JP2013100446A - Water-soluble processing liquid for abrasive grain-fixed wire saw, and cutting method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble processing liquid for abrasive grain-fixed wire saw, which is excellent in lubricating properties and permeability and is hardly foamed; and to provide a cutting method using the same.SOLUTION: A water-soluble processing liquid for abrasive grain-fixed wire saw comprises: an alkyleneoxide adduct (A) of polyamine; an acid phosphate (b1) and/or a dicarboxylic acid (b2); and water (C).

Description

  The present invention relates to a water-soluble machining fluid for a fixed abrasive wire saw and a cutting method using the same.

In recent years, a fixed abrasive wire saw in which abrasive grains are fixed to a wire has been developed and used for cutting brittle materials such as silicon ingots. When cutting using a fixed abrasive wire saw, a working fluid is used for lubrication, cooling, cleaning, and the like. Conventionally, processing oils containing lubricating base oils such as mineral oils, synthetic oils and fats and oils have been mainly used as the processing fluids. However, since processing oil has environmental problems and safety problems, an aqueous processing liquid having a high water content has recently been desired.
In response to such a demand, for example, Patent Documents 1 to 3 disclose water-soluble processing liquids containing glycols, carboxylic acids, basic compounds, and water. Patent Document 4 discloses a water-soluble processing oil containing an alkylene oxide adduct of an organic amine, an aliphatic carboxylic acid, a basic substance, and water. Patent Document 5 discloses a water-soluble cutting fluid containing a polyoxyalkylene adduct having a number average molecular weight of 500 or less and a monovalent to divalent aliphatic carboxylic acid having 4 to 10 carbon atoms or a salt thereof.

JP 2003-82334 A JP 2003-82335 A Japanese Patent Application Laid-Open No. 2011-21096 JP 2009-57423 A JP 2011-68884 A

However, such machining fluids as disclosed in Patent Documents 1 to 5 have a problem in that when the foaming is performed during the cutting process or when moisture is increased, the lubricity and permeability are lowered and the cutting performance is lowered. When the lubricity of the working fluid is low, the friction between the processed portion of the work material and the wire increases, and fixed abrasive grains are peeled off and the wire is easily worn. In addition, when the permeability is low, the machining liquid does not easily reach the wire or the machining site, and lubricity, cooling efficiency, cleaning properties, etc. are insufficient.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a water-soluble machining liquid for a fixed abrasive wire saw which is excellent in lubricity and permeability and hardly foams, and a cutting method using the same. To do.

The present invention for solving the above problems has the following aspects.
(1) A water-soluble machining fluid for a fixed abrasive wire saw, comprising an alkylene oxide adduct (A) of polyamine, an acidic phosphate ester (b1) and / or dicarboxylic acid (b2), and water (C).
(2) The polyamine alkylene oxide adduct (A) is represented by the following general formula (I):
_{^{R 1 - [(R 2 O}} ) n -H] m (I)
(In the formula, m represents a number of 2 to 8; n represents a number of 0 to 25, and m n may be the same or different, but the m n is not all 0; R ¹ represents a residue obtained by removing m active hydrogens of an amino group or imino group from a polyamine; R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and when n × m is 2 or more, n × m R ² O may be the same or different.)
The water-soluble processing liquid for fixed abrasive wire saws according to (1), which is a compound represented by:
(3) The water-soluble processing liquid for fixed abrasive wire saws according to (1) or (2), containing 75 to 99.8% by mass of the water (C).
(4) The acidic phosphate ester (b1) is represented by the following general formula (II):
(R ³ O) _x PO (OH) _3-x (II)
(Wherein x represents 1 or 2; R ³ represents an alkyl group or alkenyl group having 4 to 18 carbon atoms, and when x is 2, two R ^{3 s} may be the same or different. )
The water-soluble processing liquid for fixed abrasive wire saws according to any one of (1) to (3), which is a compound represented by:
(5) The water-soluble processing liquid for fixed abrasive wire saws according to any one of (1) to (4), wherein the dicarboxylic acid (b2) has a total carbon number of 11 to 18.
(6) The water-soluble machining liquid for a fixed abrasive wire saw according to any one of (1) to (5), which is used for cutting a brittle material.
(7) The water-soluble processing liquid for a fixed abrasive wire saw according to (6), wherein the brittle material is silicon.
(8) A method of cutting a brittle material with a fixed abrasive wire saw,
The cutting process is a water-soluble machining liquid for a fixed abrasive wire saw containing an alkylene oxide adduct (A) of polyamine, an acidic phosphate ester (b1) and / or dicarboxylic acid (b2), and water (C). The cutting method characterized by performing using.
(9) A method of cutting a brittle material with a fixed abrasive wire saw,
The cutting process is carried out by adding a polyamine alkylene oxide adduct (A) and the following general formula (II):
(R ³ O) _x PO (OH) _3-x (II)
(Wherein x represents 1 or 2; R ³ represents an alkyl group or alkenyl group having 4 to 18 carbon atoms, and when x is 2, two R ^{3 s} may be the same or different. )
A step of using a water-soluble processing liquid for a fixed abrasive wire saw, which contains an acidic phosphate ester (b1 ′) represented by: and water (C),
A step of removing at least the cutting waste from a post-cutting working fluid containing the water-soluble working fluid for the fixed abrasive wire saw and the cutting waste of the brittle material generated by the cutting;
The residual liquid obtained by removing at least the cutting waste from the post-cutting working liquid is reused as a water-soluble working liquid for fixed abrasive wire saws, or the alkylene oxide adduct (A) of the polyamine is used as the residual liquid. , Adding the acidic phosphate ester (b1 ′) or water (C) to obtain a water-soluble working fluid for a fixed abrasive wire saw, and using the water-soluble processing fluid for a fixed abrasive wire saw for cutting a brittle material Including
The step of removing the cutting waste,
A first step of separating the post-cutting working fluid into an upper layer mainly composed of the water-soluble working fluid for the fixed abrasive wire saw, and a precipitate layer (lower layer) of the cutting waste;
And a second step of removing the sediment layer (lower layer) of the cutting waste from the post-cutting working fluid separated in the first step.
(10) The cutting method according to (8) or (9), wherein the brittle material is silicon.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in lubricity and osmosis | permeability, and can provide the water-soluble processing liquid for fixed-abrasive wire saws which are hard to foam, and the cutting method using the same.

