CN108779419B - Cleaning agent composition for electronic material, cleaning agent stock solution, and method for cleaning electronic material - Google Patents

Cleaning agent composition for electronic material, cleaning agent stock solution, and method for cleaning electronic material Download PDF

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Publication number
CN108779419B
CN108779419B CN201680070975.9A CN201680070975A CN108779419B CN 108779419 B CN108779419 B CN 108779419B CN 201680070975 A CN201680070975 A CN 201680070975A CN 108779419 B CN108779419 B CN 108779419B
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cleaning agent
water
tertiary amine
cleaning
agent composition
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CN108779419A (en
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井内洋介
田中俊
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Arakawa Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • C11D2111/22—

Abstract

The cleaning agent composition for electronic materials comprises a tertiary amine (A) which azeotropes with water and water (B), wherein the boiling point of the tertiary amine (A) is 130-250 ℃ at 1 atm, and the weight ratio (%) of the tertiary amine (A) to the total amount of the tertiary amine (A) and the water (B) in the cleaning agent composition is not more than the weight ratio of the tertiary amine (A) to an azeotropic mixture composed of the tertiary amine (A) and the water (B). The cleaning agent composition can remove particles attached to an electronic material even with a very small amount (low concentration), and can provide a cleaning agent composition for an electronic material, a cleaning agent stock solution, and a cleaning method including a cleaning step for an electronic material, in which residues of a cleaning agent are not left even if a rinsing step for washing away cleaning agent components is not performed.

