JP6460536B2 - Water-soluble rust preventive additive and water-soluble metalworking fluid - Google Patents

Description

  The present invention relates to a water-soluble rust preventive additive and a water-soluble metalworking fluid that are excellent in low foaming properties and low environmental impact.

  Conventionally, many proposals have been made for water-soluble anticorrosive additives. Patent Document 1 discloses an organic boron-based water-soluble rust preventive containing a dehydration condensate of alkanolamine and boric acid and a water-soluble organic acid. Patent Document 2 contains a water-soluble rust preventive composition containing a surfactant and a carboxylate or sulfonate, and Patent Document 3 contains glycol and a carboxylate or carboxylic acid amide as a water-soluble rust preventive. A water-soluble lubricating oil is disclosed. Patent Document 4 describes a water-soluble rust preventive composition containing a carboxylic acid or dicarboxylic acid or a salt thereof, a higher alkylamine, a solvent and a surfactant. Patent Document 5 discloses an organic amine-based water-soluble rust and corrosion inhibitor composed of an alkylenediamine derivative. Patent Document 6 discloses a water-soluble processing oil having excellent rust prevention properties containing an alkanolamine and an organic carboxylic acid and / or phosphonic acid compound, and Patent Document 7 discloses a rust preventive composition for metals containing a thiocarboxylic acid compound. Is disclosed.

  As the water-soluble rust preventive additive, those composed of a compound containing at least one of nitrogen (N), phosphorus (P) and sulfur (S) as described above are generally used. .

  Metalworking fluids containing water-soluble rust preventive additives such as alkanolamine salts, alkyl phosphate ester salts, carboxylate salts and sulfonate salts disclosed in Patent Documents 2, 4, 5, and 6 described above have many bubbles. This has caused various adverse effects such as deterioration of workability, rust prevention, and work efficiency during handling. Moreover, the water-soluble rust preventive additive containing the inorganic metal (K, Na, Ca, Ba) salt shown in Patent Documents 3 and 4 causes hydrolysis and disproportionation reaction when used in circulation, etc. It is known that since soap is formed, scum is frequently generated and consumed when taken out during use, and the effect decreases with time. Furthermore, a water-soluble rust preventive additive containing a compound containing at least one of boron (B), sulfur (S), and phosphorus (P) shown in Patent Documents 1, 6, and 7 is discarded in a waste water system or water area. Then, it is feared that phosphorus-based compounds have various adverse effects on the environment such as eutrophication, sulfur-based compounds are sulfur rain generated during incineration, acid rain, and boron-based compounds have water pollution.

JP-A-52-000737 JP-A-6-41772 JP 2006-83378 A JP-A-8-319499 JP 2002-129367 A JP 2008-201875 A JP 2000-239868 A

  An object of the present invention is to provide a water-soluble rust preventive additive and a water-soluble metalworking fluid that are excellent in rust prevention, have low foaming properties, and have little adverse effect on the environment.

  As a result of earnest research in view of the above problems, the present inventors have found that a salt of a reaction product (hereinafter, polyethylene polyamine derivative) of polyethyleneimine and alkyl glycidyl ether not using inorganic metal, boron, sulfur, or phosphorus is used. It has been found that it is a low-foam water-soluble rust-preventive additive, and has led to the completion of the present invention. That is, the present invention provides the following inventions.

（一般式（１）中、Ｒは炭素数４〜１８の飽和または不飽和の直鎖又は分岐の炭化水素基を示し、ｎは１〜１７００の整数を示す。但し、ｎ個の（ＣＨ_２ＣＨ_２Ｎ）は直鎖でも分岐していてもよい。ｍは１または２である。Ａは炭素数６〜１８の飽和または不飽和の直鎖又は分岐の脂肪酸残基、炭素数８〜２２の二塩基酸残基、炭素数７〜１２の芳香族カルボン酸残基を示す）で表されるポリエチレンポリアミン誘導体の塩を含有する水溶性防錆添加剤。 1. The following general formula (1)

(In the general formula (1), R represents a saturated or unsaturated linear or branched hydrocarbon group having 4 to 18 carbon atoms, and n represents an integer of 1 to 1700, provided that n (CH ₂ CH ₂ N) may be linear or branched, m is 1 or 2. A is a saturated or unsaturated linear or branched fatty acid residue having 6 to 18 carbon atoms, and 8 to 22 carbon atoms. A dibasic acid residue, and an aromatic carboxylic acid residue having 7 to 12 carbon atoms).

  2. The water-soluble rust preventive additive according to Item 1, wherein in General Formula (1), A is a linear or branched fatty acid residue having 8 to 10 carbon atoms, and m = 1.

