JP2013216755A - Water-soluble processing liquid for fixed abrasive grain wire saw and cutting method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble processing liquid for fixed abrasive grain wire saw, which is excellent in lubricity and permeability and is easy to recycle, and a cutting method using the same.SOLUTION: A water-soluble processing liquid for fixed abrasive grain wire saw contains: an alkylene oxide adduct of polyamine (A); an acidic phosphate (B) represented by the following general formula (I); and water. (RO-(RO))-PO(OH)(I). [In the formula, x represents 1 or 2; y represents a number of 1-14 when x is 1, and represents a number of 0-14 when x is 2, two pieces of y may be the same or different, and at least one of two pieces of y is alkyl or alkenyl; Rrepresents 4-22C alkyl or alkenyl, and when x is 2, two pieces of Rmay be the same or different; and RO represents 2-4C oxyalkylene, and when x×y is 2 or more, x×y pieces of RO in the formula may be the same or different].

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.
On the other hand, in recent years, attempts have been made to reuse the machining fluid from the viewpoint of improving productivity and economy. Since cutting waste is mixed in the working fluid used for cutting an ingot or the like, when the working fluid is reused, it is necessary to separate and regenerate the cutting waste. As a method for separating the working fluid and the cutting waste, for example, Patent Documents 6 to 7 disclose a method using centrifugal separation. In Patent Document 8, water is contained in an oil drainage liquid generated by cutting an ingot with a fixed abrasive wire saw using a cutting oil composition containing a specific polyether compound, and the cloud point of the polyether compound A method of heating to the above temperature is disclosed.

JP 2003-82334 A JP 2003-82335 A Japanese Patent Application Laid-Open No. 2011-21096 JP 2009-57423 A JP 2011-68884 A JP 2010-29998 A JP 2010-253621 A JP 2011-230275 A

However, the water-soluble machining fluids disclosed in Patent Documents 1 to 5 have a problem that when the water content is increased, the lubricity and permeability are lowered and the cutting performance is lowered. If 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.
Furthermore, the conventional water-soluble processing liquid has problems such as poor regeneration efficiency and troublesome regeneration. For example, when a method using centrifugal separation as disclosed in Patent Documents 6 to 7 is applied, it takes a very long time to separate the cutting waste even if the separation operation is performed by a high-speed centrifugal separation method. Inefficient. The method described in Patent Document 8 has a problem that it takes time to process such as heating to decompose. Therefore, a water-soluble working fluid that can easily and efficiently separate cutting scraps after use and can be easily regenerated is desired.

  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 that is excellent in lubricity and permeability and can be easily regenerated, and a cutting method using the same. And