Hereinafter, the present invention will be described in detail.
The water-soluble processing liquid for a fixed abrasive wire saw of the present invention (hereinafter simply referred to as “water-soluble processing liquid”) is used when a workpiece is cut with a fixed abrasive wire saw.
“Water-soluble” means that the water-soluble processing liquid of the present invention is dissolved in water when diluted with water.
The water-soluble working fluid of the present invention is called polyamine alkylene oxide adduct (A) (hereinafter referred to as “component (A)”) and acidic phosphate ester (b1) (hereinafter referred to as “component (b1)”. ) And / or dicarboxylic acid (b2) (hereinafter referred to as “component (b2)”) and water (C).
Containing water improves safety and reduces adverse effects on the environment.
By containing the component (A), even when the content of water is large, excellent permeability is exhibited, and the water-soluble processing liquid easily reaches the processing site of the fixed abrasive wire saw or the material to be processed. Therefore, the cooling efficiency at the time of cutting improves, and cutting can be performed with excellent cutting performance. Moreover, the washing | cleaning property of the chip produced at the time of cutting improves.
The (b1) component and the (b2) component each contribute to improvement in lubricity. By containing the component (b1) and / or the component (b2) in addition to the component (A), even when the water content is high, excellent lubricity is exhibited, and the fixed abrasive of the fixed abrasive wire saw Since peeling, wire wear, and the like are suppressed, machinability is improved. In addition, the water-soluble processing liquid has low foamability. Furthermore, since pH falls, the corrosion of the wire saw and processing apparatus which contact the said water-soluble processing liquid can be prevented.

In the component (A), the polyamine is a compound having two or more amino groups or imino groups in one molecule, and the alkylene oxide adduct of the polyamine is an active hydrogen possessed by the amino group or imino group in the polyamine molecule. However, it is a compound obtained by adding 1 mol or more of alkylene oxide to one molecule of polyamine.
The active hydrogen is a hydrogen atom bonded to the nitrogen atom of the amino group or imino group. The amino group includes two active hydrogens and the imino group includes one active hydrogen.

The polyamine preferably has 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
2-6 are preferable and, as for the number of the amino group or imino group which polyamine has (when it has both an amino group and imino group), 2-6 are especially preferable.
Examples of polyamines include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, methylaminoethylamine, ethylaminoethylamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, 1,3-propanediamine, and methylamino. Propylamine, ethylaminopropylamine, N, N'-di-tert-butylethylenediamine, diethylenetriamine, dipropylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylene Examples include aliphatic polyamines such as pentamine and pentaethylenehexamine, and alicyclic diamines such as cyclohexanediamine. Among these, ethylenediamine, propylenediamine, tetramethylenediamine and diethylenetriamine are preferable, and ethylenediamine is particularly preferable.

