JP4421521B2 - Antibacterial rust inhibitor - Google Patents

Description

  The present invention relates to an antibacterial rust inhibitor. More specifically, the present invention relates to an antibacterial rust inhibitor that can be blended in water-soluble metalworking oil.

Emulsion-type cutting oils based on mineral oils, fatty acid esters and other animal and vegetable oils and synthetic oils, soluble-type cutting oils based on surfactants and solution-based water-soluble cutting oils based on polyethers In order to impart rust prevention and antibacterial properties, fatty acid and dibasic acid amine salts are usually used. As the amine constituting the amine salt, primary amines such as monoethanolamine and isopropanolamine, secondary amines such as diethanolamine and diisopropanolamine, and tertiary amines such as triethanolamine and an alkylene oxide adduct of amine are used. It is common.
However, primary amine salts such as monoethanolamine salts are strongly irritating to the skin, and secondary amine salts such as diethanolamine salts are pointed to carcinogenic problems due to the formation of nitrosamines. Further, triethanolamine salts and salts of monoalkylamine alkylene oxide adducts are not sufficient in antibacterial properties and do not have sufficient rust preventive power.
Also, propylene oxide adducts such as amines having an alkyl group or alkenyl group having 8 to 18 carbon atoms (see Patent Document 1), alkylene diamines having an alkylene group having 2 to 3 carbon atoms (see Patent Document 2), And ethylene oxide adducts of cycloaliphatic amines (see Patent Document 3) have been proposed, but these compounds have poor separability from oil when mixed with oil such as sliding surface oil, In addition, there is a problem that foamability is large.
JP-A-1-98696 JP-A-2-228394 Japanese Patent Publication No.56-5480

  In view of the above problems, an object of the present invention is to provide an antibacterial rust inhibitor having excellent antibacterial properties, good oil separation, low foaming properties and excellent rust prevention properties.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides an antibacterial antibacterial agent containing an alkylene oxide adduct (E) represented by the general formula (1) and / or a salt (Q) of the (E) and a carboxylic acid having 6 to 20 carbon atoms. A rusting agent; and a water-soluble metalworking oil containing the antibacterial rustproofing agent.

In the formula, R is a divalent linear alkylene group having 4 to 18 carbon atoms, A ^{1 to} A ⁴ are alkylene groups having 2 to ⁴ carbon atoms, m ^{1 to} m ⁴ are 0 or an integer of 1 to 3, The sum total of m ^{1 to} m ⁴ is 4 to 12.

The antibacterial rust inhibitor of the present invention is
(1) The oil separability of mineral oil based lubricating oil such as sliding surface oil is good.
(2) Low foaming property.
(3) Corruption is unlikely to occur.
(4) Excellent antibacterial properties.
(5) Excellent rust prevention.

The alkylene oxide adduct (E) represented by the general formula (1) in the antibacterial rust inhibitor of the present invention will be described.
R in the general formula (1) is Ru divalent linear alkylene Motodea 4 to 18 carbon atoms.

The divalent straight-chain alkylene group having 4 to 18 carbon atoms, butylene group, pentylene group, hexylene group, octylene group, decylene group, undecylene group, dodecylene group, tetradecylene group, an alkylene group such as pentadecylene and octadecylene Can be mentioned.

Particularly preferred among R, the rust resistance of the viewpoint et al, an alkylene group having a carbon number of 6-12.

A ^{1 to} A ⁴ in the general formula (1) are alkylene groups having 2 to ⁴ carbon atoms, the alkylene group having 2 carbon atoms is an ethylene group, and the alkylene group having 3 to 4 carbon atoms is a 1,2-propylene group. And 1,2-, 2,3- and 1,4-butylene groups. Among these, preferred are an ethylene group, a 1,2-propylene group and a combination thereof, and particularly preferred is a case where A ^{1 to} A ⁴ are all ethylene groups from the viewpoint of solubility in water.
m ¹ ~m ⁴ is 0 or an integer of 1-3, the sum of m ¹ ~m ⁴ 4-12, preferably 4-8. If the total of m ^{1 to} m ⁴ is less than 4, oil separability is deteriorated, and if it exceeds 12, rust prevention is deteriorated.

(E) is produced by subjecting a diamine represented by the general formula H ₂ N—R—NH ₂ (R is the same as in the general formula (1)) to an addition reaction of a C 2-4 alkylene oxide. .

