JPH10237476A - Water-soluble metal working oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metal working oil which allows the coolant to be kept clear and clean even after repeated use and does not stain the environment around a machine, work clothing, etc., by adding a cationic polymer to a soluble-type or solution-type water-soluble metal working oil. SOLUTION: A cationic polymer represented by for example formula I (wherein X is Cl or OH; and n is 100-1,300) or formula II (wherein s is 100-2,000) is added to a water-soluble metal working oil comprising an organic amine, an inorganic alkali, a fatty acid, an aromatic carboxylic acid, an amino acid, a surfactant and water and is added in an amount of usually about 0.01-10w/v%, desirably 0.1-5w/v% based on the working oil. Because the obtained working oil contains the polymer, it does not putrefied even when used repeated and can be kept in a state of a freshly formed bath. This oil can be desirably used for metal cutting and grinding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble metal working fluid, and more particularly to a water-soluble cutting and grinding fluid.

[0002]

2. Description of the Related Art There are two types of water-soluble metal working oils, which are called a soluble type and a solution type. In either type, mineral oils and fats are scarcely contained, fatty acids and water-soluble extreme pressure additives. , A surfactant, an antifoaming agent, a metal anticorrosive, an antioxidant, an antiseptic / antifungal agent (bactericide), and the like as constituent components, and are produced by appropriately mixing these according to the purpose.

[0003] In actual use, an aqueous solution obtained by diluting this composition stock solution with water (generally a 1 to 10% concentration diluent) is supplied to a processing portion for cooling and lubrication, and is circulated. As described above, the water-soluble metalworking fluid has many advantages, such as less risk of fire, low cost, less oil smoke and improved working environment, compared with the water-insoluble fluid, and the use of the fluid is increasing. It is thriving.

[0004] However, the biggest disadvantage of the water-soluble metalworking oil is that it decomposes and degrades in the state of circulating use. When a water-soluble metal working fluid (hereinafter referred to as a coolant) circulated during use deteriorates by decay, the primary performance decreases, that is, the tool life decreases, and the dimensional accuracy of the workpiece deteriorates. In addition, secondary performance, that is, generation of offensive odor due to deterioration by decay, reduction of rust prevention, and adhesion of dirt around the machine due to reduction of cleaning power of the coolant occur. In general, water-soluble metal working oils contain various surfactants (hydraulic working oil, sliding surface lubricating oil, and rust preventive applied to working materials) mixed with a coolant because a surfactant is added to impart detergency. Oil and the like) are emulsified and suspended, resulting in disadvantages such as making the working point difficult to see. Further, there is a disadvantage that fine metal powder, grinding stone powder, and other fine powder generated during processing are dispersed in the coolant and have no transparency, resulting in a black state. Of course, due to this coolant stain,
The splashed liquid dries and becomes dirty around the machine, and also stains work clothes. Therefore, it is desirable to keep the state in which the coolant has been newly bathed (usually almost colorless and transparent).

[0005]

The problem to be solved by the present invention is to solve the above-mentioned problems of the conventional water-soluble metal working oils, and more particularly, to the water-soluble metal working oils which are used in circulation. In a newly built bath.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, the present inventors have developed a water-soluble metalworking oil which keeps the coolant transparent and clean and does not stain the machine surroundings and work clothes. Various studies have been repeated for the purpose of. As a result, they have found that a water-soluble metal working oil which satisfies the above-mentioned requirements can be obtained by adding and blending a special cationic polymer in a conventional water-soluble metal working oil called a solution type or a solution type. The present invention has been completed based on such findings.

[0007]

That is, the present invention relates to a conventional water-soluble metalworking oil, usually an organic amine, an inorganic alkali, an inorganic salt, a fatty acid, an aromatic carboxylic acid, an amino acid, a surfactant (an ethylene oxide, a propylene oxide random). Or a water-soluble metalworking fluid comprising water and a water-soluble metalworking fluid comprising water and a water-soluble metalworking fluid comprising water and a water-soluble metalworking fluid. .

