JP6181403B2 - Water-soluble functional fluid with rot resistance - Google Patents

Description

  The present invention relates to a novel technique for imparting antiseptic and bactericidal properties to water-soluble functional fluids such as water-soluble cutting oils, water-soluble grinding oils, and water-soluble cleaning agents.

  Water-soluble functional fluids such as water-soluble cutting oils, water-soluble grinding oils, and water-soluble cleaning agents are often affected by microorganisms depending on the conditions used, and often lose their original performance due to spoilage.

  For example, in water-soluble cutting oil and grinding oil, by diluting to the concentration used and circulating for a long time, microorganisms enter from the outside, so that the decay progresses and gives off a bad odor. Diluted liquid separation causes troubles in cutting work, and rust prevention performance, which is an important performance, is also reduced, causing rusting of processing machines and workpieces. In addition, the amount of stock solution to be replenished due to the decrease in concentration increases, and the cost also increases. The same applies to water-soluble cleaning agents, and the original functions such as a decrease in concentration and a decrease in detergency are lost due to decay. Similar problems include water-soluble plastic processing oil (for bending, pressing, forging, rolling, pressure adjustment, etc.), water-soluble cutting oil, water-soluble polishing oil (glass, cutting of silicon, polishing oil, etc.) It also occurs in various water-soluble functional fluids such as water-soluble hydraulic oil, cooling water for air conditioning, and latex products.

  In order to preserve these water-soluble functional fluids, an amine-based or thiazoline-based antiseptic / bactericidal agent is usually added to the fluid (Patent Document 1, etc.). However, these preservatives and disinfectants are expensive and have high skin irritation, so the amount added is as low as a few hundred ppm or less at the concentration used, and the sterilization performance initially set during actual use It was often found that they were not fully satisfied. In addition, oil agents that use primary amines as antiseptic disinfectants exhibit antiseptic and disinfecting properties at high pH, so there is a risk of discoloration of non-ferrous metals (particularly aluminum).

  Alternatively, antiseptic / bactericidal agents other than amines and thiazolines are also proposed (Patent Document 2, etc.), but applied to water-soluble functional fluids such as water-soluble cutting oils, water-soluble grinding oils, and water-soluble cleaning agents. In some cases, it has not been confirmed whether it has sufficient antiseptic and sterilizing properties, and no influence on the workpiece or cleaning material or on the processing equipment has been confirmed.

  As described above, the conventional antiseptic / disinfectant may not exhibit sufficient antiseptic / sterilization performance when applied to a water-soluble functional fluid, and has an adverse effect on the work material or the material to be cleaned. (Discoloration, etc.) was also a concern.

JP 2011-79956 A Japanese National Patent Publication No. 11-508544

  Therefore, an object of the present invention is to provide a water-soluble functional fluid that has sufficient antiseptic and sterilizing performance and has reduced adverse effects on a workpiece or the like.

In view of the above problems, the present inventors have conducted extensive research and as a result, have obtained the following knowledge.
(1) A triazole derivative obtained by derivatizing a triazole known as a copper alloy corrosion inhibitor with a predetermined group exhibits antiseptic and bactericidal properties when added to a water-soluble functional fluid. The antiseptic and bactericidal properties of the triazole derivative are superior to the case where a triazole and a compound having a predetermined group are simply mixed and added (for example, when a triazole and an amine are mixed and added as a salt). It will be a thing.
(2) Since the above triazole derivative exhibits a sufficient antiseptic and bactericidal effect at a pH in a substantially neutral range, it has an adverse effect on a workpiece such as aluminum as compared with known amine-based antiseptic and bactericides. Is reduced.
(3) The triazole derivative has less skin irritation and the like, and can increase the concentration in the water-soluble functional fluid, as compared with known amine-based antiseptic / bactericides.

The present invention has been made based on the above findings. That is,
1st this invention is a water-soluble functional fluid containing the triazole derivative shown by following General formula (1).

