JP3317839B2 - Detergent composition and method for cleaning sliced wafer or plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition and a cleaning method for a sliced wafer or plate, and more particularly, to a method of slicing a wafer or plate such as silicon or glass from an ingot or a column. During production, contaminants such as cutting oil, abrasive grains, and cutting powder after slicing, and exfoliation from a slice base such as a carbon beam fixed with an epoxy adhesive, as well as safety and wastewater treatment The present invention relates to a cleaning composition and a cleaning method having excellent cleaning properties.

[0002]

2. Description of the Related Art Silicon, gallium / arsenic, gallium
Ingots of semiconductor and crystal materials such as phosphorus, materials related to electronic components such as quartz, quartz, glass, and piezoelectric materials, magnetic materials such as ferrite, samarium and cobalt, magnetic materials such as magnetic heads, and wafers or plate-like objects such as ceramics Alternatively, an inner peripheral blade type or band saw type cutting device (slicer) has been conventionally used for slicing and manufacturing from a columnar material. These cutting devices cut by using a blade having ultra-hard cutting particles such as diamond fixed on the surface, while supplying a water-diluting type coolant or a low-viscosity cutting oil.

In recent years, wire saw type cutting devices have been introduced for cutting ingots and columns having a large diameter in order to improve the yield and shorten the cutting time. This cutting device cuts a fine steel wire of about 180 μm by entangled with fine particles (abrasive grains) of silicon carbide having an average particle diameter of about 20 μm with a high-viscosity cutting oil and rubbing it with an ingot or the like. Is what you do. Contaminants such as cutting oil, abrasive grains, cutting powder and the like generated by this cutting method are difficult to clean, and in particular, in the state of the ingot after cutting, about 200
Such contaminants were tightly packed in the gaps of μm, and it was difficult to clean by the usual method.

Conventionally, an ingot cut with a wire saw is spray-washed with warm water, then immersed in acetic acid at 90 ° C. or higher, and the wafer is peeled off from the slice base fixed with an epoxy-based adhesive. Put in a cassette. Then, after washing with an alkaline detergent,
Rinsing was performed by rinsing with pure water, then alkali etching, and then rinsing. In this method, one wafer
Since only 25 sheets can be processed per cassette, it takes a long time to clean a large number of wafers, and a large cleaning tank is required. In addition, a large amount of oily wastewater mixed with particles is generated, and a large cost is required for the treatment. In addition, the use of acetic acid for slice-based stripping also resulted in a poor working environment.

[0005] Recently, in order to shorten the processing time, cleaning in an ingot state has been studied. First, the oily stain is mainly washed with kerosene, and then the particle stain is mainly washed with an alkaline cleaner. After rinsing with pure water, the slice base is peeled off by immersion in acetic acid at 80 ° C. or higher, and 25 slices are placed in a cassette. Thereafter, alkali etching is performed, followed by rinsing with pure water and washing.

[0006] In order to obtain high detergency in a short time when cleaning oily contaminants mixed with particles, particularly dirt in narrow gaps, a method of simultaneously cleaning oily dirt and particle dirt is advantageous. In the above-described cleaning method using a kerosene / alkali cleaning agent, the oil in the gaps between the particles cannot be sufficiently cleaned in the kerosene cleaning, so that the particle contamination cannot be sufficiently cleaned by the subsequent alkali cleaning, resulting in poor cleaning. Also, kerosene has a danger of ignition, and increases the wastewater treatment load together with the oily soil containing particles. When the oily dirt is mixed in, the cleaning ability of the alkaline cleaning agent rapidly decreases. In addition, as in the case of cleaning the cassette, the use of acetic acid for stripping the slice base deteriorates the working environment.

That is, in the conventional cleaning method, not only the cleaning property is insufficient, but also kerosene is flammable, and there is a risk of fire and explosion. In addition, there is a problem that the working environment is deteriorated due to the use of acetic acid. Further, there is a problem in that a large load is applied to the treatment of the drainage and alkaline wastewater containing kerosene and the like in addition to the cutting oil, abrasive grains and cutting powder.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve a problem which has not been solved thus far. That is, to improve the disadvantages of conventional cleaning agents,
An object of the present invention is to provide a cleaning composition and a cleaning method which are excellent in cleaning property and safety, can reduce the load of drainage treatment, can peel off an epoxy-based adhesive in a short time, and can greatly shorten the entire cleaning time.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that specific hydrocarbons,
Using a detergent composition in which an alkylene oxide compound, a nonionic surfactant and water are combined in a specific ratio,
Controlling the concentration of fine particles mixed in the detergent composition low, washing while removing the oil component mixed in the rinsing liquid, further, by peeling the slice base with hot water after the rinsing step, Excellent cleanability and safety,
The present inventors have found that the load on the wastewater treatment can be reduced, the epoxy adhesive can be peeled off in a short time, and the entire cleaning time can be greatly reduced, and the present invention has been completed.

