JP6283552B2 - Water-soluble metalworking oil and coolant for metalworking - Google Patents
Water-soluble metalworking oil and coolant for metalworking Download PDFInfo
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- JP6283552B2 JP6283552B2 JP2014070521A JP2014070521A JP6283552B2 JP 6283552 B2 JP6283552 B2 JP 6283552B2 JP 2014070521 A JP2014070521 A JP 2014070521A JP 2014070521 A JP2014070521 A JP 2014070521A JP 6283552 B2 JP6283552 B2 JP 6283552B2
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
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- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/70—Soluble oils
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Description
本発明は水溶性金属加工油、およびそれを水で希釈してなる金属加工用クーラントに関する。 The present invention relates to a water-soluble metalworking oil and a metalworking coolant obtained by diluting it with water.
金属加工に用いられる金属加工油剤には油系(油性)と水系(水性)があるが、冷却性、浸潤性に優れ、火災の危険がない水性タイプが多用されている。
特に、研削用途では油剤の冷却性が重要なため、鉱油を含まないソリューション系油剤が多用される(例えば特許文献1参照)。ソリューション系油剤は、冷却性、耐腐敗性は良好であるが、潤滑性に関しては不水系、エマルション系、ソルブル系に劣る。潤滑性の不足は、加工面粗度の悪化や砥石寿命の低下、または研削焼けの原因ともなる。
そこで、ソリューション系油剤に潤滑性を付与するため、油剤にポリアルキレングリコール(PAG)を配合することが行われている(特許文献2、3参照)。
Metalworking fluids used in metalworking are classified into oil-based (oil-based) and water-based (water-based), but water-based types that are excellent in cooling and infiltration properties and do not pose a fire hazard are frequently used.
In particular, since the cooling property of the oil agent is important in grinding applications, a solution-based oil agent that does not contain mineral oil is frequently used (for example, see Patent Document 1). Solution oils have good cooling and rot resistance, but are inferior to non-water, emulsion, and solve systems in terms of lubricity. Insufficient lubricity causes deterioration of the machined surface roughness, reduction of the grinding wheel life, or grinding burn.
Then, in order to provide lubricity to a solution type oil agent, polyalkylene glycol (PAG) is mix | blended with an oil agent (refer patent document 2, 3).
特許文献2、3に記載のソリューション系油剤では、PAGの配合量を増やすことにより潤滑性は良好となる。しかし、PAGを多量に配合しても潤滑性を上げるには限界がある。そのため、厳しい加工条件では砥石と被削材間の摩擦係数が大きくなり、砥石寿命の低下や研削焼けが起こる。 In the solution oils described in Patent Documents 2 and 3, the lubricity is improved by increasing the blending amount of PAG. However, there is a limit to improving the lubricity even if a large amount of PAG is blended. For this reason, under severe processing conditions, the coefficient of friction between the grindstone and the work material increases, resulting in a decrease in the grindstone life and grinding burn.
本発明は、厳しい加工条件でも潤滑性および耐摩耗性に優れる水溶性金属加工油、およびそれを水で希釈してなる金属加工用クーラントを提供することを目的とする。 An object of the present invention is to provide a water-soluble metal working oil that is excellent in lubricity and wear resistance even under severe working conditions, and a metal working coolant obtained by diluting it with water.
本発明者らは、スルフィド構造を有するジカルボン酸、PAG、ペンタエスリトール等の多価アルコールのポリアルキレンオキサイド付加物、およびモノカルボン酸を併用した水溶性油剤を用いることで、潤滑性と耐摩耗性を向上させ、砥石寿命の低下や研削焼けを抑制できることを見いだした。本発明はこの知見をもとに完成されたものである。
すなわち、本発明は、以下のような水溶性金属加工油および金属加工用クーラントを提供するものである。
〔1〕(A)スルフィド構造を含有するジカルボン酸、(B)ポリアルキレングリコール、(C)多価アルコールポリアルキレンオキサイド付加物、および(D)モノカルボン酸を配合してなることを特徴とする水溶性金属加工油。
〔2〕上述の〔1〕に記載の水溶性金属加工油において、前記(A)成分が下記式(1)の化合物であることを特徴とする水溶性金属加工油。
HOOC−R1−Sn−R2−COOH (1)
(R1およびR2は、各々独立して炭素数1以上5以下の炭化水素基であり、nは1以上8以下の整数である)
〔3〕上述の〔1〕または〔2〕に記載の水溶性金属加工油において、前記(A)成分の配合量が、当該加工油全量基準で0.1質量%以上14質量%以下であることを特徴とする水溶性金属加工油。
〔4〕上述の〔1〕から〔3〕までのいずれか1つに記載の水溶性金属加工油において、前記(B)成分が、下記式(2)の化合物および下記式(3)の化合物の少なくともいずれかであることを特徴とする水溶性金属加工油。
HO−(EO)a−(PO)b−(EO)c−H (2)
(EOはエチレンオキサイド単位、POはプロピレンオキサイド単位を意味する。a、cは各々独立に1以上30以下の整数であり、bは5以上100以下の整数である。)
R3O−(R’O)d−H (3)
(R3は、炭素数が1以上30以下のアルキル基である。R’OはPOおよびEOから選択されたオキサイド単位であり混合して用いてもよい。ただし、R’OにおけるEOのモル分率は1未満である。dは1以上50以下の整数である。)
〔5〕上述の〔1〕から〔4〕までのいずれか1つに記載の水溶性金属加工油において、前記(B)成分の配合量が、当該加工油全量基準で10質量%以上60質量%以下であることを特徴とする水溶性金属加工油。
〔6〕上述の〔1〕から〔5〕までのいずれか1つに記載の水溶性金属加工油において、前記(C)成分が、下記式(4)の化合物から下記式(7)の化合物までの少なくともいずれかであることを特徴とする水溶性金属加工油。
The present inventors use a water-soluble oil agent in combination with a dicarboxylic acid having a sulfide structure, a polyalkylene oxide adduct of a polyhydric alcohol such as PAG or pentaesitol, and a monocarboxylic acid, thereby improving lubricity and resistance. It has been found that the wearability can be improved, and the reduction of the grinding wheel life and grinding burn can be suppressed. The present invention has been completed based on this finding.
That is, the present invention provides the following water-soluble metalworking oil and metalworking coolant.
[1] A blend of (A) a dicarboxylic acid containing a sulfide structure, (B) a polyalkylene glycol, (C) a polyhydric alcohol polyalkylene oxide adduct, and (D) a monocarboxylic acid. Water-soluble metal processing oil.
[2] The water-soluble metalworking oil according to the above [1], wherein the component (A) is a compound of the following formula (1).
HOOC-R 1 -S n -R 2 -COOH (1)
(R 1 and R 2 are each independently a hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 8)
[3] In the water-soluble metal processing oil according to [1] or [2], the blending amount of the component (A) is 0.1% by mass or more and 14% by mass or less based on the total amount of the processing oil. Water-soluble metalworking oil characterized by that.
[4] The water-soluble metalworking oil according to any one of [1] to [3] above, wherein the component (B) is a compound of the following formula (2) and a compound of the following formula (3) A water-soluble metalworking oil characterized by being at least one of the following.
HO- (EO) a- (PO) b- (EO) c-H (2)
(EO means an ethylene oxide unit, PO means a propylene oxide unit. A and c are each independently an integer of 1 to 30, and b is an integer of 5 to 100.)
R 3 O- (R'O) d- H (3)
(R 3 is an alkyl group having 1 to 30 carbon atoms. R′O is an oxide unit selected from PO and EO and may be used in combination. However, the mole of EO in R′O (The fraction is less than 1. d is an integer from 1 to 50.)