The alkylene oxide added to the polyamine is preferably one having 2 to 4 carbon atoms, and examples thereof include ethylene oxide, propylene oxide, 1,2-, 2,3-, 1,3- and 1,4-butylene oxide. . Among these, ethylene oxide or propylene oxide is preferable.
The alkylene oxide added to the polyamine may be one type or two or more types. When two or more types of alkylene oxide are added, the addition form may be either block addition or random addition, and the order of addition is not particularly limited.
The number of moles of alkylene oxide added is preferably from 3 to 100 moles, particularly preferably from 4 to 70 moles, per mole of polyamine, from the viewpoints of permeability and lubricity.
In the present invention, it is preferable that alkylene oxide is added to all active hydrogens derived from the amino group or imino group of the polyamine. For example, when the polyamine is ethylenediamine, it is preferable that alkylene oxide is added to four active hydrogens of ethylenediamine.

(A) As a component, since it is excellent in the improvement effect of permeability, lubricity, and washability, the compound represented by the following general formula (I) is preferable.
_{^{R 1 - [(R 2 O}} ) n -H] m (I)
In formula, m represents the number of 2-8, 3-8 are preferable and 3-6 are more preferable.
n represents a number of 0 to 25, and m n in the formula may be the same or different. However, the m n's are not all zero. That is, at least one of m n is 1-25.
R ¹ represents a residue obtained by removing all m active hydrogens of amino group or imino group from polyamine. The polyamine may be any one having m active hydrogens, and can be appropriately selected from the polyamines mentioned above.
R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and is preferably an oxyethylene group or an oxypropylene group.
When n × m is 2 or more, n × m R ² Os may be the same or different.

The component (A) can be obtained by adding an alkylene oxide to a polyamine. The addition of alkylene oxide can be carried out by a usual method for adding alkylene oxide to an amine compound.
As the component (A), it is possible to use a commercially available product. For example, Adeka Pluronic TR series (produced by ADEKA) such as Adeka Pluronic TR701 and TR702 which are propylene oxide / ethylene oxide block adducts of ethylenediamine, ethylenediamine ADEKA polyether EDP series (manufactured by ADEKA) such as ADEKA polyether EDP-300 and EDP-450, which are propylene oxide adducts.

The content of the component (A) in the water-soluble processing liquid is preferably from 0.1 to 20% by mass, particularly preferably from 0.15 to 10% by mass, based on the total mass of the water-soluble processing liquid. If it is less than 0.1% by mass, there is a concern that the permeability is insufficient and the machining fluid does not reach the cutting surface sufficiently. If it exceeds 20% by mass, there is a concern that the working fluid will thicken, thereby reducing cooling efficiency and machinability, and that foaming is likely to occur.
As the component (A), one type may be used alone, or two or more types may be used.

In the component (b1), the acidic phosphate ester is a compound in which one or two of the three hydroxyl groups of phosphoric acid (P (═O) (OH) ₃ ) are esterified (phosphoric monoester or phosphoric acid). Acid diester).
The component (b1) is preferably an acidic phosphate having an alkyl group or alkenyl group having 4 to 18 carbon atoms from the viewpoint of lubricity and low foamability. The acidic phosphate ester can be represented by the following general formula (II).
(R ³ O) _x PO (OH) _3-x (II)
(Wherein x represents 1 or 2; R ³ represents an alkyl group or alkenyl group having 4 to 18 carbon atoms, and when x is 2, two R ^{3 s} may be the same or different. )

Specific examples of the alkyl group or alkenyl group having 4 to 18 carbon atoms include n-butyl group, iso-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, and 2-ethyl-hexyl. Group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, butenyl group, hexenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, etc. . Among these, an n-hexyl group having 6 to 12 carbon atoms, a cyclohexyl group, an n-octyl group, a 21-ethyl-hexyl group, a nonyl group, a decyl group, a dodecyl group, a hexenyl group, an octenyl group, a nonenyl group, A decenyl group and a dodecenyl group are preferable.
As the component (b1), an acidic phosphate ester having an alkyl group or an alkenyl group having 6 to 12 carbon atoms (in the general formula (II), R ³ is 6 to 12 carbon atoms) in terms of lubricity and low foaming properties. Are particularly preferred alkyl groups or alkenyl groups.

The content of the component (b1) in the water-soluble processing liquid is preferably 0.01 to 1% by mass and particularly preferably 0.05 to 0.5% by mass with respect to the total mass of the water-soluble processing liquid. If it is less than 0.01% by mass, there is a concern that sufficient machinability cannot be exhibited. When it exceeds 1% by mass, there are concerns that it becomes difficult to maintain sufficient machinability and foaming is likely to occur.
As the component (b1), one type may be used alone, or two or more types may be used.

