JP3267894B2 - Water-soluble oil for metal processing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble oil agent for metal working which can be widely applied to plastic working such as grinding and cutting. The present invention relates to a metal working water-soluble oil agent that does not accumulate or is easy to clean even when scattered or adheres to a surface or a floor, does not deteriorate the surrounding working environment, and contributes to an improvement in productivity.

[0002]

2. Description of the Related Art Cutting fluids widely used in the field of cutting and grinding are based on mineral oil and contain a water-insoluble cutting fluid which is not diluted with water, a mineral oil, a surfactant, an organic amine and the like. There are water-soluble oils to be diluted ("JIS K
2241 cutting fluid "). However, with the recent increase in productivity, the requirements for machining conditions have become more and more strict, and in the cutting and grinding fields where water-insoluble oils have been applied, problems such as smoke, mist, and ignition have occurred. The water-soluble oil agent has been widely used instead of the water-insoluble oil agent in cutting, drilling, milling, etc. and many grinding fields where water-insoluble oil agent was used in the past. . The composition of the water-soluble oil, which has been widely used in this way, is obtained by adding a surfactant, an organic amine, and the like to mineral oil, which is a base oil of the water-insoluble oil, in order to maintain cutting and grinding properties. And an oil agent (stock solution) of a type that can be diluted with water (usually called an emulsion type). When this oil solution (stock solution) is used after being diluted with water, for example, about 10 to 50 times, the problems such as smoke, mist, and ignition during machining which have conventionally been problems with water-insoluble oil agents have been solved. .

However, when this type of oil is diluted with water and used, the diluted oil (emulsion) is liable to decay due to the mineral oil contained in the undiluted solution of the oil, and as a result, a bad smell is generated and the surrounding work environment is generated. There is a problem that worsens. Further, a new problem arises in that diluent oil scattered around the machine tool and on the floor accumulates as a sticky substance and contaminates the surroundings. The cause of this decay, the generation of sticky substances,
As described above, it is known that the mineral oil is used in a large amount in this water-soluble oil agent composition (added and used to contribute to the improvement of the cutting property and the grinding property). Therefore, the development of alternative materials to replace this mineral oil was studied. As such a mineral oil substitute, a polyoxyalkylene glycol compound represented by the following structural formula B or C has been developed. HO- [CH ₂ CH ₂ O] l- [CH ₂ -CH (CH ₃ ) -O] m- [CH ₂ CH ₂ O] nH (B) CH ₃ CH ₂ CH ₂ CH _2- [CH ₂ -CH (CH ₃ ) -0] a- [CH ₂ CH ₂ O] bH (C) Commercially available products include (Pluronic (UCC USA), Unilube (Nippon Oil & Fats Co., Ltd.), Pronon (Sanyo Chemical Co., Ltd.), Newpole (Newpole PE64, etc.) (Sanyo Chemical Co., Ltd.).

A water-soluble metal working oil (stock solution) obtained by adding a surfactant and an organic amine to this compound is particularly called a synthetic fluid, and is used as a new type of water-soluble oil for cutting and grinding. Widely used in the field. This oil agent uses polyoxyalkylene glycol instead of mineral oil as a cutting and grinding property improver. Unlike conventional metal working oil agents (emulsion type) to which mineral oil has been added, decay and peripheral parts of machine tools The working environment was improved without the floor being contaminated with stickies. However, when used in a grinding process (especially creep grinding, double-sided flat surface machining), etc., which requires a large amount of lubrication of metalworking fluids, or in transfer machines for processing engine parts of automobiles, the defoaming properties of diluent fluids are poor, and coolant tanks and grinding It was found that the foam overflowed from the board, contaminating the floor.

In order to improve the defoaming property, a polyoxyalkylene glycol compound represented by the following structural formula D (which is called a reverse type for distinguishing from a conventional polyoxyalkylene glycol compound) has been developed. (BASFJAPAN, trade name 25 R-4
, BASF USA trade name 10R-5). _{HO- [CH 2 CH (CH 3} ) O] a- [CH 2 CH 2 O] b- [CH 2 CH (CH 3) O] cH (D) Then, defoaming of using the compounds of this such Excellent water-soluble metalworking oils have also been proposed (JP-A-8-2319).
No. 77, JP-A-8-239683). However, when the reverse type polyoxyalkylene glycol compound is used for a water-soluble metalworking oil, the influence of the hydrophobic group [CH ₂ —CH (CH ₃ ) O] appears strongly, and hydrogen bonding and chain matching are reduced. As a result, there is a problem that the compatibility with water is weakened, and the contribution to the improvement of the cutting property and the grinding property of the metal working oil is reduced.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the cutting and grinding properties, to have excellent defoaming properties, to improve the productivity without deteriorating the working environment, and to improve the productivity. It is to provide an oil agent.

