KR20130046290A - Aqueous sawing fluid composition - Google Patents

Abstract

PURPOSE: An aqueous cutting fluid composite is provided to remarkably reduce machining cost in a process and to improve viscosity stability due to the content of abrasive particles. CONSTITUTION: An aqueous cutting fluid composite includes 0.01 to 10 wt% of polycarboxylic based-modified silicon, 10 to 95 wt% of glycol compound, 1 to 30 wt% of glycol ether compound, 0.01 to 10 wt% of at least one or two kinds of acids selected from a group of an aliphatic carboxylic acid, an aromatic carboxylic acid, and an inorganic acid, 0.01 to 10 wt% of at least one or two kinds selected from a group of an aliphatic amine, an aromatic amine, and an inorganic base, and remnant water. The glycol compound is at least one or two kinds selected from a group of ethylene glycol, propylene glycol, diethylene glycol, triethyleneglycol, tetraethylene glycol, butylene glycol, hexylene glycol, glycerine, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, and polyalkylene glycol.

Description

Aqueous sawing fluid composition

The present invention relates to an aqueous cutting fluid composition.

When cutting a workpiece using cutting tools such as wire saws or band saws, an aqueous cutting fluid composition is used for the purpose of lubricating between the cutting tool and the workpiece, removing frictional heat, and cleaning cutting chips. .

The conventional aqueous cutting fluid composition has a problem in that process defects such as saw marks of wires are generated during cutting of the ingot due to agglomeration of the abrasive contained in the slurry during the process. In addition, the precipitated abrasive particles hardened over time, making it difficult to regenerate the aqueous cutting fluid slurry.

For example, Korean Patent No. 0520714 discloses an aqueous composition comprising colloidal silicate particles dispersed in a dispersion medium containing a hydrophilic polyhydric alcohol compound, a lipophilic polyhydric alcohol compound, and water. The compositions disclosed in this patent have a high viscosity of the cutting fluid slurry, and hardcake formation of abrasive particles can be produced. In addition, agglomeration of abrasive particles may cause problems in processing precision during the process.

In addition, the Republic of Korea Patent Publication No. 2010-0133907 discloses an aqueous cutting fluid, characterized in that it comprises 0.01 to 20% by weight modified silicone. The cutting fluid disclosed in the above patent has a problem in that the dispersibility of the abrasive particles is inferior and not sufficient to prevent hard cake of the abrasive particles.

KR 0520714 B1 KR 2010-0133907 A

It is an object of the present invention to provide an aqueous cutting liquid composition which is excellent in viscosity stability according to the content of abrasive particles and which can prevent high dispersibility and hard cake formation of precipitates.

It is an object of the present invention to provide an aqueous cutting liquid composition which can easily remove abrasives, cutting debris and the like remaining after a cutting process.

It is an object of the present invention to provide an aqueous cutting liquid composition which enables the regeneration of the aqueous cutting liquid slurry to significantly reduce the processing cost in the process and also improve the environmental problems caused by the disposal of the aqueous cutting liquid slurry.

The present invention is a polycarboxy modified silicone represented by the following formula (1); Glycol compounds; Glycol ether compounds represented by the following Formula 3; One or two or more acids selected from the group consisting of aliphatic organic acids, aromatic organic acids and inorganic acids; One or two or more selected from the group consisting of aliphatic amines, aromatic amines, and inorganic bases; And an aqueous cutting fluid composition comprising water.

In Chemical Formula 1 and Chemical Formula 3,

R ₁ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms,

x, y are integers from 1 to 1000,

R ₂ is a carboxyl compound represented by the following formula (2),

In Formula 2, R is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms,

R ₃ is a hydrogen atom or a methyl group,

R ₄ is a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms,

m is an integer of 1-20.

