JPH04249595A - Water-soluble oil for metal working - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble metalworking oil, and more specifically, to a water-soluble metalworking oil that is less susceptible to deterioration due to microorganisms in metalworking such as cutting and grinding.

0002

[Prior Art] Water-soluble metal processing oils are used for purposes such as mineral oils, animal and vegetable oils, fatty acids, fatty acid esters, extreme pressure additives, surfactants, antifoaming agents, metal anticorrosives, antioxidants, and preservatives. The composition is mixed as appropriate depending on the composition. Such water-soluble metal processing oils are usually used by diluting them 10 to 100 times with water, and this diluted liquid is called a coolant. This coolant has lubricating performance (hereinafter referred to as "primary performance").
That's what it means. ) and performance related to workability and others (hereinafter referred to as "secondary performance") are required. Among these, secondary performance includes: - less corrosion to metals, - less deterioration of coolant, - harmless to the human body, - less foaming, and - no bad odor. In particular, low deterioration caused by microorganisms is an important performance. As the coolant deteriorates due to microbial deterioration, it not only generates a bad odor and worsens the working environment, but also significantly reduces the emulsification state of the coolant.
This is because it also reduces the primary performance and other secondary performances.
Furthermore, if mold grows in the coolant, it not only reduces the performance of the oil but also causes pipe clogging in the coolant circulation system. For this reason, as a method for preventing the deterioration of water-soluble metalworking oils due to microorganisms, for example, addition of a formalin slow-release preservative (bactericidal agent), etc. has been carried out.

0003

[Problems to be Solved by the Invention] However, although these preservatives generally have excellent quick-acting properties, they decompose or become inactive in a short period of time, so they have a problem in that their antiseptic and sterilizing effects are less durable. . In addition, many preservatives contain highly toxic compounds, so when using preservatives, it is necessary to always control their concentration while taking into account the effectiveness of the preservative, which requires a lot of effort and cost. There is. Additionally, various amine compounds have been added as a countermeasure against microbial deterioration; however, these amines are harmful to bacteria (
In particular, it has not been possible to impart a wide range of antibacterial properties against fungi. In this way, deterioration of the coolant due to microorganisms (bacteria, fungi) can be prevented for a long period of time.
The reality is that no water-soluble metalworking oil has been found that has little effect on the human body and is easy to manage. The present invention has been made in view of the above points, and includes cutting,
The object of the present invention is to provide a water-soluble metal processing oil that can prevent coolant from deteriorating due to microorganisms over a long period of time in metal processing such as grinding.

0004

[Means for Solving the Problem] As a result of extensive research into the relationship between the deterioration of water-soluble metal processing oils caused by microorganisms (bacteria and fungi) and the oil components, the present inventors discovered that quaternary ammonium salts and anion The present invention was completed based on the finding that deterioration caused by microorganisms can be prevented by using a surfactant in combination with a surfactant. That is, the water-soluble metal processing oil of the present invention has general formulas (I) to (V) of Chemical Formula 1.
and one or more compounds selected from quaternary ammonium salts represented by general formulas (VI) to (IX) of Chemical Formula 2, and an anionic surfactant. do. Specific examples of the quaternary ammonium salts represented by the general formulas (I) to (IX) include the following compounds. First, the compounds represented by the general formula (I) include dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, etc., and the compounds represented by the general formula (II) include:
didodecyldimethylammonium chloride, dioctyldimethylammonium chloride, dioctadecyldimethylammonium chloride, etc., represented by the general formula (III)
Examples of the compound represented by the above include dodecyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride, and octadecyldimethylbenzylammonium chloride. In addition, examples of the compound represented by the general formula (IV) include laurylpyridinium chloride, and examples of the compound represented by the general formula (V) include coconut alkylmethyldipolyoxyethylene ammonium chloride, oleylmethyldipolyoxy Examples of compounds represented by the general formula (VI) such as ethylene ammonium chloride include heptadecylamidoethylmethylammonium methosulfate and the like. Furthermore, as a compound represented by the general formula (VII), tridecylamide propyldimethylbenzyl ammonium chloride etc. can be used as a compound represented by the general formula (VII).
Examples of the compound represented by the formula (VIII) include tridecylamide propyldimethylhydroxyethylammonium perchlorate, and examples of the compound represented by the general formula (IX) include undecylamide ethylpyridium chloride. can. Further, as shown in the second invention, the content of the quaternary ammonium salt is preferably in the range of 0.01 to 10 parts by weight, when the entire oil solution is 100 parts by weight. If this content is less than 0.01 part by weight, the ability of the coolant to prevent deterioration caused by microorganisms will deteriorate.
On the other hand, if the amount exceeds 10 parts by weight, the rust prevention properties and liquid stability, which are one of the secondary performances of the coolant, will deteriorate.