The present invention for solving the above problems has the following aspects.
(1) Polyamine alkylene oxide adduct (A) and the following general formula (I):
^{_{(R 1 O- (R 2 O}} ) y) x -PO (OH) 3-x (I)
[Wherein x represents 1 or 2; y represents a number of 1 to 14 when x is 1, and a number of 0 to 14 when x is 2; But at least one of the two y is 1 to 14; R ¹ represents an alkyl or alkenyl group having 4 to 22 carbon atoms, and when x is 2, two R ¹ May be the same or different; R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and when x × y is 2 or more, x × y R ² O in the formula is the same or different. It may be. ]
The water-soluble processing liquid for fixed abrasive grain wire saws containing acidic phosphate ester (B) represented by and water.
(2) The water-soluble processing liquid for fixed abrasive wire saws according to (1), containing 75 to 99.8% by mass of the water.
(3) The polyamine alkylene oxide adduct (A) is represented by the following general formula (a1):
_{^{R 3 - ((R 4 O}} ) n -H) m (a1)
[In the formula, m represents a number of 2 to 8; n represents a number of 0 to 25, and n of m may be the same or different, but m of n is not all 0; R ³ represents a residue obtained by removing m active amino or imino group hydrogens from a polyamine; R ⁴ O represents an oxyalkylene group having 2 to 4 carbon atoms, and n × m R ^{4 in the} formula O may be the same or different. ]
The water-soluble processing liquid for fixed abrasive wire saws according to (1) or (2), which is a compound represented by:
(4) The water-soluble machining liquid for a fixed abrasive wire saw according to any one of (1) to (3), which is used for cutting a brittle material.
(5) The water-soluble processing liquid for fixed abrasive wire saws according to (4), wherein the brittle material is silicon.
(6) 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 (I):
^{_{(R 1 O- (R 2 O}} ) y) x -PO (OH) 3-x (I)
[Wherein x represents 1 or 2; y represents a number of 1 to 14 when x is 1, and a number of 0 to 14 when x is 2; But at least one of the two y is 1 to 14; R ¹ represents an alkyl or alkenyl group having 4 to 22 carbon atoms, and when x is 2, two R ¹ May be the same or different; R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and when x × y is 2 or more, x × y R ² O in the formula is the same or different. It may be. ]
The cutting method characterized by performing using the water-soluble processing liquid for fixed abrasive wire saws containing acidic phosphate ester (B) represented by these, and water.
(7) 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 (I):
^{_{(R 1 O- (R 2 O}} ) y) x -PO (OH) 3-x (I)
[Wherein x represents 1 or 2; y represents a number of 1 to 14 when x is 1, and a number of 0 to 14 when x is 2; But at least one of the two y is 1 to 14; R ¹ represents an alkyl or alkenyl group having 4 to 22 carbon atoms, and when x is 2, two R ¹ May be the same or different; R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and when x × y is 2 or more, x × y R ² O in the formula is the same or different. It may be. ]
A step performed using a water-soluble processing liquid for a fixed abrasive wire saw containing the acidic phosphate ester (B) represented by
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. The acidic phosphate ester (B) represented by the general formula (I) or water 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 cut into a brittle material. Including processes used for processing,
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.
(8) The cutting method according to (6) or (7), 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 can be reproduced | regenerated easily, 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 comprises a polyamine alkylene oxide adduct (A) (hereinafter referred to as “component (A)”) and an acidic phosphate ester (B) represented by the general formula (I) (hereinafter referred to as “the component (A)”). , “(B) component”) and water.
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 component (B) contributes to improvement in lubricity. By including the component (B) in addition to the component (A), excellent lubricity is exhibited even when the amount of water is large, and the fixed abrasive wire saw can remove the fixed abrasive grains, wear the wires, etc. Since it is suppressed, machinability is improved. Moreover, since pH falls, corrosion of the wire saw and processing apparatus which contact the said water-soluble processing liquid can be prevented.
Furthermore, the water-soluble machining fluid of the present invention contains the component (A) and the component (B), so that cutting waste generated when a workpiece, particularly a brittle material, is cut by a fixed abrasive wire saw, Aggregation easily occurs in the water-soluble processing liquid. For this reason, the processed machining fluid containing the water-soluble machining fluid and the cutting waste is separated into two layers by simple operations such as standing at room temperature (about 25 ° C.) and short-time centrifugation. By removing the lower layer (cutting waste sedimentation layer), the cutting waste can be easily removed from the machining fluid after cutting. The recovered upper layer can be reused as a water-soluble processing liquid as it is or by adding components (A), (B), water, etc.) removed together with the lower layer as necessary.

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 1 mol 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. Of 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.

As the component (A), a compound represented by the following general formula (a1) is preferable because of excellent effects of improving permeability, lubricity and detergency.
_{^{R 3 - ((R 4 O}} ) n -H) m (a1)
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 ³ represents a residue obtained by removing all m active hydrogens of an amino group or imino group from a polyamine. The polyamine may be any one having m active hydrogens, and can be appropriately selected from the polyamines mentioned above.
R ⁴ O represents an oxyalkylene group having 2 to 4 carbon atoms, and is preferably an oxyethylene group or an oxypropylene group. N × m R ⁴ O in the formula 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.
Commercially available products can be used as the component (A), and examples thereof include Adeka Pluronic TR series (made by ADEKA) such as Adeka Pluronic TR701 and TR702 which are propylene oxide / ethylene oxide block adducts of ethylenediamine. It is done.

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.

Component (B) is a compound (phosphoric acid) in which one or two of the three hydroxyl groups of phosphoric acid (P (═O) (OH) ₃ ) are esterified with an alkylene oxide adduct of a specific aliphatic alcohol. Monoester or phosphoric acid diester) and represented by the following general formula (I).
^{_{(R 1 O- (R 2 O}} ) y) x -PO (OH) 3-x (I)
[Wherein x represents 1 or 2; y represents a number of 1 to 14 when x is 1, and a number of 0 to 14 when x is 2; But at least one of the two y is 1 to 14; R ¹ represents an alkyl or alkenyl group having 4 to 22 carbon atoms, and when x is 2, two R ¹ May be the same or different; R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and when x × y is 2 or more, x × y R ² O in the formula is the same or different. It may be. ]

In the general formula (I), specific examples of the alkyl group or alkenyl group having 4 to 22 carbon atoms of R ¹ include an n-butyl group, an iso-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, n-octyl group, 2-ethyl-hexyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, butenyl group, hexenyl group, octenyl group, nonenyl group, decenyl group , Dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, eicocenyl group, dococenyl group and the like.
R ¹ is preferably an alkyl group or alkenyl group having 6 to 18 carbon atoms because it has an excellent effect of improving lubricity, and an alkyl group or alkenyl group having 6 to 12 carbon atoms (n-hexyl group, cyclohexyl group, n-octyl group, 21-ethyl-hexyl group, nonyl group, decyl group, dodecyl group, hexenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group and the like are particularly preferable.