[5] The water-soluble metal processing oil according to any one of [1] to [4] above, wherein the blending amount of the component (B) is 10% by mass or more and 60% by mass based on the total amount of the processing oil. % Water-soluble metalworking oil characterized by being less than or equal to%.
[6] The water-soluble metalworking oil according to any one of [1] to [5] above, wherein the component (C) is a compound of the following formula (7) from a compound of the following formula (4) Water-soluble metalworking oil characterized by being at least one of the above.
(R11からR14までは、各々独立に炭素数1以上5以下のアルキレン基である。eからhまでは、各々独立に1以上30以下の整数である。)
(R 11 to R 14 are each independently an alkylene group having 1 to 5 carbon atoms. E to h are each independently an integer of 1 to 30.)
(R4は、炭素数1から30までのアルキル基である。R21からR23までは、各々独立に炭素数1以上5以下のアルキレン基である。iからkまでは、各々独立に1以上30以下の整数である。)
(R 4 is an alkyl group having 1 to 30 carbon atoms. R 21 to R 23 are each independently an alkylene group having 1 to 5 carbon atoms. Each of i to k is independently 1 It is an integer of 30 or more.)
(R5およびR6は、各々独立に炭素数1から30までのアルキル基である。R31およびR32は、各々独立に炭素数1以上5以下のアルキレン基である。lおよびmは、各々独立に1以上30以下の整数である。)
(R 5 and R 6 are each independently an alkyl group having 1 to 30 carbon atoms. R 31 and R 32 are each independently an alkylene group having 1 to 5 carbon atoms. Each is independently an integer of 1-30.)
(R7からR9までは、各々独立に炭素数1から30までのアルキル基である。R41は、炭素数1以上5以下のアルキレン基である。nは、1以上30以下の整数である。)
〔7〕上述の〔1〕から〔6〕までのいずれか1つに記載の水溶性金属加工油において、前記(C)成分の配合量が、当該加工油全量基準で5質量%以上30質量%以下であることを特徴とする水溶性金属加工油。
〔8〕上述の〔1〕から〔7〕までのいずれか1つに記載の水溶性金属加工油において、前記(D)成分が、下記式(8)の化合物であることを特徴とする水溶性金属加工油。
R10−COOH (8)
(R10は炭素数が11以上の炭化水素基である。)
〔9〕上述の〔1〕から〔8〕までのいずれか1つに記載の水溶性金属加工油において、前記(D)成分の配合量が、当該加工油全量基準で1質量%以上20質量%以下であることを特徴とする水溶性金属加工油。
〔10〕上述の〔1〕から〔9〕までのいずれか1つに記載の水溶性金属加工油において、さらに、(E)アセチレングリコール系界面活性剤を配合してなることを特徴とする水溶性金属加工油。
〔11〕上述の〔10〕に記載の水溶性金属加工油において、前記(E)成分がアセチレングリコールエチレンオキサイド付加物であることを特徴とする水溶性金属加工油。
〔12〕上述の〔10〕または〔11〕に記載の水溶性金属加工油において、前記(E)成分の配合量が、当該加工油全量基準で1質量%以上15質量%以下であることを特徴とする水溶性金属加工油。
〔13〕上述の〔1〕から〔12〕までのいずれか1つに記載の水溶性金属加工油が、水を15質量%以上75質量%以下配合してなる原液であることを特徴とする水溶性金属加工油。
〔14〕上述の〔1〕から〔13〕までのいずれか1つに記載の水溶性金属加工油を、水で2倍以上200倍以下(容量)に希釈してなることを特徴とする金属加工用クーラント。
〔15〕上述の〔14〕に記載の金属加工用クーラントが研削用であることを特徴とする金属加工用クーラント。
(R 7 to R 9 are each independently an alkyl group having 1 to 30 carbon atoms. R 41 is an alkylene group having 1 to 5 carbon atoms. N is an integer of 1 to 30. is there.)
[7] In the water-soluble metalworking oil according to any one of [1] to [6], the blending amount of the component (C) is 5% by mass or more and 30% by mass based on the total amount of the processing oil. % Water-soluble metalworking oil characterized by
[8] The water-soluble metalworking oil according to any one of [1] to [7] above, wherein the component (D) is a compound of the following formula (8) Metal processing oil.
R 10 -COOH (8)
(R 10 is a hydrocarbon group having 11 or more carbon atoms.)
[9] The water-soluble metal processing oil according to any one of [1] to [8] above, wherein the blending amount of the component (D) is 1% by mass or more and 20% by mass based on the total amount of the processing oil. % Water-soluble metalworking oil characterized by being less than or equal to%.
[10] The water-soluble metalworking oil according to any one of [1] to [9] above, further comprising (E) an acetylene glycol surfactant. Metal processing oil.
[11] The water-soluble metalworking oil according to the above [10], wherein the component (E) is an acetylene glycol ethylene oxide adduct.
[12] The water-soluble metal processing oil according to [10] or [11] above, wherein the blending amount of the component (E) is 1% by mass or more and 15% by mass or less based on the total amount of the processing oil. Features a water-soluble metalworking oil.
[13] The water-soluble metalworking oil according to any one of [1] to [12] above is a stock solution in which water is blended in an amount of 15% by mass to 75% by mass. Water-soluble metal processing oil.
[14] A metal obtained by diluting the water-soluble metalworking oil according to any one of [1] to [13] above with water to 2 to 200 times (volume) Coolant for processing.
[15] A coolant for metal processing, wherein the coolant for metal processing described in [14] is for grinding.
本発明の水溶性金属加工油(原液)は、水で希釈して金属加工用クーラントとしたときに、良好な潤滑性と耐摩耗性を示す。それ故、本発明の金属加工用クーラントを研削に用いた場合、厳しい加工条件であっても加工面粗度の悪化を起こしにくく、研削焼けや砥石寿命の低下を十分に抑制できる。 The water-soluble metalworking oil (stock solution) of the present invention exhibits good lubricity and wear resistance when diluted with water to form a metalworking coolant. Therefore, when the coolant for metal processing of the present invention is used for grinding, it is difficult to cause deterioration of the machined surface roughness even under severe processing conditions, and it is possible to sufficiently suppress grinding burn and a decrease in the life of the grindstone.
本発明の水溶性金属加工油(以下、「本加工油」ともいう)は、(A)スルフィド構造を含有するジカルボン酸、(B)ポリアルキレングリコール、(C)多価アルコールポリアルキレンオキサイド付加物、および(D)モノカルボン酸を配合してなることを特徴とする。本加工油は原液であって、これを水で希釈して本発明の金属加工用クーラントとする。以下、本発明を詳細に説明する。 The water-soluble metal processing oil of the present invention (hereinafter also referred to as “the present processing oil”) includes (A) a dicarboxylic acid containing a sulfide structure, (B) a polyalkylene glycol, and (C) a polyhydric alcohol polyalkylene oxide adduct. And (D) a monocarboxylic acid. This processing oil is a stock solution, which is diluted with water to obtain the metal processing coolant of the present invention. Hereinafter, the present invention will be described in detail.
〔(A)成分〕
本加工油における(A)成分は、スルフィド構造を含有するジカルボン酸であり、潤滑性を向上させる効果を有する。
(A)成分としては、特に下記式(1)で示される構造のジカルボン酸が潤滑性向上の観点より優れている。
HOOC−R1−Sn−R2−COOH (1)
ここで、R1およびR2は炭素数1以上5以下の炭化水素基であり、nは1以上8以下の整数である。R1やR2の炭素数が6以上であると水溶性が低下するおそれがある。
[Component (A)]
The component (A) in the present processing oil is a dicarboxylic acid containing a sulfide structure and has an effect of improving lubricity.