That is, the gist of the present invention is as follows: (1) The following components (a) to (e): (a) 25 to 65% by weight of a hydrocarbon having 10 to 18 carbon atoms; (b) a general formula (I) R ¹ —O— (C _k H _2k O) _j —H (I) (wherein, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, k represents a number of 2 or 3, and j represents 1 15 to 45% by weight of an alkylene oxide compound represented by the following formula: (c) General formula (II) R ² —O— (C _m H _2m O) _n —R ³ (II) (Formula Wherein R ² and R ³ represent a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, m represents a number of 2 or 3, and n represents a number of 1 to 3 (D) 5 to 30% by weight of a nonionic surfactant having an average HLB of 4 to 18; (e) 3 to 15% by weight of water; Contains, components (a) and ((b) + (c)) and weight ratio of (a) / [(b) + (c)] is 0.50 to 3.20
Characterized in that, the cleaning composition of a sliced wafer or plate-like material,

(2) When the temperature of a diluent obtained by diluting the detergent composition 20-fold with ion-exchanged water is increased at a rate of 1 ° C./min, the temperature at which the diluent becomes cloudy is clouded. When the cloud point is 5 to 100 ° C., the cleaning composition according to the above (1), (3) the sliced wafer or plate is washed using the cleaning composition or an aqueous solution thereof. in the washing process with a rinse step of the rinsing and washing step, the
The detergent according to the above (1) or (2) as a detergent composition
A method for cleaning a sliced wafer or plate using the composition and having the following steps: Cleaning step: introducing a part or all of the cleaning solution into a particle removing apparatus, a cleaning tank and a particle removing apparatus (4) rinsing with a rinsing liquid at 5 to 100 ° C .; and (4) rinsing. Cleaning method according to (3), wherein the rinse drainage is discharged to a temperature higher than the cloud point of the drainage to separate and remove oily components. ( 5 ) the method of washing the (3) or (4), wherein subjecting the washing step is peeled off from the ingot slice base, the wafer or plate-like material was (6) slices, ingot slice base After the rinsing step, or after the rinsing step, a further rinsing using a rinsing liquid consisting of water at 5 to 100 ° C. is performed, and then the ingot is heated in hot water at 80 ° C. or higher. The method according to (3) or (4) , further comprising a step of dipping the wafer or the plate-like material from the slice base in the hot water by immersion in the hot water.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

1. About a detergent composition About a (a) component As a hydrocarbon of a (a) component, as long as it has a carbon number of 10-18, any may be sufficient, for example, decane, dodecane,
Tetradecane, hexadecane, octadecane, decene,
Linear or branched saturated or unsaturated hydrocarbons such as dodecene, tetradecene, hexadecene, octadecene; alkylbenzenes such as nonylbenzene and dodecylbenzene;
Naphthalene compounds such as methylnaphthalene and dimethylnaphthalene; and cyclo compounds such as cyclodecane and cyclododecene. Of these, those having 12 to 18 carbon atoms
Are preferred. Straight-chain or branched-chain saturated or unsaturated hydrocarbons are preferred, and olefin-based hydrocarbons are particularly preferred in view of detergency, handling, and the like.

The content of these hydrocarbons in the detergent composition of the present invention may be from 25 to 65% by weight, and from 30 to 65% by weight.
More preferably, it is 60% by weight. The content is preferably 25% by weight or more from the viewpoint of the cleaning property of the cutting oil, and is preferably 65% by weight or less from the viewpoint of the rinsing property and the releasability of the epoxy adhesive.

Component (b) Of the components used in the cleaning composition of the present invention, component (b)
The component alkylene oxide compound is represented by the general formula (I). R ¹ —O— (C _k H _2k O) _j —H (I) In the general formula (I), R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, k represents a number of 2 or 3, j shows the number of 1-3.
In the general formula (I), R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, particularly preferably a hydrocarbon group having 3 to 6 carbon atoms. If the carbon number of R ¹ exceeds 8, the solubility in water becomes worse and the viscosity also rises, so that the workability may become worse. Specific examples of the hydrocarbon group for R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an allyl group, a butyl group, an isobutyl group, a hexyl group,
Examples include a 2-ethylhexyl group, an octyl group, a phenyl group, and a benzyl group. j is a number from 1 to 3. j is 3
If it exceeds, the viscosity may increase and the workability may deteriorate.

Specific examples of such an alkylene oxide compound include the following compounds. Monoethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether [each of the above compounds (POE) ₁
It may be abbreviated as monomethyl ether, (POE) ₂ monomethyl ether, or (POE) ₃ monomethyl ether. Further, these compounds are collectively referred to as (POE) ₁
It may be abbreviated as ~ ₃ monomethyl ether. In addition,
Similar compounds and the like may be abbreviated as described above in corresponding expressions. ], (POE) ₁ ~ ₃ monoethyl ether, (POE) ₁ ~ ₃ monopropyl ether, (P
OE) ₁ ~ ₃ monoisopropyl ether, (POE) _1
1-3 monoallyl ether, (POE) ₁ ~ ₃ monobutyl ether, (POE) _{1 1-3} monoisobutyl ether,
(POE) ₁ ~ ₃ mono-hexyl ether, (POE) ₁
~ ₃ mono 2-ethylhexyl ether, (POE) ₁ ~
₃ monooctyl ether, (POE) _1-3 monophenyl ether, (POE) ethylene glycol monomethyl ethers such as _1-3 monobenzyl ether.

