JPH0797590A - Water-soluble machining and grinding oil - Google Patents

Abstract

PURPOSE:To obtain a water-soluble machining and grinding oil having lowered foaming properties, no odor, improved rustproof properties, lubricity and pressure resistance. CONSTITUTION:The water-soluble machining oil comprises (A) an 18C monoand/or dihydroxy-fatty acid, (B) dihydric to hexahydric polyol and (C) a 4-36C aliphatic dibasic acid wherein any alkali metal salt or amine salt of (1) the polycondensate of component A (acid value: 30 to 150), (2) the polycondensate from an esterified product from A and B and the polycondensate of A (acid value: 20 to 120), (3) the polycondensate from A and C (acid value: 30 to 150) and (4) esterified product from A and B and the polycondensate from A and C (acid value: 20 to 120) is included.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil agent for metal processing which can be used in the field of metal processing, and more particularly to a water-soluble cutting and grinding oil agent.

[0002]

2. Description of the Related Art Conventionally, various oil agents have been used when cutting or grinding metals, and in particular, water-soluble oil agents have been preferably used. As a component of the water-soluble cutting and grinding oil, an alkali metal salt such as a higher fatty acid or a chlorinated fatty acid, or an amine salt has been used. However, water-soluble cutting and grinding fluids containing these components are generally prone to foaming, have a significant odor, and reduce workability,
It had a drawback that the rust preventive effect was likely to decrease.

[0003]

SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to provide a water-soluble cutting and grinding oil agent having a low foaming property, no odor, and good rust preventive properties.

[0004]

Means for Solving the Problems As a result of various studies to achieve this object, the present inventors have found that a salt of a specific polycondensate containing at least a hydroxy long-chain fatty acid as a raw material is a water-soluble cutting and grinding oil agent. As a result, the present invention has been completed, and the present invention has been completed.

That is, in the present invention, the raw material components are component A:
When a mono- and / or dihydroxy fatty acid having 18 carbon atoms, a component B: a divalent to hexavalent polyol, and a component C: an aliphatic dibasic acid having a carbon number of 4 to 36, any of the following (1) to (4) A water-soluble cutting and grinding oil agent containing an alkali metal salt or an amine salt of the polycondensate shown in (3). (1) Component A polycondensate (provided that the acid value is 30 to 15)
0). (2) Polycondensate of component A and esterified product of component B and component A (provided that the acid value is 20 to 120). (3) Polycondensate of component A and component C (provided that the acid value is 30
~ 150). (4) Polycondensates of component A and component B and component A and component C (provided that the acid value is 20 to 120).

In the present invention, the mono- and / or dihydroxy fatty acid having 18 carbon atoms which can be used as a raw material component is
Monohydroxy fatty acids such as stearic acid, oleic acid or linoleic acid having a hydroxyl group at any of the 9, 10, 12, 13, 15 or 16 positions, and 9 and 10
Positions, 12 and 13th, 15 and 16th, 9 and 12th,
9th and 13th, 9th and 15th, 9th and 16th, 10th and 12th, 10th and 13th, 10th and 15th, 10th and 1st
6th, 12th and 15th, 13th and 15th, or 13th
And dihydroxy fatty acids such as stearic acid, oleic acid or linoleic acid having a hydroxyl group at any of the 16-position and the like. Of these, 10-hydroxystearic acid, 12-hydroxystearic acid and ricinoleic acid are easily available as monohydroxy fatty acids, and 9,10-dihydroxystearic acid, 9,10-dihydroxyoleic acid, 9,1 as dihydroxy fatty acids.
0-dihydroxylinoleic acid, 12,13-dihydroxyoleic acid and 15,16-dihydroxylinoleic acid are preferred.

Specific examples of the divalent to hexavalent polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,9-nonanediol, glycerin, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol and the like. And polycondensation products thereof. Specific examples of the aliphatic dibasic acid, succinic acid, fumaric acid, maleic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, octadecamethylenedicarboxylic acid, eicosamethylenedicarboxylic acid, tetracosamethylenedicarboxylic acid, Octacosamethylene dicarboxylic acid, dotriacontane methylene dicarboxylic acid, 1-decene-
Examples thereof include 1,10-dicarboxylic acid and dimer acid.