In the present invention, the above-mentioned special polymer used is represented by the following general formula:

Embedded image

Embedded image

Embedded image and

A polymer represented by the formula: ## STR4 ## and one or more of them are contained in conventional water-soluble metalworking oils.

[0009]

Wherein X represents Cl or OH, and n is 1
Represents an integer of 00 to 1300.

[0010]

Wherein Y in the above formula is

Embedded image

Embedded image or

Wherein R ₁ and R ₂ represent the same or different hydrogen or methyl groups. N 'represents an integer of 10 to 800.

[0011]

Wherein M in the above formula represents an alkali metal, an alkaline earth metal, or NH ₄ . m is 1 or 1/2.
N ″ is an integer of 100 to 35000.

[0012]

Wherein s is an integer of 100 to 200.

Preferred specific examples of the special polymer used in the present invention are as follows.
"Polyallylamine PAA-HCl-10L" (manufactured by Nitto Boseki Co., Ltd., molecular weight about 100,000), "Polyallylamine P
AA-L "(manufactured by the company, molecular weight of about 10,000)," PAS-PAS "
-A-5 "(manufactured by the company, molecular weight about 4000)," Pass P
AS-H-5L "(manufactured by the company, molecular weight about 40,000),
"PAS-J-81" (manufactured by the company, molecular weight of about 200,000), "PAS-PAA-880" (manufactured by the company, molecular weight of about 40,000), "Separan SA1742L" (manufactured by Dow Chemical Company, USA),
"Busan 77" (manufactured by Sanai Sekiyu KK), "Pass PA
S-410 "(manufactured by Nitto Boseki Co., Ltd., molecular weight of about 200,000", "PAS-PAA-D11-HCl" (manufactured by the company, molecular weight of about 5
10,000).

In the present invention, the amount of the special polymer is usually 0.01 to 10% in the metal working oil of the present invention.
It is good to be about 0 w / v%, preferably about 0.1 to 5.0 w / v%. The amount of the polymer is 0.01 w /
If it is less than v%, the resulting oil agent tends to have poor coolant cleanliness and anti-machine stains.
If it is more than 0 w / v%, the cleanliness of the coolant and the anti-fouling property around the machine are not improved, which is not economically preferable.

In the present invention, the object to which the special polymer is to be added and blended is a conventional water-soluble metalworking oil. These conventional water-soluble metalworking oils may be those conventionally used. Usually, these conventional water-soluble metalworking oils include organic amines, fatty acids, surfactants (including polyalkylene glycols), preservatives, inorganic salts, other water-soluble extreme pressure additives, defoamers, Consists of antioxidants and the like.

In the present invention, in principle, any conventional water-soluble metalworking oil can be used.

The main components will be described in more detail below. As the organic amine compounded in the metal working oil agent of the present invention, conventionally known organic amines can be widely used, and examples thereof include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and N-ethyl. Diethanolamine, N, N-diethanolamine, Nn-butylethanolamine, N
-N-butylethanolamine, N-cyclohexyldiethanolamine, mono-sec-butanolamine,
Examples thereof include alkanolamines such as di-sec-butanolamine and 2-methylpropanolamine, and polyvalent amines such as ethylenediamine and N, N-dimethylaminopropylamine. Among them, diethanolamine, Nn-butylethanolamine,
N, N-dimethylaminopropylamine is preferred.

The compounding amount of the amine is usually about 5 to 60 w / v%, preferably 10 to 50 w /% in the oil agent of the present invention.
/ V. If the amount of the organic amine is less than 5 w / v%, the pH of the oil agent is too low, which may hinder the rust prevention of the iron-based parts of the machine. Conversely, if it is more than 60 w / v%, the pH of the oil agent will be high. Too much skin irritation can cause severe skin irritation, dermatitis, etc., which are both undesirable. If the amount of the amine is less than 5% w / v, other components, especially organic acids, are also reduced to reduce rust resistance.
H needs to be 8.5 or more. Therefore, it is necessary to use the coolant with a high concentration of the coolant, which is uneconomical. From this viewpoint, if the amount of the amine is more than 60 m / v%, the amount of the organic acid must be increased accordingly, and the metal working oil itself may not be formed.

