JPH0753872B2 - Water-soluble cutting oil composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water-soluble cutting oil composition. More specifically, by using an hydroxylated oil or fat obtained by epoxidizing an animal or vegetable oil or fat or its hardened oil having an unsaturated double bond, or an alkali metal salt or amine salt thereof, the emulsion stability and lubricity are improved. The present invention relates to a water-soluble cutting oil composition having excellent rustproofing properties and antiseptic properties, and having extremely low foaming power, which can be used for cutting and heavy cutting agents that do not require polishing after cutting.

[Conventional technology]

Conventional water-soluble cutting oils that use compounds containing chlorine or sulfur (1), those that use amine compounds such as alkanolamines (2), or those that contain alkali metal or amine salts of fatty acids (3) Etc. are often used. It is also known that a hydrophobic substance such as mineral oil or higher fatty acid ester is used in combination with a surfactant to form an emulsion of the above compound.

However, the one using a compound containing chlorine and sulfur has extreme pressure property and excellent lubricity, but has a problem that rust is easily generated. Further, those using alkanolamine are excellent in rust prevention and defoaming properties, but are inferior in lubricity and can only be used for grinding of general steel materials. In addition, the soluble type cutting surface containing fatty acid alkali metal or amine salt has excellent cleanability and rust prevention, but it cannot be used for cutting unless an extreme pressure additive is added to improve lubricity. . Emulsion-type cutting oil based on mineral oil has the best lubricity among water-soluble cutting oils, so it is widely used for cutting steel, cast iron, and non-ferrous metals. However, it has a problem in that it requires equipment for treatment of waste water, requires a large amount of cost, deteriorates emulsion stability when used for a long period of time, and easily decomposes. In addition, it is known that emulsion type cutting oil has a better lubricity than oil-based bases such as animal and vegetable oils and fatty acid esters, and is suitable for cutting under severe conditions such as heavy cutting. ,
The stability as an emulsion is extremely poor as compared with mineral oil, and there is a drawback that it cannot be used as a base oil and cannot be mixed with a large amount of mineral oil.

[Problems to be Solved by the Present Invention]

In the conventional water-soluble cutting oil as described above, a hydrophobic substance such as mineral oil is not used as much as possible, and a hydrophobic substance such as oil and fat and a polymer of acrylic acid amide are used together (4) 59-227985), a method using a salt obtained by neutralizing the carboxyl group of oxidized paraffin and a salt of ricinoleic acid polycondensate (5) (JP-A-59-71394), and a method using a salt of hydroxylated fatty acid (6). (JP-A-60-88096) and the like have been reported. The method (4) has good lubricity, but has a drawback that it is inferior in rust prevention. The methods (5) and (6) are excellent in rust prevention and cleanability, but inferior in lubricity. , (4) ~
The drawback common to (6) is inferior antiseptic properties.

As mentioned above, if the conventional emulsion type cutting oil can maintain the lubricity, the anti-rust property, the cleaning property and the antiseptic property are inferior, and if the anti-rust property and the cleaning property are improved, the lubrication property is inferior. There is no solution to the drawbacks of oil.

Focusing on these problems, as a result of intensive studies by the present inventors, in a water-soluble cutting oil to be a solubilized product or an emulsion, excellent in emulsion stability, lubricity, rust prevention, antiseptic properties, In addition, the present invention succeeded in obtaining an excellent water-soluble cutting oil composition that has extremely low foaming power and can perform heavy cutting or cutting that does not require polishing after cutting, and has reached the present invention.

[Specific means for solving problems]

That is, the present invention has an unsaturated double bond, animal or vegetable oils or fats or hydrogenated oils thereof as a starting material, and after the unsaturated double bond is epoxidized, the ring is opened to generate a hydroxyl group, and a hydroxyl value (hereinafter "OHV") is 100
~ 450 and oxirane value (hereinafter referred to as "OXV") of 0.05 ~
Hydroxylated fats and oils having properties of 5.0 (hereinafter referred to as "O
"H-oil and fat") or as a salt neutralized with an alkali metal or an alkanolamine is used to provide excellent emulsion stability, lubricity, rust prevention, antiseptic properties, and foamability. The present invention has succeeded in obtaining an excellent water-soluble cutting oil composition which has almost no effect and has the effect of suppressing foaming or defoaming against foaming caused by other substances.