Examples of the anionic surfactants include fatty acid soaps, fatty acid derivatives such as naphthenic acid soaps, sulfuric acid ester types such as long-chain alcohol sulfuric ester salts, polyoxyethylene alkylphenyl ether sulfuric ester salts, alkanesulfonates, Examples include sulfonate types such as petroleum sulfonates, phosphate types such as alkyl phosphate ester salts, and polyoxyethylene alkyl ether phosphate ester salts. Among these, carboxylic acid amine soap, tall oil, petroleum stophonate, and alkylbenzene sulfonate are particularly preferred. Here, as the carboxylic acid of the carboxylic acid amine soap, natural and synthetic fatty acids having 8 to 24 carbon atoms can be used, and as the amine, alkanolamines such as monoethanolamine and diethanolamine, morpholine, alkylamines and Cyclohexylamine etc. can be used. Further, as shown in the second invention, the content of this anionic surfactant is preferably in the range of 2 to 60 parts by weight, based on 100 parts by weight of the entire oil solution. If this content is less than 2 parts by weight, the stability when diluting the oil and the rust prevention properties will deteriorate, while if the content exceeds 60 parts by weight, there will be a lot of foaming and other oils will be easily drawn in, leading to drainage. This is because there are disadvantages such as time-consuming processing.

[0006] The water-soluble metal processing oil of the present invention includes:
In addition to the above essential ingredients, conventional cutting and grinding fluids include mineral oil, animal and vegetable oils, fatty acids, fatty acid esters, extreme pressure additives, surfactants, inorganic salts, antifoaming agents, preservatives, anticorrosives, antioxidants, etc. Those used can be appropriately added and used. Here, examples of the mineral oil include spindle oil, machine oil, cylinder oil, turbine oil, mineral bright stock, and the like. In addition, fatty acids include caprylic acid, capric acid, lauric acid, oleic acid,
stearic acid, behenic acid, adipic acid, pimelic acid,
Examples include suberic acid, azelaic acid, sebacic acid, ricinoleic acid, and ricinoleic acid. Furthermore, as extreme pressure additives, chlorinated extreme pressure additives such as chlorinated paraffin, chlorinated diphenyl, chlorinated naphthalene, chlorinated fatty acids, chlorinated fatty oils, sulfurized oils and fats, sulfurized olefins, dibenzyl disulfide, dodecyl Examples include sulfur-based extreme pressure additives such as disulfide, diphenyl disulfide, saturated fatty acid sulfide dialkyl dithiocarbamic acid-metal compounds, and phosphorus-based extreme pressure additives such as phosphite esters and phosphate esters. In addition, as nonionic surfactants, polyhydric alcohol fatty acid esters (sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene glycol fatty acid ester, polyoxyethylene glycerin fatty acid ester ), polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, long-chain alkyl sulfates, synthetic sulfonates (alkanesulfonates, arylsulfonates, alkylarylsulfonates, etc.), petroleum sulfonates, etc. Examples of the surfactant include fatty acid alkylolamide and the like. In addition, examples of inorganic salts include phosphates, borates, and the like.