In the aqueous cutting fluid composition of the present invention, the modified silicon prevents agglomeration of the abrasive in the slurry so that the abrasive is evenly distributed in the slurry, thereby improving the processing precision when cutting the ingot, and the organic acid and the amine or the inorganic base disperse the abrasive particles. It is possible to maintain excellent processing precision, and to prevent hard cake formation, thereby regenerating the aqueous cutting fluid slurry, which greatly reduces the processing cost in the process and improves the environmental problems caused by the disposal of the aqueous cutting fluid slurry. In addition, it is environmentally friendly because it is water-soluble, and enables washing with water.

Hereinafter, the present invention will be described in more detail.

The present invention is a polycarboxy modified silicone represented by the following formula (1); Glycol compounds; Glycol ether compounds represented by the following Formula 3; One or two or more acids selected from the group consisting of aliphatic organic acids, aromatic organic acids and inorganic acids; One or two or more selected from the group consisting of aliphatic amines, aromatic amines, and inorganic bases; And an aqueous cutting fluid composition comprising water.

 [Formula 1]

In Formula 1,

R ₁ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms,

x, y are integers from 1 to 1000,

R ₂ is a carboxyl compound represented by the following formula (2),

[Formula 2]

In Formula 2, R is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

Examples of the group R ₁ in the formula (1), an ethyl group, a propyl group, a butyl group, Pen alkyl group such group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Fluorine substituted alkyl groups, such as a trifluoro propyl group and a heptadeca fluorodecyl group, etc. are mentioned.

In Formula 2, R is an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include methyl group, ethyl group, propyl group and butyl group.

The polyether-based modified silicone compound represented by Formula 1 is preferably included in 0.01 to 10% by weight, more preferably 0.01 to 5% by weight based on the total weight of the composition. If it is included in the above-described range, agglomeration of the abrasive particles occurs to reduce the processing accuracy, and if it exceeds the above range, insoluble matter may occur.

The glycol compound is not particularly limited, but ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, butylene glycol, hexylene glycol, glycerin, 1,3-propanediol, 1,4- It is preferable that it is 1 type, or 2 or more types chosen from the group which consists of butanediol, 1, 6- hexanediol, polyethyleneglycol, polypropylene glycol, and polyalkylene glycol. More preferably, it is 1 type or 2 types selected from the group which consists of propylene glycol and diethylene glycol.

The glycol compound is preferably contained in 10 to 95% by weight relative to the total weight of the aqueous cutting liquid composition. If it is contained below the above-mentioned range, sufficient lubricating action cannot be caused around the abrasive grains, and if it exceeds the above-mentioned range, the viscosity of the slurry including the abrasive grains becomes high, resulting in poor process characteristics.

The glycol ether compounds contained in the aqueous cutting fluid composition of the present invention are represented by the following general formula (3).

(3)

In Formula 3, R ₃ is a hydrogen atom or a methyl group, R ₄ is a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms, and m is an integer of 1 to 20.

The glycol ether compound represented by the formula (3) has one hydroxyl group and has a low surface tension, thus uniformly dispersing the abrasive particles, thereby having excellent viscosity stability according to the content of the abrasive particles, thereby preventing hard cake formation. do.

The glycol ether compounds represented by the formula (3) include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, Triethylene glycol monoethyl ether, polyethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl Ether, tripropylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol Mono 2-ethylhexyl ether, diethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether It is preferable that it is 1 type, or 2 or more types selected from the group. Among them, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether having a flash point of 100 ° C. or higher, and ethylene Glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, diethylene glycol mono 2-ethylhexyl ether, ethylene glycol monophenyl ether, and propylene glycol monobutyl ether are more preferable.

Glycol ether compounds represented by the formula (3) is preferably contained in 1 to 30% by weight based on the total weight of the aqueous cutting liquid composition. If it is included in the above-described range, the viscosity of the slurry including the abrasive particles increases, and if it exceeds the above-mentioned range, the dispersion performance of the slurry including the abrasive of the slurry is reduced.

The one or two or more acids selected from the group consisting of aliphatic organic acids, aromatic organic acids and inorganic acids included in the aqueous cutting fluid composition of the present invention are arranged around the abrasive particles to generate electrical repulsion to improve the dispersibility of the abrasive particles and to polish It serves to prevent hard cake of the particles.