The dicarboxylic acid of component (b2) is a compound having two carboxy groups, and preferably has a total carbon number of 11 to 18 in terms of lubricity and low foamability. The total carbon number is more preferably 11-14.
Examples of the dicarboxylic acid having 11 to 18 carbon atoms include compounds represented by the following general formula (III).
^HOOC-R 4 -COOH (III)
In the formula, R ⁴ represents a divalent hydrocarbon group having 9 to 16 carbon atoms.
The number of carbon atoms in the hydrocarbon group R ⁴ is 9-12 are preferred.
As the hydrocarbon group for R ^4, a linear or branched group is preferable, and an alkylene group is particularly preferable.
Specific examples of the component (b2) include undecanedioic acid (1,9-nonamethylenedicarboxylic acid), dodecanedioic acid (1,10-decamethylenedicarboxylic acid), and tetradecanedioic acid (1,12-dodecamethylenedicarboxylic acid). ), Hexadecanedioic acid (1,14-tetradecane dicarboxylic acid), octadecanedioic acid (1,16-hexadecane dicarboxylic acid) and the like. Among these, dodecanedioic acid and tetradecanedioic acid are preferable, and dodecanedioic acid is particularly preferable.
0.05-5 mass% is preferable with respect to the total mass of a water-soluble processing liquid, and, as for content of (b2) component in a water-soluble processing liquid, 0.1-2 mass% is especially preferable. If it is less than 0.05% by mass, there is a concern that sufficient machinability cannot be exhibited, and even if it exceeds 5% by mass, the improvement in performance commensurate with the blending amount tends to decrease.
As the component (b2), one type may be used alone, or two or more types may be used.

In the water-soluble processing liquid of the present invention, any one of the component (b1) and the component (b2) may be used alone, or both may be used in combination.
The (A) component and the (b1) component, the (A) component and the (b2) component, or the (A) component, the (b1) component, and the (b2) component so that the pH of the water-soluble processing liquid is 6 to 9. It is preferable to add to the above because it is not necessary to adjust the pH to a preferable pH range by adding a pH adjusting agent later.

The water (C) is not particularly limited, but purified water, particularly deionized water is preferred.
In the water-soluble processing liquid, the water content is preferably 75 to 99.8% by mass and particularly preferably 80 to 99% by mass with respect to the total mass of the water-soluble processing liquid in consideration of safety, environment and the like.

The water-soluble processing liquid of the present invention is excellent in that it has no low foaming property, lubricity and permeability due to the combination of the above components.
The water-soluble processing liquid of the present invention comprises (A) component 0.1 to 20% by mass, (b1) component 0.01 to 1% by mass and / or (b2) component 0.05 to 5% by mass, water (C) It is preferable to contain 75-99.8 mass%. By having such a composition, lubricity and penetrability are particularly excellent, cooling properties and the like are improved, and cutting with a fixed abrasive wire saw can be performed with excellent cutting properties. Moreover, the effect of suppressing foaming is also excellent.
In particular, in the combination of (A) component 0.1-20 mass%, (b1) component 0.01-1 mass%, and water (C), foamability becomes remarkably low.
In addition, in the combination of 0.1 to 20% by mass of component (A), 0.05 to 5% by mass of component (b2) and water (C), in addition to lubricity, permeability and low foamability, it is stable. It is also excellent in properties.

The water-soluble processing liquid of the present invention is not limited to the object of the present invention. More commonly used additives can be blended. For example, examples of the rust preventive agent include alkylbenzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester and the like. Examples of the antifoaming agent include silicone oil, fluorosilicone oil, and fluoroalkyl ether. Examples of the antioxidant include a phenolic antioxidant and an amine antioxidant. Examples of the metal deactivator include imidazoline, pyridine derivatives, thiadiazole, benzotriazole and the like. Examples of the pH adjuster include acetic acid, boric acid, citric acid, carbonic acid, ammonia, and sodium bicarbonate. Examples of the disinfectant / preservative include paraoxybenzoic acid esters, benzoic acid, salicylic acid, sorbic acid, dehydroacetic acid, p-toluenesulfonic acid and salts thereof, phenoxyethanol, and the like.
The compounding amount of these additives may be determined depending on the purpose, but is usually about 0.01 to 5% by mass with respect to the total amount of the water-soluble processing liquid.

The water-soluble processing liquid of the present invention preferably has a pH of 5 to 10, particularly preferably 6 to 9. If the pH is less than 5, the processing apparatus may be rusted, and if the pH exceeds 10, the silicon of the workpiece may be corroded.
This pH can be adjusted by adjusting the blending ratio of the component (A) to the component (b1) and / or the component (b2). Moreover, you may add a pH adjuster as needed.
The pH is a value at 20 ° C.