As the component (A), a dicarboxylic acid having a structure represented by the following formula (1) is particularly excellent from the viewpoint of improving lubricity.
HOOC-R 1 -S n -R 2 -COOH (1)
Here, R 1 and R 2 are hydrocarbon groups having 1 to 5 carbon atoms, and n is an integer of 1 to 8 inclusive. If the carbon number of R 1 or R 2 is 6 or more, the water solubility may decrease.
上記式(1)のジカルボン酸における総炭素数は4以上12以下であるが、6以上10以下であることが水溶性および潤滑性の観点より好ましい。R1やR2としては、アルキレン基であることが好ましく、メチレン基、エチレン基、メチルエチレン基、プロピレン基、およびブチレン基等が挙げられる。水溶性および潤滑性の観点より特に、エチレン基が好ましい。
また、nが9以上であると、構造が不安定となり分解するおそれがある。それ故、nは6以下であることが好ましく、より好ましくは2以下であり、さらに好ましくは1である。
The total carbon number in the dicarboxylic acid of the above formula (1) is 4 or more and 12 or less, but 6 or more and 10 or less is preferable from the viewpoint of water solubility and lubricity. R 1 and R 2 are preferably alkylene groups, and examples thereof include a methylene group, an ethylene group, a methylethylene group, a propylene group, and a butylene group. An ethylene group is particularly preferable from the viewpoints of water solubility and lubricity.
Further, when n is 9 or more, the structure becomes unstable and may be decomposed. Therefore, n is preferably 6 or less, more preferably 2 or less, and even more preferably 1.
このようなジカルボン酸としては、例えば、チオジプロピオン酸、ジチオジプロピオン酸、チオ二酢酸、チオジこはく酸、ジチオ二酢酸、およびジチオ二酪酸などが挙げられる。
(A)成分の配合量としては、原液全量基準で0.1質量%以上14質量%以下が好ましく、1質量%以上10質量%以下がより好ましく、2質量%以上5質量%以下がさらに好ましい。(A)成分の配合量が多すぎると、原液を水で希釈した際の防錆性が低下するおそれがある。
Examples of such dicarboxylic acids include thiodipropionic acid, dithiodipropionic acid, thiodiacetic acid, thiodisuccinic acid, dithiodiacetic acid, and dithiodibutyric acid.
(A) As a compounding quantity of a component, 0.1 mass% or more and 14 mass% or less are preferable on the basis of the stock solution whole quantity, 1 mass% or more and 10 mass% or less are more preferable, and 2 mass% or more and 5 mass% or less are more preferable. . When there are too many compounding quantities of (A) component, there exists a possibility that the rust prevention property at the time of diluting a stock solution with water may fall.
〔(B)成分〕
本加工油における(B)成分は、ポリアルキレングリコールであり、(A)成分と同様に潤滑性の向上に寄与するが、さらに耐摩耗性の向上にも寄与する。このような(B)成分としては、潤滑性向上および耐摩耗性向上の観点より、下記式(2)、(3)で示されるポリアルキレングリコールのうち少なくともいずれか1種を用いることが好ましい。
HO−(EO)a−(PO)b−(EO)c−H (2)
R3O−(R’O)d−H (3)
[(B) component]
(B) component in this processing oil is polyalkylene glycol, and contributes to improvement of lubricity similarly to (A) component, but also contributes to improvement of abrasion resistance. As such a component (B), it is preferable to use at least one of polyalkylene glycols represented by the following formulas (2) and (3) from the viewpoint of improving lubricity and wear resistance.
HO- (EO) a- (PO) b- (EO) c-H (2)
R 3 O- (R'O) d- H (3)
式(2)において、EOはエチレンオキサイド単位、POはプロピレンオキサイド単位を意味する。a、cは各々独立に1以上30以下の整数であり、bは5以上100以下の整数である。式(2)におけるEO構造の総数は、好ましくは10以上30以下であり、PO構造の総数は、好ましくは10以上50以下、より好ましくは20以上40以下である。EO構造の総数が60を超えると、水で希釈した際の潤滑性が低下するおそれがある。また、PO構造の総数が100を超えると、水溶性が低下するおそれがある。
式(3)において、R3は、炭素数が1以上30以下のアルキル基である。R3の炭素数が30を超えると、水溶性が低下するおそれがある。R’OはPOおよびEOから選択されたオキサイド単位であり混合して用いてもよい。ただし、R’OにおけるEOのモル分率は水で希釈した際の消泡性の観点より1未満であることが好ましい。dは1以上50以下の整数である。R3の炭素数が30を超えると、水溶性が低下するおそれがある。
In the formula (2), EO means an ethylene oxide unit, and PO means a propylene oxide unit. a and c are each independently an integer of 1 to 30, and b is an integer of 5 to 100. The total number of EO structures in formula (2) is preferably 10 or more and 30 or less, and the total number of PO structures is preferably 10 or more and 50 or less, more preferably 20 or more and 40 or less. If the total number of EO structures exceeds 60, the lubricity when diluted with water may be reduced. Further, if the total number of PO structures exceeds 100, the water solubility may decrease.
In Formula (3), R 3 is an alkyl group having 1 to 30 carbon atoms. If the number of carbon atoms in R 3 exceeds 30, water solubility may be reduced. R′O is an oxide unit selected from PO and EO and may be used as a mixture. However, the molar fraction of EO in R′O is preferably less than 1 from the viewpoint of defoaming properties when diluted with water. d is an integer of 1 to 50. If the number of carbon atoms in R 3 exceeds 30, water solubility may be reduced.
上記した(B)成分の質量平均分子量は、500以上10000以下であることが好ましく、1000以上5000以下であることがより好ましい。質量平均分子量が500未満の場合、あるいは10000を超える場合のいずれにおいても、水で希釈した際の潤滑性が低下してしまうおそれがある。
(B)成分である式(2)および式(3)のポリアルキレングリコールは各々単独でも混合して用いてもよい。また、式(2)および式(3)のポリアルキレングリコールは、EO構造やPO構造の単位数等が異なる種々の構造のものを混合して用いてもよい。
(B)成分の好ましい配合量は、原液全量基準で10質量%以上60質量%以下であり、より好ましい配合量は、20質量%以上40質量%以下、さらに好ましい配合量は、20質量%以上30質量%以下である。この配合量が多すぎると通常の希釈率では潤滑性が高くなりすぎ、研削の際に砥石の食い付き性が低下するおそれがある。
The mass average molecular weight of the component (B) described above is preferably 500 or more and 10,000 or less, and more preferably 1000 or more and 5000 or less. In any case where the mass average molecular weight is less than 500 or more than 10,000, there is a possibility that the lubricity when diluted with water is lowered.
The (B) component polyalkylene glycols of the formulas (2) and (3) may be used alone or in combination. In addition, the polyalkylene glycols of the formulas (2) and (3) may be used in a mixture of various structures having different EO structures and PO unit numbers.
(B) The preferable compounding quantity of a component is 10 mass% or more and 60 mass% or less on the basis of the undiluted | stock solution whole quantity, A more preferable compounding quantity is 20 mass% or more and 40 mass% or less, Furthermore, a more preferable compounding quantity is 20 mass% or more. 30% by mass or less. If the amount is too large, the lubricity becomes too high at a normal dilution rate, and the biting ability of the grindstone may be lowered during grinding.
〔(C)成分〕
本加工油における(C)成分は、下記式(4)の化合物から下記式(7)の化合物までの少なくともいずれかである。(C)成分は、耐摩耗性の向上に寄与する
[Component (C)]
(C) component in this processing oil is at least any one from the compound of following formula (4) to the compound of following formula (7). Component (C) contributes to improvement of wear resistance.