As an inorganic alkali in place of or in part of the organic amine, it does not hinder the mixing of sodium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, and the like. The compounding amount may be within the range of the pH when the organic amine is used alone.

As the fatty acids and organic acids to be blended in the oil agent of the present invention, those which are conventionally known rust preventive additives can be widely used. Among them, fatty acids having 6 to 10 carbon atoms, benzoic acid, paranitrobenzoic acid and the like can be used. And dibasic acids such as adipic acid, azelaic acid and phthalic acid. Other commercially available rust preventive additives (organic acid amine salts) are also suitable. At this time, the fatty acid amine salt having a fatty acid having a carbon number as large as 11 or more is produced by the special polymer of the present invention.
It tends to gel and separate.

The amount of the fatty acid or organic acid is about 0.5 to 30 w / v%, preferably 2 to 20 w / v
It is better to be about v%. 0.5w / v% of acid
If the amount is less, the rust-proofing ability of the obtained oil agent tends to be poor. Conversely, if it is more than 30 w / v%, the rust-proofing ability is not further exhibited, and the addition of amine for neutralizing acid is not achieved. Since a large amount is required, it is not economically preferable. If the amount of the acid is out of the above range, as in the description of the amount of the amine added, the dilution concentration may be too high to be uneconomical in actual use, or the water-soluble metalworking oil itself may not be able to be produced. Also, addition of acids and known inorganic salt rust preventive additives as a part of commercially available rust preventive additives, such as molybdate, tungstate, borate, phosphate, azicahydrochloride (for example, NaN ₃ ). It does not hinder.

Surfactants to be added to the water-soluble metalworking oil of the present invention are known nonionic surfactants, and among others, relatively nonionic surfactants. L. Those having high B are preferred. The reason for this is described in the section on fatty acids. L. When B is low, even if the surfactant is dissolved in a stable state when the special polymer of the present invention is not blended, the nonionic surfactant is gel-separated when the special polymer is blended,
This is because handling becomes difficult. Therefore, if ethylene oxide is added to nonylphenol,
H. L. B. Is preferably 8 or more. In addition, those obtained by adding ethylene oxide to polyhydric alcohol, those obtained by random polymerization of ethylene oxide / propylene oxide, those obtained by block polymerization (pluronic nonionic activator), and those obtained by addition polymerization of propylene oxide to polyethylene glycol (reverse) Pluronic activator). Of these, a pluronic nonionic activator and a reverse pluronic activator are preferred.
The amount of the surfactant may be 60 w / v% or less. This is because when the surfactant is 0 w / v%, the special polymer can play its role. Preferably it is 50% or less. The reason that the amount of the surfactant is large is that the above surfactant is effective in heavy cutting and grinding when the metal working oil of the present invention is used for heavy cutting and grinding when the large amount is blended. Because there is.

The water-soluble metalworking oil of the present invention may further contain a conventional chlorine / sulfur extreme pressure additive, if necessary.

The water-soluble metalworking oil of the present invention is easily prepared according to a conventionally known method by blending the above components.

The water-soluble metal working oils of the present invention typically include water-soluble metal cutting oils and water-soluble metal grinding oils, as well as other water-soluble cleaning agents, water-soluble rust inhibitors, and water-soluble forming agents. Agents, water-soluble heat-treated oil agents, water-soluble forging oil agents, and the like.

In particular, the oil agent of the present invention is suitable as a metal cutting and grinding oil agent. In this use, there is no particular limitation, and it can be used in the same manner as a conventional cutting oil composition.

[0027]

The present invention will be further clarified with reference to the following examples and comparative examples. The following experiments were performed on water-soluble cutting fluids having the compositions shown in Table 1, and the performance of each water-soluble cutting fluid was evaluated. The unit of the numerical value related to the composition in each table is w / v%.