(In the general formula (1), R ¹ is hydrogen or a methyl group, and X is a hydroxyl group or an amino group represented by the following general formula (2).)

(In the general formula (2), R ² and R ³ are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, and an aralkyl group having 6 to 8 carbon atoms. Or an alkylaralkyl group having 6 to 8 carbon atoms, except when R ² and R ³ are both hydrogen, and the terminal of R ^{2 and} the terminal of R ³ are heteroatoms. And may be wound around a ring.)

  The water-soluble functional fluid according to the first aspect of the present invention preferably contains 0.1% by mass or more of the triazole derivative. This is because more excellent antiseptic / sterilizing performance can be maintained over a long period of time.

  The water-soluble functional fluid according to the first aspect of the present invention includes water-soluble cutting oil, water-soluble grinding oil, water-soluble cleaning agent, water-soluble press oil, water-soluble forging oil, water-soluble rolling oil, water-soluble cutting oil, water-soluble cutting oil It is preferably used as a polishing oil or a water-soluble hydraulic oil.

  The second aspect of the present invention provides a water-soluble functional fluid which is adjusted so that the concentration by mass of the triazole derivative is 500 ppm or more when the water-soluble functional fluid according to the first aspect of the present invention is diluted with water. How to use.

  According to the present invention, it is possible to provide a water-soluble functional fluid that has sufficient antiseptic and sterilizing performance and has reduced adverse effects on a workpiece or the like.

<Water-soluble functional fluid>
The water-soluble functional fluid according to the present invention is characterized by containing a triazole derivative represented by the following general formula (1).

(In the general formula (1), R ¹ is hydrogen or a methyl group, and X is a hydroxyl group or an amino group represented by the following general formula (2).)

(In the general formula (2), R ² and R ³ are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, and an aralkyl group having 6 to 8 carbon atoms. Or any one of an alkylaralkyl group having 6 to 8 carbon atoms, except when R ² and R ³ are both hydrogen.)

  In general, triazoles typified by benzotriazole are commercially available as corrosion inhibitors for copper alloys, and are added to the stock solution in an amount of 1% by mass or less, and have a low concentration of several hundred ppm or less when diluted. However, no antiseptic and bactericidal properties of these series of compounds in water-soluble functional fluids have been found.

  On the other hand, the present inventors sufficiently show the antiseptic and bactericidal properties required when used for water-soluble functional fluids by derivatizing the triazoles as shown in the general formula (1). As a result, the present invention has been completed.

In the general formula (2), R ² and R ³ are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, and an aralkyl group having 6 to 8 carbon atoms. Or an alkylaralkyl group having 6 to 8 carbon atoms. However, the case where both R ² and R ³ are hydrogen is excluded. In addition, the terminal of R ^{2 and} the terminal of R ³ may be bonded via a hetero atom and may be wound around a ring.

  Among these, for example, the alkyl group has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an octyl group, and a cyclohexyl group. Among these, a methyl group, an ethyl group, and a propyl group are preferable. The carbon number of the hydroxyalkyl group is 1 or more and 6 or less, preferably 2 or more and 4 or less, more preferably 2 or more and 3 or less. Specific examples include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a 2-methyl 2-hydroxypropyl group. Among these, a hydroxymethyl group and a hydroxyethyl group are preferable.

The combination of R ² and R ³ is not particularly limited, and may be a combination of the same groups or a combination of different groups. The triazole derivative is a primary amine derivative (for example, one of R ² and R ³ is hydrogen, and the other is any of the alkyl group, hydroxyalkyl group, aralkyl group, or alkylaralkyl group described above) ).

  The triazole derivatives described above are, for example, (1) a method for obtaining a water-insoluble hydroxymethyl derivative by adding formaldehyde to a triazole acetate aqueous solution, and (2) using an amine, formaldehyde and triazole as shown below. It can be easily obtained by a synthesis method by a Mannich reaction.