The aliphatic organic acid is formic acid, acetic acid, propionic acid, butyric acid, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, glutaric acid, adipic acid, sulfosuccinic acid, valeric acid And one or two or more selected from the group consisting of caproic acid, caprylic acid, capric acid, loric acid, myristic acid, lactic acid, malic acid, citric acid and tartaric acid.

The aromatic organic acid is preferably one or two or more selected from the group consisting of benzoic acid, salicylic acid, paratoluenesulfonic acid, naphthoic acid, nicotinic acid, toluic acid, aniseic acid, cuminic acid and phthalic acid.

The inorganic acid is preferably one or two or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid.

Among these, it is preferable to use formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, fumaric acid, salicylic acid, glycolic acid, and benzoic acid which have excellent solubility in the aqueous cutting fluid composition of the present invention. More preferred. Moreover, it is more preferable to use the inorganic acid which does not react with the aqueous cutting fluid composition of this invention.

The one or two or more acids selected from the group consisting of aliphatic organic acids, aromatic organic acids and inorganic acids are preferably included in an amount of 0.01 to 10% by weight based on the total weight of the aqueous cutting fluid composition. If it is contained below the above-mentioned range, sufficient electrical repulsive force cannot be caused around the abrasive grain, and if it exceeds the above-mentioned range, the dispersibility of the abrasive grain is deteriorated.

One or two or more selected from the group consisting of aliphatic amines, aromatic amines, and inorganic bases included in the aqueous cutting fluid composition of the present invention are arranged around the abrasive particles to cause electrical repulsion to improve dispersibility of the abrasive particles. It serves to prevent hard cake of the abrasive particles.

The aliphatic amines include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, N-methyldiethanolamine, monomethylethanolamine, diglycolamine; Cyclic amines such as morpholine; One or two or more selected from the group consisting of N-aminoethylpiperazine, dimethylaminopropylamine, N, N-dimethylcyclohexylamine, ethylenediamine, diethylenetriamine, triethylenetetraamine and tetraethylenepentaamine It is preferable.

The aromatic amine is preferably one or two selected from the group consisting of aniline and pyridine.

The inorganic base is preferably one or two selected from the group consisting of sodium hydroxide and potassium hydroxide.

Of these, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, nitric acid and phosphoric acid which are excellent in solubility in the aqueous cutting liquid composition of the present invention are more preferable. Or it is most preferable to use the inorganic base which does not react with the aqueous cutting fluid of this invention.

The aliphatic or aromatic amine or inorganic base is preferably included in an amount of 0.01 to 10% by weight, more preferably 0.01 to 5% by weight based on the total weight of the aqueous cutting fluid composition. When included below the above-mentioned range, sufficient electrical repulsive force cannot be generated around the abrasive particles, and when above the above-mentioned range, the viscosity of the slurry including the abrasive particles increases.

The water contained in the aqueous cutting fluid composition of the present invention is contained in the remaining amount so that the total weight of the composition is 100% by weight. The water is preferably deionized water.

It is preferable that pH of the aqueous cutting fluid composition of this invention is 5-8. If the above range is satisfied, it is possible to improve the working environment of workers and environmental problems that can occur using acidic or alkaline.

The present invention provides a water-soluble slurry for processing comprising the above-described aqueous cutting fluid composition and abrasive grains.

The abrasive grain is not particularly limited, but is preferably one or two selected from the group consisting of silicon carbide, aluminum oxide, zirconium oxide, silicon dioxide, cesium dioxide, and diamond. It is preferable that the average particle diameter of the said abrasive grain is 0.5-50 micrometers. The aqueous cutting fluid composition and the abrasive grains are preferably mixed in a weight ratio of 1: 0.5 to 1: 1.2.