  3. The water-soluble rust preventive additive according to item 1, wherein A is a dodecanedioic acid residue and m = 2 in the general formula (1).

  4). The water-soluble metalworking fluid containing the water-soluble rust preventive additive according to any one of Items 1 to 3.

  5. Item 5. The water-soluble metalworking fluid according to Item 4, wherein the content of the water-soluble rust preventive additive is 0.1 to 10% by mass based on the total amount of the metalworking fluid.

  The product of the present invention is excellent in low foaming property and low environmental impact, has excellent rust preventive properties, does not generate scum, and is effective as a rust preventive additive for water-soluble metalworking fluids.

It is a graph which shows transition of foaming amount (bubble height).

  In the water-soluble rust preventive additive of the present invention, a salt of a polyethylene polyamine derivative represented by the following general formula (1) can be produced by reacting polyethyleneimine with an alkyl glycidyl ether and then chlorinating with an organic acid.

一般式（１）で表わされるポリエチレンポリアミン誘導体の製造のための、ポリエチレンイミンは一般式(２)で表わされ、ｎは１〜１７００の整数を示す。但し、ｎ個の（ＣＨ_２ＣＨ_２Ｎ）は直鎖でも分岐していてもよく、数平均分子量が約６０〜７００００(ｎ＝１〜１７００)であり、好ましくは、数平均分子量が約１００〜１００００（ｎ＝２〜２５０）のものから選択できる。具体的には例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミンや、数平均分子量が約３００〜７００００のポリエチレンイミンが挙げられる。

Polyethyleneimine for the production of the polyethylene polyamine derivative represented by the general formula (1) is represented by the general formula (2), and n represents an integer of 1 to 1700. However, n (CH ₂ CH ₂ N) may be linear or branched and has a number average molecular weight of about 60 to 70000 (n = 1 to 1700), preferably a number average molecular weight of about 100. 10000 (n = 2 to 250). Specific examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine having a number average molecular weight of about 300 to 70000.

General formula (2)

  The alkyl glycidyl ether used for the production of the salt of the polyethylene polyamine derivative represented by the general formula (1) is represented by the general formula (3), and R is a saturated or unsaturated linear or branched carbon having 4 to 18 carbon atoms. Indicated by hydrogen group. Specifically, R is a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a dodecenyl group, a stearyl group, an oleyl group, and the like. Preferably, R has 4 to 8 carbon atoms. It is.

General formula (3)

  Various organic acids can be used for the production of the salt of the polyethylene polyamine derivative represented by the general formula (1). In the general formula (1), as a saturated fatty acid residue having 6 to 18 carbon atoms in A Are the linear fatty acids n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, n-undecanoic acid, n-dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, Hexadecanoic acid, heptadecanoic acid, octadecanoic acid, branched fatty acids iso-hexanoic acid, iso-octanoic acid, iso-nonanoic acid, iso-decanoic acid, iso-undecanoic acid, iso-dodecanoic acid, neodecanoic acid, unsaturated fatty acid Is hexenoic acid, octenoic acid, decenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecene Acid, include residues such octadecenoic acid, having 5 or less carbon atoms is required to pay attention to the odor because the number 19 or more carbon atoms may be soluble and hard water stability decreases. Preferably, it is the most preferable saturated fatty acid residue having 8 to 10 carbon atoms, which has rust prevention and low foaming properties. In the general formula (1), the dibasic fatty acid residue having 8 to 22 carbon atoms of A includes suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, octenylsuccinic acid, dodecenylsuccinic acid, etc. Residues are mentioned, and when the number of carbon atoms is smaller than 8, the rust prevention property is not sufficient, and when the number of carbon atoms is 23 or more, there is a problem of stability of hard water. Preferred is dodecanedioic acid, which has the best antirust and low foaming properties. Examples of the aromatic carboxylic acid residue having 7 to 12 carbon atoms include residues such as benzoic acid, salicylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and 4-tert-butylbenzoic acid. It is done. In addition, m = 1 for monobasic acids and m = 2 for dibasic acids.

  In the production of the water-soluble rust preventive additive of the general formula (1), the catalyst used for the reaction of polyethyleneimine and alkyl glycidyl ether is synthesized with an alkali catalyst such as NaOH or KOH or without catalyst. Although the reaction atmosphere is not limited, it is synthesized under a nitrogen atmosphere or an air atmosphere. The reaction temperature is 25 to 130 ° C., preferably in the range of 25 to 100 ° C., more preferably 40 to 80 ° C., depending on the reaction cost and product coloring. The temperature at which the unreacted product is distilled off under reduced pressure is 25 to 180 ° C, preferably 130 ° C or less. The reaction temperature of chlorination of the polyethylene polyamine derivative with an organic acid is 25 to 80 ° C, preferably 50 ° C or less.