上記式(4)において、R11からR14までは、各々独立に炭素数1以上5以下のアルキレン基である。eからhまでは、各々独立に1以上30以下の整数である。
上記式(5)において、R4は、炭素数1から30までのアルキル基である。R21からR23までは、各々独立に炭素数1以上5以下のアルキレン基である。iからkまでは、各々独立に1以上30以下の整数である。
上記式(6)において、R5およびR6は、各々独立に炭素数1から30までのアルキル基である。R31およびR32は、各々独立に炭素数1以上5以下のアルキレン基である。lおよびmは、各々独立に1以上30以下の整数である。
上記式(7)において、R7からR9までは、各々独立に炭素数1から30までのアルキル基である。R41は、炭素数1以上5以下のアルキレン基である。nは、1以上30以下の整数である。
In the above formula (4), R 11 to R 14 are each independently an alkylene group having 1 to 5 carbon atoms. e to h are each independently an integer of 1 to 30.
In the above formula (5), R 4 is an alkyl group having 1 to 30 carbon atoms. R 21 to R 23 are each independently an alkylene group having 1 to 5 carbon atoms. i to k are each independently an integer of 1 to 30.
In the above formula (6), R 5 and R 6 are each independently an alkyl group having 1 to 30 carbon atoms. R 31 and R 32 are each independently an alkylene group having 1 to 5 carbon atoms. l and m are each independently an integer of 1 to 30.
In the above formula (7), R 7 to R 9 are each independently an alkyl group having 1 to 30 carbon atoms. R 41 is an alkylene group having 1 to 5 carbon atoms. n is an integer of 1-30.
上記した(C)成分のうち、耐摩耗性向上の観点より、ペンタエリスリトールのEO付加物、あるいはトリメチロールプロパンのEO付加物がより好ましい。
(C)成分の配合量は、通常の希釈率における耐摩耗性の観点より、加工油全量基準で5質量%以上30質量%以下であることが好ましい。
Among the components (C) described above, an EO adduct of pentaerythritol or an EO adduct of trimethylolpropane is more preferable from the viewpoint of improving wear resistance.
The blending amount of component (C) is preferably 5% by mass or more and 30% by mass or less based on the total amount of processing oil from the viewpoint of wear resistance at a normal dilution rate.
〔(D)成分〕
本加工油における(D)成分は、モノカルボン酸であり、潤滑性および耐摩耗性の向上に寄与する。このようなモノカルボン酸としては、いわゆる長鎖カルボン酸が好ましく、具体的には下記式(8)の化合物が好ましい。
R10−COOH (8)
ここで、R10は炭素数が11以上の炭化水素基である。炭化水素基としては直鎖でも分岐を有していてもよく、飽和でも不飽和でもよい。潤滑性および耐摩耗性の観点からは、トール油脂肪酸が好ましい。
長鎖カルボン酸としては、具体的には、ラウリン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、エルカ酸、パルミチン酸、リシノレイン酸、ヒドロキシ脂肪酸(例えば、リシノール酸、12−ヒドロキシステアリン酸等)、アラキン酸、ベヘン酸、メリシン酸、イソステアリン酸、油脂より抽出された大豆油脂肪酸、ヤシ油脂肪酸、ナタネ油脂肪酸、およびトール油脂肪酸(C18)などが挙げられる。
(D)成分の配合量としては、通常の希釈率における潤滑性および耐摩耗性の観点より、加工油全量基準で1質量%以上20質量%以下であることが好ましい。
[Component (D)]
(D) component in this processing oil is monocarboxylic acid, and contributes to improvement of lubricity and abrasion resistance. As such a monocarboxylic acid, a so-called long-chain carboxylic acid is preferable, and specifically, a compound of the following formula (8) is preferable.
R 10 -COOH (8)
Here, R 10 is a hydrocarbon group having 11 or more carbon atoms. The hydrocarbon group may be linear or branched and may be saturated or unsaturated. From the viewpoints of lubricity and wear resistance, tall oil fatty acids are preferred.
Specific examples of the long chain carboxylic acid include lauric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, palmitic acid, ricinoleic acid, hydroxy fatty acids (eg, ricinoleic acid, 12-hydroxystearic acid, etc. ), Arachidic acid, behenic acid, melissic acid, isostearic acid, soybean oil fatty acid extracted from oil and fat, coconut oil fatty acid, rapeseed oil fatty acid, tall oil fatty acid (C18) and the like.
The blending amount of component (D) is preferably 1% by mass or more and 20% by mass or less based on the total amount of processing oil from the viewpoint of lubricity and wear resistance at a normal dilution rate.
本加工油は、上記した(A)成分から(D)成分までを、水に配合して原液としたものである。本加工油(原液)は、加工油全量基準で、(A)成分から(D)成分を合わせた配合量が40質量%以上90質量%以下であることが好ましく、より好ましい配合量は60質量%以上80質量%以下である。
(A)成分から(D)成分までを合わせた配合量が40質量%未満であると、現場での本加工油使用時に水による希釈率が高すぎた場合、潤滑性の低下(摩擦係数の上昇)を招くおそれがある。一方、(A)成分から(D)成分までを合わせた配合量が90質量%を超えると原液安定性が低下するおそれがある。ここで、原液安定性とは、相分離、固体の不溶解、析出等で原液の均一性がなくなることをいう。
This processing oil mix | blends above-mentioned (A) component to (D) component with water, and makes it a stock solution. This processing oil (stock solution) is preferably 40% by mass or more and 90% by mass or less, and more preferably 60% by mass, based on the total amount of processing oil based on the total amount of processing oil (A) to (D). % To 80% by mass.
When the blending amount of the component (A) to the component (D) is less than 40% by mass, when the dilution ratio with water is too high when the processing oil is used in the field, the lubricity decreases (the friction coefficient) Rise). On the other hand, if the blending amount of the component (A) to the component (D) exceeds 90% by mass, the stock solution stability may be lowered. Here, the stock solution stability means that the stock solution is not uniform due to phase separation, solid insolubility, precipitation, or the like.
原液調製用の水の割合は加工油全量基準で15質量%以上75質量%以下が好ましい。水の割合が15質量%未満であると、(A)成分と(B)成分の溶解が困難となり、原液の調製が煩雑となる。また、原液調製用の水の割合が75質量%を超えると、原液としての保管量や輸送量が過大となりハンドリング性が低下する。
なお、本加工油(原液)は、そのままの濃度で使用してもよいが、好ましくは水で2倍以上200倍以下、より好ましくは5倍以上100倍以下の比率(容量比)に希釈され金属加工用クーラントとして使用される。
The proportion of water for preparing the stock solution is preferably 15% by mass or more and 75% by mass or less based on the total amount of processing oil. When the proportion of water is less than 15% by mass, it becomes difficult to dissolve the components (A) and (B), and the preparation of the stock solution becomes complicated. Moreover, when the ratio of the water for stock solution preparation exceeds 75 mass%, the storage amount and transport amount as stock solution will become excessive, and handling property will fall.
The processing oil (stock solution) may be used as it is, but is preferably diluted with water to a ratio (volume ratio) of 2 to 200 times, more preferably 5 to 100 times. Used as coolant for metal processing.