Examples of the diamine represented by the general formula H ₂ N—R—NH ₂ include tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decylmethylenediamine, dodecylmethylenediamine, hexadecylmethylenediamine and octadecylmethylenediamine. And alicyclic diamines such as cyclohexyldiamine, and aromatic diamines such as phenylenediamine and xylylenediamine.

  Examples of the alkylene oxide having 2 carbon atoms include ethylene oxide (abbreviated as EO), and examples of the alkylene oxide having 3 to 4 carbon atoms include 1,2-propylene oxide (abbreviated as PO), 1,2-, 2, Examples include 3-, 1,3- and iso-butylene oxide, and tetrahydrofuran (THF). Among these, EO, PO, and combinations thereof are preferable, and EO is particularly preferable.

The addition reaction can be usually performed at a temperature of 100 to 180 ° C., a pressure of 0 to 0.6 MPa, and a reaction time of 2 to 15 hours. The reaction is usually carried out without a catalyst, and if necessary, in the presence of a catalyst. Examples of the catalyst include an alkali catalyst such as a hydroxide [a hydroxide of an alkali metal or an alkaline earth metal such as KOH, NaOH, CsOH, or Ca (OH) ₂ ] or an oxide (K ₂ O ₂ , CaO, BaO). Alkali metal or alkaline earth metal oxides)
Etc.

The antibacterial rust inhibitor of the present invention is an antibacterial rust inhibitor containing the above (E), and an antibacterial rust inhibitor containing the above (E) and a salt (Q) of a carboxylic acid having 6 to 12 carbon atoms. It is either a rusting agent or an antibacterial rustproofing agent containing the above (E) and salt (Q).
When the antibacterial rust inhibitor contains (Q), rust preventive properties not only for iron but also for non-ferrous metals can be exhibited.

  In the present invention, examples of the carboxylic acid (F) having 6 to 20 carbon atoms constituting the salt (Q) include aliphatic chain carboxylic acid, alicyclic carboxylic acid, and aromatic carboxylic acid.

Examples of the aliphatic chain carboxylic acid include aliphatic chain monocarboxylic acids (hexanoic acid, caprylic acid, caprylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like having 6 to 20 carbon atoms. Alkane monocarboxylic acids and alkenyl monocarboxylic acids such as oleic acid) and aliphatic chain dicarboxylic acids (alkane dicarboxylic acids having 6 to 20 carbon atoms such as azelaic acid, sebacic acid and dodecanedioic acid, and octenyl succinic acid, Alkenyl succinic acid such as dodecenyl succinic acid and pentadecenyl succinic acid).
Examples of the alicyclic carboxylic acid include naphthenic acid and cyclohexanecarboxylic acid.
Examples of the aromatic carboxylic acid include benzoic acid and cinnamic acid.

  Among these, preferred from the viewpoints of lubricity and rust prevention are aliphatic chain monocarboxylic acids having 6 to 20 carbon atoms, aliphatic chain dicarboxylic acids having 6 to 20 carbon atoms and fats having 6 to 20 carbon atoms. One or more selected from the group consisting of cyclic carboxylic acids.

  As a method for producing an antibacterial rust inhibitor when the antibacterial rust inhibitor of the present invention contains a salt (Q), a salt (Q) produced in advance may be used, but the production process is simple. From the viewpoint of being present, the carboxylic acid (F) and the alkylene oxide adduct (E) are blended in any equivalent ratio as components of the antibacterial rust inhibitor, and a neutralization reaction between (F) and (E) is caused. Thus, a method of producing the salt (Q) in the blending step is preferable.

In the method of producing the salt (Q) in the blending step, the blending amount of (E) and (F) is generally 0 to the total acid number of (F) with respect to the total amine value of (E). .2 to 2.0 times, preferably 0.3 to 1.5 times. If the total amount of the total acid value is 1.5 times or less, the antibacterial rust inhibitor is not easily insoluble in water.
The weight ratio of (E) and (F) is (E) / (F) = 10/1 to 1/10, preferably 8/2 to 2/8.
Calculation of the blending amounts of (E) and (F) is, for example, that (E) with a total amine number of 300 is 100 parts by weight, and (F) with a total acid number of 389 is 300 × 100/389 = 77.1. When blended by weight, the total amount of all acid values of (F) is 1.0 times the total amount of all amine values of (E).
When the total amount of the total acid number of (F) is less than 1.0 times the total amount of the total amine number of (E), (E) becomes excessive, and the antibacterial rust inhibitor of the present invention is (Q) and When (E) is contained and exceeds 1.0 times, (F) becomes excessive, and the antibacterial rust inhibitor of the present invention contains (Q) and further (F).
Therefore, the antibacterial and rust preventive agent of the present invention contains (Q) and / or (E), and (F) if necessary.

