイソシアネート、１．６−へキサメチレン
ジイソシアネート、０−キシリレンジイソシアネート、
オルソトリジンジイソシアネート、２゜７−ナフタレン
ジイソシアネート等がある。アミンとしては、基油に十
分に分散するために少なくとも一方のウレア結合にアル
キル基が結合する必要があり、脂肪族アミンを使用する
必要′があり、脂肪族アミンとしては炭素数４〜２２の
ものが望ましく、炭素数６〜１２がより望ましい。脂肪
族アミンのみでも良いし、芳香族アミンや脂環アミンな
どを脂肪族アミンに対するモル比で５０％以内で併用す
ることが出来る。最も、適切なジウレア化合物としては
、４．４′ −ジフェニルメタンジイソシアネートと、
ｎ−オクチルアミンの組み合せによるもので、ｎ−オク
チルアミンにモル比で５０％以内のアニリンを混合した
ものが次で適切である。The difference in energy level between the ■-type and ■-type is small, and it can be expected that the energy required for the transition is not very large. It is necessary for the diurea compound of the present invention to have a chemical structure in which two urea bonds are arranged in a straight line, and by discovering this principle, the present invention was completed. In order to obtain the diurea compound used in the present invention, 2
It is necessary that the two urea bonds are arranged in a straight line,
The chemical structure of the diisocyanate is important. Examples of diisocyanates that can be used in the present invention include 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 0-xylylene diisocyanate,
Examples include orthotolidine diisocyanate and 2°7-naphthalene diisocyanate. The amine needs to have an alkyl group bonded to at least one urea bond in order to be sufficiently dispersed in the base oil, so it is necessary to use an aliphatic amine. The number of carbon atoms is preferably 6 to 12, and more preferably 6 to 12 carbon atoms. The aliphatic amine alone may be used, or aromatic amines, alicyclic amines, etc. can be used in combination at a molar ratio of 50% or less to the aliphatic amine. The most suitable diurea compounds include 4,4'-diphenylmethane diisocyanate;
A combination of n-octylamine, in which n-octylamine is mixed with aniline in a molar ratio of up to 50%, is suitable for the following.
本発明のグリース組成物においては、Ｉ型ミセルで形成
されたグリースと、■型ミセルで形成されたグリース間
の違いは、ちょう度数率においては■型が１型より優れ
ており、潤滑箇所での金属表面への吸着能はＩ型が■型
より優れている。この理由としては、■型ミセルはらせ
ん状のＬ／Ｄ（Ｌ：ミセルの長さ、Ｄ：ミセルの直径）
の大きい繊維状を呈しているためちょう度数率が良いも
のと思われる。また、ウレア化合物の金属表面への吸着
はウレア結合の窒素上の不対電子によると考えられ、ミ
セル形状が大きく、平面的な結晶のＩ型ミセルが有利な
ことによると考えられる。In the grease composition of the present invention, the difference between the grease formed with type I micelles and the grease formed with type ■ micelles is that the type ■ is superior to type 1 in terms of consistency rate, and the grease formed with type I micelles is superior to type 1 in consistency rate. The adsorption ability of type I to the metal surface is superior to type II. The reason for this is that ■-type micelles have a spiral L/D (L: micelle length, D: micelle diameter)
It is thought that the consistency rate is good because it has a large fibrous shape. Further, the adsorption of the urea compound onto the metal surface is thought to be due to the unpaired electron on the nitrogen of the urea bond, and it is thought that this is due to the fact that the micelle shape is large and I-type micelles with planar crystals are advantageous.
本発明のグリース組成物が実用上有利な点は、上記のこ
とと共に、Ｉ型＃■型の遷移が、熱と機械的剪断の如き
物理条件により起こり、その遷移のためのエネルギーの
供給方法のされ方が潤滑されている箇所での条件と適合
することにある。すなわち、■型ミセルのグリースを給
脂した場合、マクロ的には潤滑部の掻く近傍での強い剪
断を受け、その結果、■型ミセルのグリースに遷移軟化
し、潤滑部へ流入し易（なり、同時に潤滑部の金属に吸
着するため、潤滑性が向上する。また、ミクロ的には潤
滑部では極部的には熱が発生しているため、吸着したミ
セルは溶融し、高粘性の潤滑Ｈ！Ｊを形成するし、吸着
しないミセルはその熱により■型ミセルのグリースに再
遷移し、構造粘性が太き（なり良好なグリース膜をも形
成し、その総合的な結果として優れた潤滑特性を示すこ
とになる。この遷移は可逆性であるから、結果的に、グ
リースの消費が少なく、長寿命が達成される。一方・、
潤滑部より離れた部分でのグリースはほとんど剪断を受
けないため■型への遷移はなく■型のままのため、半固
体状を維持し、グリース本来のシール性に何ら悪影響を
与えることはない。The practical advantage of the grease composition of the present invention is that, in addition to the above, the type I type #■ type transition is caused by physical conditions such as heat and mechanical shear, and the method of supplying energy for the transition is The method of lubrication is compatible with the conditions at the location being lubricated. In other words, when grease with ■-shaped micelles is supplied, from a macroscopic perspective, it is subjected to strong shearing in the vicinity of the lubricated part, and as a result, the grease transitions to ■-shaped micelles, softens, and easily flows into the lubricated parts. At the same time, it adsorbs to the metal in the lubricated part, improving lubricity.In addition, since heat is generated locally in the lubricated part, the adsorbed micelles melt and become a highly viscous lubricant. H!J is formed, and the unadsorbed micelles retransform into ■-type micelle grease due to the heat, and the structural viscosity is thick (and a good grease film is formed, and the overall result is excellent lubrication. This transition is reversible, resulting in less grease consumption and longer service life.On the other hand...