Next, the present invention is characterized in that the above raw materials are used in a specific combination and subjected to a polycondensation reaction to obtain the following four types of polycondensates. That is, according to the present invention,
As the first polycondensate, a polycondensate obtained only from mono- and / or dihydroxy fatty acids having 18 carbon atoms as a raw material is obtained.
The polycondensate is a mono- and / or dihydroxy fatty acid in which hydroxyl groups and carboxyl groups are mainly intermolecularly and intramolecularly esterified, and particularly 12-
A polycondensate of hydroxystearic acid is preferred. It is essential that the acid value is 30 to 150. Acid value is 30
If it is less than 150%, the viscosity is increased and the workability is deteriorated, and an appropriate lubricating coating is not formed. If it exceeds 150, the lubricating performance effect is not exhibited, which is not preferable.

The second polycondensate has 18 carbon atoms.
Is a product obtained by further subjecting an esterified product of the mono- and / or dihydroxy fatty acid and a divalent to hexavalent polyol to a dehydration polycondensation reaction with a mono- and / or dihydroxy fatty acid having 18 carbon atoms. The polycondensate is obtained by esterifying the hydroxyl group and the carboxyl group of the raw material mainly intermolecularly and intramolecularly, and has an acid value of 20 to 120. this is,
The degree of polycondensation differs from the product obtained by simply polycondensing the hydroxy fatty acid and the polyol at the same time.
In the case of the present invention, the viscosity of the polycondensate can be adjusted appropriately.
When the acid value is out of the range of 20 to 120, the viscosity is increased and the workability is deteriorated, a proper lubricating film is not formed, or the effect of lubricating performance is deteriorated.

The third polycondensate is a polycondensate of a mono- and / or dihydroxy fatty acid having 18 carbon atoms and an aliphatic dibasic acid having 4 to 36 carbon atoms, and its acid value is 30 to 150. Requires that. If the acid value is less than 30, the viscosity will be increased and the workability will be reduced, and the amount of residual carboxyl groups required for forming a lubricating coating will be insufficient. If it exceeds 150, the effect of lubricating performance will appear. Disappear.

The fourth polycondensate is an esterified product of a mono- and / or dihydroxy fatty acid having 18 carbon atoms and a divalent to hexavalent polyol, and further, a mono- and / or dihydroxy fatty acid having 18 carbon atoms and 4 to 4 carbon atoms. It is the product of dehydration polycondensation reaction with 36 aliphatic dibasic acids. The polycondensate is obtained by further polycondensing the second polycondensate with the dibasic acid and has an acid value of 20 to 120.
When the acid value is out of this range, the viscosity increases and the workability decreases,
In addition, a proper lubricating film is not formed, or the effect of lubricating performance does not appear. The polycondensate has a different degree of polycondensate from the product obtained by simply reacting the raw materials at the same time as in the case of the second polycondensate, and the viscosity can be appropriately adjusted.

In order to prepare the above-mentioned esterified product and polycondensate, known methods of esterification reaction and polycondensation reaction can be adopted. That is, a raw material is appropriately selected, and a catalyst is or is not added to the raw material in the presence or absence of a solvent and gas inert to the reaction at 180 to 220 ° C. at 3 to 3 ° C.
By stirring for 5 hours, water produced as a by-product is removed to the outside of the system to obtain a reaction product, and if necessary, further purification treatment such as decolorization and deodorization is performed.

The polycondensate of the present invention thus obtained is used as an alkali metal salt or amine salt. Examples of the alkali metal include sodium and potassium, and examples of the amine include mono-, di- or tri-type ethanolamine, propanolamine, isopropanolamine, butanolamine, isobutanolamine, hexanolamine, octanolamine and isooctanolamine. Various amines can be used, but especially mono,
Lower alkanolamines such as di- or tri-type ethanolamine and propanolamine are preferred. Such salts of polycondensates include hydroxides and oxides of the alkali metals,
It can be converted into the salt by a conventional method using the hydrochloride salt of the amine.