[0007]

The present invention provides a compound represented by the following structural formula A:
The present invention provides a water-soluble oil agent for metal working, which comprises a block type polyoxyalkylene glycol represented by the formula: Formula _{A HO- [CH 2 CH (CH} 3) O / CH 2 CH 2 O] x- [CH 2 CH 2 O] y- [CH 2 CH (CH 3) O / CH 2 CH 2 O] zH ( x and z are integers of 8 to 450, y is an integer of 3 to 200, and CH ₂ CH (CH ₃ ) O and CH in x and z blocks
The weight ratio of ₂ CH ₂ O is 5:95 to 95: 5, respectively. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The preferred water-soluble oil agent for metal working of the present invention contains the following components. (a) a polyoxyalkylene glycol represented by the general formula A, (b) a direct or branched monocarboxylic acid and / or dicarboxylic acid having 6 to 22 carbon atoms, and (c) a neutralized aqueous solution of the carboxylic acid. Basic substances necessary for the transformation.

The molecular weight of the block type polyoxyalkylene glycol represented by the structural formula A used in the present invention is preferably from 1,000 to 50,000, more preferably from 1200 to 30,000. The weight ratios of CH ₂ CH (CH ₃ ) O and CH ₂ CH ₂ O are respectively
Preferably 5:95 to 95: 5, more preferably 10
90 to 90:10. Structural formula A used in the present invention
Can be easily produced by reacting ethylene glycol with a desired amount of propylene oxide, ethylene oxide or a mixture thereof. The content of the component (a) in the oil solution (stock solution) of the present invention is preferably 1
%, More preferably 5 to 70% by weight, most preferably 5 to 60% by weight. If the amount is less than 1% by weight, the contribution to the improvement of cutting and grinding properties is small. Sometimes.

In the present invention, examples of the straight-chain or branched monocarboxylic acid and / or dicarboxylic acid having 6 to 22 carbon atoms used as the component (b) include capric acid, caprylic acid, nonanoic acid and lauryl acid. , Myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linoleic acid, arachinic acid, behenic acid, coconut oil fatty acids extracted from oils, soybean oil fatty acids, cottonseed oil fatty acids, etc. Include isononanoic acid, neodecanoic acid, isolauric acid, isostearic acid and the like. Examples of the dicarboxylic acid include adipic acid, sebacic acid, and dodecane diacid. Furthermore, examples of special monocarboxylic acids include hydroxystearic acid, ricinolenic acid, and naphthenic acid. Oil agent of the present invention (stock solution)
Wherein the content of the component (b) is preferably 1 to 30% by weight,
More preferably, the content is 3 to 30% by weight. If the content is less than 1% by weight, the properties cannot be sufficiently exhibited.
If it exceeds 0% by weight, cutting and grinding will be 10 times to 100 times.
When used as a double dilution oil, foaming may occur and the working environment may be deteriorated.

The basic substance of the component (c) according to the present invention comprises a component
It is added to neutralize the carboxylic acid of (b) and solubilize it in water, and also has the effect of maintaining the rust resistance of the oil agent well. Examples of such basic substances include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine,
Alkanolamines such as dipropanolamine and tripropanolamine; alicyclic amines such as cyclohexylamine and dicyclohexylamine; synthetic amines obtained by adding 1 to 6 mol of ethylene oxide to these amines;
3-bisaminomethylcyclohexane and the like.
Examples of the aliphatic amine include primary or secondary alkylamines having 8 to 18 carbon atoms (eg, 2-ethylhexylamine, laurylamine, stearylamine, oleylamine, etc.), and ethylene oxide added to these amines.
And synthetic amines such as isodecyl and isostearyl. Examples of the aromatic amine include benzylamine, metaxylenediamine, and synthetic amines obtained by adding 1 to 6 mol of ethylene oxide to these amines. Examples of the inorganic basic substance include a hydroxide of an alkali metal belonging to Group 1A of the periodic table (eg, lithium hydroxide, sodium hydroxide, and potassium hydroxide). In the oil agent (stock solution) of the present invention, the content of the component (c) is at least an amount necessary for neutralizing the carboxylic acid of the component (b) and solubilizing in water. If the amount of the basic substance added is less than the amount of neutralization of the carboxylic acid, the carboxylic acid cannot be solubilized in water. The total content of component (b) and component (c) is preferably 2 to 70% by weight, more preferably 3 to 70% by weight.
-60% by weight, most preferably 5-50% by weight.
If the amount is less than 2% by weight, the effect is insufficient because the amount is too small, and if it exceeds 70% by weight, the basicity is strong, causing dermatitis to the operator to use and the defoaming property of the oil agent is extremely low. It may decrease.