(1) Preparation of Sample A water-soluble cutting oil having the composition shown in Table 1 was diluted with tap water (Tsui, Yamatokoriyama-shi) to prepare a sample liquid. In this case, each of the water-soluble cutting oils shown in Table 1 (Examples 1 to 10 and Comparative Examples 1 to 4) was diluted so as to contain 3% by volume of tap water.

[0029]

[Table 1]

In Table 1, the amine used, the cationic polymer of the present invention and other components are as follows. Example or amine cation Comparative example Polymer Example 1; monoethanolamine polymer 1 Example 2; diethanolamine polymer 2 Example 3; triethanolamine polymer 3 Example 4; monoisopropanolamine polymer 4 Example 5; diethanolamine 15 Polymer 5 N, N-diethanolamine 15 Example 6; N, N-butylethanolamine Polymer 6 Example 7; Triethanolamine 30 N, N-dimethylamino polymer 7 Propylamine 10 Example 8; Monoethanolamine 15 Polymer 8 Monoisopropanolamine Example 9; Monoethanolamine 10 Polymer 7 N, N-butylethanolamine 5 Example 10; Diethanolamine Polymer 8 Comparative Example 1; Triethanolamine Comparative Example 2; N, N-butyl Ethanolamine Comparative Example 3; monoethanolamine Comparative Example 4; monoethanolamine 15 monoisopropanolamine 15

Polymer 1: "Polyallylamine PAA-HCl-10L" manufactured by Nitto Boseki Co., Ltd.

Embedded image X = Cl Molecular weight: about 100,000 Polymer 2: “Polyallylamine PAA” manufactured by Nitto Boseki
-L "

Embedded image X = OH Molecular weight: about 10,000 Polymer 3; “PAS-A-5” manufactured by Nitto Boseki Co., Ltd.

Embedded image R ₁ , R ₂ 3CH ₃ Y = SO ₂
000 Polymer 4; Nitto Boseki's "Pass-PAS-H-5L"

Embedded image R ₁ , R ₂ 3CH ₃ Molecular weight: about 40,000 Polymer 5; “PAS-PAS-J-81” manufactured by Nitto Boseki Co., Ltd.

Embedded image R ₁ , R ₂ = CH ₃ Y = CH ₂ —CH (—CO
—NH ₂ ) —Molecular weight about 200,000 Polymer 6; “PAS-PAA-880” manufactured by Nitto Boseki Co., Ltd.

Embedded image R ₁ , R ₂ ＣＨCH ₃ Y =

Embedded image Polymer 7, molecular weight: about 40,000 Polymer 7; “Separan SA1” manufactured by Dow Chemical Company, USA
742L "

## STR3 ## Polymer 8; "Busan 7" manufactured by Sanai Sekiyu KK
7 "

Embedded image

The surfactants and commercial preservatives are as follows. Bluronic nonionic activator; "Pronon # 204" Bluronic nonionic activator; "PEP-3070"
(Hoechst Industry Co., Ltd.) Commercial preservative A; "Perma G" (Permachem Asia Co.) Commercial preservative B; "Sodium Omazine" (San-ai Sekiyu KK) In addition, the number after the amine shows the compounding amount.

(2) Microbial Deterioration Test 300 ml of each sample solution is placed in a 500 ml flat-bottomed flask that has been washed, dried and dried. Assuming an actual coolant tank, the sliding surface lubricating oil (Mobile Bactra No.
2) was added with 5% w / v% of 3% by volume cast cutting chips (obtained by dry cutting). Further, the emulsion liquid spoiled as a seed fungus (viable bacteria 2 × 10 ⁸ cells / ml, filamentous fungus 1 × 1
0 ³ cells / ml, yeast fungi 5 × 10 ³ cells / ml) were added at the start of each 3% by volume test, and 1% by volume was inoculated every 7 days from the start of the test. After 14 days from the start of the test, the cells were cultured at 30 ° C. with shaking (60 rpm).
Incubated at ℃.