In general formula (I), examples of the oxyalkylene group having 2 to 4 carbon atoms of R ² O include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Among these, an oxyethylene group is preferable because of its excellent effect of improving permeability.
In general formula (I), y represents the number of added moles of alkylene oxide. When x is 1, y represents a number from 1 to 14. When x is 2, y represents a number from 0 to 14, two y may be the same or different, and at least one of the two y is 1 to 14.
Although y depends on the type of R ¹ , y is preferably 2 to 12 and particularly preferably 4 to 10 because it is excellent in the effect of improving lubricity and permeability.

The content of the component (B) in the water-soluble processing liquid is preferably 0.01 to 5% by mass and particularly preferably 0.05 to 2% 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. If it exceeds 5% by mass, it may be difficult to maintain sufficient machinability.
As the component (B), one type may be used alone, or two or more types may be used.

Although there is no restriction | limiting in particular as water, Purified water, especially deionized water are preferable.
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 working fluid of the present invention is superior in lubricity and permeability due to the combination of the above components.
The water-soluble processing liquid of the present invention contains (A) component 0.1 to 20% by mass, (B) component 0.01 to 5% by mass, and water 75 to 99.8% by mass. Preferably there is. 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.

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 4 to 10, particularly preferably 5 to 8. If the pH is less than 4, the processing apparatus may be rusted, and if the pH exceeds 10, the silicon of the workpiece may be corroded.
The pH of the water-soluble processing liquid can be adjusted by adjusting the blending ratio of the component (A) and the component (B), adding a pH adjuster, or the like.
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, but the content of water is low by increasing the content of component (A) and the content of component (B). There is no problem in preparing a stock solution and diluting it with water so that the content of each component becomes a preferable content at the time of use.

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 workpiece with a fixed abrasive wire saw and performs cutting with high machining accuracy. be able to.
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, as described above, the water-soluble working fluid of the present invention contains the component (A) and the component (B), so that when a work material, particularly a brittle material, is cut by a fixed abrasive wire saw. The generated cutting waste tends to aggregate in the water-soluble machining fluid. 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.
The following brittle material cutting method (1) is a preferred example of the brittle material cutting method using the water-soluble working fluid of the present invention. 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,
Performing the cutting using a water-soluble working fluid for a fixed abrasive wire saw (the water-soluble working fluid of the present invention) containing the component (A), the component (B), and water;
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 residual liquid is converted into the component (A) and the component (B). Adding a component or water 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,
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 some of the components (component (A), component (B), water, etc.) constituting the water-soluble processing fluid. 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 the component (A), component (B), and water in the residual liquid is 90% by mass or more of the concentration in the first water-soluble processing liquid, it can be used as a water-soluble processing liquid for cutting brittle materials. Can be reused. Among the components (A), (B), 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, by adding the component Can be reused for cutting 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 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.
B-1: Phosphoric ester of ethylene oxide 5 mol adduct of 2-ethylhexyl alcohol (mixture of monoester: diester mol ratio = 1: 1).
B-2: Phosphoric ester of tridecanol ethylene oxide 7 mol adduct (mixture of monoester body: diester body molar ratio = 1: 1).
B-3: Phosphoric ester of ethylene oxide 8 mol adduct of cetyl alcohol (mixture of monoester: diester isomer ratio = 1: 1).
B-4: Phosphate ester of stearyl alcohol ethylene oxide 10 mol adduct (mixture of monoester: diester isomer ratio = 1: 1).
D-1: Diethylene glycol.
D-2: Propylene glycol.
D-3: Diethylene glycol monomethyl ether.

[Example 1]
While 5 parts of (A-1) and 0.2 part of (B-1) were uniformly mixed, 94.8 parts of water was added and uniformly mixed and dissolved to prepare a water-soluble processing liquid.
The following reciprocating friction 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. 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.

3. 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 10, Comparative Examples 1 to 8]
The water-soluble processing of Examples 2 to 10 and Comparative Examples 1 to 8 was carried out in the same manner as in Example 1 except that the types and amounts of raw materials used were changed so that the mixing ratios shown in Tables 1 and 2 were obtained. A liquid was prepared.
The obtained water-soluble working fluid was subjected to the above-mentioned reciprocating friction test, surface tension test and cutability test. The results are shown in Tables 1 and 2.