  The water-soluble processing liquid of the present invention preferably contains 75 to 99.8% by mass of water (C), but the content of component (A) and the content of component (b1) and / or (b2) Prepare a stock solution with a small amount of water (C) by increasing the amount, and dilute with water (C) so that the content of each component becomes a preferable content when using it for cutting. There is no problem.

The water-soluble working fluid of the present invention is used when cutting a workpiece with a fixed abrasive wire saw. Since the water-soluble machining fluid of the present invention is excellent in lubricity and permeability, it exhibits excellent machinability when cutting a work material with a fixed abrasive wire saw and can perform cutting with high machining accuracy. it can. Moreover, since it is also low foaming property, work efficiency improves.
A well-known thing can be used as a fixed abrasive wire saw.
Cutting can be performed by a known method except that the water-soluble machining liquid of the present invention is used as the machining liquid.
The material to be processed is not particularly limited as long as it can be cut by a fixed abrasive wire saw, and a brittle material is preferable. That is, since the water-soluble working fluid of the present invention exhibits excellent machinability in cutting of brittle materials, particularly silicon ingots, it is suitably used in a method of cutting brittle materials with a fixed abrasive wire saw.
The water-soluble working fluid of the present invention is suitably used when cutting silicon ingots with a wire saw, but can also be used as it is when cutting brittle materials other than silicon, such as quartz, carbon, and glass. .

Furthermore, when the water-soluble processing liquid of the present invention contains an acidic phosphate represented by the general formula (II) (hereinafter referred to as (b1 ′) component) as the component (b1), the water-soluble processing liquid Contains the component (A) and the component (b1 ′), so that cutting waste generated when cutting a work material, particularly a brittle material, with a fixed abrasive wire saw aggregates in the water-soluble processing liquid. It has become easier. Therefore, the cutting waste can be separated from the machining fluid after cutting with a simple operation with high separation efficiency, and can be easily regenerated.
As a suitable example of the cutting method of a brittle material using such a water-soluble working fluid, the following brittle material cutting method (1) may be mentioned. This brittle material cutting method (1) utilizes the fact that the cutting waste in the machining fluid after cutting is aggregated and separated from the water-soluble machining fluid due to the effects of the composition and components in the water-soluble machining fluid of the present invention. Therefore, the machining fluid after cutting can be regenerated in a short time with a simple operation. Moreover, since the separation efficiency between the cutting waste and the water-soluble machining fluid is very excellent, the residual liquid (upper layer) obtained by removing the separated cutting waste can be efficiently reused as the water-soluble machining fluid. .

[Cutting method of brittle material (1)]
A method of cutting a brittle material with a fixed abrasive wire saw,
The cutting is performed using a water-soluble processing liquid for a fixed abrasive wire saw (the water-soluble processing liquid of the present invention) containing the component (A), the component (b1 ′), and water (C). Process,
A step of removing at least the cutting waste from a post-cutting working fluid containing the water-soluble working fluid for the fixed abrasive wire saw and the cutting waste of the brittle material generated by the cutting;
The residual liquid obtained by removing at least the cutting waste from the post-cutting processing liquid is reused as a water-soluble processing liquid for a fixed abrasive wire saw, or the component (A), (b1 ′) ) Component or water (C) is added to obtain a water-soluble working fluid for a fixed abrasive wire saw, and the water-soluble processing fluid for a fixed abrasive wire saw is used for cutting a brittle material.
The step of removing the cutting waste,
A first step of separating the post-cutting working fluid into an upper layer mainly composed of the water-soluble working fluid for the fixed abrasive wire saw, and a precipitate layer (lower layer) of the cutting waste;
And a second step of removing the sediment layer (lower layer) of the cutting waste from the post-cutting working fluid separated in the first step.

The description of the cutting process is the same as described above.
Separation in the first step of removing the cutting waste can be performed, for example, by allowing the post-cutting machining fluid to stand still or centrifuging the post-cutting machining fluid.
The cutting scraps of the brittle material are likely to aggregate in the machining fluid after cutting, for example, simple standing such as standing at room temperature (about 25 ° C.) or short-time centrifugation (for example, about 1000 to 4000 rpm for about 1 to 30 minutes). Even in the operation, a large amount of cutting waste in the machining fluid after cutting precipitates and separates into an upper layer mainly composed of a water-soluble machining fluid and a precipitation layer (lower layer) of the cutting waste.
The precipitation layer (lower layer) is almost composed of cutting waste, but because the cutting waste is precipitated by utilizing the agglomeration action of the components that constitute the water-soluble machining fluid, the precipitation layer (lower layer) is made of other than cutting waste. May contain a part of the components (component (A), component (b1 ′), water, etc.) constituting the water-soluble processing liquid. In this case, the residual liquid obtained by removing the precipitate layer (lower layer) from the machining fluid after cutting has a concentration of one or more of the components constituting the water-soluble machining fluid first (used before cutting). It becomes lower than the concentration in the water-soluble processing fluid of the previous). If the concentration of component (A), component (b1 ′) and water in the residual liquid is 90% by mass or more of the concentration in the first water-soluble processing liquid, cutting of brittle material as it is as a water-soluble processing liquid Can be reused. Among the components (A), (b1 ′), and water, if there is a component whose concentration in the residual liquid is less than 90% by mass of the concentration in the first water-soluble processing liquid, add the component Thus, it can be reused for cutting of brittle materials.