Since the grease in the area away from the lubricated part is hardly subjected to shearing, there is no transition to the shape, and it remains in the shape, so it maintains a semi-solid state and does not have any negative effect on the original sealing properties of the grease. .
本発明の組成物は、■型ミセルのグリースとして潤滑箇
所へ給脂されることが本来の使用方法であるが、■型ミ
セルのグリースとして配管内を移送し、潤滑部直前に加
熱工程を設けることで、集中給脂における圧損失を低減
する等の使用も可能であり、このことも本発明の利点で
ある。The composition of the present invention is originally used to be supplied to lubricated parts as a ■-type micelle grease, but it is transported inside piping as a ■-type micelle grease and a heating process is provided just before the lubricated part. Therefore, the present invention can be used to reduce pressure loss during centralized lubrication, and this is also an advantage of the present invention.
本発明に使用する潤滑油としては、潤滑粘度を有する鉱
物油、α−オレフィンオリゴマー、エステル系合成油、
エーテル系合成油などの合成潤滑油のいずれも使用でき
る。増ちょう剤の含有量を１〜３０重景％重量定した理
由は、増ちょう剤量が１重量％未満では増ちょう効果が
少なく半固体状にならず、３０重量％を越えるとちょう
度が硬すぎ、通常のグリースとしての用途では使用され
ないためであり、この範囲内であれば、潤滑用のグリー
スとして適当である。The lubricating oil used in the present invention includes mineral oil having lubricating viscosity, α-olefin oligomer, ester-based synthetic oil,
Any synthetic lubricating oil such as ether based synthetic oil can be used. The reason why the content of the thickener is determined to be 1 to 30% by weight is that if the amount of the thickener is less than 1% by weight, the thickening effect will be small and it will not become semi-solid, and if it exceeds 30% by weight, the consistency will decrease. This is because it is too hard to be used as a normal grease, and if it is within this range, it is suitable as a lubricating grease.
本発明には、本来の成分とは別に耐酸化性、防錆などを
向上する各種添加剤を添加することも出来る。In addition to the original components, various additives that improve oxidation resistance, rust prevention, etc. can also be added to the present invention.
（実施例および比較例） 以下、本発明を実施例および比較例により説明する。(Example and comparative example) The present invention will be explained below with reference to Examples and Comparative Examples.
ス１１１１
基油として鉱油（粘度１３０ｃＳｔ■４０°Ｃ）ジウレ
ア化合物として４．４′ −ジフェニルメタンジイソシ
アネートと、ｎ−オクチルアミンとアニリンの混合物と
の反応生成物を使用した例について述べる。An example will be described in which mineral oil (viscosity 130 cSt and 40° C. is used as the base oil) and a reaction product of 4,4'-diphenylmethane diisocyanate and a mixture of n-octylamine and aniline are used as the diurea compound.
■型ミセルグリースの製造方法
鉱油の配合量の内３７．７１５重量％を反応釜Ａに仕込
み８０°Ｃに加熱し、ジフェニルメタン−４，４’ −
ジイソシアネートの配合量の内３．６４ｆｉ量％を反応
釜Ａに加え撹拌し混合した。別に鉱油の配合量の内の３
７．７１５重量％を溶解釜Ｃに仕込み８０°Ｃに加熱し
オクチルアミンの全量を溶解釜Ｃに加え撹拌し溶解しこ
れを反応釜Ａに加え撹拌して反応させた。■Production method of type micellar grease 37.715% by weight of the blended amount of mineral oil was charged into reaction vessel A, heated to 80°C, and diphenylmethane-4,4'-
Of the blended amount of diisocyanate, 3.64 fi amount % was added to reaction vessel A and mixed by stirring. Separately, 3 of the blended amount of mineral oil
7.715% by weight was charged into dissolving pot C and heated to 80° C. The entire amount of octylamine was added to dissolving pot C, stirred and dissolved, and this was added to reaction pot A and stirred to react.