Description

Cleaning agent composition for electronic material, cleaning agent stock solution, and method for cleaning electronic material
Technical Field
The present invention relates to a cleaning agent composition for electronic materials, a cleaning agent stock solution, and a method for cleaning electronic materials.
Background
In recent years, the electronic industry has been moving to an information, energy-saving and low-carbon society, and the miniaturization and high performance of electronic parts have been rapidly developed. In addition, in this background, the technique of polishing and planarization is greatly affected.
For example, in the field of semiconductors, in the photolithography process for manufacturing digital ICs such as CMOS and TTL, oxygen formed on a silicon wafer is used for the purpose of accurately and efficiently transferring fine circuit patternsSilicon (SiO)2) Silicon nitride (Si)3N4) And a phosphosilicate glass (PSG) or the like. In the field of processing magnetic disks such as Hard Disk Drives (HDDs) and the like, the surface of a magnetic disk is polished and planarized in order to control the distance between the surface of the magnetic disk and a magnetic head to a nanometer level and to achieve both recording density and reliability. In the field of processing optical devices such as semiconductor Lighting (LED) and power devices such as high power diode and transistor, sapphire (Al) is polished by a polishing step2O3) Concave-convex, deformed and polluted parts of the surface of the substrate such as silicon carbide (SiC), gallium nitride (GaN) and the like are removed, so that the product performance and the yield are improved.
The polishing method includes the following steps: using a Silica (SiO) dispersed in an aqueous solvent or the like2) Alumina (Al)2O3) Or cerium oxide (CeO)2) Chemical Mechanical Polishing (CMP) using a Polishing agent (slurry) formed of fine particles; and a method of mechanically polishing the surface of the substrate with a brush, pad, wheel, or the like, to which hard particles such as diamond are dispersed.
However, in either method, a large amount of abrasive grains, abrasive dust, and the like (hereinafter referred to as particles) adhere to the electronic material after polishing, and this causes a reduction in performance and yield. Therefore, a cleaning step for removing these is indispensable, and development of a cleaning agent composition which is functional and effective in removing particles is urgently required. As such a cleaning agent composition, for example, the following cleaning agent compositions have been disclosed.
The cleaning agent composition disclosed in patent document 1 contains a fluorine-based anionic surfactant and a quaternary ammonium hydroxide, and contains an alkanolamine as an optional component. According to the same document, it is shown that the cleaning agent composition is suitable for removing particles on the surface of a semiconductor wafer. However, this cleaning agent composition contains a nonvolatile surfactant and the like, and it is considered that a rinsing step for washing off these is necessary after the cleaning step.
The cleaning agent composition disclosed in patent document 2 contains an alkylamine, an aromatic diamine, a urea, a thiourea, an azo compound, a nitrogen-containing heterocyclic compound, and a specific amino acid. According to the same document, it is shown that the cleaning agent composition is suitable for removing copper oxide and particles on the surface of a semiconductor after copper wiring is performed. However, this cleaning agent composition contains a nonvolatile acid (e.g., glycine) and the like, and it is considered that a rinsing step for washing off these is necessary after the cleaning step.
The cleansing composition disclosed in patent document 3 contains glycine, an acrylic polymer, a specific nonionic compound, and water. According to the same document, it is shown that the cleaning agent composition is suitable for removing particles from a slurry for Chemical Mechanical Polishing (CMP). However, this cleaning agent composition contains a nonvolatile acid (e.g., glycine), a polymer, and the like, and it is considered that a rinsing step for washing them off is necessary after the cleaning step.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3624809
Patent document 2: japanese patent No. 4821082
Patent document 3: japanese laid-open patent publication No. 2008-147449
Disclosure of Invention
Problems to be solved by the invention
The present invention can provide a cleaning agent composition for electronic materials, a cleaning agent stock solution, and a cleaning method for electronic materials, which can remove particles adhering to a cleaning object even with a very small amount (low concentration) and can prevent residues of a cleaning agent from remaining even without a rinsing step for washing away cleaning agent components.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, they have found that the above problems can be solved by using a tertiary amine (a) and water (B) which are azeotropic with water at a specific ratio, and have completed the present invention. Namely, the present invention is the following items 1 to 9.
Item 1 is a cleaning agent composition for electronic materials, which contains a tertiary amine (a) that azeotropes with water and water (B), characterized in that the boiling point of the tertiary amine (a) is 130 to 250 ℃ under 1 atm, and the weight ratio (%) of the tertiary amine (a) to the total amount of the tertiary amine (a) and the water (B) in the cleaning agent composition is not more than the weight ratio of the tertiary amine (a) to an azeotropic mixture composed of the tertiary amine (a) and the water (B).
Item 2. the cleaning agent composition for electronic materials according to the item 1, further comprising a glycol solvent (C) represented by the general formula (1) that azeotropes with water, wherein the general formula (1): r1-O-[CH2-CH(X)-O]n-H, (in the general formula (1), R1The cleaning agent composition is characterized by representing an alkyl group with 1-4 carbon atoms, n represents 1-3, X represents hydrogen or methyl), the boiling point of the dihydric alcohol solvent (C) is 120-275 ℃ under 1 atmospheric pressure, the weight ratio (%) of the dihydric alcohol solvent (C) in the total amount of the dihydric alcohol solvent (C) and the water (B) in the cleaning agent composition is less than or equal to the weight ratio of the dihydric alcohol solvent (C) in an azeotropic mixture formed by the dihydric alcohol solvent (C) and the water (B).