〔その他の成分〕
本加工油には、(E)成分としてノニオン系界面活性剤をさらに配合することが好ましい。このような界面活性剤を配合することにより、本加工油の濡れ性が向上し砥石と被削材との間に本加工油が浸透しやすくなる。
(E)成分としては、その効果の観点よりアセチレングリコール系界面活性剤が特に好ましい。このようなアセチレングリコール系界面活性剤としては、例えば、特開2011−12249号公報に記載されているアセチレングリコールやそのアルキレンオキサイド付加物を好適に使用可能である。例えば、アセチレングリコールEO付加物が好適である。市販品としては、エアープロダクツアンドケミカルズ製のダイノール604、サーフィノール420、およびサーフィノール465などが挙げられる。
(E)成分の配合量としては、原液全量基準で0.1質量%以上20質量%以下であることが好ましく、1質量%以上10質量%以下であることがより好ましい。(E)成分の配合量が多すぎると希釈時の消泡性が悪化する。
[Other ingredients]
It is preferable that a nonionic surfactant is further blended in the processing oil as the component (E). By blending such a surfactant, the wettability of the processing oil is improved and the processing oil can easily penetrate between the grindstone and the work material.
As the component (E), an acetylene glycol surfactant is particularly preferable from the viewpoint of its effect. As such an acetylene glycol-based surfactant, for example, acetylene glycol and its alkylene oxide adduct described in JP2011-12249A can be suitably used. For example, an acetylene glycol EO adduct is suitable. Examples of commercially available products include DYNOL 604, SURFINOL 420, SURFINOL 465 and the like manufactured by Air Products and Chemicals.
(E) As a compounding quantity of a component, it is preferable that it is 0.1 mass% or more and 20 mass% or less on the basis of the undiluted solution whole quantity, and it is more preferable that it is 1 mass% or more and 10 mass% or less. When there are too many compounding quantities of (E) component, the defoaming property at the time of dilution will deteriorate.
本加工油には、(F)成分として、さらにアルカノールアミンを配合することが好ましい。このアルカノールアミンは、上述の(A)成分あるいは(D)成分と反応し、アルカノールアミンカルボン酸塩となって潤滑性をより高める。また、アルカノールアミンは、防錆剤としても機能する。
アルカノールアミンとしては、特に制限はなく、一級、二級、および三級アミンを組み合わせて使用することができる。ただし、一級アミンのみを使用するとアミンの揮発性が高く、臭気性の点で作業環境を悪化するおそれがある。それ故、一級アミンを使用する際は、二級アミンや三級アミンを組み合わせることが好ましい。また、臭気性の観点より三級アミンが好ましい。
The processing oil preferably further contains alkanolamine as the component (F). This alkanolamine reacts with the above-mentioned component (A) or component (D) to become an alkanolamine carboxylate and further improve the lubricity. Alkanolamine also functions as a rust inhibitor.
The alkanolamine is not particularly limited, and primary, secondary, and tertiary amines can be used in combination. However, if only a primary amine is used, the amine is highly volatile, and the working environment may be deteriorated in terms of odor. Therefore, when a primary amine is used, it is preferable to combine a secondary amine or a tertiary amine. A tertiary amine is preferred from the viewpoint of odor.
一級アミンの具体例としては、例えば、1−アミノ−2−プロパノール、2−アミノ−2−メチル−1−プロパノール、1−アミノ−2−ブタノール、2−アミノ−1−プロパノール、3−アミノ−2−ブタノールなどが挙げられる。これらの中でも、鉄に対する防錆性の点で1−アミノ−2−プロパノールや2−アミノ−2−メチル−1−プロパノールが特に好ましい。本加工油においては、上記した成分は1種用いてもよく、2種以上を用いてもよい。
二級アミンの具体例としては、例えばジエタノールアミン、ジ(n−プロパノール)アミン、ジイソプロパノールアミン、N−メチルモノエタノールアミン、N−エチルモノエタノールアミン、N−シクロモノエタノールアミン、N−n−プロピルモノエタノールアミン、N−i−プロピルモノエタノールアミン、N−n−ブチルモノエタノールアミン、N−i−ブチルモノエタノールアミン、およびN−t−ブチルモノエタノールアミンなどが挙げられる。本加工油においては、上記した成分は1種用いてもよく、2種以上を用いてもよい。
Specific examples of the primary amine include, for example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 1-amino-2-butanol, 2-amino-1-propanol, and 3-amino- Examples include 2-butanol. Among these, 1-amino-2-propanol and 2-amino-2-methyl-1-propanol are particularly preferable from the viewpoint of rust prevention against iron. In this processing oil, the above-described components may be used singly or in combination of two or more.
Specific examples of the secondary amine include, for example, diethanolamine, di (n-propanol) amine, diisopropanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, N-cyclomonoethanolamine, Nn-propyl. Examples thereof include monoethanolamine, Ni-propyl monoethanolamine, Nn-butyl monoethanolamine, Ni-butyl monoethanolamine, and Nt-butyl monoethanolamine. In this processing oil, the above-described components may be used singly or in combination of two or more.
三級アミンの具体例としては、N−メチルジエタノールアミン、N−エチルジエタノールアミン、トリエタノールアミン、N−シクロヘキシルジエタノールアミン、N−n−プロピルジエタノールアミン、N−i−プロピルジエタノールアミン、N−n−ブチルジエタノールアミン、N−i−ブチルジエタノールアミン、およびN−t−ブチルジエタノールアミンなどが挙げられる。上記した成分は1種用いてもよく、2種以上を用いてもよい。 Specific examples of the tertiary amine include N-methyldiethanolamine, N-ethyldiethanolamine, triethanolamine, N-cyclohexyldiethanolamine, Nn-propyldiethanolamine, Ni-propyldiethanolamine, Nn-butyldiethanolamine, N -I-butyldiethanolamine, Nt-butyldiethanolamine and the like. One kind of the above-described components may be used, or two or more kinds may be used.
上述の(F)成分の配合量は、加工油(原液)全量基準で20質量%以上55質量%以下であることが好ましい。(F)成分の配合量が20質量%未満であると、現場での本加工油使用時に水による希釈率が高すぎた場合、防錆性の低下を招いてしまうおそれがある。一方、(F)成分の配合量が55質量%を超えると原液安定性が低下する。
ここで、防錆性を高めるため、防錆剤として硫黄を含有しないカルボン酸を(F)成分と併用することが好ましい。このようなカルボン酸としては、消泡性の観点および硬水安定性の観点より、炭素原子数8から10までのカプロン酸、ノナン酸、イソノナン酸、トリメチルヘキサン酸、ネオデカン酸、およびデカン酸などのようなモノカルボン酸や、炭素原子数9から12までのノナン二酸、ウンデカン二酸、セバシン酸、およびドデカン二酸などのようなジカルボン酸が好ましく挙げられる。
特に上記したトリメチルヘキサン酸は、加工油(原液)を水で希釈した時、固形物が液面にできるのを低減する効果(硬水安定性)に優れている。
また、カルボン酸の主鎖を構成するアルキル基としては耐腐敗性の点で分岐構造を有するものが好ましい。カルボン酸としては二塩基酸を用いた方が塩として用いた場合に防錆性に優れるが、原液の安定性(不溶化しにくいこと)の観点より、二塩基酸と一塩基酸とを混合して使用することが好ましい。
The blending amount of the component (F) is preferably 20% by mass or more and 55% by mass or less based on the total amount of processing oil (stock solution). When the blending amount of the component (F) is less than 20% by mass, if the dilution ratio with water is too high when the processing oil is used in the field, the rust prevention property may be lowered. On the other hand, when the blending amount of the component (F) exceeds 55% by mass, the stock solution stability is lowered.
Here, in order to improve rust prevention property, it is preferable to use together with (F) component carboxylic acid which does not contain sulfur as a rust preventive agent. Examples of such carboxylic acids include caproic acid, nonanoic acid, isononanoic acid, trimethylhexanoic acid, neodecanoic acid, and decanoic acid having 8 to 10 carbon atoms from the viewpoint of defoaming property and stability of hard water. Preferred are monocarboxylic acids such as these, and dicarboxylic acids such as nonanedioic acid having 9 to 12 carbon atoms, undecanedioic acid, sebacic acid, and dodecanedioic acid.