  The salt of the polyethylene polyamine derivative of the present invention can be contained in an existing water-soluble metalworking fluid as a rust preventive additive. In addition to the above rust preventive additives, the metalworking fluids of the present invention are also known other additives such as organic acids, organic amines, extreme pressure agents (phosphorous and sulfur), antioxidants, and surface active agents. Agents, preservatives and the like can be used in combination as necessary.

  As the organic acid, C8-C36 organic acids (organic acids having a carboxyl group and derivatives thereof are collectively referred to as organic acids) are generally used.

  Examples of the C8 to C36 organic acids include monocarboxylic acids and dicarboxylic acids. Examples of the monocarboxylic acid include octylic acid, pelargonic acid, isononanoic acid, isodecanoic acid, oleic acid, isostearic acid, ricinoleic acid, and natural products such as coconut oil fatty acid, tall oil fatty acid, and castor oil fatty acid. Examples of the dicarboxylic acid include adipic acid, sebacic acid, dodecanedioic acid and the like.

  Examples of organic amines include alkanolamines (monoethanolamine, diglycolamine, monoisopropanolamine, 2-amino-2-methylpropanol, 2- (sec-butylamino) ethanol, diethanolamine, diisopropanolamine, N-methylethanolamine. N-ethylethanolamine, triethanolamine and triisopropanolamine, etc.), aliphatic amines (n-octylamine, n-oleylamine, cyclohexylamine, dicyclohexylamine, etc.), aromatic amines (benzylamine, dibenzylamine, etc.) Of organic amines.

  Examples of extreme pressure agents include phosphorus-based alkylphosphonic acids, sulfur-based fats and oils, sulfurized olefins, sulfurized lard, polysulfide, and the like.

  Examples of the antioxidant include BHT (2,6-di-t-butyl-p-cresol), phenyl-β-naphthylamine, dilauryl thiodipropionate, and tridecyl phosphite.

As the surfactant, a nonionic surfactant is generally used. Nonionic surfactants include, for example, HO- (EO) l (PO) m (EO) n-H, R-O (EO) n-H, R-O (AO) n-H and EOPO addition of glycerin. Things can be mentioned.
(In the formula, R is an alkyl group (including linear, branched, cyclic, and those having a double bond or triple bond) AO (alkylene oxide) is EO (oxyethylene group), PO (oxypropylene group) , One kind or a mixture of two kinds, and their arrangement may be random or block.
In addition to the above, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant may be blended.

  Examples of the preservative include triazine compounds, isothiazoline compounds, and morpholine compounds.

  The metalworking fluid of the present invention can also be used as an emulsion containing a base oil. The base oil can be selected from at least one of mineral oil, synthetic oil, animal and vegetable oil and fat, and synthetic ester.

  Mineral oil includes spindle oil, machine oil, refrigerating machine oil, turbine oil, etc. Synthetic oil includes poly α-olefin, and animal and plant oils include whale oil, beef tallow, pig oil, rapeseed oil, castor oil, nuka oil, palm Oil, coconut oil, etc. are mentioned. Synthetic esters are esters synthesized from fatty acids and alcohols, fatty acids are C12-C36 monobasic acids or dibasic acids, and alcohols are C1-C18 ones. Examples thereof include glycerol triester, trimethylolpropane triester, neopentyl glycol triester, and the like.

  Water is blended in the stock solution of the water-soluble metalworking fluid of the present invention. The water used may be tap water, industrial water, ion exchange water, distilled water or the like, and it does not matter whether the water is hard water or soft water. A water-soluble metalworking fluid is used as a coolant by diluting a stock solution with water in actual use.

  Although the usage-amount of the rust preventive additive of this invention should just determine suitably according to a required performance, it is preferable to make it exist 0.1-10 mass% on the basis of water-soluble metalworking fluid total amount. This is because when the amount is 0.1% by mass or less, sufficient performance does not appear, and when it is 10% by mass or more, it is economically undesirable.

  Although the manufacturing method of the water-soluble antirust additive containing the salt of the polyethylene polyamine derivative of this invention is not restrict | limited at all, if it demonstrates as a specific example, the salt of a polyethylene polyamine derivative will be manufactured by the following methods, for example.