The water-soluble oil agent for metalworking of the present invention may contain the above component (a) alone, but preferably contains components (b) and (c), and further contains water (industrial water, tap water, deionized water). , Distilled water), and if necessary, an anionic surfactant, a nonionic surfactant, a preservative, a fungicide, a non-ferrous metal anticorrosive, an antifoaming agent and the like may be appropriately contained. In addition, in order to contribute to the improvement of machinability and grindability, base oils of synthetic oils, oil agents such as esters and higher alcohols, organic metal salts (molybdates, phosphates, phosphoric acid-zinc salts, alkaline earths) It is also possible to add and contain a friction modifier such as a salt and the like, and an extreme pressure agent such as a chlorine compound, a sulfur compound and a phosphorus compound. The oil agent of the present invention is used as an oil agent for metal working such as cutting, grinding, pressing, rolling, forging, drawing, etc., and is five-fold with water.
It is used after being diluted 200 times, usually 10 times to 100 times.

[0013]

EXAMPLES Hereinafter, the contents of the water-soluble oil agent of the present invention will be described in detail with reference to Examples and Comparative Examples in Table 1. In addition, the oil agent composition exemplified in Table 1 was diluted 30 times with tap water, and the performance of the diluted oil agent was examined in the same manner as in the example of use at the actual machining site of the factory. In addition, if the oil composition (stock solution) is cloudy, separated, or too viscous, the commercial value of the oil solution naturally declines. An evaluation was performed.

Test Method Appearance of oil composition (stock solution): 200 ml of 100 ml of stock solution
It is collected in a glass container with a lid, left at room temperature for one week, and the appearance after one week is visually determined. Judgment ：: Passing Transparent, no two-layer separation, and having fluidity ×: Rejection Turbidity, two-layer separation, precipitate formation, or viscous defoaming test 30-fold dilution 400 ml of the oil agent is collected in a 720 ml mixer for home electric appliances (manufactured by Toshiba) and operated at 9000 rpm for 3 minutes. Thereafter, the diluted oil agent is transferred to a 500 ml measuring cylinder, and the time until the bubbles disappear is measured. Grindability test 50 liters of a 30-fold diluted oil solution was placed in the coolant tank of a cylindrical grinder, and a grinding experiment was performed under the following grinding conditions in the same manner as in practice, and the grindstone was dressed once (sharpening).
Find out how many materials can be ground. The grinding wheel life is defined as the power value when the power consumption of the grinding machine increases by 30% from the power consumption value of the motor, and the quality of the oil agent is determined based on the number of processed materials to be ground up to that time.

(Grinding specifications) Machine tool: Cylindrical grinding machine Gup-32, manufactured by Toyota Koki Grinding wheel: WA100K (405 mmφ) Work material: Bearing steel (50 mmφ × 10 mm width) Grinding condition: Wheel peripheral speed: 2700 m / min Depth of cut : 2mm / min Cutting allowance: 1mm Measurement item: Grinding machine motor power (kw) Coolant tank: 60 liters Cutting performance test 70 liters of 30 times diluent is put into the coolant tank to the machining center machine, and the same cutting test as the actual under the following cutting conditions (Rolling tap test) is performed, and the quality of the oil agent is determined based on how many tap holes are opened before the rolling tap breaks. (Cutting specifications) Machine tool: Machining center machine made by Mori Seiki Processing method: Tapping Tool: Rolled tap (8mmφ) Material: Alloy steel (SCM21 300 × 400 × 30mm) Prepared hole: 7.2mm reamer finish (blind hole) Measurement items: Number of holes drilled before the rolled tap breaks Coolant tank: 100 liters

From the results of the actual rotation examples and comparative examples shown in Table 1, the actual rotation examples 1 to 5 of the water-soluble oil solutions (stock solutions) containing the components (a) to (c) of the present invention show the grindability and machinability. It can be seen that it sufficiently contributes to the improvement of the water content and that the defoaming property of the diluent oil is excellent. On the other hand, it can be seen that the oil agent containing the reverse type polyoxyalkylene glycol compound (Comparative Example 1) has excellent defoaming properties, but is inferior in cutting properties and grinding properties. Further, it can be seen that the conventional oil agent containing a normal type polyoxyalkylene glycol compound (Comparative Example 2) is excellent in grindability but inferior in defoaming property. Further, Comparative Example 3
From formulas 4 and 4, structural formula A: HO- [CH ₃ CH (CH ₃ ) O / CH ₂ CH ₂ O] x- [CH ₂ CH ₂ O] y- [CH ₃ CH (CH ₃ ) O /
In CH ₂ CH ₂ O] zH, CH ₂ CH (CH ₃ ) O in x and z blocks
It turns out that it is important that the weight ratio of CH ₂ CH ₂ O is 5:95 to 95: 5.