The animal and vegetable fats and oils or hydrogenated oils thereof having an unsaturated double bond used in the present invention are required to have an average of at least two unsaturated double bonds in the triglyceride molecule, which has an iodine value (hereinafter 55) as IV)
It is preferably not less than 80, more preferably not less than 80. Animal and vegetable oils and fats that can be used for these include palm oil,
Flaxseed oil, millet oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, olive oil, cottonseed oil, rice bran oil, beef tallow, pork fat, cod oil, sardine oil, mackerel oil, squid oil, orange ruffy, etc., Further, as these hardened oils, hydrogenated ones are used so that an average of two or more unsaturated double bonds remain in the molecule after hardening. One or more selected from these animal and vegetable oils and fats and hydrogenated oils thereof are used as the raw material of the present invention. These oils and fats are epoxidized, and then part or most of the produced epoxy ring is opened to obtain an OH oil and fat. The epoxidation reaction and hydroxylation reaction are described in Japanese Patent Application No. 61-287411. It was performed by the method of.

OH-containing fats and oils have a hydroxyl group and an oxirane group in the molecule, but the presence of hydroxyl groups makes the fats and oils hydrophilic, making them soluble or emulsifying in water and having low foaming properties that also have defoaming properties. Further, it has cleaning properties. Also, by having both a hydroxyl group and an oxirane group, it suppresses the growth of bacteria, bacteria, etc. and has antiseptic properties, and since OH-ized oils and fats have a triglyceride structure, they are not adsorbed on the metal surface. Has a high oil film strength, has superior lubricity compared to emulsion type cutting oil based on mineral oil, and can perform cutting without polishing after cutting or cutting of superalloy. It has characteristics not found in oil.

The molecule of a normal surfactant is divided into two groups, a hydrophobic group and a hydrophilic group, but the OH-modified fat and oil used in the present invention has a hydrophobic group at the end of the three fatty acid groups constituting the triglyceride. It has three ester groups, and there is a hydroxyl group and an oxirane group between the hydrophobic group and the ester group,
Hydroxyl group acts as a hydrophilic group, and hydrophobic group-hydrophilic group-
It has the structure of an ester group, and the ester group is more hydrophobic than the hydroxyl group. Therefore, there is a hydrophilic group between the hydrophobic groups. It is a substance. It seems that it is derived from such a structure, but by using OH-modified fats and oils,
With conventional water-soluble cutting oils, 20-
In contrast to the use of a large amount of 40%, in the present invention, since the OH-ized oil and fat or its neutralized product itself has an emulsifying property and acts as a lubricity improver, it is necessary to use a large amount of emulsifier as in the past. There is no problem, the problem that waste liquid treatment is difficult is small, and it has the feature that it can be easily treated.

The OH-oil and fat used here has OHV100-450 and OXV0.05-5.0, but if OHV is 100 or less, the surface activity is low,
It has almost no hydrophilicity or emulsifying property. Further, when OHV is 450 or more, the hydrophilicity is high, it is transparently dissolved in water, and the emulsifying property is extremely high, but the OXV is low, so that the antiseptic property is lowered or almost disappeared. OHV is preferably 180 to 360 as the range having hydrophilicity and emulsifying property, and at the same time, OXV needs to be in the range of 0.05 to 5.0 in order to have antiseptic properties.
When OXV is 0.05 or less, it has almost no antiseptic property, and when it is 5.0 or more, hydrophilicity, emulsifying property and antiseptic property are deteriorated. From the viewpoint of antiseptic property, the preferable range of OXV is 0.1 to 4.0.