If necessary, the antibacterial rust inhibitor of the present invention can be diluted with water. In the case of dilution, the total weight concentration of (E) and (Q) in the antibacterial rust inhibitor is 5 to 95% (hereinafter,% represents% by weight), preferably 20 to 60%. It is preferable to dilute with water from the viewpoint of ease of handling.
Furthermore, it can be further diluted with water so that it becomes 0.2 to 20% (preferably 1 to 20%) at the time of use.

  Another method of using the antibacterial rust preventive agent of the present invention is that the concentration of the antibacterial rust preventive agent is 0.01 to 30% (preferably 0.8%) in water or an organic solvent (for example, ethyl alcohol, acetone, dimethylformamide, etc.) The method of adding and using it so that it may become 5 to 20%) is mentioned.

  Furthermore, as another usage method, it can mix | blend with cleaning agents, for example, the cleaning agent for conventional metals, the cleaning agent for electronic components, etc., and can improve the antibacterial property and rust prevention property of cleaning agents.

  The antibacterial rust preventive agent of the present invention has not only the effects of oil separation, antibacterial property, rust proofing and low foaming property, but also has a low permeability to the paint surface and resin of the paint. Peeling and swelling of the coating film around is difficult.

The water-soluble metalworking oil of the present invention contains the above antibacterial rust preventive and various other components (hereinafter abbreviated as other components) used in ordinary water-soluble metalworking oils. Become.
In the water-soluble metalworking oil of the present invention, as other components other than the antibacterial rust preventive agent, water-soluble polyether, hydrocarbon-based lubricating oil, emulsifier, extreme pressure agent, oiliness agent, rust preventive agent, etc. Can be mentioned. These may use 1 type (s) or 2 or more types.

  Examples of the water-soluble polyether include polyethylene glycol having a number average molecular weight of 500 to 20,000, a pluronic surfactant, a PO block adduct of polyethylene glycol, and an EO / PO random adduct of dihydric alcohol (20 to 40 mol). Addition), or EO / PO random addition (20 to 100 mol addition) of a tri- to hexavalent polyhydric alcohol such as glycerin or sorbitol. The content of the water-soluble polyether is preferably 40% or less based on the weight of the water-soluble metal working oil.

  Examples of the hydrocarbon-based lubricating oil include solvent refined oil, paraffinic mineral oil, naphthenic mineral oil, poly-α-olefin (weight average molecular weight 200 to 4,000), polybutene (weight average molecular weight 200 to 4,000), and the like. It is done. Of these, solvent refined oil, paraffinic mineral oil, and naphthenic mineral oil are preferred. The content of the hydrocarbon-based lubricating oil is preferably 70% or less based on the weight of the water-soluble metalworking oil.

  Examples of the emulsifier include Na and K salts of sulfonic acids having 10 to 40 carbon atoms (alkylbenzene sulfonic acid, petroleum sulfonic acid, alkylnaphthalene sulfonic acid, etc.), fatty acids having 8 to 22 carbon atoms (palmitic acid, myristic acid, Oleic acid, castor oil fatty acid, etc.) Na, K salts, etc., PEG esters obtained by esterifying these fatty acids and polyethylene glycols having a number average molecular weight of 500-5,000, and alcohols having 8-24 carbon atoms (octyl alcohol, decyl alcohol) Nonionic active agent obtained by adding 2 to 40 mol of ethylene oxide to dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, oleyl alcohol, stearyl alcohol, etc.), sorbitan fatty acid ester and these ethylene oxides. Examples include a nonionic active agent added in an amount of 5 to 40 mol. The amount of emulsifier used is preferably 30% or less based on the weight of the water-soluble metalworking oil.

Extreme pressure agents include dialkyl (C1-36) zinc dithiophosphates such as zinc dioctyl dithiophosphate and zinc diallyl dithiophosphate; organic sulfides having 3 to 60 carbon atoms such as dilauryl thiodipropionate and tetrakis [methylene-3 -(Dodecylthio) propionate] methane and the like.
The amount of extreme pressure agent used is preferably 5% or less based on the weight of the water-soluble metalworking oil.