  The water-soluble functional fluid according to the present invention preferably contains 0.1% by mass or more of the above-described triazole derivative. The lower limit of the triazole derivative content is more preferably 0.2% by mass or more, particularly preferably 0.3% by mass or more, and the upper limit is preferably 20.0% by mass or less, more preferably 5.0% by mass. Hereinafter, it is particularly preferably 1.0% by mass or less. Thus, in this invention, it is preferable to make content of the said triazole derivative increase rather than the conventional benzotriazole content added as a corrosion inhibitor. As a result, the antiseptic / sterilizing performance of the water-soluble functional fluid can be further enhanced, and the antiseptic / sterilizing performance can be stably expressed over a long period of time.

  The water-soluble functional fluid according to the present invention exhibits high antiseptic and bactericidal properties even in a relatively neutral pH range (pH 8 to 10, preferably pH 8 to 9). For this reason, it can be suitably used for a workpiece or a material to be cleaned that is liable to have alkaline corrosion.

  Furthermore, the excellent point of the water-soluble functional fluid according to the present invention is that it has rust prevention not only for non-ferrous metals but also for ferrous metals and that there is almost no inadvertent foaming when used. . That is, in the present invention, by derivatizing triazole, it is possible to express a plurality of unconventional functions.

  Further, in the past, for the purpose of improving antiseptic properties, for example, primary amines that exhibit antiseptic and bactericidal properties at high pH are used, and there have been concerns about discoloration of aluminum and irritation to the skin. As described above, the triazole derivative can exhibit sufficient antiseptic and bactericidal properties at a substantially neutral pH, reduces adverse effects on the workpiece such as aluminum, and has skin irritation and the like. Few. Therefore, even when the concentration in the water-soluble functional fluid is increased, it is possible to suppress adverse effects on the workpiece and the worker.

  In addition, as long as the effects according to the present invention are not impaired, it is possible to add conventionally used amine-based preservatives and thiazoline-based preservatives, and further primary amine fatty acid salts, etc. What is necessary is just to adjust suitably according to the development objective. In this case, the amount of the above-mentioned triazole derivative can be reduced, and it is economical.

<Application>
The water-soluble functional fluid according to the present invention includes a water-soluble cutting oil, a water-soluble grinding oil, a water-soluble cleaning agent, a water-soluble press oil, a water-soluble forging oil, a water-soluble rolling oil, a water-soluble cutting oil, a water-soluble polishing oil, or It can be applied as a water-soluble hydraulic oil. Depending on the application, necessary components other than the above-mentioned triazole derivatives such as base oils, alcohols (glycols) and ethers (glycol ethers), various additives such as fatty acids and surfactants may be included.

<How to use water-soluble functional fluid>
The above-described water-soluble functional fluid according to the present invention can be diluted and used. More specifically, when diluting with water, it is preferable to adjust so that the mass% concentration of the triazole derivative is 500 ppm or more. More preferably, the concentration is adjusted to 1000 ppm or more, more preferably 2000 ppm or more, and particularly preferably 3000 ppm or more. Thereby, sufficient antiseptic and bactericidal properties can be expressed in the water-soluble functional fluid during actual use.

  In addition, also when diluting and using the water-soluble functional fluid which concerns on this invention with water, as above-mentioned, pH can be used as a substantially neutral range (pH8-10, Preferably pH8-9). Thereby, it is possible to suppress the bad influence to a workpiece, equipment, or an operator.

  As described above, according to the present invention, sufficient antiseptic / sterilizing performance can be expressed in the water-soluble functional fluid by including the predetermined triazole derivative. The antiseptic and bactericidal properties of the triazole derivative are superior to those obtained when a triazole and a compound having a predetermined group are simply mixed and added (for example, when a salt of a triazole and an amine is added). In addition, compared to known amine-based antiseptic / bactericides, etc., the adverse effect on workpieces such as aluminum is reduced, there is less skin irritation, etc., and the concentration in water-soluble functional fluids can be increased. There is also a feature in that it is possible, and there is almost no foaming at the time of use, and the antiseptic and sterilizing performance can be stably expressed over a long period of time with respect to the water-soluble functional fluid.