Next, 7, 14, 21, 3 after the start of the test
On days 5, 49, and 63, each sample was aseptically collected, and the viable cell count, filamentous fungal count, and yeast fungal count were determined.
The measurement of H and the observation of the presence or absence of odor were performed. However, since sliding surface lubricating oil and casting chips were added to the sample liquid, care was taken not to mix them into the sample liquid. Furthermore, from the outside of the flask, the state of the floating oil, the appearance of the intermediate liquid phase,
The state of the casting chips was observed. 7th, 14th while shaking
On the day, the measurement was evaluated one hour after the shaking culture was stopped. The test results are shown in Tables 2 to 7. However, the measurement of pH, viable cell count and fungal count was carried out by the following method.

(I) pH pH was measured with a glass electrode pH meter. Here, a decrease in pH indicates the degree of microbial degradation, and it is considered that the more severe the decrease in pH, the more the microbial degradation is progressing.

(Ii) Measurement of viable cell count and fungal cell count The viable cell count was measured by a plate count method using an ordinary agar medium. The number of filamentous fungi was determined by the plate count method using the potato dextrose agar medium supplemented with the antibiotic (chloramphenicol), and the number of yeast fungi was determined by plate counting using the Sabouraud agar medium also supplemented with the antibiotic (chloramphenicol). Was. In this case, since there is a possibility that both fungi would grow in either medium, the morphology of the colony was sufficiently observed, and it was checked whether the fungus was a filamentous fungus or a yeast fungus and counted.

(Iii) Evaluation of odor The odor was evaluated by dividing the odor intensity into three ranks as follows. ；: No rotting odor Δ: Slightly rotting odor
X: There is a rotten odor.

(Iv) Evaluation of the state of the floating oil ○: The fluidity is close to that of the new oil. Further, the boundary with the sample solution is clear and there is no creamy layer. Δ: No obvious mold-like substance was observed in the floating oil, but the boundary with the sample solution was not clear and a creamy layer was observed. ×: Moldy substance adhered and lacked fluidity. Also, the boundary with the sample solution is not clear, and a creamy layer is observed.

(V) Appearance of the liquid phase of the sample liquid ○: close to the hue before the start of the test and transparent. Δ: Slightly colored, slightly turbid in the liquid. ×: Colored brown, which is considered to be iron ions, and the added oil became an emulsion, which was highly turbid.

(Vi) Evaluation results The following can be understood from the above. (1) pH; In the sample of Example, the decrease in pH value was 0.2 at the maximum even after 63 days. On the other hand, the sample of the comparative example decreased by 2.0 at the maximum.

(2) Viable bacterial count and fungal count: The viable bacterial count was 10 ³ or less in all of the samples of each example even after 63 days, whereas the number of viable bacteria was 2 × 10 3 in the sample of each comparative example. ₇
~ 2 × 10 ⁸ . In addition, the number of filamentous or yeast fungi could not be detected in all Examples, which was 10 or less.

(3) Odor; 63% for all samples in Examples
After the passage of days, no odor was generated, whereas in Comparative Examples, all had a putrid odor.

(4) Evaluation of the state of the floating oil content: In each of the samples of the examples, the oil layer mixed after 63 days had a fluidity in a state of being almost new, and at the same time the boundary between the sample aqueous solution and the oil layer was clear. Met. In each of the comparative examples, the floating oil had no fluidity, and a cream layer was observed at the boundary between the sample aqueous solution and the oil layer. This is considered to be due to the fact that in the conventional coolant of the comparative example, the mixed oil, which has lost fluidity, adheres around the machine and further embraces cutting chips, fine grinding stones, and the like, causing dirt around the machine.