The present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
Hereinafter, “parts” indicates parts by mass unless otherwise specified.
The pH was measured at 20 ° C.
The raw materials used in Examples and Comparative Examples to be described later are summarized below.
A-1: propylene oxide 42 mol / ethylene oxide 6 mol block adduct of ethylenediamine
A-2: Propylene oxide 48 mol / ethylene oxide 16 mol block adduct of ethylenediamine.
A-3: Propylene oxide 4 mol adduct of ethylenediamine.
A-4: Propylene oxide 6.8 mol adduct of ethylenediamine.
b1-1: Phosphoric acid 2-ethylhexyl ester (mixture of monoester body: diester body molar ratio = 1: 1).
b1-2: Phosphoric acid lauryl ester (a mixture of a monoester body: diester body molar ratio = 1: 1).
b2-1: dodecanedioic acid.
b3-1: Lauric acid.
D-1: Diethylene glycol.
D-2: Propylene glycol.
D-3: Polyalkylene glycol (7 mol of propylene oxide / 4 mol block adduct of ethylene oxide).
D-4: Diethylene glycol monomethyl ether.
D-5: 20 mol adduct of stearylamine with ethylene oxide.
E-1: Triethanolamine.

[Example 1]
While 1 part of (A-1) was dissolved in 99.99 parts of water, 0.01 part of (b1-1) was added and uniformly dissolved to prepare a water-soluble processing liquid. The pH of the water-soluble processing liquid was 8.
The following reciprocating friction test, foaming property test, surface tension test and cutting property test were performed using this water-soluble working fluid. The results are shown in Table 1.

1. Reciprocating friction test:
Using a surface testing machine (Tribo Station Type 32, manufactured by Shinto Kagaku Co., Ltd.), according to the instruction manual of the surface testing machine, 500 reciprocating dynamic friction tests were performed under the following test conditions, and a friction coefficient (dynamic friction coefficient) was measured. .
It shows that lubricity is so high that this dynamic friction coefficient is small. In a working fluid application for a fixed abrasive wire saw, the dynamic friction coefficient is preferably 0.05 to 0.20, more preferably 0.07 to 0.15. If the dynamic friction coefficient is too large, the lubricity is insufficient, and if the dynamic friction coefficient is too small, wire slipping or the like may occur during cutting, and the machinability may be reduced.
(Test conditions)
-Sphere: SUJ2 with a diameter of 6 mm
・ Load: 400g
・ Sliding distance: 10mm
・ Sliding speed: 500 mm / min ・ Test plate: single crystal silicon ・ Measurement temperature: 20 ° C.

2. Foam test:
In a 1 L graduated cylinder (inner diameter: 6.3 cm), 100 mL of the prepared water-soluble processing liquid was placed. Using an air pump equipped with a two-ball filter, 800 mL of air was continuously blown from the bottom of the water-soluble machining fluid for 5 minutes, and the height of bubbles from the liquid surface of the water-soluble machining fluid after 5 minutes (cm) Was measured (measurement temperature: 20 ° C.).
It shows that foamability is so low that this height is low. The height is preferably 10 cm or less, more preferably 3 cm or less.

3. Surface tension test:
In a 100 mL glass beaker, 50 mL of the prepared water-soluble processing liquid for fixed abrasive wire saw was put, and the surface tension (mN / m) at 20 ° C. was measured using SURFACE TENSIOMETER CBVP-A3 (manufactured by Kyowa Interface Science Co., Ltd.).
It shows that permeability is so high that this surface tension is small. The surface tension is preferably 50 mN / m or less, more preferably 40 mN / m or less.