  Examples of the oily agent include amine salts or alkali metal salts of fatty acids having 8 to 22 carbon atoms, alkali metal salts of alkyl phosphate esters having 8 to 22 carbon atoms, and fatty acids having 8 to 22 carbon atoms and 8 to 22 carbon atoms. Monohydric alcohol or polyhydric alcohol having 2 to 6 or more valences (ethylene glycol, propylene glycol, hexylene glycol, glycerin, neopentyl alcohol, pentaerythritol, etc.), animal and vegetable oils, and the like. The amount of the oily agent used is preferably 20% or less based on the weight of the water-soluble metalworking oil.

Examples of the rust preventive include organic amines having 2 to 36 carbon atoms (aliphatic amines such as butylamine, octylamine, laurylamine, oleylamine; alicyclic amines such as cyclohexylamine; heterocyclic amines such as morpholine; C6-C36 aliphatic carboxylic acid amide (caprylic acid, lauric acid, nonanoic acid, decanoic acid, oleic acid amide, etc.); C6-C24 dibasic acid amide (azelaic acid, sebacic acid, dodecane 2) Acid, dimer acid amide, etc.); C6-C36 alkenyl succinic acid amide (octenyl succinic acid, dodecenyl succinic acid, pentadecenyl succinic acid, amide of octadecenyl succinic acid, etc.); aromatic carboxylic acid amide ( Benzoic acid, p-tert-butylbenzoic acid, nitrobenzoic acid amide, etc.); cyclohexyla Benzotriazole, mercaptobenzothiazole, N, N′-disalicylidene-1,2-diaminopropane, alizarin, etc. Examples of amines that are constituents of the amide include the above amines and ammonia. .
The amount of the rust inhibitor used is preferably 10% or less based on the weight of the water-soluble metalworking oil.

The water-soluble metalworking oil of the present invention contains the above-mentioned antibacterial rust inhibitor, the above-mentioned other components, and water as necessary.
The content of antibacterial rust inhibitor (active ingredient) / other constituents / water based on the weight of the water-soluble metalworking oil is preferably 5-80 / 5-70 / 10-80, and more preferably Preferably it is 10-60 / 10-40 / 30-60.

  The water-soluble metalworking fluid of the present invention can be obtained by mixing the above (E) and / or (Q) and, if necessary, (F) and / or other components with a conventionally known mixing device. The mixing conditions are not particularly limited, but the mixing conditions are preferably obtained by mixing at 0 to 30 ° C. for 0.5 to 3 hours.

  It is preferable that the water-soluble metalworking oil obtained by blending is further diluted with water so that the concentration of (E) + (Q) + (F) is 0.5 to 30%.

  The water-soluble metalworking fluid of the present invention can be diluted to an arbitrary concentration in water, and is excellent in oil separation, rust prevention, and low foamability. The water-soluble metalworking fluid of the present invention is preferably used for processing such as cutting oil, grinding oil, polishing oil, rolling oil, drawing oil, press oil, quenching oil, polishing and cutting of aluminum disks and silicon wafers. it can.

[Example]
The following examples further illustrate the invention, but the invention is not limited thereto. Below, a part represents a weight part.

Example 1
After 116 parts (1 mole) of hexamethylenediamine was charged into a glass autoclave, and 176 parts (4 moles) of EO charged in a pressure-resistant dropping funnel was dropped over 6 hours while maintaining the reaction temperature at 140 to 150 ° C. Further reaction was performed at 145 ° C. for 2 hours. Then, after cooling to 80 ° C., stripping was performed under reduced pressure to obtain 292 parts of the antibacterial rust inhibitor (E1) of the present invention having a total amine value of 292.

Example 2
A glass autoclave was charged with 116 parts (1 mole) of hexamethylenediamine, and 232 parts (4 moles) of PO was dropped from a pressure-resistant dropping funnel over 6 hours while maintaining the reaction temperature at 140 to 150 ° C. Further reaction was carried out at 2 ° C. for 2 hours. Thereafter, in the same manner as in Production Example 1, 348 parts of the antibacterial rust inhibitor (E2) of the present invention having a total amine value of 322 were obtained by stripping under reduced pressure.

Example 3
After 200 parts (1 mole) of dodecamethylenediamine was charged into a glass autoclave, 176 parts (4 moles) of EO was added dropwise from a pressure-resistant dropping funnel over 5 hours while maintaining the reaction temperature at 140 to 150 ° C. The mixture was reacted at 2 ° C. for 2 hours, and then stripped under reduced pressure in the same manner as in Production Example 1 to obtain 376 parts of the antibacterial rust inhibitor (E3) of the present invention having a total amine value of 298.