The water-soluble slurry for processing may be performed by cutting, grinding, polishing or cutting. In the processing using the water-soluble slurry for processing, the workpiece is preferably one or two or more selected from the group consisting of single crystal silicon, polycrystalline silicon, quartz, quartz, compound semiconductor, ceramic, glass, metal oxide, cemented carbide and sintered alloy. Do.

Examples of the cutting device in which the effects of the aqueous cutting liquid composition of the present invention and the aqueous slurry for processing using the same are particularly remarkable include a wire saw, a band saw, a multi-wire saw multiplexed these, a multi-band saw, and the like.

Hereinafter, the present invention will be described in more detail using examples. However, the following examples are provided to illustrate the present invention, and the present invention is not limited to the following examples and may be variously modified and changed.

Example  1 to 5, Comparative example  1 to 3: Preparation of Aqueous Cutting Fluid Composition

An aqueous cutting liquid composition (Examples 1 to 5) according to the present invention and an aqueous cutting liquid composition (Comparative Examples 1 to 3) not according to the present invention were prepared to have the composition of Table 1 below. Furthermore, GC particle | grains (# 1200) were added to 50 weight% with respect to each aqueous cutting fluid composition, and the aqueous cutting fluid slurry for processing was obtained by stirring at 150 rpm for 1 hour with the stirrer. The numerical value corresponding to each component of Table 1 is a weight part of each component based on the total weight of a composition.

a1 a2 a3 b1 b2 c1 d1 d2 e1 f1 Example 1 68.2 25 0.5 0.3 One 5 Example 2 78.2 15 0.5 0.3 One 5 Example 3 68.2 20 0.5 0.3 One 10 Example 4 83.3 5 0.5 0.2 One 10 Example 5 73.3 20 0.5 0.2 One 5 Comparative Example 1 80 20 Comparative Example 2 69.5 20 0.5 10 Comparative Example 3 79.5 10 0.5 10

A): propylene glycol

   a2: diethylene glycol

   a3: polyethylene glycol 300

   b1: diethylene glycol monomethyl ether

   b2: triethylene glycol monomethyl ether

   c1: malonic acid

   d1: diethylenetriamine

   d2: potassium hydroxide

   e1: Polycarboxy-type modified silicone (Product name-(X-22-3701E), a manufacturer-Shin-Etsu Silicone)

f1: water

Test Example : Characterization of Aqueous Cutting Fluid Composition

<Dispersion Measurement>

50% by weight of the prepared aqueous cutting fluid slurry for processing was placed in a 200 ml beaker immediately after preparation to measure the dispersion degree according to sedimentation of GC particles in units of 2, 4, 8, 12, 24, 48 and 72 hours. Dispersion is expressed in%. After measuring the dispersion degree, the presence or absence of hard cake formation by sedimentation of GC particles was observed. The results are shown in Table 2 below.

time
(hr) 2 4 8 12 24 48 72 Hard cake Example 1 96.11 90.99 81.35 76.19 69.22 64.37 64.22 none Example 2 92.25 86.37 76.94 71.25 66.48 64.68 63.30 none Example 3 95.66 92.20 82.11 75.38 68.23 65.53 63.96 none Example 4 93.72 87.42 77.15 73.89 65.25 64.05 63.56 none Example 5 96.74 92.00 84.56 76.22 68.85 66.02 65.33 none Comparative Example 1 91.25 82.42 73.42 65.83 58.67 57.75 57.75 has exist Comparative Example 2 90.83 81.42 72.00 64.75 57.25 56.50 56.50 has exist Comparative Example 3 90.83 82.42 74.75 66.67 59.42 56.67 56.67 has exist

As shown in Table 2, the dispersion degree of the aqueous cutting fluid slurry for processing of the present invention was high for each time, compared to the low dispersion of the aqueous cutting fluid slurry for processing of the comparative example. Further, the aqueous cutting fluid slurry for processing of the present invention was excellent in dispersion stability without hard cake formation.