In particular, the above-described trimethylhexanoic acid is excellent in the effect (hard water stability) of reducing the formation of a solid on the liquid surface when the processing oil (stock solution) is diluted with water.
Moreover, as an alkyl group which comprises the principal chain of carboxylic acid, what has a branched structure is preferable at the point of decay resistance. As the carboxylic acid, dibasic acid is superior in rust prevention when used as a salt, but from the viewpoint of stability of the stock solution (hard to insolubilize), dibasic acid and monobasic acid are mixed. Are preferably used.
また、本加工油には、本発明の目的を阻害しない範囲で各種公知の添加剤を適宜配合することができる。例えば、極圧剤、油性剤、殺菌剤(防腐剤)、金属不活性化剤、および消泡剤などである。
極圧剤としては、硫黄系極圧剤、リン系極圧剤、硫黄および金属を含む極圧剤、リンおよび金属を含む極圧剤が挙げられる。これらの極圧剤は一種を単独でまたは二種以上組み合わせて用いることができる。極圧剤としては、分子中に硫黄原子やリン原子を含み、耐荷重性や耐摩耗性を発揮しうるものであればよい。分子中に硫黄を含む極圧剤としては、例えば、硫化油脂、硫化脂肪酸、硫化エステル、硫化オレフィン、ジヒドロカルビルポリサルファイド、チアジアゾール化合物、アルキルチオカルバモイル化合物、トリアジン化合物、チオテルペン化合物、ジアルキルチオジプロピオネート化合物などを挙げることができる。これらの極圧剤の配合量は、配合効果の点から、最終的な希釈液(クーラント)基準で、0.05質量%以上0.5質量%以下程度となるように原液に配合される。
Moreover, various well-known additives can be suitably mix | blended with this processing oil in the range which does not inhibit the objective of this invention. For example, extreme pressure agents, oily agents, bactericides (preservatives), metal deactivators, and antifoaming agents.
Examples of the extreme pressure agent include a sulfur-based extreme pressure agent, a phosphorus-based extreme pressure agent, an extreme pressure agent containing sulfur and a metal, and an extreme pressure agent containing phosphorus and a metal. These extreme pressure agents can be used singly or in combination of two or more. Any extreme pressure agent may be used as long as it contains a sulfur atom or a phosphorus atom in the molecule and can exhibit load resistance and wear resistance. Examples of extreme pressure agents containing sulfur in the molecule include sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiadiazole compounds, alkylthiocarbamoyl compounds, triazine compounds, thioterpene compounds, dialkylthiodipropionate compounds, etc. Can be mentioned. The blending amount of these extreme pressure agents is blended in the stock solution so as to be about 0.05% by mass or more and 0.5% by mass or less on the basis of the final diluent (coolant) from the viewpoint of the blending effect.
油性剤としては、脂肪族アルコールや脂肪酸金属塩などの脂肪族化合物、ポリオールエステル、ソルビタンエステル、およびグリセライドなどのエステル化合物を挙げることができる。これらの油性剤の配合量は、配合効果の点から、クーラント基準で、0.2質量%以上2質量%以下程度となるように原液に配合される。 Examples of the oily agent include aliphatic compounds such as aliphatic alcohols and fatty acid metal salts, and ester compounds such as polyol esters, sorbitan esters, and glycerides. The blending amount of these oil-based agents is blended in the stock solution so as to be about 0.2% by mass or more and 2% by mass or less based on the coolant from the viewpoint of the blending effect.
殺菌剤としては、例えば、2−ピリジルチオ−1−オキシド塩が挙げられる。具体的には、2−ピリジルチオ−1−オキシドナトリウム、ビス(2−ピリジルジチオー1−オキシド)亜鉛、およびビス(2−スルフィドピリジン−1−オラト)銅などが挙げられる。これらの殺菌剤の配合量は、配合効果の点から、クーラント基準で、0.01質量%以上5質量%以下程度となるように原液に配合される。 As a bactericidal agent, 2-pyridylthio-1-oxide salt is mentioned, for example. Specific examples include sodium 2-pyridylthio-1-oxide, bis (2-pyridyldithio-1-oxide) zinc, and bis (2-sulfidepyridine-1-olato) copper. The blending amount of these bactericides is blended in the stock solution so as to be about 0.01% by mass or more and 5% by mass or less based on the coolant from the viewpoint of blending effect.
金属不活性化剤としては、例えば、ベンゾトリアゾール、ベンゾトリアゾール誘導体、イミダゾリン、ピリミジン誘導体、およびチアジアゾール等が挙げられる。これらの1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。金属不活性化剤の配合量は、配合効果の点から、クーラント基準で、0.01質量%以上3質量%以下程度となるように原液に配合される。
消泡剤としては、メチルシリコーン油、フルオロシリコーン油、ポリアクリレートなどを挙げることができる。これらの消泡剤の配合量は、配合効果の点から、クーラント基準で、0.004質量%以上0.08質量%以下程度となるように原液に配合される。
Examples of the metal deactivator include benzotriazole, benzotriazole derivatives, imidazoline, pyrimidine derivatives, and thiadiazole. One of these may be used alone, or two or more may be used in combination. The blending amount of the metal deactivator is blended in the stock solution so as to be about 0.01% by mass or more and 3% by mass or less based on the coolant from the viewpoint of blending effect.
Examples of the antifoaming agent include methyl silicone oil, fluorosilicone oil, and polyacrylate. The blending amount of these antifoaming agents is blended in the stock solution so as to be about 0.004 mass% or more and 0.08 mass% or less on the basis of the blending effect.
本発明の水溶性金属加工油は、前記したようにその使用目的に応じて適当な濃度になるよう適宜水に希釈して、研削加工や切削加工をはじめ、研磨、絞り、抽伸、圧延等の各種の金属加工分野に好適に利用することができる。なお、研削加工としては、円筒研削加工、内面研削加工、平面研削加工、心なし研削加工、工具研削加工、ホーニング加工、超仕上げ加工、および特殊曲面研削加工(例えばねじ研削、歯車研削、カム研削、ロール研削)などが挙げられる。 As described above, the water-soluble metalworking oil of the present invention is appropriately diluted with water so as to have an appropriate concentration according to the purpose of use, and includes grinding, cutting, polishing, drawing, drawing, rolling, etc. It can be suitably used in various metal processing fields. Grinding includes cylindrical grinding, internal grinding, surface grinding, centerless grinding, tool grinding, honing, super-finishing, and special curved grinding (eg screw grinding, gear grinding, cam grinding) , Roll grinding).
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
〔実施例1〜5、比較例1〜7〕
表1に示す配合処方により水溶性金属加工油(原液)を調製した後、各原液を水道水で20倍(容量)に希釈して各供試油を得た。各供試油についてブロック・オン・リング試験を行い、潤滑性と耐摩耗性を評価した。試験条件および評価項目(評価方法)は下記の通りである。結果を表1に示す。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[Examples 1-5, Comparative Examples 1-7]
After preparing a water-soluble metalworking oil (stock solution) according to the formulation shown in Table 1, each stock solution was diluted 20 times (volume) with tap water to obtain each sample oil. Each sample oil was subjected to a block-on-ring test to evaluate lubricity and wear resistance. Test conditions and evaluation items (evaluation methods) are as follows. The results are shown in Table 1.