[0016] (POP) ₁ ~ ₃ monomethyl ether,
(POP) ₁ ~ ₃ monoethyl ether, (POP) ₁ ~
₃ monopropyl ether, (POP) ₁ ~ ₃ monoisopropyl ether, (POP) ₁ ~ ₃ monoallyl ether, (POP) ₁ ~ ₃ monobutyl ether, (POP)
_1-3 monoisobutyl ether, (POP) _1-3 monohexyl ether, (POP) _1-3 mono-2-ethylhexyl ether, (POP) _1-3 monooctyl ether, (POP) _1-3 monophenyl ether, ( PO
P) of propylene glycol monomethyl ethers such as _1-3 monobenzyl ether. Note that (POP) is the same abbreviation as (POE) except that ethylene is propylene.

[0017] Among the above compounds, (POE) ₁ ~ ₃ monomethyl ether, (POE) ₁ ~ ₃ monoethyl ether, (POE) ₁ ~ ₃ monoisopropyl ether, (P
OE) ₁ ~ ₃ monoallyl ether, (POE) ₁ ~ ₃ monobutyl ether, (POE) ₁ ~ ₃ monoisobutyl ether, (POE) ₁ ~ ₃ monohexyl ether, (P
OE) ₁ ~ ₃ mono-2-ethylhexyl ether, (PO
E) ₁ ~ ₃ monophenyl ether, (POE) ₁ ~ ₃ monobenzyl ether, (POP) ₁ ~ ₃ monomethyl ether, (POP) ₁ ~ ₃ monoethyl ether, (PO
P) ₁ ~ ₃ monopropyl ether, (POP) ₁ ~ ₃ monobutyl ether, and (POP) ₁ ~ ₃ monophenyl ether can be preferably used in view of easy availability and performance. These alkylene oxide compounds may be used alone or in combination.

The content of the alkylene oxide compound (b) in the detergent composition may be from 15 to 45% by weight, more preferably from 30 to 40% by weight. Outside these ranges, sufficient performance may not be obtained in terms of detergency, rinsing, oil-water separation, and peelability of the epoxy adhesive.

Component (c) Of the components used in the cleaning composition of the present invention, component (c)
The component alkylene oxide compound is represented by the general formula (II). R ² —O— (C _m H _2m O) _n —R ³ (II) In the general formula (II), R ² and R ³ represent a hydrocarbon group having 1 to 8 carbon atoms, and even if they are the same, It may be different. m shows the number of 2 or 3, and n shows the number of 1-3.
In the general formula (II), R ² and R ³ are a hydrocarbon group having 1 to 8 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms. If the number of carbon atoms in R ² and R ³ exceeds 8, solubility in water is lowered and viscosity is also increased, so that workability may be lowered. Specific examples of R ² and R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an allyl group, a butyl group, an isobutyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a phenyl group, and a benzyl group. No. n is preferably a number from 1 to 3. When n exceeds 3, the viscosity increases,
Workability may deteriorate.

Specific examples of such an alkylene oxide compound include the following compounds. (PO
E) ₁ ~ ₃ dimethyl ether, (POE) ₁ ~ ₃ diethyl ether, (POE) ₁ ~ ₃ dipropyl ether,
(POE) ₁ ~ ₃ of diisopropyl ether, (POE)
_1-3 diallyl ethers, (POE) _1-3 dibutyl ether, (POE) _1-3 diisobutyl ethers, (P
OE) ₁ ~ ₃ dihexyl ether, (POE) ₁ ~ _{3-di-2-ethylhexyl} ether, (POE) ₁ ~ ₃ dioctyl ether, (POE) ₁ ~ ₃ ether,
(POE) ethylene glycol diethers such as _1-3 dibenzyl ether (Incidentally, R ² = R ^3).

[0021] (POE) ₁ ~ ₃ methyl ether,
(POE) ₁ ~ _3-isopropyl ether, (PO
E) ₁ ~ _3-butyl methyl ether, (POE) ₁ ~ _3-hexyl methyl ether, (POE) ₁ ~ ₃ 2- ethylhexyl ether, (POE) ₁ ~ ₃ ethylene glycol ethers such as phenyl ether (Incidentally, R ² ≠ R ³ ).