  Hereinafter, based on an Example, this invention is explained in full detail.

<Sample synthesis>
As Examples 1 to 11, triazole derivatives represented by the following formulas (A) to (K) were synthesized by Mannich reaction.
Further, as Examples 12 and 13, formaldehyde is added to an aqueous acetate solution of benzotriazole or tolyltriazole according to the method described in J, H, Burck Halter et al., J. Am, chem., Soc, Vol 74 3868. Thus, triazole derivatives represented by the following formulas (L) and (M) were synthesized.
Furthermore, as Comparative Examples 1 and 2, benzotriazole or tolyltriazole and diethanolamine were mixed to obtain a salt. Tables 1 and 2 below show each synthesis condition and properties of the obtained compound.

  In Tables 1 and 2 and the table shown below, “BT” is “benzotriazole”, “TT” is “tolyltriazole”, “PFA” is “paraformaldehyde”, “FO” is “formalin ( 37-40%) "," DEA "is" diethanolamine "," DIPA "is" diisopropanolamine "," MO "is" morpholine "," DCHA "is" dicyclohexylamine "," DBA "is" dibenzylamine " "," "DMA" represents "dimethylamine", "DPA" represents "di-n-propylamine", and "D2EHA" represents "bis (2-ethylhexyl) amine".

  Furthermore, as Comparative Example 3, a mixture of benzotriazole and methanol in equimolar amounts was prepared, and as Comparative Example 4, a mixture of tolyltriazole and methanol in equimolar amounts was prepared. Further, as Reference Example 1, benzotriazole was used alone, and as Reference Example 2, tolyltriazole was used alone. Since benzotriazole and tolyltriazole (Reference Examples 1 and 2) have low solubility, a dilute solution was once prepared with ethanol and added to a predetermined concentration before use. In addition, when benzotriazole or tolyltriazole and methanol are mixed (Comparative Examples 3 and 4), the solubility of triazole in methanol is not so high, so a uniformly dissolved product cannot be obtained, and methanol is not contained in the triazole powder. It became a state that was absorbed. For this reason, a dilution liquid was prepared with ethanol in the same manner as in Reference Examples 1 and 2, and then added to a predetermined concentration.

<Evaluation of antiseptic and bactericidal properties>
(Experiment 1)
About each sample, the antiseptic action and the bactericidal action in the water-soluble functional fluid were confirmed. Specifically, each sample was added to a septic solution of a water-soluble emulsion type cutting fluid (Pseudomonas SP, septic solution containing enteric bacteria, viable cell count 3 × 10 ⁷ cells / ml), and then stirred. The sample was allowed to stand at 30 ° C. for one day and night, and then one platinum loop was applied to a normal agar plate and cultured for 48 hours to check for the presence of viable bacteria. The results are shown in Table 3 below. In Table 2, “++” indicates the number of viable bacteria, “+” indicates that there are viable bacteria that are reduced from the blank, and “−” indicates that there are no viable bacteria (complete sterilization). .

As is clear from the results shown in Table 3, first, the triazoles that are not derivatives or salts themselves (Reference Examples 1 and 2) do not exhibit antiseptic / bactericidal properties.
Moreover, although the salt (comparative examples 1 and 2) of triazoles and amines can obtain antiseptic / bactericidal effects at a concentration of about 3000 to 10,000 ppm, the effect is not sufficient. On the other hand, when triazole is derivatized with an amine (Examples 1 to 11), strong antiseptic and bactericidal properties are exhibited, and a sufficient effect is exhibited at a concentration of about 1000 to 3000 ppm.
Furthermore, the mixture of triazoles and methanol (Comparative Examples 3 and 4) does not exhibit antiseptic / bactericidal properties. On the other hand, when the triazole is a 1-hydroxymethyl derivative (Examples 12 and 13), extremely strong antiseptic and bactericidal properties are exhibited, and a sufficient effect is exhibited at a concentration of about 1000 to 2000 ppm.
From this, it can be seen that a very prominent antiseptic / bactericidal effect is exhibited only after derivatization of triazoles as in the present invention.