In the production of the water-soluble cutting and grinding fluid of the present invention, the alkali metal salts or amine salts of the above-mentioned four kinds of polycondensates may be used alone as they are, or known mineral oils and synthetic oils may be used. Oil, extreme pressure additives, fatty acids, antioxidants, surfactants, etc. may be added to form an emulsion type or soluble type composition. In such a water-soluble cutting and grinding fluid, the effective compounding ratio of the salt of the polycondensate according to the present invention is appropriately selected depending on the purpose of use, the situation of use, etc. 1 to
It is 50% by weight, preferably 1 to 30% by weight, more preferably 1 to 5% by weight.

[0015]

EXAMPLES In the following synthesis examples and examples, parts and%
Are based on weight. Synthesis Example 1 12-hydroxystearic acid 3 was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a water separation tube.
Charge 00 parts and 30 parts of xylene and raise the temperature to 220 ° C.
It dehydrated at this temperature for 3 hours and the polycondensation reaction was performed. After the reaction, xylene was distilled off under reduced pressure to give the polycondensate of the present invention (acid value 5
270 parts of 0) were obtained. Hereinafter, this is referred to as sample A.

Synthetic Example 2 The reaction apparatus described in Synthetic Example 1 was charged with 240 parts of ricinoleic acid, 60 parts of glycerin and 30 parts of xylene, and 180-2
An esterification reaction was carried out at 20 ° C. for 5 hours to obtain 265 parts of a ricinoleic acid glyceride mixture. The composition of this product was: ricinoleic acid and its polycondensate: 25%, monoglyceride of ricinoleic acid and its polycondensate: 40%, diglyceride of ricinoleic acid and its polycondensate: 25%, other mixed glycerides: 10%, The acid value was 45. Then,
240 parts of this ricinoleic acid glyceride mixture, 60 parts of 12-hydroxystearic acid and 30 parts of xylene were charged, the temperature was raised to 220 ° C. in the same manner as in Synthesis Example 1, and dehydration was carried out at this temperature for 5 hours to carry out a polycondensation reaction. After the reaction, xylene was distilled off under reduced pressure to obtain 268 of the polycondensate of the present invention (acid value 53).
I got a copy. Hereinafter, this is referred to as sample B.

Synthesis Example 3 Sorbitol 13 parts, 12-hydroxystearic acid 1
37 parts and xylene 30 parts were charged, and 2 parts were prepared in the same manner as in Synthesis Example 1.
The temperature was raised to 00 ° C. and dehydration was carried out at this temperature for 5 hours to carry out a polycondensation reaction. After cooling, 150 parts of dihydroxy fatty acid (Hartle Q-1, manufactured by Harima Kasei Co., Ltd.) was charged, the temperature was similarly raised to 220 ° C., and dehydration was carried out at this temperature for 4 hours to carry out a polycondensation reaction. After the reaction, xylene was distilled off under reduced pressure to obtain 245 parts of the polycondensate of the present invention (acid value 30). Hereinafter, this is referred to as sample C.

Synthesis Example 4 145 parts of dimer acid, 12-hydroxystearic acid 1
55 parts and 30 parts of xylene were used, and 22
The temperature was raised to 0 ° C. and dehydration was carried out at this temperature for 5 hours to carry out a polycondensation reaction. After the reaction, xylene was distilled off under reduced pressure to obtain 268 parts of the polycondensate of the present invention (acid value 68). Hereinafter, this is referred to as sample D.

Synthesis Example 5 Using 192 parts of dihydroxy fatty acid (Hartle Q-1, manufactured by Harima Kasei Co., Ltd.), 102 parts of azelaic acid and 30 parts of xylene, the temperature was raised to 220 ° C. in the same manner as in Synthesis Example 1,
It dehydrated at this temperature for 5 hours and the polycondensation reaction was performed. After the reaction, xylene was distilled off under reduced pressure to give the polycondensate of the present invention (acid value 7
272 parts of 4) were obtained. Hereinafter, this is referred to as sample E.