[0022] (POP) ₁ ~ ₃ dimethyl ether, (P
OP) ₁ ~ ₃ diethyl ether, (POP) ₁ ~ ₃ dipropyl ether, (POP) ₁ ~ ₃ of diisopropyl ether, (POP) ₁ ~ ₃ diallyl ether, (POP)
_1-3 dibutyl ether, (POP) _1-3 diisobutyl ethers, (POP) _1-3 dihexyl ether,
(POP) ₁ ~ _{3-di-2-ethylhexyl} ether, (P
OP) ₁ ~ ₃ dioctyl ether, (POP) ₁ ~ ₃ ether, (POP) ₁ ~ ₃ dibenzyl propylene glycol ethers such as ether (Incidentally, R ²
= R ^3).

[0023] (POP) ₁ ~ ₃ methyl ether,
(POP) ₁ ~ _3-isopropyl ether, (PO
P) _1-3 butyl methyl ether, (POP) _1-3-hexyl methyl ether, (POP) _1-3 2-ethylhexyl methyl ethers, (POP) Propylene glycol diethers, such as _1-3 phenyl methyl ether (Incidentally, R ² ≠ R ³ ).

[0024] Among the above compounds, (POE) ₁ ~ ₃ dimethyl ether, (POE) ₁ ~ ₃ diethyl ether,
(POE) ₁ ~ ₃ of diisopropyl ether, (POE)
_1-3 dibutyl ether, (POE) _1-3 dihexyl ether, (POE) _1-3 ether, (P
OE) ₁ ~ ₃ methyl ether, (POE) ₁ ~ ₃
Isopropyl methyl ether, (POE) ₁ ~ _3-butyl methyl ether, (POP) ₁ ~ ₃ dimethyl ether,
(POP) ₁ ~ ₃ diethyl ether, (POP) ₁ ~ ₃
Diisopropyl ether, (POP) ₁ ~ ₃ dibutyl ether, (POP) ₁ ~ ₃ dihexyl ether, (PO
P) ₁ ~ ₃ ether, (POP) ₁ ~ ₃ methyl ether, (POP) ₁ ~ _3-isopropyl ether, (POP) ₁ ~ ₃ isopropyl ethyl ether, and (POP) ₁ ~ _3-butyl methyl ether performance available It can be preferably used from the viewpoint of easiness.
These alkylene oxide compounds may be used alone or in combination.

The content of the alkylene oxide compound (c) in the detergent composition may be 5 to 15% by weight, more preferably 6 to 13% by weight. Outside of these ranges, sufficient performance may not be obtained in terms of cleaning properties, rinsing properties, and peelability of the epoxy adhesive.
The alkylene oxide compound of the component (b) is, for example, an alcohol having 1 to 8 carbon atoms in the presence of a catalyst such as caustic soda while heating the alkylene oxide having 2 to 3 carbon atoms (ethylene oxide, propylene oxide) in liquid or gaseous form. And reacting it. Further, if the terminal hydroxyl groups of these alkylene oxide adducts are further alkylated using an alkyl chloride or the like, the dialkyl ether of the component (c) can be obtained.

In the cleaning composition of the present invention, the weight ratio of component (a) to component ((b) + (c)) is (a) /
[(B) + (c)] is 0.50 to 3.20, preferably 0.60 to 3.16. Outside these ranges, sufficient performance may not be obtained in terms of detergency and peelability of the epoxy adhesive.

Component (d) Of the components used in the cleaning composition of the present invention, component (d)
Specific examples of the nonionic surfactant having an average HLB of 4 to 18 include the following compounds. (PO
E) ₁ to ₄₀ octyl ether, 1 to 40 mer ethylene oxide and ether of a synthetic alcohol having 12 to 14 carbon atoms (abbreviated as (POE) ₁ to ₄₀ carbon alcohol having 12 to 14 synthetic alcohol ether), ( (POE) ₁ to ₄₇ lauryl ether, (POE) ₂ to ₂₀ cetyl ether, (POE)
E) polyoxyethylene alkyl ethers such as ₂ to ₃₀ stearyl ether, (POE) ₂ to ₃₅ oleyl ether, (POE) ₂ to ₄₀ octylphenyl ether, and (POE) ₂ to ₄₅ nonylphenyl ether;

Sorbitan monoalkyl esters such as sorbitan monolauryl ester, sorbitan monopalmityl ester, sorbitan monostearyl ester and sorbitan monooleyl ester; (POE) ₁ to ₂₅ sorbitan monolauryl ester, (POE) ₁ to ₂₅ sorbitan mono palmityl ester, (POE) _1-30 sorbitan monostearyl ester, (POE) polyoxyethylene sorbitan alkyl esters such as ₁ to ₃₀ sorbitan mono-oleyl ester; (POE) ₁₀ ~ ₄₀ sorbitan tristearate Lil ester, (POE) _And polyoxyethylene sorbitan trialkyl esters such as ₁₀ to ₄₀ sorbitan trioleyl ester.