4). Cutability test:
Using a cutting device (multi-wafer manufacturer PV500D, manufactured by Komatsu NTC Ltd.), a workpiece cutting test was performed under the following test conditions to produce a wafer. The accuracy (Ra, Rz, SORI) of the obtained wafer was measured with a surface roughness measuring machine (Surfcoder SE500-18D, manufactured by Kosaka Laboratory Ltd.).
Ra, Rz, and SORI indicate that the smaller the value, the higher the wafer accuracy. Ra needs to be 1 μm or less, preferably 0.5 μm or less. Rz needs to be 4 μm or less, and preferably 2 μm or less. The SORI needs to be 70 μm or less, and preferably 40 μm or less.
(Test conditions)
・ Wire: Core wire diameter 120μm, diamond diameter 15-20μm
-Cutting device: Multi-wafer manufacturer PV500D manufactured by Komatsu NTC Ltd.
・ Work: Single crystal silicon ingot (rectangular of 125mm x 125mm x 190mm)
・ Wire speed: 900m / min
・ Feed speed: 1mm / min
・ Wire tension: 25N

[Examples 2 to 17, Comparative Examples 1 to 10]
Except having changed the kind and the compounding quantity of the raw material to be used so that it may become the compounding ratio shown to Tables 1-3, it is the same as Example 1, and the water-soluble processing liquid of Examples 2-17 and Comparative Examples 1-10 Was prepared. In Examples 5, 6, and 7, the pH of the water-soluble processing liquid for fixed abrasive wire saw was adjusted to 6 using an appropriate amount of citric acid.
The obtained water-soluble working fluid was subjected to the above-mentioned reciprocating friction test, foamability test, surface tension test and cutability test. The results are shown in Tables 1 to 3.

  As shown in the results of Tables 1 to 3, the water-soluble processing liquids of Examples 1 to 17 had low foaming properties and had moderate lubricity and good permeability even when they contained a large amount of water. . Therefore, by using these water-soluble machining fluids, cutting with a fixed abrasive wire saw can be performed with good machinability. Actually, a high-accuracy wafer is used in a cutting test using these water-soluble machining fluids. was gotten. Moreover, it is excellent also in a washability and can remove a chip | tip favorably. Further, since the water-soluble working fluid contains a large amount of water, it can be cut in a state excellent in terms of work environment and safety.

[Example 18]
While 5 parts of (A-1) and 0.05 part of (b1-1) were uniformly mixed, 94.95 parts of water was added and mixed and dissolved uniformly to prepare a water-soluble processing liquid.
The following separation / recovery test was conducted using this water-soluble processing liquid.
<Separation / recovery test>
10 g of silicon cutting waste model (Silicon diode: S5631, manufactured by sigma-aldrich) is added to 100 g of water-soluble machining fluid, and stirred and dispersed to prepare a post-cutting machining fluid for test fluid, and then at 25 ° C. Left for 1 hour. The post-cutting machining fluid for testing after being left for 1 hour was separated into two layers, an upper layer (slightly water-soluble machining fluid layer) and a lower layer (precipitation layer of silicon chip model).
The upper layer of the post-cutting working fluid separated into the two layers was collected by decantation, and the mass of the collected upper layer was measured. The remaining lower layer was filtered using filter paper, the residue (chip model) was dried, and the mass was measured.
From these measurement results, the separation efficiency (%) of cutting swarf from the post-cutting machining fluid, the recovery rate (%) of the upper layer from the post-cutting machining fluid, and the swarf content in the recovered upper layer (%) ) Were determined by the following formulas. The results are shown in Table 4.

  Cutting waste separation efficiency (%) = [dry weight of residue (chip model) (g) / dry weight of added chip model (10 g)] × 100

  Recovery rate of upper layer (%) = [mass of recovered upper layer (g) / mass of water-soluble processing liquid used in test (100 g)] × 100

  Cutting scrap content (%) in the collected upper layer = [dry mass of added chip model (10 g) −dry mass of residue (chip model) (g)] / mass of upper layer (g) × 100

[Examples 19 to 29, Comparative Examples 11 to 15]
The water-soluble processing of Examples 19 to 29 and Comparative Examples 11 to 15 was carried out in the same manner as Example 18 except that the types and amounts of raw materials used were changed so that the mixing ratios shown in Tables 4 to 5 were obtained. A liquid was prepared.
The obtained water-soluble machining fluid was subjected to the above separation / recovery test, and the cutting waste separation efficiency (%), the upper layer recovery rate (%), and the recovered cutting waste content (%) in the upper layer were determined. The results are shown in Tables 4-5.
In addition, about Comparative Examples 11-15, since it was not isolate | separated into two layers when it was left to stand at 25 degreeC for 1 hour, the part seen as a precipitation layer was considered as the lower layer, and upper layers were collect | recovered.

As shown in the results of Tables 4 to 5, the water-soluble machining fluids of Examples 18 to 27 have high cutting waste separation efficiency, low cutting scrap content in the recovered upper layer, and water-soluble machining fluid recovery efficiency. It was excellent.
On the other hand, the water-soluble working fluids of Comparative Examples 11 to 15 were not separated, so there were few parts that were seen as a precipitation layer, and the upper layer recovery rate was high, but the cutting scrap separation efficiency was very poor, and the recovered upper layer A large amount of cutting waste remained.