To use the OH-ized oil and fat having the above properties as a water-soluble cutting oil, the OH-oiled oil has a high OHV, has sufficient hydrophilicity, and solubilizes in water as it is, or stably in water. In the case of dispersion, the OH-ized fat and oil is dissolved or dispersed in water as a single substance and used. Also, when the solubility or dispersibility in water is not sufficient, the carboxyl group generated during the production of OH-modified fats and oils is neutralized with an alkali metal or alkanolamine, ammonia, etc. to form a salt, which is then dissolved in water. Property or dispersibility is improved. If the dispersibility is still insufficient, an emulsifier is added for use.

It is also possible to use an OH-modified fat or oil or a neutralized product thereof mixed with a mineral oil. In this case, if the two are not uniformly dissolved even when mixed, a fatty acid ester, a fatty acid, a surfactant, etc. are added to control the dissolution. Other oils and fats and extreme pressure additives may be added as appropriate to control the lubricity and extreme pressure properties. The weight ratio of the OH-oiled fat or oil or its neutralized product to the mineral oil is preferably 1 to 4: 9 to 6, respectively.

The mineral oil used here is machine oil (JIS K-223
8), turbine oil (JIS K-2213), light oil (JIS K-220)
4), gear oil (JIS K-2219), liquid paraffin (JIS
K-2231) and the like can be mentioned, and all those specified in each JIS can be used.

Other base oils or oiliness agents include synthetic oils such as diesters and hinder esters, animal and vegetable oils and fats, and alcohol esters of fatty acids obtained by decomposing animal and vegetable oils and the like.

As the surfactant, anionic and nonionic surfactants are mainly used, and as the anionic surfactant, fatty acid soap, naphthenic acid soap, alkyl sulfate ester salt, sulfated oil of animal and vegetable oil, Petroleum sulfonates and the like, and as the nonionic surfactant, higher alcohols, alkylphenols, polyoxyethylene nonionic surfactants obtained by addition reaction of oxyethylene with fatty acids, and sorbitan fatty acid esters, Examples thereof include polyhydric alcohol ester-based nonionic activators such as glycerin fatty acid ester, and fatty acid alkylolamide activators such as fatty acid diethanolamide.

As the rust preventive agent, in addition to the above fatty acid soaps, sulfonates, amines such as triethanolamine, carboxylic acid amides, organic rust preventive agents such as alkyl phosphates, and the like,
Examples of the inorganic rust preventive include nitrite, phosphate and borate.

Further, examples of the extreme pressure additive include chlorinated paraffin, chlorinated fatty acid, hardened oil and fat, alkyl phosphate, alkyl phosphite, molybdenum disulfide, graphite and the like.

In addition, pour point depressants such as ethylene glycol and propylene glycol, and thickeners such as polyethylene glycol and CMC sodium polyacrylate may be appropriately mixed and used as necessary.

As described above, a water-soluble cutting oil composition obtained by using an OH-modified fat or oil is solubilized or emulsified in water to form a stable emulsion, and the metal is cut using the emulsion. Higher machinability is obtained by
After processing, the metal has excellent rust resistance, and its emulsion has extremely low foaming properties.
It has the properties of suppressing foaming or defoaming, and preventing spoilage of the emulsion due to long-term use.

〔Example〕

 The present invention will be described in detail below with reference to examples.

First, OH-modified fats and oils having the properties shown in Table 1 (Measurement Examples 1 to 1
7) was synthesized, and those having low hydrophilicity were neutralized, and the emulsion stability, foaming property and pressure resistance thereof were measured, and the results are shown in Table-1.

The sample of the measurement example was synthesized by the method described in Japanese Patent Application No. 61-287411, and the test method was as follows.

i) Emulsion stability: 100 ml of a 10 wt% aqueous solution of each sample was placed in a 100 ml graduated cylinder having a scale height of 200 mm with a stopper and allowed to stand for 1 minute and then allowed to stand, and the height of the solution layer after 24 and 48 hours ( mm) is measured.

ii) Foaming property: 10 ml of 5% by weight aqueous solution or dispersion of each sample
In a 100 ml graduated cylinder with stopper and
The foaming force was measured by the foaming height (mm) immediately after stopping the shaking at 1 ° C for 1 minute and after 5 minutes.

iii) Pressure resistance: Using a shell-type four-ball friction tester, in each of Measurement Examples 1 to 7, OH-oiled oil (unneutralized) was directly fed, and a pressure-resistant load (kg / cm ² ) at 20 ° C. and 600 rpm was applied. It was measured.