(Experiment 2)
About 5% by mass of the triazole derivative according to Examples 1 and 2 is blended in an emulsion type oil, and a 10% dilution is prepared and mixed with a decayed emulsion type dilution at a constant rate and kept at room temperature for 24 hours. After standing, 1 platinum loop was applied to a normal agar plate and cultured to confirm the effect. The oil agent composition is shown in Table 4 below, and the evaluation results are shown in Table 5 below. Sample A was blank and contained no preservative fungicide, Sample B was blended with about 5% of the triazole derivative of Example 1, and Sample C was blended with about 5% of the triazole derivative of Example 2.

  From the results of Table 5, samples B and C containing a triazole derivative showed a better antiseptic / bactericidal effect as compared to sample A which is a blank. Sample B was completely sterilized at a mixing ratio of 4 parts of sample liquid and 6 parts of septic liquid, and sample C was completely sterilized at a mixing ratio of 3 parts of sample liquid and 7 parts of septic liquid. At this time, the concentration of the triazole derivative was about 2000 ppm for sample B and about 1500 ppm for sample C.

(Experiment 3)
About 4.5% by mass of the triazole derivative according to Example 12 was blended in an emulsion type oil agent, and a 10% dilution was prepared and mixed with a decayed emulsion type dilution at a constant rate, and allowed to reach room temperature for 24 hours. After standing, 1 platinum loop was applied to a normal agar plate and cultured to confirm the effect. The evaluation results are shown in Table 6 below. Sample D is a blank and does not contain an antiseptic disinfectant, and Sample E contains about 4.5% of the triazole derivative of Example 12.

  From the results shown in Table 6, Sample E containing a triazole derivative showed a better antiseptic / bactericidal effect as compared with Sample D, which is a blank. Sample E was completely sterilized at a mixing ratio of 4 parts of sample solution and 6 parts of septic solution. At this time, the concentration of the triazole derivative was about 1800 ppm.

<Evaluation of rust prevention and discoloration for metal materials>
For each of the samples according to Examples 1 to 13, a 1% diluted solution (water diluted solution or ethanol diluted solution) was prepared, and the polished test piece was fully immersed therein, and the sample was immersed at room temperature (30 ± 5 ° C.) for 24 hours. Left to stand. Thereafter, the test piece was taken out, the change in the appearance of the sample solution and the test piece was observed, and the change in the weight of the test piece was measured.
Moreover, the same evaluation was performed also about Comparative Examples 1-4.
Further, as reference examples, when triazoles are added alone (Reference Examples 1 and 2), oleylsarcosine DEA equivalent salt (OZ-DEA salt) is used (Reference Example 3), nonionic higher alcohol When EO 7 mol adduct is used (Reference Example 4), when triazine preservative (manufactured by Clariant) is used (Reference Example 5), when water (tap water) is used as it is without adding preservatives, etc. The same evaluation was performed for (Reference Example 6).

  The results when steel pieces (SPCC, 30 × 50 × 1 mm) are used as test pieces are shown in Table 7, the results when aluminum pieces (A5052, 30 × 50 × 3 mm) are used are shown in Table 8, and brass pieces ( Table 9 shows the results when C2801, 30 × 50 × 2 mm) are used.

  As is clear from the results according to Tables 7 to 9, it can be seen that the triazole derivative does not cause discoloration of various metals and has rust prevention properties. In particular, from the results in Table 7, it is clear that rust prevention can be imparted not only to non-ferrous metals but also to ferrous metals. That is, for example, it is assumed that the steel material is used in equipment using the functional fluid, such as piping for circulating the functional fluid, nozzles for spraying the functional fluid, etc. In such a case, the present invention It can be seen that by adding a triazole derivative as described above, it is possible to prevent the rust of the equipment as well as to preserve the functional fluid.