[0007]

[Examples] The present invention will be explained in detail with reference to Examples below. Table 1 shows the composition of the emulsion-type water-soluble cutting fluid used in the present example and comparative example, and Table 2 shows the composition of the soluble-type water-soluble cutting fluid of the present example and comparative example. Note that the units of numerical values regarding the compositions in each table are parts by weight.

[Table 1]

[Table 2] In Tables 1 and 2, surfactants A1 to A4 are anionic surfactants, and surfactants B1 to B2 are nonionic surfactants. Specifically, surfactant A1 is diethanolamine oleate soap, surfactant A2 is sodium petroleum sulfonate, surfactant A3 is diethanolamine caprylate soap, and surfactant A4 is triethanolamine ricinoleate soap. Each is shown below. Further, surfactant B1 represents polyoxyethylene nonylphenol (9 moles of EO added), and surfactant B2 represents coconut fatty acid diethanolamide. Further, ammonium salt A is hexamethylenetrimethylammonium chloride, ammonium salt B is didodecyldimethylammonium chloride, ammonium salt C is
represents dodecyldimethylbenzylammonium chloride, ammonium salt D represents undecylamide ethylpyridium chloride, and ammonium salt E represents hexadecyltrimethylammonium chloride. Also,
A triazine preservative was used as the preservative. In order to clarify the performance of the water-soluble cutting fluid of the present invention shown in Tables 1 and 2, the following performance tests and actual machine tests were conducted.

A. Performance test (microbial deterioration test) (1)
Preparation of sample solutions Each of the oils shown in Tables 1 and 2 was diluted with sterilized water to prepare sample solutions. That is, the oil in Table 1 has a concentration of 3% by weight (hereinafter referred to as "%").
”. ), the oils in Table 2 were diluted with sterilized water to a concentration of 2%. (2) Test items and test conditions Pour 400ml of each sample solution into a sterilized flat-bottomed flask,
Shaking culture (rotation number: 200 rpm) was carried out at 0°C for 21 days. During the test period, a rotten emulsion (viable bacteria count: 2 x 104 cells/ml, yeast: 1 x 104 cells/ml) was used as the inoculum.
) 1% was inoculated on days 1, 2, 4, 8, 13 and 17 after the start of the test. A portion of each sample solution was aseptically collected on the test day, and the number of viable bacteria (cells/ml), filamentous fungi (cells/ml), and yeast (cells/ml), pH, and odor were examined. These measurement methods are shown below. (2) Measurement of the number of viable bacteria, filamentous fungi, and yeast The number of viable bacteria was determined by the plate counting method using an ordinary agar medium. In addition, the number of filamentous bacteria was measured by the plate counting method using potato dextrose agar medium supplemented with antibiotics (chloramphenicol and tetracycline), and the number of yeast bacteria was measured using Sapro agar medium supplemented with antibiotics (tetracycline). . (2) Measurement of pH pH was measured using a glass electrode pH meter. In addition, p
The decrease in H is considered to be caused by microorganisms decomposing sample components, and is estimated to be correlated with the degree of microbial deterioration. ■Evaluation of Odor Odor was evaluated by dividing the odor strength into three ranks as shown below. ○: No putrid odor, △: Slightly putrid odor, ×: Putrid odor. The above results are shown in Tables 3 to 8.

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

(3) Performance evaluation Tables 3 to 8 show that the pH of the sample solution of the comparative example decreased to 0.7 or more after 21 days (comparative example 3), whereas In the example, it is 0.4 or less. In addition, after 21 days, the number of viable bacteria in the sample solution of the comparative example was at least 5×
104 cells/ml (Comparative Example 1), whereas in the example, even the largest number was 3×102 cells/ml (Example 1).
). Furthermore, it can be seen that the number of fungi increased significantly less in the sample solution of the example than in the sample solution of the comparative example. Regarding odor, the sample solutions of all Examples showed no odor even after 21 days, whereas the sample solutions of Comparative Examples developed odor as early as 3 days (Comparative Example 4). As described above, the water-soluble metal processing oil of the present invention has superior microbial deterioration resistance compared to conventional oils.