Comparative Examples 1-3
A glass autoclave is charged with 116 parts (1 mole) of hexamethylenediamine and 4.8 parts of powdered KOH, and 880 parts (20 moles) of EO from a pressure dropping funnel, and the reaction temperature is controlled to be kept at 140 to 150 ° C. The solution was dropped over 10 hours, reacted at 145 ° C. for 2 hours, cooled to 80 ° C., treated with an adsorption treatment agent (Kyowad 600 manufactured by Kyowa Chemical Industry Co., Ltd.), filtered, and reduced in pressure at 110 ° C. for 1 hour. Dehydration gave 996 parts of a comparative antibacterial rust inhibitor (E′1) having a total amine number of 112.
Comparative Examples 2 and 3
As Comparative Example 2, triethanolamine was used, and as Comparative Example 3, a PO4 molar adduct of ethylenediamine was used.

Evaluation of antibacterial rust inhibitor;
About antibacterial rust preventives (E1) to (E3) of the present invention and (E'1) as a comparative antibacterial rust preventive, PO4 mol adduct of triethanolamine and ethylenediamine, antibacterial and rust preventive The foaming property and the oil separation property were evaluated.
The evaluation method is as follows.
(1) Antibacterial Into a 200 ml glass bottle, add 100 ml of 1% aqueous solution of the sample, add 2 g of corn flour, 3 g of cast iron chips, and 1 ml of spoiled cutting fluid to pH 9.5 to hydrochloric acid or potassium hydroxide. After adjustment, the pH was lowered and the number of general bacteria (measured using a simple culture measurement kit, Easy-Cult TTC (Daiichi Chemical Co., Ltd.)) after 14 days was measured. The smaller the pH drop, the less the rot and the better the antibacterial properties.
(2) Rust prevention 5% of cast iron (FC-25) chips are immersed in a 1% aqueous solution of the sample for 10 minutes and then taken out, spread on a petri dish with filter paper, capped and covered with rust after 24 hours at room temperature. The state to do was observed. ○: No rust, △: Tens of points of rust generated, ×: Rust generated in half of the total area (3) Foaming property After 100 ml of 2% aqueous solution of the sample was placed in a 200 ml graduated cylinder and shaken vigorously for 30 seconds The foam volume (ml) was measured after standing for 1 minute.
(4) Oil separability In a 100 ml graduated cylinder with a stopper, add 90 ml of 2% aqueous solution of the sample, add 10 ml of sliding surface oil (Dynaway 68: manufactured by Cosmo Oil), shake for 30 seconds, and let stand. The oil separation rate (%) was measured from the volume (ml) of the separated oil 30 minutes later.

The evaluation results are shown in Table 1.

Examples 4-8, Comparative Examples 4-7
Based on the formulation shown in Table 2, a water-soluble metalworking oil was obtained.

The evaluation was performed by further diluting the prepared water-soluble metalworking oil and adjusting the concentration of components other than water to 4%.
The evaluation method is the same as described above.

  It can be seen that the antibacterial rust preventive agent of the present invention has antibacterial properties, low foaming, good oil separation, and excellent rust prevention properties.

  The antibacterial rust inhibitor of the present invention has antibacterial properties, low foaming, good oil separation properties such as sliding surface oil, and excellent rust prevention properties. For this reason, it can use suitably as a rust preventive agent mix | blended with processing oils, such as metal cutting, grinding, press, rolling, drawing, quenching, grinding | polishing and cutting | disconnection of an aluminum disk and a silicon wafer.

Claims (4)

An antibacterial rust inhibitor containing an alkylene oxide adduct (E) represented by the general formula (1) and / or a salt (Q) of the (E) and a carboxylic acid having 6 to 20 carbon atoms.



(Wherein R is a divalent linear alkylene group having 4 to 18 carbon atoms, A ^{1 to} A ⁴ are alkylene groups having 2 to ⁴ carbon atoms, and m ^{1 to} m ⁴ are 0 or an integer of 1 to 3) , M ^{1 to} m ⁴ are 4 to 12 in total.) Claim A ¹ to A ⁴ in the general formula (1) are both an ethylene group 1 The antibacterial rust inhibitor described. The carboxylic acid having 6 to 20 carbon atoms is composed of an aliphatic chain monocarboxylic acid having 6 to 20 carbon atoms, an aliphatic chain dicarboxylic acid having 6 to 20 carbon atoms, and an alicyclic carboxylic acid having 6 to 20 carbon atoms. The antibacterial rust inhibitor according to claim 1 or 2, which is at least one selected from the group. A water-soluble metalworking oil comprising the antibacterial rust inhibitor according to any one of claims 1 to 3 .