(5) Appearance of liquid phase of sample liquid; all of the samples in the examples are transparent after 63 days, have little discoloration which seems to be accompanied by an increase in iron ions, and are considered to be excellent in workability in actual equipment. . On the other hand, in the comparative example, the elution of iron ions was increased due to a decrease in rust-preventive power due to a decrease in pH, and the sample solution was discolored to brown, and there was no transparency.

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

[Table 5]

[0049]

[Table 6]

[0050]

[Table 7]

<Field Experiment> In order to further clarify the practical effectiveness of the water-soluble cutting oil of the present invention, at a production site where a water-soluble cutting oil is used (an automobile camshaft polishing line), First, the water-soluble grinding fluid of Comparative Example 3 and the water-soluble grinding fluid of Example 1 were subjected to an execution test under the following processing conditions.
And Table 9 below.

(Processing conditions) Material to be processed: Casting system (Details unknown) (1,000 c
For c-class gasoline engines) Processing method: Polishing of journal and cam parts Grinding fluid tank capacity: 50.000L Grinding oil dilution ratio: 50 times Test period: 6 months or 1 year

[0053]

[Table 8]

[0054]

[Table 9]

As shown in Tables 8 and 9, the water-soluble grinding oil of the present invention has excellent rot resistance in practical use as compared with the conventional water-soluble grinding oil, and also has a high degree of cleanliness of coolant and machinery. Significantly improved. Furthermore, while the conventional grinding oil was used after 6 months of use and caused defects due to polishing cracks, the water-soluble grinding oil of the present invention did not cause polishing cracks even after one year, and the productivity was low. The improvement is remarkable.

In order to improve the cleanliness of the coolant, the splashed liquid adheres to the work clothes, and black fine stains of the casting fine powder (where the fine powder cannot be removed when washed are changed to brown iron rust). It was no longer possible, and an effect that was very pleasing to workers was also recognized.

The present invention is not limited to the specific embodiments described above, but may be variously modified within the scope of the present invention in accordance with the purpose and application.

[0058]

Since the water-soluble metalworking fluid of the present invention is water-soluble, there is no problem of fire danger and deterioration of the environment due to generation of oil mist and harmful gas. Moreover, the processing oil agent of the present invention exhibits excellent workability, especially cutting and grinding properties, and at the same time, keeps the coolant transparent and clean, does not stain the surroundings of the machine, has a high anti-corruption ability and can greatly extend the life of the coolant. . Therefore, the metalworking oil of the present invention
It is suitably used as a water-soluble metal working oil, especially as a cutting and grinding oil.

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[Procedure amendment]

[Submission date] April 7, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

[0012]

Wherein s is an integer of 100 to 2,000 .

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

[0025] The present invention water-soluble metalworking fluid has as its typical, water-soluble metal cutting fluid, include water-soluble metal grinding oil, and other water-soluble detergent, water-soluble corrosion inhibitor, water
Soluble forming oils , water-soluble heat-treated oils, water-soluble forging oils and the like are included.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

Embedded image

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C10M 173/02 C10M 173/02 // C10N 10:02 10:04 30:04 30:16 40:20 (72) Inventor Iwamoto Keiji 1021 Natabe-Kitamachi, Yamatokoriyama-shi, Japan Daido Chemical Co., Ltd.Nara Production Technology Office, Technology Research Laboratory (72) Inventor Kazumi Matsumura 1021, Nawatabe-Kitamachi, Yamatokoriyama-shi, Daiwa Chemical Industry

Claims (1)

[Claims] (1) The following formula: , Embedded image , And At least one of the compounds represented by
A water-soluble metalworking oil containing 0% by weight. Wherein X represents Cl or OH, and n is 1
Represents an integer of 00 to 1300. Wherein Y in the above formula is , Or And R ₁ and R ₂ represent the same or different hydrogen or methyl groups. N 'represents an integer of 10 to 800. Wherein M in the above formula represents an alkali metal, an alkaline earth metal, or NH ₄ . m is 1 or 1/2.
N ″ represents an integer of 100 to 35000. In the formula, s represents an integer of 100 to 2000.