この時反応生成物は全量の約９重量％になった。At this time, the reaction product amounted to about 9% by weight of the total amount.
一方鉱油の配合量の内７．７８重量％を反応釜Ｂに仕込
み８０°Ｃに加熱し、ジフェニルメタン−４，４’ −
ジイソシアネートの内の残量の０．８８重量％を反応釜
已に加え撹拌し混合した。On the other hand, 7.78% by weight of the blended amount of mineral oil was charged into reaction vessel B and heated to 80°C.
0.88% by weight of the remaining diisocyanate was added to the reaction pot and mixed by stirring.
別に鉱油の残量７．７８重重量を溶解釜りに仕込み８０
″Ｃに加熱しアニリンの全量を溶解釜りに加え撹拌し溶
解しこれを反応釜Ｂに加え撹拌して反応させた。この時
も反応生成物の量は全量の約９％になった。反応釜Ａ、
Ｂ共反応熱により温度が上昇して１００″Ｃになった。Separately, charge the remaining amount of mineral oil (7.78 weight) into the melting pot.80
The whole amount of aniline was added to the dissolving pot and stirred to dissolve it, and then added to the reaction pot B and stirred and reacted. At this time as well, the amount of the reaction product was about 9% of the total amount. Reaction pot A,
The temperature rose to 100''C due to the heat of B co-reaction.
各省の温度を１００’Ｃに一定に保ち撹拌を継続し３０
分後にそれぞれ反応組成物の赤外吸収を測定したところ
イソシアネートの吸収を認めなかったので、反応釜Ｂの
反応組成物を全量反応釜Ａに加え混合し１００°Ｃで３
０分間撹拌を継続した。Keep the temperature of each chamber constant at 100'C and continue stirring for 30 minutes.
After a few minutes, the infrared absorption of each reaction composition was measured and no isocyanate absorption was observed, so the entire amount of the reaction composition in reaction pot B was added to reaction pot A and mixed at 100°C for 3 minutes.
Stirring was continued for 0 minutes.
その後撹拌しつつ加熱し温度を１９０°Ｃまで上昇させ
た。この時の温度上昇速度を毎分０．５°Ｃとして１９
０’Ｃまで上昇させ、ついで１９０°Ｃで６０分間温度
を保持した後、冷却しロールミルで混練し試料とした。Thereafter, the mixture was heated while stirring to raise the temperature to 190°C. Assuming that the temperature rise rate at this time is 0.5°C per minute, 19
After raising the temperature to 0'C and then maintaining the temperature at 190C for 60 minutes, the mixture was cooled and kneaded in a roll mill to prepare a sample.
１型ミセル≠■型ミセルの変態は、次の方法で確認した
。The transformation of type 1 micelles≠■type micelles was confirmed by the following method.
■型ミセルからＩ型ミセルへの遷移は、ＡＳＴＭ Ｄ１
８３７に準拠した含水シェルロールテストで剪断を与え
、■型ミセルの生成を調べた。同時に完全にＩ型ミセル
に遷移するまでの時間を示した。Ｉ型ミセルから■型ミ
セルへの遷移は、Ｉ型ミセルのグリースを加熱し、■型
ミセルの生成を調べた。■The transition from type micelle to type I micelle is determined by ASTM D1.
Shearing was applied using a water-containing shell roll test in accordance with 837, and the formation of ■-type micelles was investigated. At the same time, the time required for complete transition to type I micelles is shown. For the transition from type I micelles to type ■ micelles, grease of type I micelles was heated, and the formation of type ■ micelles was investigated.
同時にその遷移が生じる最低温度を表示した。Ｉ型ミセ
ル≠■型ミセルの可逆性は、上記の試験の繰返しで確認
した。評価はいずれの現象も認められる場合はＯと表示
し、認められない場合は×と表示した。At the same time, the lowest temperature at which the transition occurs is displayed. The reversibility of type I micelles≠type micelles was confirmed by repeating the above test. For evaluation, when any of the phenomena was observed, it was indicated as O, and when not observed, it was indicated as ×.
実用上の寿命性はＡＳＴＭ Ｄ １７４１に準拠し、１
５０°Ｃでの寿命時間で評価した。Practical lifespan is based on ASTM D 1741, 1
The life time at 50°C was evaluated.
表１に示すジイソシアネートとアミンを用い実施例１と
同様に、グリースを製造し、性能を評価した。Grease was produced in the same manner as in Example 1 using the diisocyanate and amine shown in Table 1, and its performance was evaluated.