<Evaluation of foaming>
For each of the samples according to Examples 1 to 13, 50 ml of a 1% diluted solution (water diluted solution or ethanol diluted solution) was prepared, and after shaking 20 times in a cylinder, the volume change of the diluted solution was measured. Was evaluated for foaming.
Moreover, the same evaluation was performed also about Comparative Examples 1-4.
Furthermore, as reference examples, when triazoles are added alone (Reference Examples 1 and 2), when oleylsarcosine-diethanolamine equivalent salt (OZ-DEA salt) is used (Reference Example 3), nonionic high grade When an alcohol EO 7 mol adduct was used (Reference Example 4), when a triazine preservative (manufactured by Clariant) was used (Reference Example 5), water (tap water) was used as it was without adding the preservative. The same evaluation was performed for the case (Reference Example 6).

  Table 10 shows the volume (ml) of each diluted solution immediately after shaking, 30 seconds later, 1 minute later, 2 minutes later, 3 minutes later, 4 minutes later and 5 minutes later.

  As is clear from the results shown in Table 10, in the dilute solution containing the triazole derivative, foaming slightly occurred immediately after shaking 20 times, but the foaming disappeared rapidly over time. . On the other hand, in the diluents according to Comparative Example 1 and Reference Examples 3 and 4, foaming immediately after shaking 20 times was not eliminated. Thus, it can be seen that the water-soluble functional fluid according to the present invention is free from inconvenience during use and has excellent handling properties.

<Evaluation of pH dependence>
(Sample adjustment)
An emulsion type reference formulation was made and diluted to 5% with water. The above-mentioned Examples 1-13, Comparative Examples 1-4, Reference Examples 1-5, 2-amino-2-methyl-1-propanol derivative (primary amine derivative) of tolyltriazole was used for 100 g of the diluted solution. In Example 14, a solution containing a sample according to Reference Example A using a commercially available benzoisothiazoline preservative (BIT preservative) was added so as to correspond to 0.25 g as a pure component, did. The obtained evaluation solution corresponds to a sample added with 5% per stock solution.

  The pH of the obtained evaluation liquid was 7.9, and evaluation was performed using two levels of sample liquid in which diethanolamine was added to adjust the pH to 8.8 and 9.6, respectively.

(Bactericidal test)
Each evaluation solution and a septic solution containing 5 × 10 ⁶ viable bacteria / ml were mixed at a fixed ratio, and stirred and allowed to stand for 24 hours. Thereafter, one platinum loop of the mixed solution was collected and cultured on a normal agar plate medium, the presence or absence of viable bacteria was confirmed, and the minimum bacterial concentration (ppm) of the mixed system was determined.

  In addition to the evaluation of the above Examples, Comparative Examples, and Reference Examples, as a “Comparative Sample Oil”, a commercially available amine-based biostatic oil (primary amine 6%, manufactured by Yushiro Chemical Industry Co., Ltd.), and a spoiled liquid Evaluation was also performed for the case of mixing with. Usually, amine-based biostatic oils are used in the high pH range, but in this experiment, in order to confirm the effect of pH (preservative performance in the neutral range), acetic acid was added to adjust the pH. Adjusted to sex range (8.0 or 9.2).

  The evaluation results are shown in Table 11.

As is clear from the results shown in Table 11, in Examples 1 to 14 containing the triazole derivative, sterilization was possible at an extremely low concentration of 500 ppm even at a relatively neutral pH. On the other hand, in Comparative Examples 1 and 2 containing an amine salt of a triazole, it was necessary to make the concentration at least twice as high as that in Examples, and the bactericidal properties were inferior. In addition, the bactericidal properties were also poor in Reference Examples 1 and 2 when triazoles were used alone, and Comparative Examples 3 and 4 where triazoles and methanol were simply mixed.
Further, when comparing the primary amine derivative of triazole (Example 14) with the conventional primary amine-based anti-septic oil (comparative sample oil), in Example 14, the pH was 8.0. Even if it is about 9.2, sufficient antiseptic and bactericidal properties are exhibited, whereas in the comparative sample oil, the oil exhibits a function at a high pH, so that the pH is 8.0. It was confirmed that a low pH of about 9.2 does not function sufficiently as a preservative.
From this, it can be seen that not only secondary amine derivatives but also primary amine derivatives, when triazole amine derivatives are used, extremely remarkable antiseptic and bactericidal performance is expressed in the neutral range. It was.