From the results shown in Table 1, in Measurement Example 1, the particles are dispersed in water to some extent without being neutralized and have almost no foaming property, but the pressure resistance is extremely low and the machinability is poor. Measurement Examples 2 and 3 do not disperse in water unless they are neutralized and have a certain level of pressure resistance, but their foaming properties are extremely large, and they are not suitable for use as a water-soluble cutting oil.
In measurement example 4, neutralization provides good emulsion stability, low foaming property, and extremely high pressure resistance, and is suitable for water-soluble cutting oil. Measurement Example 5 has excellent water solubility without neutralization, high stability, low foaming power, high pressure resistance, and is suitable for water-soluble cutting oil. Measurement Example 6 is dispersed as it is in water,
Foamability is low, but pressure resistance is not good. Measurement Example 7 was dissolved in water, was excellent in stability, and had no foaming property.
Although it is satisfactory as an aqueous solution, it has low pressure resistance and cannot be used as cutting oil.

Example 1 Using mixed fish oil [IV180.5, saponification value (hereinafter referred to as "SV") 191.1] mainly composed of sardine oil as a raw material, epoxidation followed by hydroxylation resulted in OHV264.0, OXV0.5, AV68.5. OH
A fat and oil (A) was obtained.

40 parts by weight of triethanolamine (hereinafter referred to as "TEA") was added to 60 parts by weight of the OH-ized oil and fat (A) and mixed well to obtain a cutting oil (A).

Example 2 Epoxidized OHV190.2, OXV3.8 and AV24.8 OH-modified fats and oils (B) were obtained from soybean white oil (IV133.6, SV191.9) as a raw material. TEA (8.5 parts by weight) was added to OH-ized oil (B) (91.5 parts by weight), and the mixture was neutralized and mixed well to obtain (B) neutralized product.
(B) 82 parts by weight of neutralized product, 5 parts by weight of tertiary nonyl polysulfide and TEA salt of lauryl phosphate monoester 13
Parts by weight were added and mixed well to obtain cutting oil (B).

Example 3 The same mixed fish oil as used in Example 1 was epoxidized to obtain OHV430, OXV0.2, AV0.05 OH-modified fats and oils (C),
This OH-ized oil and fat was used as cutting oil (C) without being neutralized.

Example 4 1 to 75 parts by weight of the OH-modified fat and oil (C) obtained in Example 3
25 parts by weight of No. spindle oil was added and mixed well to obtain a cutting oil (D).

Example 5 The same mixed fish oil as used in Example 1 was epoxidized to obtain OHV oils of OHV303, OXV1.2 and AV30.2. To 61 parts by weight of this, 39 parts by weight of TEA was added to give a neutralized product (E)
To get 77 parts of the neutralized product (E) and 23 parts of oil were mixed to obtain a cutting oil (E).

Comparative Examples 1 and 2 were respectively prepared in the cutting oils (A) to (E) obtained as described above, and the emulsion stability, antiseptic property, rust preventive property, cutting performance, and surface roughness were measured. I went.

Regarding the emulsion stability, antiseptic property and rust preventive property during cutting, a total of 7 points of Examples and Comparative Examples were arranged and tested under the same conditions. Regarding the cutting performance test, four points of Examples 1, 3, and 4 and Comparative Example 1 were broaching using soft iron as a work material, and three points of Examples 2 and 5 and Comparative Example 2. Was subjected to a grinding process using alloy steel as a work material and compared with each other.