且４月殊］こ＝１
表１に示すジイソシアネートとアミンを用い実施例１と
同様に、グリースを製造した。但し比較例４．５は市販
品を用いた。各グリースの性能を実施例１と同様にして
評価した。Grease was produced in the same manner as in Example 1 using the diisocyanates and amines shown in Table 1. However, in Comparative Examples 4.5, commercially available products were used. The performance of each grease was evaluated in the same manner as in Example 1.
（発明の効果）
実施例に示される様に、本発明のグリース組成物は、２
つの可逆性のあるミセル状態を有することにより、その
機能により優れた潤滑特性をもち、優れた潤滑寿命をも
つことが確認された。(Effect of the invention) As shown in the examples, the grease composition of the present invention has two
It was confirmed that by having a reversible micellar state, it has excellent lubrication properties and has an excellent lubrication life.
第１図は本発明のグリース組成物と、従来のグリース組
成物のミセルのエネルギー準位を示す曲線図、
第２図は本発明で用いる増ちょう剤の■型ミセル繊維お
よび■型ミセル繊維の形状を示すための６０００倍の電
子顕微鏡写真で、（ａ）は■型ミセル繊維の形状、（ｂ
）は水により遷移した■型ミセル繊維の形状、（Ｃ）は
水及び機械的剪断によって遷移した■型ミセル繊維の形
状、（ｄ）は［有］）、 （Ｃ）の２型ミセルに熱を加
えることにより遷移した■型ミセル繊維の形状を示す。
第１図Fig. 1 is a curve diagram showing the energy levels of micelles in the grease composition of the present invention and a conventional grease composition. Fig. 2 is a curve diagram showing the energy levels of micelles in the grease composition of the present invention and the conventional grease composition. Electron micrographs with a magnification of 6,000 times to show the shape; (a) is the shape of a ■-type micelle fiber, (b)
) is the shape of ■-type micelle fibers transitioned by water, (C) is the shape of ■-type micelle fibers transitioned by water and mechanical shearing, (d) is This figure shows the shape of ■-type micelle fibers that were transformed by adding . Figure 1
Claims (1)
学構造を有するジウレア化合物増ちょう剤からなり、潤
滑油中での増ちょう剤ミセルが２種の安定な構造を形成
し得るように、かつこの２種のミセルの変態がグリース
中で物理条件によって可逆的に起るように成らしめた上
記増ちょう剤を１〜３０重量％含有したことを特徴とす
るグリース組成物。1. Consists of a lubricating oil and a diurea compound thickener with a chemical structure in which two urea bonds are arranged in a straight line, so that the thickener micelles in the lubricating oil can form two types of stable structures. , and a grease composition containing 1 to 30% by weight of the above-mentioned thickener in which the transformation of these two types of micelles occurs reversibly depending on physical conditions in the grease.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30890486A JPS63162789A (en) | 1986-12-26 | 1986-12-26 | Grease composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30890486A JPS63162789A (en) | 1986-12-26 | 1986-12-26 | Grease composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63162789A true JPS63162789A (en) | 1988-07-06 |
Family
ID=17986668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30890486A Pending JPS63162789A (en) | 1986-12-26 | 1986-12-26 | Grease composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63162789A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63162790A (en) * | 1986-12-26 | 1988-07-06 | Kyodo Yushi Kk | Urea/grease composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4971357A (en) * | 1972-11-14 | 1974-07-10 | ||
| JPS52156274A (en) * | 1976-06-21 | 1977-12-26 | Nippon Oil Co Ltd | Break grease composition |
| JPS6088095A (en) * | 1983-10-20 | 1985-05-17 | Nippon Steel Corp | Sealing grease for pallet sealing device of sintering machine |
| JPS60231796A (en) * | 1984-05-02 | 1985-11-18 | Showa Shell Sekiyu Kk | Urea grease composition |
| JPS63162790A (en) * | 1986-12-26 | 1988-07-06 | Kyodo Yushi Kk | Urea/grease composition |
-
1986
- 1986-12-26 JP JP30890486A patent/JPS63162789A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4971357A (en) * | 1972-11-14 | 1974-07-10 | ||
| JPS52156274A (en) * | 1976-06-21 | 1977-12-26 | Nippon Oil Co Ltd | Break grease composition |
| JPS6088095A (en) * | 1983-10-20 | 1985-05-17 | Nippon Steel Corp | Sealing grease for pallet sealing device of sintering machine |
| JPS60231796A (en) * | 1984-05-02 | 1985-11-18 | Showa Shell Sekiyu Kk | Urea grease composition |
| JPS63162790A (en) * | 1986-12-26 | 1988-07-06 | Kyodo Yushi Kk | Urea/grease composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63162790A (en) * | 1986-12-26 | 1988-07-06 | Kyodo Yushi Kk | Urea/grease composition |
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