<ブロック・オン・リング試験>
試験機 :ブロック・オン・リング試験機(丸菱エンジニアリング株式会社製)
荷重 :100N
回転数 :500rpm(53m/min)
時間 :10min
リング :SAE 4620STEEL
ブロック:S45C
<Block-on-ring test>
Testing machine: Block-on-ring testing machine (manufactured by Maruhishi Engineering Co., Ltd.)
Load: 100N
Rotation speed: 500rpm (53m / min)
Time: 10min
Ring: SAE 4620STEEL
Block: S45C
<評価項目(評価方法)>
・潤滑性
摩擦力(N)より以下の基準で評価した。
○:13.5N以下
×:13.5Nを超える
・耐摩耗性
摩耗痕幅(μm)より以下の基準で評価した。
○:1000μm以下
△:1000μmを超え1100μm以下
×:1100μmを超える
<Evaluation item (evaluation method)>
・ Lubricity Evaluation was made based on friction force (N) according to the following criteria.
○: 13.5 N or less ×: Exceeding 13.5 N ・ Abrasion resistance Evaluation was made according to the following criteria from the wear scar width (μm).
○: 1000 μm or less △: Over 1000 μm and 1100 μm or less ×: 1 Over 100 μm
2)HO(EO)8.5−(PO)30.2−(EO)8.5H:三洋化成製
3)HO(EO)13.2−(PO)30−(EO)13.2H:三洋化成製
4)CH3O(PO)a((EO)b/(PO)c)(PO)dH:三洋化成製ブレンバーLUB82
5)ペンタエリスリトールポリオキシエチレンエーテル:日本乳化剤製 PNT−60U
6)ペンタエリスリトールポリオキシエチレンエーテル:日本乳化剤製 PNT−40
7)トリメチロールプロパントリポリオキシエチレンエーテル:日本乳化剤製TMP−60
8)アセチレングリコール系界面活性剤:エアープロダクツアンドケミカルズ製のダイノール604、サーフィノール420、およびサーフィノール465を混合して使用
9)その他の成分:(ポリエチレンイミン(分子量1000)の30質量%水溶液:0.3質量%、ベンゾトリアゾール:1.0質量%、ベンゾイソチアゾリンの35質量%水溶液:0.2質量%、ピリチオンナトリウム:0.2質量%、シリコーン系消泡剤:0.4質量%)
2) HO (EO) 8.5- (PO) 30.2- (EO) 8.5 H: Sanyo Chemical 3) HO (EO) 13.2- (PO) 30- (EO) 13.2 H : Sanyo Chemical 4) CH 3 O (PO) a ((EO) b / (PO) c) (PO) dH: Sanyo Chemical's Brember LUB82
5) Pentaerythritol polyoxyethylene ether: PNT-60U made by Nippon Emulsifier
6) Pentaerythritol polyoxyethylene ether: Nippon Emulsifier PNT-40
7) Trimethylolpropane tripolyoxyethylene ether: Nippon Emulsifier TMP-60
8) Acetylene glycol surfactant: used by mixing Dinol 604, Surfynol 420 and Surfynol 465 manufactured by Air Products and Chemicals 9) Other components: 30% by mass aqueous solution of (polyethyleneimine (molecular weight 1000)): 0.3 mass%, benzotriazole: 1.0 mass%, 35 mass% aqueous solution of benzoisothiazoline: 0.2 mass%, sodium pyrithione: 0.2 mass%, silicone-based antifoaming agent: 0.4 mass%)
〔評価結果〕
実施例1〜5の原液を希釈してなるクーラントは、本発明の(A)成分から(D)成分までを配合してなるため、いずれも潤滑性および耐摩耗性に優れている。
これに対して比較例1〜6の原液を希釈してなるクーラントは、上記(A)成分から(D)成分までのいずれかを欠いているため、潤滑性と耐摩耗性を両立させることができない。
〔Evaluation results〕
Since the coolant obtained by diluting the stock solutions of Examples 1 to 5 is composed of the components (A) to (D) of the present invention, both have excellent lubricity and wear resistance.
On the other hand, since the coolant obtained by diluting the stock solutions of Comparative Examples 1 to 6 lacks any of the components (A) to (D), it is possible to achieve both lubricity and wear resistance. Can not.
Claims (12)
ことを特徴とする水溶性金属加工油。
HO−(EO)a−(PO)b−(EO)c−H (2)
(EOはエチレンオキサイド単位、POはプロピレンオキサイド単位を意味する。a、cは各々独立に1以上30以下の整数であり、bは5以上100以下の整数である。)
R 3 O−(R’O)d−H (3)
(R 3 は、炭素数が1以上30以下のアルキル基である。R’OはPOおよびEOから選択されたオキサイド単位であり混合して用いてもよい。ただし、R’OにおけるEOのモル分率は1未満である。dは1以上50以下の整数である。)
(R 11 からR 14 までは、各々独立に炭素数1以上5以下のアルキレン基である。eからhまでは、各々独立に1以上30以下の整数である。)
(R 4 は、炭素数1から30までのアルキル基である。R 21 からR 23 までは、各々独立に炭素数1以上5以下のアルキレン基である。iからkまでは、各々独立に1以上30
以下の整数である。)
(R 5 およびR 6 は、各々独立に炭素数1から30までのアルキル基である。R 31 およびR 32 は、各々独立に炭素数1以上5以下のアルキレン基である。lおよびmは、各々独立に1以上30以下の整数である。)
(R 7 からR 9 までは、各々独立に炭素数1から30までのアルキル基である。R 41 は、炭素数1以上5以下のアルキレン基である。nは、1以上30以下の整数である。)
R 10 −COOH (8)
(R 10 は炭素数が11以上の炭化水素基である。) (A) a dicarboxylic acid containing a sulfide structure, (B) a compound of the following formula (2) and / or a compound of the following formula (3) , (C ) a compound of the following formula (4) to the following formula (7) And (D) a monocarboxylic acid which is a compound represented by the following formula (8) .
HO- (EO) a- (PO) b- (EO) c-H (2)
(EO means an ethylene oxide unit, PO means a propylene oxide unit. A and c are each independently an integer of 1 to 30, and b is an integer of 5 to 100.)
R 3 O- (R'O) d- H (3)
(R 3 is an alkyl group having 1 to 30 carbon atoms. R′O is an oxide unit selected from PO and EO and may be used in combination. However, the mole of EO in R′O (The fraction is less than 1. d is an integer from 1 to 50.)
(R 11 to R 14 are each independently an alkylene group having 1 to 5 carbon atoms. E to h are each independently an integer of 1 to 30.)
(R 4 is an alkyl group having 1 to 30 carbon atoms. R 21 to R 23 are each independently an alkylene group having 1 to 5 carbon atoms. Each of i to k is independently 1 30 or more
The following integers. )
(R 5 and R 6 are each independently an alkyl group having 1 to 30 carbon atoms. R 31 and R 32 are each independently an alkylene group having 1 to 5 carbon atoms. Each is independently an integer of 1-30.)
(R 7 to R 9 are each independently an alkyl group having 1 to 30 carbon atoms. R 41 is an alkylene group having 1 to 5 carbon atoms. N is an integer of 1 to 30. is there.)
R 10 -COOH (8)
(R 10 is a hydrocarbon group having 11 or more carbon atoms.)
前記(A)成分が下記式(1)の化合物である
ことを特徴とする水溶性金属加工油。
HOOC−R1−Sn−R2−COOH (1)
(R1およびR2は、各々独立して炭素数1以上5以下の炭化水素基であり、nは1以上8以下の整数である) In the water-soluble metalworking oil according to claim 1,
The said (A) component is a compound of following formula (1). Water-soluble metalworking oil characterized by the above-mentioned.