(Synthesis Example 1)
In a 1000 mL four-necked flask equipped with a stirrer, a thermometer, and a condenser tube, 58.5 g (0.400 mol) of triethylenetetramine was added. Butyl glycidyl ether 52.1g (0.400mol) was dripped over 1.5 hours, and it was made to react at 60 degreeC for 7 hours. After completion of the reaction, the temperature was raised to 130 ° C. under a reduced pressure of 2 mmHg, and it was allowed to cool after confirming that the distillate disappeared. To 64.7 g of the obtained product, 13.4 g (0.058 mol) of dodecanedioic acid was added dropwise and stirred at 50 ° C. for 1 hour. Thereafter, 78.1 g of water was added, and the mixture was stirred at 50 ° C. for 30 minutes to obtain a yellow transparent liquid containing 50% of a salt of a polyethylene polyamine derivative as a target active ingredient (Compound 1).

(Synthesis Example 2)
In a 1000 mL four-necked flask equipped with a stirrer, a thermometer, and a condenser tube, 58.5 g (0.400 mol) of triethylenetetramine was added. Butyl glycidyl ether 52.1g (0.400mol) was dripped over 1.5 hours, and it was made to react at 60 degreeC for 7 hours. After completion of the reaction, the temperature was raised to 130 ° C. under a reduced pressure of 2 mmHg, and it was allowed to cool after confirming that the distillate disappeared. To 64.7 g of the obtained product, 16.9 g (0.117 mol) of n-octanoic acid was added dropwise and stirred at 50 ° C. for 1 hour. Thereafter, 81.6 g of water was added and stirred at 50 ° C. for 30 minutes to obtain a yellow transparent liquid containing 50% of a salt of a polyethylene polyamine derivative as a target active ingredient (Compound 2).

(Synthesis Example 3)
In a 1000 mL four-necked flask equipped with a stirrer, a thermometer, and a condenser tube, 58.5 g (0.400 mol) of triethylenetetramine was added. Butyl glycidyl ether 52.1g (0.400mol) was dripped over 1.5 hours, and it was made to react at 60 degreeC for 7 hours. After completion of the reaction, the temperature was raised to 60 ° C. under a reduced pressure of 2 mmHg, and it was allowed to cool after confirming that the distillate disappeared. 18.5 g (0.117 mol) of isononanoic acid (trade name “Kyowanoic N”, manufactured by KH Neochem) was added dropwise to 64.7 g of the obtained product, and the mixture was stirred at 50 ° C. for 1 hour. Thereafter, 83.2 g of water was added and stirred at 50 ° C. for 30 minutes to obtain a yellow transparent liquid containing 50% of a salt of a polyethylene polyamine derivative as a target active ingredient (Compound 3).

(Synthesis Example 4)
In a 1000 mL four-necked flask equipped with a stirrer, thermometer, and condenser, 61.2 g (0.204 mol) of polyethyleneimine having a molecular weight of 300 (trade name “Epomin SP-003”, manufactured by Nippon Shokubai Co., Ltd.) I put it in. Butyl glycidyl ether 26.6g (0.204mol) was dripped over 1.5 hours, and it was made to react at 60 degreeC for 7 hours. After completion of the reaction, the temperature was raised to 130 ° C. under a reduced pressure of 2 mmHg, and it was allowed to cool after confirming that the distillate disappeared. 10.8 g (0.069 mol) of isononanoic acid (trade name “Kyowanoic N”, manufactured by KH Neochem) was added dropwise to 58.9 g of the obtained product, and the mixture was stirred at 50 ° C. for 1 hour. Thereafter, 69.7 g of water was added, and the mixture was stirred at 50 ° C. for 30 minutes to obtain a yellow transparent liquid containing 50% of a salt of a polyethylene polyamine derivative as a target active ingredient (Compound 4).