Synthesis Example 6 102 parts of 12-hydroxystearic acid, 64 parts of 12-hydroxystearic acid monoglyceride, 117 parts of dodecanedioic acid, 18 parts of neopentyl glycol, xylene 3
Using 0 part, the temperature was raised to 220 ° C. in the same manner as in Synthesis Example 1 and dehydration was carried out at this temperature for 5 hours to carry out a polycondensation reaction. After the reaction, xylene was distilled off under reduced pressure to obtain the polycondensate of the present invention (acid value 30).
270 parts were obtained. Hereinafter, this is referred to as sample F.

Synthesis Example 7 Ricinoleic acid 38 parts, Neopentyl glycol 13 parts,
30 parts of xylene was charged, the temperature was raised to 220 ° C. in the same manner as in Synthesis Example 1, and dehydration was carried out at this temperature for 4 hours to carry out a polycondensation reaction. After cooling, 108 parts of ricinoleic acid, 14 of dimer acid
1 part was charged, the temperature was similarly raised to 220 ° C., and dehydration was carried out at this temperature for 3 hours to carry out a polycondensation reaction. After the reaction, xylene was distilled off under reduced pressure to give 265 the polycondensate of the present invention (acid value 45).
I got a copy. Hereinafter, this is referred to as Sample G.

Example 1 3 parts of each of the polycondensates (Samples A to G) obtained in Synthesis Examples 1 to 7 and 5 parts of triethanolamine were mixed to form an amine salt of each polycondensate. A 2% aqueous solution was used to prepare an aqueous solution sample for performance evaluation of a water-soluble cutting and grinding fluid. In the following performance evaluation tests, the polycondensates of the present invention (Samples A to G) were used as Comparative Examples, Comparative Example 1: 12-hydroxystearic acid, Comparative Example 2: Ricinoleic acid, Comparative Example 3:
Using dimer acid, each amine salt was made into a similar aqueous solution to prepare a sample.

(1) Friction coefficient The friction coefficient was measured using a Soda pendulum friction tester. The results are shown in Table 1. (2) Pressure resistance performance was measured by a step load method (0.5 kg) at 200 rpm using a Soda-type four-ball type tester. The results are shown in Table 1.

[0024]

[Table 1] * All formulations were triethanolamine salts, and the performance was evaluated as a 2% aqueous solution.

(3) Anticorrosion Performance 100 ppm of salt was added to a 2% aqueous solution of the triethanolamine salt of each sample, and the antirust effect was compared by an iron piece immersion test. The results are shown in Table 2.

[0026]

[Table 2] *: Same as Table 1 *: ◎ → No rust, ○ → Several points of rust, × → Tens of points of rust

(4) Defoaming performance 2% aqueous solution of triethanolamine salt of each sample 25
Pour ml into a 50 ml graduated cylinder, shake for 30 seconds,
The volume after foaming at each time was measured. The results are shown in Table 3.

[0028]

[Table 3] *: Same as Table 1. * *: The numerical value in the table shows the volume (ml) of the sample and bubbles in the 50 ml graduated cylinder.

As the results in Table 1, Table 2 and Table 3 show,
The water-soluble cutting and grinding fluid of the present invention is superior to conventional ones in lubricity, pressure resistance, rust resistance and defoaming property. Further, all the products of the present invention had no odor.

[0030]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a water-soluble cutting and grinding oil agent which has a low foaming property, has no odor, is excellent in rust prevention, and is excellent in terms of lubricity and pressure resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical indication (C10M 109/02 105: 14 105: 24 105: 26) C10N 30:06 30:12 30:18 40:22

Claims (1)

[Claims] 1. When the raw material components are component A: mono- and / or dihydroxy fatty acid having 18 carbon atoms, component B: divalent to hexavalent polyol, component C: aliphatic dibasic acid having 4 to 36 carbon atoms A water-soluble cutting and grinding oil agent containing an alkali metal salt or amine salt of a polycondensate represented by any of the following (1) to (4). (1) Component A polycondensate (provided that the acid value is 30 to 15)
0). (2) Polycondensate of component A and esterified product of component B and component A (provided that the acid value is 20 to 120). (3) Polycondensate of component A and component C (provided that the acid value is 30
~ 150). (4) Polycondensates of component A and component B and component A and component C (provided that the acid value is 20 to 120).