The contents and test methods of Comparative Examples 1 and 2 are as follows: i) Comparative Example Comparative Example 1: Emulsifying cutting oil in which a mineral oil is used as a base oil, and a chlorine-based extreme pressure additive and an emulsifier are added. Comparative Example 2: High grade Water-soluble cutting oil based on TEA salt of fatty acid and added with emulsifier ii) Emulsion stability test during cutting 100% 5% aqueous solution of each sample was prepared and used to cut the work material with a band saw. The stability of the solution was determined up to 20,000 times, and the presence or absence of the oil layer was visually judged to determine the stability of the solution, and the results were shown by the number of cuts when the oil layer separation was observed (Table-2). Machine name Band saw machine Material SKH57 ・ Work material S45C (80φ × 620mm) ・ Hardness (HB) 174 to 176 ・ Cutting speed 200m / min ・ Cutting agent flow rate 10 / min iii) Antiseptic test i) In the emulsification stability test, after filtering each sample solution after cutting the work material 10,000 times, collect 2 g of the filtrate, Add 10 g of agar medium, mix, put in a container, and leave it in an incubator at 37 ℃ for 30 days. During that time, observe the condition after 1, 7, 14, 30 days with a microscope, and check for the presence or absence of various bacteria. It was judged. The results are shown in Table-2.

iv) Anticorrosion test After filtering each sample solution after cutting the work material 10,000 times in the emulsion stability test of i), 300 ml of the filtrate and 100 g of dry cut cast iron chips were put in a 500 ml Erlenmeyer flask, 6 tightly closed
It was put in a constant temperature bath at 0 ° C. and left standing for 48 hours. Meanwhile, 0, 10, 2
After 4 and 48 hours, the rusting condition of the cast iron chips was visually observed and evaluated according to the following criteria. The results are shown in Table 2.

⊚: No rust generation ○: Slight rust formation

X: Remarkable occurrence is seen.

v) Machinability test Using the 10 wt% solution of each sample of Examples 1, 3 and 4 and Comparative Example 1, a surface broaching test was performed on 10 workpieces under the conditions described below, and the cutting resistance value was obtained. Was measured and the average value was calculated.

○ Cutting conditions Tester name Surface broach tester Tool name 6-blade surface broach (80μ / blade) Rake angle: 15 degrees Slope angle: 2 degrees Same material SKH55 Work material Scr22 (Brinell hardness: 85-93) Cutting speed 4m / min vi) Surface roughness For every 10 workpieces after the machinability test,
After cleaning by wiping with hexane, the surface roughness was measured with a stylus type surface roughness meter, and the average value of 10 sheets was obtained.

vii) Grindability test Using 1% by weight solutions of the samples of Examples 2 and 5 and Comparative Example 2, the number of strokes was changed to 100 to 500 by a surface grinder under the conditions described below, and each stroke was covered. Grinding was performed on 10 pieces of the cutting material, and the grinding resistance value was measured.

○ Grinding conditions Test machine name Surface grinder (PSG-5EV type) Grinding method Plunge cut Work material: Material Ti-6AL-4V: Shape 100 x 4.7 x 70 mm: Hardness (HB) 562 Grindstone: Specification WA80K8V: Dimension 205φ × 19 mm or more, Table-2 shows the results of the emulsion stability, antiseptic and rustproof tests, Table-3 shows the test results of the machinability and surface roughness, and Table-4 shows the test results of the grindability. showed that.

[Effects of the Invention] As described above, the water-soluble cutting oil composition of the present invention has an unsaturated double bond, and has a hydroxyl value of 100 to 450 and an oxirane value of 0.05, which are obtained by deriving from animal or vegetable oils and fats or hydrogenated oils thereof. A hydroxylated fat or oil having ~ 5.0 or a neutralized product thereof is used, and as compared with a conventional water-soluble cutting oil, the composition does not use an emulsifier, or even if it is used in a small amount, it has an extremely stable emulsifying property. Can be obtained for a long period of time, and high rust resistance and antiseptic property can be obtained without adding an anticorrosive agent or an antiseptic agent. With this, extremely smooth surface cutting can be performed without polishing after cutting. It has an effect that cutting of stainless steel, superalloy, etc. can be performed.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area C10N 30:12 30:16 40:22

Claims (1)

[Claims] 1. A hydroxyl value of 100 obtained by deriving from an animal or vegetable oil or fat or a hydrogenated oil thereof having an unsaturated double bond.
A water-soluble cutting oil composition comprising a hydroxylated oil or fat having an oxirane number of 0.05 to 5.0 or a neutralized product thereof.