HOOC-R 1 -S n -R 2 -COOH (1)
(R 1 and R 2 are each independently a hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 8)
前記(A)成分の配合量が、当該加工油全量基準で0.1質量%以上14質量%以下である
ことを特徴とする水溶性金属加工油。 In the water-soluble metalworking oil according to claim 1 or 2,
The water-soluble metalworking oil, wherein the blending amount of the component (A) is 0.1% by mass or more and 14% by mass or less based on the total amount of the processing oil.
前記(B)成分の配合量が、当該加工油全量基準で10質量%以上60質量%以下である
ことを特徴とする水溶性金属加工油。 In the water-soluble metalworking oil according to any one of claims 1 to 3 ,
The amount of the component (B) is 10% by mass or more and 60% by mass or less based on the total amount of the processing oil.
前記(C)成分の配合量が、当該加工油全量基準で5質量%以上30質量%以下である
ことを特徴とする水溶性金属加工油。 In the water-soluble metalworking oil according to any one of claims 1 to 4 ,
The amount of the component (C) is 5% by mass or more and 30% by mass or less based on the total amount of the processing oil.
前記(D)成分の配合量が、当該加工油全量基準で1質量%以上20質量%以下である
ことを特徴とする水溶性金属加工油。 In the water-soluble metalworking oil according to any one of claims 1 to 5 ,
The blending amount of the component (D) is 1% by mass or more and 20% by mass or less based on the total amount of the processing oil.
さらに、(E)アセチレングリコール系界面活性剤を配合してなる
ことを特徴とする水溶性金属加工油。 In the water-soluble metalworking oil according to any one of claims 1 to 6 ,
(E) A water-soluble metalworking oil characterized by comprising an acetylene glycol surfactant.
前記(E)成分がアセチレングリコールエチレンオキサイド付加物である
ことを特徴とする水溶性金属加工油。 In the water-soluble metalworking oil according to claim 7 ,
The water-soluble metalworking oil, wherein the component (E) is an acetylene glycol ethylene oxide adduct.
前記(E)成分の配合量が、当該加工油全量基準で1質量%以上15質量%以下である
ことを特徴とする水溶性金属加工油。 In the water-soluble metalworking oil according to claim 7 or 8 ,
The amount of the component (E) is 1% by mass or more and 15% by mass or less based on the total amount of the processing oil.
ことを特徴とする水溶性金属加工油。 The water-soluble metalworking oil according to any one of claims 1 to 9 , wherein the water-soluble metalworking oil is a stock solution in which water is blended in an amount of 15% by mass to 75% by mass. .
ことを特徴とする金属加工用クーラント。 A coolant for metalworking, wherein the water-soluble metalworking oil according to any one of claims 1 to 10 is diluted to 2 to 200 times (volume) with water.
ことを特徴とする金属加工用クーラント。 The coolant for metal processing according to claim 11 is for grinding.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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JP2014070521A JP6283552B2 (en) | 2014-03-28 | 2014-03-28 | Water-soluble metalworking oil and coolant for metalworking |
EP15768985.2A EP3124583A4 (en) | 2014-03-28 | 2015-03-23 | Water-soluble metalworking fluid, and metalworking coolant |
CN201580016335.5A CN106459823B (en) | 2014-03-28 | 2015-03-23 | Water-soluble metal working oil and coolant for metal working |
PCT/JP2015/058733 WO2015146908A1 (en) | 2014-03-28 | 2015-03-23 | Water-soluble metalworking fluid, and metalworking coolant |
US15/129,436 US20170175030A1 (en) | 2014-03-28 | 2015-03-23 | Water-soluble metalworking fluid, and metalworking coolant |
KR1020167023754A KR20160137981A (en) | 2014-03-28 | 2015-03-23 | Water-soluble metalworking fluid, and metalworking coolant |
TW104109791A TW201540825A (en) | 2014-03-28 | 2015-03-26 | Water-soluble metalworking fluid, and metalworking coolant |
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JP2014070521A JP6283552B2 (en) | 2014-03-28 | 2014-03-28 | Water-soluble metalworking oil and coolant for metalworking |
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JP2015189954A JP2015189954A (en) | 2015-11-02 |
JP6283552B2 true JP6283552B2 (en) | 2018-02-21 |
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US (1) | US20170175030A1 (en) |
EP (1) | EP3124583A4 (en) |
JP (1) | JP6283552B2 (en) |
KR (1) | KR20160137981A (en) |
CN (1) | CN106459823B (en) |
TW (1) | TW201540825A (en) |
WO (1) | WO2015146908A1 (en) |
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TWI713723B (en) * | 2016-03-31 | 2020-12-21 | 日商出光興產股份有限公司 | Water-soluble quenching oil composition, its concentrated solution and quenching method |
US11015230B2 (en) | 2016-03-31 | 2021-05-25 | Idemitsu Kosan Co., Ltd. | Water-soluble quenching oil composition |
JP6892100B2 (en) | 2016-12-27 | 2021-06-18 | 出光興産株式会社 | Water-based quenching liquid composition and method for producing metal materials using it |
WO2018124120A1 (en) * | 2016-12-28 | 2018-07-05 | 花王株式会社 | Cleaning liquid for aqueous ink |
EP3412756A1 (en) | 2017-06-06 | 2018-12-12 | Rhenus Lub GmbH & Co. KG | Cooling lubricant for composite materials |
JPWO2019189148A1 (en) * | 2018-03-30 | 2021-03-25 | 出光興産株式会社 | Water-soluble metal processing oil and metal processing method |
CN113677781A (en) | 2019-04-12 | 2021-11-19 | 巴斯夫欧洲公司 | Metalworking fluids containing branched alcohol propoxylates |
CN113337326B (en) * | 2020-06-10 | 2023-05-23 | 沙索(中国)化学有限公司 | Aqueous composition comprising a water-soluble glycerol-based polyalkylene glycol and use thereof |
EP3957708A1 (en) | 2020-08-17 | 2022-02-23 | Speira GmbH | Cooling lubricant for the cold rolling of aluminium |
CN115989312A (en) * | 2020-08-31 | 2023-04-18 | 出光兴产株式会社 | Water-soluble metal working oil |
FR3124801B1 (en) * | 2021-07-01 | 2024-07-05 | Totalenergies Marketing Services | Aqueous lubricating composition for metalworking |
FR3124800B1 (en) * | 2021-07-01 | 2024-07-05 | Totalenergies Marketing Services | Aqueous lubricating composition for metalworking |
WO2024204296A1 (en) * | 2023-03-31 | 2024-10-03 | 出光興産株式会社 | Processing fluid |
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2014
- 2014-03-28 JP JP2014070521A patent/JP6283552B2/en active Active
-
2015
- 2015-03-23 WO PCT/JP2015/058733 patent/WO2015146908A1/en active Application Filing
- 2015-03-23 US US15/129,436 patent/US20170175030A1/en not_active Abandoned
- 2015-03-23 CN CN201580016335.5A patent/CN106459823B/en active Active
- 2015-03-23 KR KR1020167023754A patent/KR20160137981A/en unknown
- 2015-03-23 EP EP15768985.2A patent/EP3124583A4/en not_active Withdrawn
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US20170175030A1 (en) | 2017-06-22 |
EP3124583A1 (en) | 2017-02-01 |
EP3124583A4 (en) | 2017-09-06 |
KR20160137981A (en) | 2016-12-02 |
JP2015189954A (en) | 2015-11-02 |
CN106459823B (en) | 2020-01-24 |
TW201540825A (en) | 2015-11-01 |
WO2015146908A1 (en) | 2015-10-01 |
CN106459823A (en) | 2017-02-22 |
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