In addition, in the results of (Experiment 1) in the above <Evaluation of antiseptic and bactericidal properties>, Comparative Example 3 and 4 and Reference Examples 1 and 2 did not show bactericidal properties, whereas in this experiment Bactericidal properties were observed for Comparative Examples 3 and 4 and Reference Examples 1 and 2. This is probably because the number of viable bacteria in the bacterial solution was as small as 5 × 10 ⁶ cells / ml. In other words, it was found that triazoles alone are extremely weak but have bactericidal properties. However, in practical use, such a bactericidal property cannot be used.

  Thus, according to the water-soluble functional fluid according to the present invention containing a triazole derivative, it can be seen that sufficient antiseptic properties are expressed at a neutral pH. Thereby, it becomes possible to suppress discoloration of the aluminum material due to high pH and skin irritation of the worker.

<Comparison between primary amine derivative and secondary amine derivative>
(Evaluation of antiseptic and bactericidal properties)
A predetermined concentration of each of the evaluation samples was added to the septic solution containing each bacterium shown in Table 12 below, and the mixture was stirred and allowed to stand at 30 ° C. for one day and night. It was cultured for a while to check for the presence of viable bacteria. As an evaluation sample, a diethanolamine derivative of tolyltriazole (Example 2) was used as a secondary amine derivative of triazole, and a 2-amino-2-methyl-1-propanol derivative of tolyltriazole as a primary amine derivative of triazole (Example 2) The same applies to Example 14) and a monoethanolamine derivative of tolyltriazole (Example 15), a salt of tolyltriazole and diethanolamine (Comparative Example 2), and a commercially available triazine preservative (Reference Example 3). The experiment was conducted. Each complete bactericidal concentration is shown in Table 12 below.

  As is clear from the results shown in Table 12, when the antiseptic / sterilizing performance is expressed by the amine derivative of triazole, the primary amine derivative is more antiseptic / sterilized than the secondary amine derivative. It was found that the performance was improved. However, even if it is a secondary amine derivative, it is as above-mentioned that there exists sufficient antiseptic and disinfection performance.

(Evaluation of pH dependence)
In order to evaluate the pH dependency of the antiseptic / sterilization performance, an evaluation solution containing each sample was prepared by the same method as described above, and each of the prepared evaluation solutions and the number of viable bacteria 5 × 10 ⁶ cells / ml The septic solution containing was mixed at a constant ratio and allowed to stand for 24 hours after stirring. Thereafter, one platinum loop of the mixed solution was collected and cultured on a normal agar plate medium, the presence or absence of viable bacteria was confirmed, and the minimum bacterial concentration (ppm) of the mixed system was determined. The results are shown in Table 13 below.

  As is clear from the results shown in Table 13, the triazole derivative according to the present invention has a neutral range of about pH 8.0 to 9.2, whether it is a secondary amine derivative or a primary amine derivative. It can be seen that sufficient antiseptic and bactericidal properties are exhibited. On the other hand, since the conventional primary amine preservative (comparative sample oil) does not exhibit sufficient antiseptic / sterilization performance at a neutral pH, the superiority of the present invention over the conventional preservative was shown. .

  In the above embodiment, the case where the cutting fluid is used as the water-soluble functional fluid has been described. However, the water-soluble functional fluid according to the present invention is not limited to the cutting fluid. Hereinafter, the evaluation results of antiseptic / disinfectant properties regarding the antiseptic / disinfectant properties of the “water-soluble detergent” will be shown.