<Measurement of abrasive particle size>

The particle size of the abrasive in the slurry was measured for the processing aqueous cutting fluid slurry using a particle size analyzer FPIA-3000 manufactured by Sysmex. The results are shown in Table 3.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Average particle size (㎛) 11.9 12.4 12.5 12.3 11.9 19.2 17.2 16.9

Claims (12)

Polycarboxylic-based modified silicone represented by the formula (1);
Glycol compounds;
Glycol ether compounds represented by the following Formula 3;
One or two or more acids selected from the group consisting of aliphatic organic acids, aromatic organic acids and inorganic acids;
One or two or more selected from the group consisting of aliphatic amines, aromatic amines, and inorganic bases; And an aqueous cutting fluid composition comprising water:
[Formula 1]

(3)

In Chemical Formula 1 and Chemical Formula 3,
R ₁ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms,
x, y are integers from 1 to 1000,
R ₂ is a carboxyl compound represented by the following formula (2),
(2)

In Formula 2, R is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms,
R ₃ is a hydrogen atom or a methyl group,
R ₄ is a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms,
m is an integer of 1-20. The method according to claim 1,
With respect to the total weight of the aqueous cutting fluid composition,
0.01 to 10% by weight of polycarboxylic acid-modified silicone represented by Formula 1;
10 to 95% by weight of the glycol compounds;
1 to 30% by weight of a glycol ether compound represented by Formula 3;
0.01 to 10% by weight of one or two or more acids selected from the group consisting of aliphatic organic acids, aromatic organic acids and inorganic acids;
0.01 to 10% by weight of one or two or more selected from the group consisting of aliphatic amines, aromatic amines, and inorganic bases; And
An aqueous cutting fluid composition comprising a residual amount of water. The method according to claim 1,
The glycol compounds include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, butylene glycol, hexylene glycol, glycerin, 1,3-propanediol, 1,4-butanediol, 1,6- Aqueous cutting fluid composition, characterized in that one or two or more selected from the group consisting of hexanediol, polyethylene glycol, polypropylene glycol and polyalkylene glycol. The method according to claim 1,
The glycol ether compounds represented by the formula (3) include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, Triethylene glycol monoethyl ether, polyethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl Ether, tripropylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol Mono 2-ethylhexyl ether, diethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether An aqueous cutting liquid composition, characterized in that one or two or more selected from the group. The method according to claim 1,
The aliphatic organic acid is formic acid, acetic acid, propionic acid, butyric acid, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, glutaric acid, adipic acid, sulfosuccinic acid, valeric acid Aqueous cutting fluid composition, characterized in that one or two or more selected from the group consisting of caproic acid, caprylic acid, capric acid, loric acid, myristic acid, lactic acid, malic acid, citric acid and tartaric acid. The method according to claim 1,
The aromatic organic acid is preferably one or two or more selected from the group consisting of benzoic acid, salicylic acid, paratoluenesulfonic acid, naphthoic acid, nicotinic acid, toluic acid, aniseic acid, cuminic acid and phthalic acid. The method according to claim 1,
The inorganic acid is preferably one or two or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid. The method according to claim 1,
The aliphatic amines are monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, N-methyldiethanolamine, monomethylethanolamine, diglycolamine, morpholine, N-aminoethylpiperazine, dimethylaminopropylamine, An aqueous cutting liquid composition, characterized in that one or two or more selected from the group consisting of N, N-dimethylcyclohexylamine, ethylenediamine, diethylenetriamine, triethylenetetraamine, and tetraethylenepentaamine. The method according to claim 1,
The aromatic amine is an aqueous cutting liquid composition, characterized in that one or two selected from the group consisting of aniline and pyridine. The method according to claim 1,
The inorganic base is an aqueous cutting fluid composition, characterized in that one or two selected from the group consisting of sodium hydroxide and potassium hydroxide. A water-soluble slurry for processing, comprising the water-soluble cutting liquid composition according to claim 1 and abrasive grains. A processing method comprising cutting, grinding, polishing or cutting using a water-soluble slurry for processing according to claim 11.