[0029] Of the above compounds, (POE) ₅ ~ ₉ carbon atoms 12 to 14 synthetic alcohol ether, (POE) _4
10 to ₁₀ lauryl ether, (POE) ₅ to ₈ cetyl ether, (POE) ₁₀ to ₁₅ stearyl ether, (POE)
_5-15 oleyl ether, (POE) ₆ ~ ₁₀ octylphenyl ether, (POE) ₅ ~ ₁₃ nonylphenyl ether, sorbitan monolauryl ester, sorbitan monopalmityl ester, sorbitan monostearyl ester, sorbitan mono-oleyl ester, (POE) _Five
~ ₂₀ Sorbitan monolauryl ester, (POE) ₅ ~
₂₀ Sorbitan monopalmityl ester, (POE) _5-
20 Sorbitan monostearyl ester, (POE) _5-
20 sorbitan oleyl ester, (POE) ₁₅ ~ ₃₀
Sorbitan tristearate Lil ester, (POE) ₁₅ ~ ₃₀
Sorbitan trioleyl ester is preferably used in terms of detergency and rinsing properties.

The nonionic surfactant having an average HLB of 4 to 18 as the component (d) has a content of 5 to 30 in the detergent composition.
% By weight, and more preferably 10 to 25% by weight. Outside of these ranges, sufficient performance may not be obtained in terms of cleaning properties, rinsing properties, and peelability of the epoxy adhesive.

Component (e) Of the components used in the cleaning composition of the present invention, component (e)
From the viewpoint of safety and detergency, the water content of the component may be 3 to 15% by weight in the detergent composition, and may be 5% by weight.
More preferably, it is 10 to 10% by weight. The water used here is not particularly limited as long as it does not impair the effect of the cleaning composition of the present invention, and ultrapure water, pure water, ion-exchanged water, distilled water, ordinary tap water, and the like. Is used.

In the cleaning composition of the present invention, hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, etc., which are usually used in cleaning compositions, as far as the effects of the present invention are not impaired. Compounds having chelating ability such as aminocarboxylic acid salts such as acetic acid, preservatives, rust inhibitors, antifoaming agents such as silicone, antioxidants, esters such as coconut fatty acid methyl and benzyl acetate, hydrocarbon solvents, alkanolamines Or alcohols can be appropriately used in combination. The cleaning composition of the present invention can be produced by mixing the above-mentioned components (a) to (e), optional components, and the like by an ordinary method.

The detergent composition of the present invention has a cloud point of 5 to 5.
The temperature is preferably 100 ° C, more preferably 10 to 90 ° C. In the present specification, the cloud point of the cleaning composition
When the temperature of the diluent obtained by diluting the detergent composition to be measured with ion-exchanged water 20-fold and the temperature is increased at a rate of 1 ° C./min, the temperature at which the diluent becomes cloudy.

2. Regarding the cleaning method The cleaning method of the present invention is a cleaning method having a cleaning step of cleaning a sliced wafer or plate using a cleaning composition or an aqueous solution thereof and a rinsing step of rinsing. Is introduced into the particle removing device, and circulated between the cleaning tank and the particle removing device to control the concentration of particles in the cleaning liquid to 1% or less, and to carry out cleaning, and a rinsing step: 5 to 100 ° C. Performing a rinsing using the rinsing liquid.

(1) Washing Step In the washing step, the washing liquid of the present invention or an aqueous solution thereof can be used, although the washing liquid is not particularly limited. The concentration of the cleaning composition in the aqueous solution can be appropriately adjusted according to the degree of contamination of the wafer or plate. The physical force of the washing step is not particularly limited,
For example, various cleaning methods such as an immersion method, an ultrasonic cleaning method, an immersion rocking method, a spray method, and a hand wiping method can be performed alone or in combination. Further, the cleaning time can be appropriately adjusted according to the degree of contamination of the wafer or the plate-like material, and is generally selected from about 3 to 20 minutes. The temperature of the cleaning liquid at the time of cleaning is preferably from 50 to 80 ° C, and more preferably from 60 to 70 ° C from the viewpoints of cleanability and reduction in the amount of water evaporation.

In the cleaning step, particle stains generated during cutting, such as abrasive grains and cutting powder, and oily stains, such as cutting oil, are removed. At this time, if the concentration (particle concentration) of the particle contamination in the cleaning liquid increases, the cleaning physical force is not sufficiently utilized, and the diffusion of the particle contamination is prevented, so that the cleaning ability is reduced. Therefore, the cleaning liquid of the cleaning tank in which the cleaning is performed, that is, a part or all of the cleaning composition or the aqueous solution thereof is introduced into the particle removing device, and the cleaning device is circulated between the cleaning tank and the device to remove the particle contamination, The concentration of the particles in the cleaning liquid may be controlled to a concentration that does not adversely affect the cleaning. As such particle concentration,
0.9% by weight or less, preferably 1% by weight or less in the washing liquid
The following is more preferred. In such an embodiment, since the cleaning liquid is circulated and reused between the cleaning tank and the particle removing device,
Economically advantageous.

As a method for removing particles used in the present invention, a filtration method, a sedimentation method, a centrifugal method, a flotation method, a distillation method, and the like can be used. , Sedimentation and centrifugation are preferred in terms of versatility of industrial equipment.