  As shown in the results of Tables 1 and 2, the water-soluble working fluids of Examples 1 to 10 had moderate lubricity and good permeability even when they contained a large amount of water. Therefore, by using these water-soluble processing 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 processing 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 11]
While 5 parts of (A-1) and 0.2 part of (B-1) were uniformly mixed, 94.8 parts of water was added and uniformly mixed and dissolved 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 3.

  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 12 to 20, Comparative Examples 8 to 16]
The water-soluble processing of Examples 12 to 20 and Comparative Examples 8 to 16 was carried out in the same manner as Example 11 except that the types and amounts of raw materials used were changed so that the mixing ratios shown in Tables 3 to 4 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 3-4.
In Comparative Examples 8 to 16, since they were not separated into two distinct layers when allowed to stand at 25 ° C. for 1 hour, the upper layer was recovered by regarding the portion that appeared to be a precipitated layer as the lower layer.

As shown in the results of Tables 3 to 4, the water-soluble machining fluids of Examples 12 to 20 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 8 to 16 were not separated, so there were few portions that were seen as a precipitate layer, and the upper layer recovery rate was high, but the cutting waste 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.
In addition, the water-soluble machining fluid for the fixed abrasive wire saw of the present invention is easy to regenerate, and after cutting a brittle material, the cutting waste is easily and efficiently separated and removed from the post-cutting machining fluid including the cutting waste. Can be recovered. Therefore, by using the water-soluble machining fluid for fixed abrasive wire saws of the present invention, it becomes possible to improve productivity and reduce costs in cutting of brittle materials.

Claims (8)

Polyalkylene oxide adduct (A) and the following general formula (I):
^{_{(R 1 O- (R 2 O}} ) y) x -PO (OH) 3-x (I)
[Wherein x represents 1 or 2; y represents a number of 1 to 14 when x is 1, and a number of 0 to 14 when x is 2; But at least one of the two y is 1 to 14; R ¹ represents an alkyl or alkenyl group having 4 to 22 carbon atoms, and when x is 2, two R ¹ May be the same or different; R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and when x × y is 2 or more, x × y R ² O in the formula is the same or different. It may be. ]
The water-soluble processing liquid for fixed abrasive grain wire saws containing acidic phosphate ester (B) represented by and water.   The water-soluble processing liquid for fixed-abrasive wire saws according to claim 1, comprising 75 to 99.8% by mass of the water. The alkylene oxide adduct (A) of the polyamine is represented by the following general formula (a1):
_{^{R 3 - ((R 4 O}} ) n -H) m (a1)
[In the formula, m represents a number of 2 to 8; n represents a number of 0 to 25, and n of m may be the same or different, but m of n is not all 0; R ³ represents a residue obtained by removing m active amino or imino group hydrogens from a polyamine; R ⁴ O represents an oxyalkylene group having 2 to 4 carbon atoms, and n × m R ^{4 in the} formula O may be the same or different. ]
The water-soluble processing liquid for fixed abrasive wire saws of Claim 1 or 2 which is a compound represented by these.   The water-soluble processing liquid for fixed abrasive wire saws according to any one of claims 1 to 3, which is used for cutting a brittle material.   The water-soluble processing liquid for fixed abrasive wire saws according to claim 4, wherein the brittle material is silicon. 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 (I):
^{_{(R 1 O- (R 2 O}} ) y) x -PO (OH) 3-x (I)
[Wherein x represents 1 or 2; y represents a number of 1 to 14 when x is 1, and a number of 0 to 14 when x is 2; But at least one of the two y is 1 to 14; R ¹ represents an alkyl or alkenyl group having 4 to 22 carbon atoms, and when x is 2, two R ¹ May be the same or different; R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and when x × y is 2 or more, x × y R ² O in the formula is the same or different. It may be. ]
The cutting method characterized by performing using the water-soluble processing liquid for fixed abrasive wire saws containing acidic phosphate ester (B) represented by these, and water. 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 (I):
^{_{(R 1 O- (R 2 O}} ) y) x -PO (OH) 3-x (I)
[Wherein x represents 1 or 2; y represents a number of 1 to 14 when x is 1, and a number of 0 to 14 when x is 2; But at least one of the two y is 1 to 14; R ¹ represents an alkyl or alkenyl group having 4 to 22 carbon atoms, and when x is 2, two R ¹ May be the same or different; R ² O represents an oxyalkylene group having 2 to 4 carbon atoms, and when x × y is 2 or more, x × y R ² O in the formula is the same or different. It may be. ]
A step performed using a water-soluble processing liquid for a fixed abrasive wire saw containing the acidic phosphate ester (B) represented by
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. The acidic phosphate ester (B) represented by the general formula (I) or water 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 cut into a brittle material. Including processes used for processing,
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 6 or 7, wherein the brittle material is silicon.