[0017]

EFFECT OF THE INVENTION The water-soluble oil agent for metalworking of the present invention sufficiently contributes to the improvement of grindability and machinability, is excellent in the defoaming property of a diluent oil agent, and contains no mineral oil. It can be said that it is a water-soluble metalworking fluid that is very balanced without deteriorating the working environment (rot, floor contamination) at the machining site.

[0018]

Table 1 Component Example Comparative Example 1 2 3 4 5 5 1 2 3 4 Polyoxyalkylene glycol (1) 35--------(2)-35-------(3)- − 70 − − − − − − (4) − − − 10 − − − − − (5) − − − − 50 − − − − (6) − − − − − − − 30 − (7) − − − − − − − − 30 (8) − − − − − 30 − − − − (9) − − − − − − − 30 − − Carboxylic acid Nonanoic acid 5 5 2 5 − 5 5 5 5 Laurylic acid 5 5 2 10 5 − 5 5 5 Dodecane diacid 5 5 2 5 3 − − 2 2 Basic substance Diethanolamine 30 30 10 40 30 20 30 30 30 Monoethanolamine − − − − − 10 − − − Water 20 20 14 30 12 35 30 28 28 of 30-fold dilutions the appearance of stock properties Yes Yes Yes Yes Yes Yes Yes Yes Yes antifoam a a a a a a C a C grindability a a - - a B a B B machinability - A A A B - B -

Characteristics of Polyoxyalkylene Glycol Molecular Weight Molecular Weight of [CH ₂ CH ₂ O] y Ratio of CH ₂ CH (CH ₃ ) O / CH ₂ CH ₂ O (1) 2000 500 90/10 (2) 3000 500 80 / 20 (3) 2000 500 70/30 (4) 5000 500 90/10 (5) 30000 400 50/50 (6) 3000 500 97/3 (7) 3000 500 3/97 (8) HO- [CH _{2 CH (CH 3) O] 15} - [CH 2 CH 2 O] 12 - [CH 2 CH (CH 3) O] 15 -H (BASF (USA) 25-R4 ) (9) HO- (CH 2 CH 2 O) 8 - [CH 2 CH (CH 3) O] 20 - (CH 2 CH 2 O) 8 -H (Sanyo Chemical Co., Ltd. Newpole PE64)

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C10M 125: 10 C10M 125: 10 133: 04) 133: 04) C10N 40:20 C10N 40:20 Z (58) Field surveyed (Int.Cl. . ^7, DB name) C10M 173/00 - 173/02 C10M 105/18 C10M 107/34 C10M 125/10 C10M 129/16 C10M 129/26 - 129/64 C10M 133/04 - 133/14 C10M 145/30 C10M 145/34 C10N 40:20-40:24

Claims (7)

(57) [Claims] 1. A water-soluble metal working oil containing a block type polyoxyalkylene glycol represented by the following structural formula A: Formula _{A HO- [CH 2 CH (CH} 3) O / CH 2 CH 2 O] x- [CH 2 CH 2 O] y- [CH 2 CH (CH 3) O / CH 2 CH 2 O] zH ( x and z are integers of 8 to 450, y is an integer of 3 to 200, and CH ₂ CH (CH ₃ ) O and CH in x and z blocks
The weight ratio of ₂ CH ₂ O is 5:95 to 95: 5, respectively. ) 2. The water-soluble oil agent for metal working according to claim 1, wherein the content of the block type polyoxyalkylene glycol represented by the structural formula A is 1 to 85% by weight. 3. The molecular weight of the block type polyoxyalkylene glycol represented by the structural formula A is from 1,000 to 5,
The water-soluble oil agent for metalworking according to claim 1, wherein the water-soluble oil agent is 0000. 4. A water-soluble metal working oil containing the following components (a) to (c): (a) a polyoxyalkylene glycol represented by the general formula A of claim 1, (b) a straight-chain or branched monocarboxylic acid and / or dicarboxylic acid having 6 to 22 carbon atoms, and (c) the carboxylic acid. Basic substances necessary for neutralization and water solubility. 5. The water-soluble oil agent for metal working according to claim 4, wherein the content of the component (a) is 5 to 70% by weight and the content of the component (b) is 1 to 30% by weight. 6. The water-soluble oil agent for metal working according to claim 4, wherein the basic substance is an organic amine and / or an inorganic basic substance. 7. The method according to claim 4, wherein the basic substance is at least one selected from the group consisting of alkanolamines, alicyclic amines, aliphatic amines, aromatic amines, and alkali metal hydroxides. 2. The water-soluble oil agent for metal working according to claim 1.