In Examples 1 to 15, the ammonium salt content was 0.5 to 5 parts by weight, and the anionic surfactant content was 100 parts by weight. It is within the range of 5 to 56 parts by weight. Therefore, for oil agents (Examples 16 to 18) whose contents of ammonium salts and anionic surfactants are outside these ranges as shown in Table 9, the same procedure as in Examples 1 to 15 was applied. A performance test was conducted.

[Table 9] According to this test, good results were obtained in Examples 16 to 18 as well as in Examples 1 to 15.

B. Actual machine test In order to confirm the practical performance of the water-soluble metal processing oil of the present invention, an actual machine test was conducted in a processing line where microbial deterioration is severe. The oils of Example 1 and Comparative Example 1 were subjected to actual machine tests under the following test conditions (processing conditions). (1) Processing conditions Processing line; Automotive engine block processing line Workpiece material; ADC-12 processing; Hole processing (drill, reamer, tap) boring Cutting oil tank capacity: 40,000 liters Cutting oil dilution ratio;
30x cutting oil stock supply amount: 1200 liters/month Test period: 6
Cutting fluid: After testing the fluid of Comparative Example 1, the fluid of Example 1 was tested. Under the above processing conditions, each evaluation of rust prevention, liquid stability, and resistance to microbial deterioration was performed. In addition, the rust prevention evaluation is as follows:
This was done using the cast iron swarf immersion method. That is, approximately 1.5 g of dry-cut cast iron chips (FC-25, 8 to 12 mesh) was placed in a Petri dish (inner diameter approximately 60 mm), approximately 25 ml of sample liquid was added thereto, and the sample liquid was subjected to a decanting method. This was done by removing the rust using a water bottle and examining the rust occurrence 24 hours later. In addition, the liquid stability was evaluated by collecting a sample liquid in a 100 ml cylinder and checking the state of oil separation when the sample liquid was left to stand for 15 minutes. Furthermore, the microbial deterioration resistance performance was evaluated using the same method as in the performance test. The above results are shown in Table 10.

[Table 10] During the above actual machine test, the oil agent of Example 1 had good rust prevention properties and liquid stability during the test period. On the other hand, in the oil agent of Comparative Example 1, a decrease in rust prevention properties and a decrease in liquid stability were observed over time. Furthermore, according to Table 10, the water-soluble metal processing oil of the present invention (Example 1) exhibits superior microbial deterioration resistance performance in practical use compared to the conventional oil (Comparative Example 1). I understand. It should be noted that the present invention is not limited to what is shown in the above-mentioned specific examples,
Various modifications may be made within the scope of the present invention depending on the purpose and use. That is, in this example, one or two types of ammonium salts were selected and used, but three or more types of ammonium salts may be selected and used within the scope of the present invention.

0012

As described above, the water-soluble metal processing oil of the present invention is less likely to be degraded by microorganisms such as bacteria, fungi, and yeast. Therefore, even when used in circulation for a long period of time, there is no odor caused by putrefaction, and there is no clogging of pipes in the coolant circulation system, making it safe to use, making it possible to reduce running costs when using oil.

Claims (2)

[Claims] [Claim 1] One or more quaternary ammonium salts selected from the quaternary ammonium salts represented by general formulas (I) to (V) of Chemical Formula 1 and general formulas (VI) to (IX) of Chemical Formula 2. 1. A water-soluble metal working oil agent characterized by containing a compound of the formula (1) and an anionic surfactant. [Chemical 1] [Chemical 2] Where, R1 is a straight chain or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, and R2 is a straight chain or branched alkyl group or alkenyl group having 11 to 17 carbon atoms. group, X1 is one selected from chloride ion, bromide ion, iodine ion or methylsulfonate ion,
, n are all integers from 2 to 15. 2. When the entire oil solution is 100 parts by weight, the content of the quaternary ammonium salts is 0.01 to 100 parts by weight.
10 parts by weight, the content of anionic surfactant is 2 to 60
The water-soluble metalworking fluid according to claim 1, which is in parts by weight.