As a filtration method used for removing particles, any of a gravity type, a vacuum type, a pressurization type and a compression type can be used. In the gravity type, a rotary screen, a sand filter, a Nutsche filter or the like is used. Drum filter, Young filter, Disc filter, Horizontal filter, Horizontal belt filter, Nutsche filter, Leaf filter, etc. For pressurized type, pressurized pre-coat filter, pressurized scraper discharge filter, bag filter, filter press, Schneider filter, automatic Nutsche type In a squeezing type such as a filter, a device such as a belt press, a screw press, a tube press, and a mars press can be used.

As a sedimentation separation method used for removing particles, there are a horizontal flow type gravity settling tank, an upward flow type gravity settling tank, an inclined pipe settling tank,
An inclined plate sedimentation tank, a center drive type circular sedimentation tank, a multi-stage thickener, a thickener with a picket, a continuous thickener, and the like can be used. As a centrifugal separation method used for particle removal, any of a centrifugal sedimentation type, a centrifugal dehydration type, and the like can be used,
For centrifugal sedimentation type, centrifugal sedimentation type, cylindrical type, separator plate type, basket type, decanter type, wet cyclone, for centrifugal dehydration type, siphon type, basket type, extrusion type, screw type, automatic discharge type, vibration type device Can be used. Examples of commercially available devices include a Tsukishima hard decanter centrifuge (manufactured by Tsukishima Kikai Co., Ltd.), a Sharpless Super Decanter (manufactured by Tomoe Industries Co., Ltd.), and a horizontal continuous centrifuge ( Screw decanter centrifuge (manufactured by Ishikawajima-Harima Industry Co., Ltd.), screw decanter centrifuge (manufactured by Kansai Centrifuge Co., Ltd.), Chemco Humboldt decanter (Kotobuki Giken Kogyo) (stock)
), Ultracentrifuge (manufactured by Heiden Co., Ltd.), nozzle separator (manufactured by Asahi Seisakusho), disk-type centrifuge (manufactured by Alfa Laval Co., Ltd.), disc separator (manufactured by Mitsubishi Kakoki Co., Ltd.) ), Sharpless Super Centrifuge (made by Tomoe Industries Co., Ltd.), KS type ultra-high speed centrifuge (made by Kansai Centrifuge Co., Ltd.), solid bowl separator (made by Saito Centrifuge Co., Ltd.), Saito Automatic Disrusher (Saito Centrifuge Co., Ltd.)
Manufactured by Oishi Kikai Co., Ltd.) and a wet cyclone classifier (manufactured by Oishi Kikai Seisakusho). Especially in the centrifugal sedimentation type, the wet cyclone has a particle classification function, so that particles having a desired specific particle size can be removed from the mixed particles in the detergent composition, and the particles can be collected and reused. It can be used for

The flotation method used for the particle remover includes:
Apparatuses such as a bubble floating separation type, a pressure floating type, and an electrolytic floating type can be used. As a distillation method used for the particle remover, batch rectification, continuous rectification, or the like can be used.

(2) Rinsing Step The rinsing step is a step of rinsing the cleaning liquid adhering to the wafer or the like, remaining oily dirt and particle dirt.
The rinsing liquid is not particularly limited as long as it can remove such components. For example, ultrapure water, pure water, ion-exchanged water, distilled water, ordinary tap water and the like are preferable from the viewpoint of rinsing properties. Further, the liquid obtained by separating and removing the oil component from the rinse drainage may be recycled. That is, the rinsing liquid is cleaned and reused as a rinsing liquid, which is preferable from the viewpoint of wastewater treatment.

The rinsing is performed by using a rinsing liquid at 5 to 100 ° C. and a rinsing method such as an immersion method, an ultrasonic cleaning method, an immersion rocking method, a spray method, and a hand wiping method. The temperature of the rinsing liquid is preferably 5 to 100 ° C., and a temperature outside this range is not preferable in consideration of cost, equipment, and the like. From the viewpoint of rinsing properties, a particularly preferred temperature is a temperature below the cloud point of the cleaning composition. The rinsing time can be appropriately adjusted according to the degree of contamination of the wafer or plate-like material, and is generally selected from about 3 to 20 minutes.

In order to separate and remove oil components such as washing liquid and contaminants from the rinse waste liquid, it is necessary to heat and maintain the rinse waste liquid at a temperature higher than its cloud point, more preferably at least 5 ° C. higher than the cloud point. good. By this heating, the nonionic surfactant derived from the cleaning composition in the rinse drainage loses its water solubility, and the oily soil emulsified or dissolved in the rinse drainage is thereby separated. That is, at a temperature lower than the cloud point, the oily stain is solubilized or emulsified by a detergent component such as a nonionic surfactant and stabilized in the rinsing liquid. However, above the cloud point, nonionic surfactants lose water solubility and separate. As a result, the oily stain that has been solubilized in the rinse drainage liquid cannot be retained in water, and the oily stain floats or sinks in water depending on the specific gravity to separate. Further, the nonionic surfactant itself loses water solubility and separates from water.