<Evaluation of antiseptic and bactericidal properties in water-soluble detergents>
For each sample, the antiseptic action and bactericidal action of the water-soluble detergent were confirmed. Specifically, after adding each sample to a septic solution (pH 8.4, viable cell count 8 × 10 ⁶ / ml) of a water-soluble detergent (manufactured by Yushiro Chemical Industry Co., Ltd., product name W80), After stirring and allowing to stand at 30 ° C. for one day and night, one platinum loop was applied to a normal agar medium plate and cultured for 48 hours to confirm the presence or absence of viable bacteria. The results are shown in Table 14 below. In Table 14, “++” indicates the number of viable bacteria, “+” indicates that there are viable bacteria that are reduced from the blank, and “−” indicates that there are no viable bacteria (complete sterilization). .

As is apparent from the results shown in Table 14, it can be seen that the amine derivatives of triazole (Examples 1 to 11) also show strong antiseptic and bactericidal properties even in the cleaning solution, and show a sufficient effect at a concentration of about 500 to 1000 ppm. On the other hand, the salt of triazoles and amines (Comparative Examples 1 and 2) shows that although the complete bactericidal effect is obtained at a concentration of about 3000 ppm or more, the effect is not sufficient.
In addition, when the triazole is a 1-hydroxymethyl derivative (Examples 12 and 13), it can be seen that strong antiseptic and bactericidal properties are exhibited, and a sufficient effect is exhibited at a concentration of about 500 to 1000 ppm. On the other hand, it can be seen that the mixture of triazoles and methanol (Comparative Examples 3 and 4) hardly exhibits antiseptic and bactericidal properties.
From this, it can be seen that not only the cutting fluid but also the cleaning fluid exhibits a very significant antiseptic and sterilizing effect only after the triazoles are derivatized as in the present invention.

  As described above, the present invention can be used as a water-soluble functional fluid as a water-soluble cutting oil, water-soluble grinding oil, water-soluble press oil, water-soluble forging oil, water-soluble rolling oil, water-soluble cutting oil, water-soluble polishing oil or water-soluble It can be seen that the present invention can be applied not only to water-soluble working fluids such as water-soluble hydraulic fluids but also to water-soluble cleaning agents.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the invention is not limited to the embodiments disclosed herein. However, the present invention can be modified as appropriate without departing from the spirit or concept of the invention which can be read from the claims and the entire specification, and the water-soluble functional fluid and the method of using the same are also included in the technical scope of the present invention. Must be understood as being.

  The present invention includes a water-soluble cutting oil, a water-soluble grinding oil, a water-soluble cleaning agent, a water-soluble press oil, a water-soluble forging oil, a water-soluble rolling oil, a water-soluble cutting oil, a water-soluble polishing oil, a water-soluble hydraulic oil, etc. It can be widely used as a technique for imparting antiseptic and bactericidal properties to water-soluble functional fluids.

Claims (3)

An antiseptic / disinfectant used in water-soluble functional fluids,
Consisting of a triazole derivative represented by the following general formula (1):
Antiseptic / disinfectant.
(In the general formula (1), R ¹ is hydrogen or a methyl group, and X is a hydroxyl group or an amino group represented by the following general formula (2).)
(In the general formula (2), R ² and R ³ are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, and an aralkyl group having 6 to 8 carbon atoms. Or an alkylaralkyl group having 6 to 8 carbon atoms, except when R ² and R ³ are both hydrogen, and the terminal of R ^{2 and} the terminal of R ³ are heteroatoms. And may be wound around a ring.) The water-soluble functional fluid is water-soluble cutting oil, water-soluble grinding oil, water-soluble cleaning agent, water-soluble press oil, water-soluble forging oil, water-soluble rolling oil, water-soluble cutting oil, water-soluble polishing oil or water-soluble operation oil an oil, preservatives, disinfectant according to claim 1. The antiseptic / bactericidal agent according to claim 1 or 2 , wherein each of R ² and R ³ is independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 2 to 4 carbon atoms. .