The water-soluble machining liquid for a fixed abrasive wire saw of the present invention exhibits good machinability when cutting a brittle material such as a silicon ingot using a fixed abrasive wire saw, and is excellent in chip cleaning performance. Moreover, the water-soluble processing liquid for fixed abrasive wire saws of the present invention can contain a large amount of moisture, and in this case, cutting can be performed in a state excellent in terms of work environment and safety.
Moreover, when the water-soluble working fluid for fixed abrasive wire saws of the present invention contains (b1 ′), the water-soluble working fluid is easy to regenerate, and after cutting the brittle material, from the post-cutting working fluid containing cutting waste. The cutting waste can be separated and removed easily and efficiently, and the water-soluble machining fluid can be recovered. Therefore, by using the water-soluble working fluid, productivity can be improved and cost can be reduced in cutting of brittle materials.

Claims (10)

  A water-soluble processing liquid for a fixed abrasive wire saw, comprising an alkylene oxide adduct (A) of polyamine, an acidic phosphate ester (b1) and / or a dicarboxylic acid (b2), and water (C). The alkylene oxide adduct (A) of the polyamine is represented by the following general formula (I):
_{^{R 1 - [(R 2 O}} ) n -H] m (I)
(In the formula, m represents a number of 2 to 8; n represents a number of 0 to 25, and m n may be the same or different, but the m n is not all 0; R ¹ represents a residue obtained by removing m active hydrogens of an amino group or imino group from a polyamine; R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and when n × m is 2 or more, n × m R ² O may be the same or different.)
The water-soluble processing liquid for fixed abrasive wire saws of Claim 1 which is a compound represented by these.   The water-soluble processing liquid for fixed-abrasive wire saws according to claim 1 or 2, comprising 75 to 99.8 mass% of the water (C). The acidic phosphate ester (b1) is represented by the following general formula (II):
(R ³ O) _x PO (OH) _3-x (II)
(Wherein x represents 1 or 2; R ³ represents an alkyl group or alkenyl group having 4 to 18 carbon atoms, and when x is 2, two R ^{3 s} may be the same or different. )
The water-soluble processing liquid for fixed abrasive wire saws as described in any one of Claims 1-3 which is a compound represented by these.   The water-soluble processing liquid for fixed abrasive wire saws as described in any one of Claims 1-4 whose total carbon number of the said dicarboxylic acid (b2) is 11-18.   The water-soluble processing liquid for fixed abrasive wire saws according to any one of claims 1 to 5, which is used for cutting a brittle material.   The water-soluble processing liquid for fixed-abrasive wire saws according to claim 6, wherein the brittle material is silicon. A method of cutting a brittle material with a fixed abrasive wire saw,
The cutting process is a water-soluble machining liquid for a fixed abrasive wire saw containing an alkylene oxide adduct (A) of polyamine, an acidic phosphate ester (b1) and / or dicarboxylic acid (b2), and water (C). The cutting method characterized by performing using. A method of cutting a brittle material with a fixed abrasive wire saw,
The cutting process is carried out by adding a polyamine alkylene oxide adduct (A) and the following general formula (II):
(R ³ O) _x PO (OH) _3-x (II)
(Wherein x represents 1 or 2; R ³ represents an alkyl group or alkenyl group having 4 to 18 carbon atoms, and when x is 2, two R ^{3 s} may be the same or different. )
A step of using a water-soluble processing liquid for a fixed abrasive wire saw, which contains an acidic phosphate ester (b1 ′) represented by: and water (C),
A step of removing at least the cutting waste from a post-cutting working fluid containing the water-soluble working fluid for the fixed abrasive wire saw and the cutting waste of the brittle material generated by the cutting;
The residual liquid obtained by removing at least the cutting waste from the post-cutting working liquid is reused as a water-soluble working liquid for fixed abrasive wire saws, or the alkylene oxide adduct (A) of the polyamine is used as the residual liquid. , Adding the acidic phosphate ester (b1 ′) or water (C) to obtain a water-soluble working fluid for a fixed abrasive wire saw, and using the water-soluble processing fluid for a fixed abrasive wire saw for cutting a brittle material Including
The step of removing the cutting waste,
A first step of separating the post-cutting working fluid into an upper layer mainly composed of the water-soluble working fluid for the fixed abrasive wire saw, and a precipitate layer (lower layer) of the cutting waste;
And a second step of removing the sediment layer (lower layer) of the cutting waste from the post-cutting working fluid separated in the first step.   The cutting method according to claim 8 or 9, wherein the brittle material is silicon.