The removal of the separated oily components such as oily dirt and cleaning liquid can be performed by a method of scooping up the oily components collected at the upper or lower part of the tank in a receiving tank for the rinse drainage or a dedicated tank for separation. Various methods can be used, such as a method of selectively extracting the material and a method of using auxiliary equipment for the separation membrane. By performing these separations efficiently, the rinse waste liquid is cleaned and can be reused as a rinse liquid, that is, can be recycled. In the case of circulating use, if necessary, treatment such as ion exchange treatment, adsorption treatment with activated carbon, or membrane separation may be performed in order to remove organic substances such as water-soluble ions and activators in the rinse solution. Note that the cloud point of the rinse drainage refers to the temperature measured in the same manner as the measurement of the cloud point of the detergent composition without diluting the rinse drainage. This cloud point is almost the same as the cloud point of the detergent composition.

In the present invention, the wafer or plate which has been cleaned and rinsed in the above steps is further subjected to 5 to 1
Finishing rinsing may be performed using a rinsing liquid composed of water at 00 ° C.

In the cleaning method of the present invention, the wafer or plate-like material may be peeled off from the slice base and cleaned in a cassette or the like (Embodiment 1). In order to shorten the time, washing may be performed in an ingot state (aspect-2) via a slice base. In the embodiment 1, as a method for peeling the sliced wafer or plate from the slice base of the ingot, a commonly known method such as immersion in an acetic acid aqueous solution at 90 ° C. or higher or hot water can be used. Mode-
In 2, cleaning is performed in an ingot state, and then the wafer or plate is peeled from the slice base. In this case, after the rinsing step or the finish rinsing, a step of peeling may be provided. Since the cleaning composition of the present invention has a function of swelling and peeling the epoxy-based adhesive, it is not necessary to use acetic acid as in the conventional method.
By immersing in hot water at a temperature of at least 85 ° C., preferably at least 85 ° C., and using the effect of softening the adhesive in combination, it is possible to peel in a shorter time. No physical force is required in the peeling step, but various physical forces such as bubbling, ultrasonic waves, rocking, and submerged jet may be used alone or in combination. The cleaning composition and the cleaning method of the present invention as described above can be used for semiconductor / crystal materials such as silicon, gallium / arsenic, gallium / phosphorus, quartz, quartz, glass, and electronic component-related materials such as piezoelectric materials, ferrite, and samarium. It is particularly useful when slicing a magnetic material such as cobalt, a magnetic material such as a magnetic head, or a wafer or plate such as ceramics from an ingot or a column.

[0047]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

Examples 1 to 10 and Comparative Examples 1 to 10 The cleaning compositions shown in Tables 1 to 4 below were prepared, respectively.
For each, the detergency, oil component separation, and peelability of the epoxy adhesive were evaluated as follows. In addition, the compounding quantity of each component in a table | surface was shown by the weight part.

(1) Detergency One side of an 8-inch silicone wafer sliced with a wire saw was used as a model stain of oily stain containing particles, wire saw oil: PS-LW-1 (Palace Chemical Co., Ltd.)
) And a green silicon carbide abrasive: GC # 600 (Fujimi Incorporated) in a weight ratio of 50:50 are uniformly applied with a bar coater to a thickness of about 200 µm. Two glass plates of 200 μm × 1 cm × 1 cm are used as spacers and sandwiched by another wafer. The spacer portion was clipped to provide a test piece for a cleaning test. After performing a cleaning test under the following conditions using the cleaning compositions having the compositions shown in Tables 1 to 4, the wafers are opened, and the removal area ratio (%) of the oil-based dirt mixed with the particles on each wafer is visually determined. The average value of the two sheets was taken to determine the cleaning rate (%). The cleaning was performed by immersion ultrasonic cleaning at 60 ° C. for 15 minutes using the cleaning composition. Rinse is
Immersion ultrasonic cleaning was performed at 25 ° C. for 15 minutes using ion-exchanged water. Finishing rinse is 25 ° C using ion-exchanged water,
Immersion ultrasonic cleaning was performed for 15 minutes. The cleaning rate was determined by visual inspection. The particle concentration in the detergent composition was adjusted by mixing the model soil with the detergent composition so that the particles had a predetermined concentration.

(2) Separability of Oil Components <Measurement of Cloud Point> Each of the detergent compositions having the compositions shown in Tables 1 to 4 was diluted 20 times with ion-exchanged water, and the cloud point was measured. <Separation rate of oil component> The rinse drainage after use in the detergency test is set to a temperature higher than the cloud point of the corresponding detergent composition by 10 to 20 ° C (the maximum temperature is 100 ° C or lower), and allowed to stand for 30 minutes. did. At this time, the oily component was separated into an upper layer in the examples. This aqueous layer was sampled, its COD (chemical oxygen demand) was measured (A value), compared with the COD (B value) of the rinse drainage solution before the heat treatment, and the oil component separation rate [(B
Value−A value) ÷ (B value)] × 100 (%).