The compounds 1 to 4 and components 1 to 12 are shown below.
Compound 1) Dibasic fatty acid salt of R of formula (1) synthesized in Synthesis Example 1 with 4 carbon atoms, n = 3, and A = 12 carbon atoms (active ingredient 50%)
Compound 2) R fatty acid of general formula (1) synthesized in Synthesis Example 2 with 4 carbon atoms, n = 3, and A = 8 carbon atoms (active ingredient 50%)
Compound 3) Branched fatty acid salt of R of general formula (1) synthesized in Synthesis Example 3 with 4 carbon atoms, n = 3, and A = 9 carbon atoms (active ingredient 50%)
Compound 4) Branched fatty acid salt of R in formula (1) synthesized in Synthesis Example 4 with 4 carbon atoms, n = 6 to 7, and A = 9 carbon atoms (active ingredient 50%)
Ingredient 1) Triethanolamine Ingredient 2) Trade name “Sunhibitor NO.50” (manufactured by Sanyo Chemical Industries)
Ingredient 3) Sunhibitor NO. 50 straight chain fatty acid salt of 8 carbon atoms (active ingredient 50%)
Ingredient 4) Sunhibitor NO. 50 C9 branched fatty acid salt (active ingredient 50%)
Ingredient 5) C8 linear fatty acid salt of monoisopropanolamine (active ingredient 50%)
Component 6) Branched fatty acid salt of 9 carbon atoms of monoisopropanolamine (active ingredient 50%)
Ingredient 7) Decylphosphonate of monoisopropanolamine (active ingredient 50%)
Component 8) Sodium laurate Component 9) Potassium oleate Component 10) Potassium alkylbenzenesulfonate (active ingredient 50%)
Ingredient 11) Potassium 4-tert-butylbenzoate (active ingredient 50%)
Ingredient 12) Trade name “AQUALOX 232” (manufactured by Lubrizol)
Water) distilled water

  Examples 1-4 and Comparative Examples 1-11 were prepared so that it might become 1 mass% aqueous solution like Tables 1-3. In Example 5 and Comparative Example 12, each component was blended as a metalworking fluid as shown in Table 4.

<Rust prevention test>
A filter paper having a diameter of 7 cm was laid on the petri dish, and 7 g of cast chips were uniformly placed in a range of 5 cm in diameter, and 2 mL of the sample was poured onto the edge of the filter paper and covered. After 3 hours, the casting chips were removed and rusting on the filter paper was observed.
The evaluation method was based on the following criteria.
○: No occurrence of rust (good)
Δ: Slightly rusted (about 5%)
X: Rust generation (50%)

  The rust prevention test results of Examples 1 to 4 and Comparative Examples 1 to 11 are shown in Tables 1 to 3. Example 5 and Comparative Example 12 were subjected to a rust prevention test using aqueous solutions having dilution concentrations of 60, 70, and 80 times. The results are shown in Table 4.

<Foaming test 1>
100 mL of the sample was placed in a 200 mL graduated cylinder, shaken up and down 20 times by hand, and allowed to stand, and the maximum foaming amount (mL) was observed.
The evaluation method was based on the following criteria.
○: ≦ 20 mL (good)
Δ: 30 mL to 50 mL (medium)
×: 50 mL <(multifoaming)

  The results of the foam test 1 of Examples 1 to 4 and Comparative Examples 1 to 11 are shown in Table 1.

<Foaming test 2>
The following operation was performed using a JIS K 2518 apparatus. Take a sample of 190 mL diluted concentration 30 times in a 1000 mL graduated cylinder, and apply air from the diffuser stone to 500 mL / min. (0 to 5 minutes), 1000 mL / min. (6 to 10 minutes), 2000 mL / min. (11 to 15 Min) and observed the change in foaming amount (bubble height). The results of the foam test 2 of Example 5 and Comparative Example 12 are shown in FIG.

  The water-soluble rust preventive additive containing the salt of the polyethylene polyamine derivative of the present invention is excellent in low foaming property and low environmental impact, and by containing the water-soluble rust preventive additive in a metal working fluid, a water-soluble metal As a processing oil, it can be widely applied to applications such as cutting / grinding, plastic working, cleaning, and heat treatment.

Claims (5)

General formula (1)

(In the general formula (1), R represents a saturated or unsaturated linear or branched hydrocarbon group having 4 to 18 carbon atoms, and n represents an integer of 1 to 1700, provided that n (CH ₂ CH ₂ N) may be linear or branched, m is 1 or 2. A is a saturated or unsaturated linear or branched fatty acid residue having 6 to 18 carbon atoms, and 2 to 8 carbon atoms. A water-soluble rust preventive additive containing a salt of a polyethylene polyamine derivative represented by a basic acid residue and an aromatic carboxylic acid residue having 7 to 12 carbon atoms.   2. The water-soluble rust preventive additive according to claim 1, wherein, in the general formula (1), A is a linear or branched fatty acid residue having 8 to 10 carbon atoms and m = 1.   The water-soluble rust preventive additive according to claim 1, wherein A is a dodecanedioic acid residue and m = 2 in the general formula (1).   The water-soluble metalworking fluid containing the water-soluble rust preventive additive according to any one of claims 1 to 3.   The water-soluble metalworking fluid according to claim 4, wherein the content of the water-soluble rust preventive additive is 0.1 to 10% by mass based on the total amount of the water-soluble metalworking fluid.

Images