(3) Releasability of epoxy-based adhesive On a glass plate of 1 cm × 6 cm × 15 cm, epoxy-based adhesive: W-Bond NC-15K (Nikka Seiko Co., Ltd., main agent / hardener = 2 / (1), bonding at 90 ° C. for 1 hour (adhesion curing treatment), the orifice portions of three wafers were bonded at 1 cm intervals, and these were used as test pieces for a peeling test. After performing the same cleaning treatment as in the cleaning test, the substrate was immersed in ion-exchanged water at the temperature shown in the table, and the time required for all three wafers to peel off was measured. Tables 1 to 4 show the above results.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

From the above results, it was found that the detergent composition of the present invention was excellent in detergency, oil component separation property, and peelability of epoxy adhesive. In particular, excellent cleaning properties were exhibited even when the distance between the wafers was 200 μm, indicating that the wafers and the like could be cleaned in an ingot state. On the other hand, the detergent compositions in which the content of each component was out of the range of the present invention were all poor in detergency (Comparative Examples 1 to 8). Furthermore, there have been examples in which the adhesive has a long peeling time. Further, from Example 9 and Comparative Example 9, it was found that when the particle concentration at the time of cleaning was higher than a predetermined range, the cleaning performance was reduced. From Example 10 and Comparative Example 10,
It has been found that when the hot water temperature at the time of peeling the epoxy-based adhesive is lower than a predetermined range, the peeling time becomes longer.

[0057]

The cleaning composition of the present invention is excellent in detergency, oily component separation property, and peelability of an epoxy adhesive. The cleaning method of the present invention using such a cleaning composition is efficient because a wafer or a plate-like substance can be cleaned in an ingot state, and is effective in prolonging the maintenance of the performance of the cleaning agent and reducing the wastewater treatment load. It is economical because it can be used, and has high safety because it does not use acetic acid or kerosene.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-208979 (JP, A) JP-A-8-8223 (JP, A) JP-A-59-1124 (JP, A) JP-A-6-8989 45297 (JP, A) JP-A-6-313192 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01L 21/304

Claims (6)

(57) [Claims] 1. The following components (a) to (e): (a) 25 to 65% by weight of a hydrocarbon having 10 to 18 carbon atoms; (b) R ¹ —O— (C _k H) of the general formula (I) _2k O) _j -H (I) (wherein, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, k represents a number of 2 or 3, and j represents a number of 1 to 3). (C) general formula (II) R ² —O— (C _m H _2m O) _n —R ³ (II) (wherein R ² and R ³ are carbon Represents an hydrocarbon group represented by Formulas 1 to 8, and may be the same or different. M represents a number of 2 or 3, and n represents a number of 1 to 3.) (D) a nonionic surfactant having an average HLB of 4 to 18; 5 to 30% by weight; water (3 to 15% by weight); and component (a) and component (( (b) + (c)) wherein the weight ratio (a) / [(b) + (c)] is 0.50 to 3.20, wherein the cleaning agent for sliced wafers or plate-like objects is provided. Composition. 2. When the temperature of a diluent obtained by diluting a detergent composition 20-fold with ion-exchanged water at a rate of 1 ° C./min is raised, the temperature at which the diluent becomes cloudy is defined as the cloud point. The cleaning composition according to claim 1, wherein the cloud point is 5 to 100C. 3. A cleaning method comprising a cleaning step of cleaning a sliced wafer or plate using a cleaning composition or an aqueous solution thereof and a rinsing step of rinsing, wherein the cleaning composition is used as the cleaning composition. Or the cleaning agent according to 2.
A method for cleaning a sliced wafer or plate using the composition, the method comprising the following steps. Cleaning step: a step of introducing a part or all of the cleaning liquid into the particle removing apparatus, circulating the cleaning liquid between the cleaning tank and the particle removing apparatus, and controlling the particle concentration in the cleaning liquid to 1% by weight or less, and a rinsing step. : as Engineering to perform a rinsing using a 5~100 ℃ rinsing liquid 4. The cleaning method according to claim 3, wherein in the rinsing step, the rinse waste liquid discharged is heated to a temperature higher than the cloud point of the waste liquid to separate and remove oily components. 5. The method of cleaning according to claim 3 or 4, wherein the sliced wafer or plate-like material, and wherein the subjecting the washing step is peeled off from the ingot slice base. 6. The sliced wafer or plate-like object is subjected to a cleaning step without peeling from the slice base of the ingot, and then, after the rinsing step or after the rinsing step, a rinsing liquid comprising water at 5 to 100 ° C. is further added. After performing the finish rinsing using the method, further comprising a step of immersing the ingot in hot water of 80 ° C. or higher and peeling the wafer or plate from the slice base in the hot water. Item 5. The cleaning method according to item 3 or 4 .