Item 3. the detergent composition for electronic materials according to item 1 or 2, wherein the tertiary amine (A) is one or more of a monoamine (A1) represented by the general formula (2) and a polyamine (A2) represented by the general formula (3), and is represented by the general formula (2): (R)2)R3N-CH2-CH (Y) -OH, (in the general formula (2), R2And R3Respectively represent the same or different alkyl groups with 1-3 carbon atoms, and Y represents hydrogen or methyl); general formula (3): (R)4)R5N-C2H4-Z-C2H4-NR6(R7) (in the general formula (3), R4、R5、R6And R7Respectively represent the same or different alkyl groups with 1-3 carbon atoms, and Z represents-CH2-、-(CH2)2-, -O-, -NH-or-N (CH)3)-)。
Item 4. the detergent composition for electronic materials according to any one of items 1 to 3, wherein a weight ratio (a/(a + B)) of the tertiary amine (a) to the total of the tertiary amine (a) and the water (B) is 1/100000 or more.
Item 5 the detergent composition for electronic materials according to any one of items 2 to 4, wherein a weight ratio ((a + C)/(a + B + C)) of a total amount of the tertiary amine (a) and the glycol-based solvent (C) to a total amount of the tertiary amine (a), the water (B), and the glycol-based solvent (C) is 1/100000 or more.
Item 6. a detergent stock solution containing the tertiary amine (a) and the water (B) for use in the preparation of the detergent composition for electronic materials described in any one of items 1 to 5 above.
Item 7 is a method for cleaning an electronic material, which comprises a step of cleaning an electronic material using the cleaning agent composition for an electronic material according to any one of items 1 to 5.
Item 8. the method for cleaning an electronic material according to item 7, wherein the method does not include a rinsing step.
Item 9. the method for cleaning an electronic material according to item 7 or 8 above, wherein the method comprises a particle removal step of the electronic material.
Effects of the invention
According to the present invention, it is possible to provide a cleaning agent composition for an electronic material, a cleaning agent stock solution, and a cleaning method for an electronic material, which can remove particles adhering to an electronic material even with a very small amount (low concentration) and can prevent residues of a cleaning agent from remaining even without a rinsing step for washing off cleaning agent components.
The cleaning agent composition of the present invention contains a tertiary amine (a) which azeotropes with water and water (B), and the weight ratio (%) of the tertiary amine (a) to the total amount of the tertiary amine (a) and the water (B) in the cleaning agent composition is not more than the weight ratio of the tertiary amine (a) to an azeotropic mixture composed of the tertiary amine (a) and the water (B), so that even if drying is performed for a short time of several minutes to several tens of minutes at, for example, about 50 ℃ to 150 ℃, the cleaning agent composition can have an effect of not leaving residues of the cleaning agent, and therefore, the cleaning agent composition is excellent in safety and productivity.
In addition, when the cleaning agent composition of the present invention further contains a glycol solvent (C) represented by the general formula (1) that azeotropes with water, the general formula (1): r1-O-[CH2-CH(X)-O]n-H, (in the general formula (1), R1Represents an alkyl group having 1 to 4 carbon atoms, n represents 1 to 3, and X represents hydrogen or methyl), and the weight ratio (%) of the glycol solvent (C) to the total amount of the glycol solvent (C) and the water (B) in the cleaning agent composition is not more than the weight ratio of the glycol solvent (C) to an azeotropic mixture composed of the glycol solvent (C) and the water (B), so that even if drying is performed for a short time of several minutes to several tens of minutes at a temperature of about 50 ℃ to 150 ℃, for example, the effect of not leaving residues of the cleaning agent can be obtained, and therefore, the cleaning agent composition is excellent in safety and productivity.
Drawings
FIG. 1 is an explanatory view showing an example of a method for removing particles from a cleaning agent composition.
Detailed Description
The cleaning agent composition of the present invention contains a tertiary amine (A) (hereinafter also referred to as component (A)) and water (B) (hereinafter also referred to as component (B)) which are azeotropic with water, the boiling point of the tertiary amine is 130 to 250 ℃ under 1 atm (normal pressure, normal atmospheric pressure), the weight ratio (%) of the tertiary amine (A) in the total of the tertiary amine (A) and the water (B) is not more than the weight ratio of the tertiary amine (A) in an azeotropic mixture composed of the tertiary amine (A) and the water (B) (the mixing ratio of the tertiary amine is not more than the composition ratio of the azeotropic mixture with water). If the boiling point of the tertiary amine (A) is less than 130 ℃ under 1 atm, the stock solution of the detergent composition may catch fire, and handling such as transportation and storage may be difficult. On the other hand, if the boiling point of the tertiary amine (a) exceeds 250 ℃ under 1 atm, an azeotropic mixture with water is difficult to form, and the drying property is deteriorated. Therefore, from the viewpoint of flammability and drying property, it is preferably about 140 to 240 ℃, and more preferably about 150 to 230 ℃.
In the cleaning agent composition of the present invention, the weight ratio (%) of the tertiary amine (a) to the total amount of the tertiary amine (a) and the water (B) is not more than the weight ratio (%) of the tertiary amine (a) to an azeotropic mixture composed of the tertiary amine (a) and the water (B). The azeotropic mixture composed of the tertiary amine (a) and water (B) means a composition in which the mixture composed of the tertiary amine (a) and water (B) forms an azeotropic mixture (constant boiling point mixture). The weight ratio of (a) in the azeotropic mixture when the mixture of the tertiary amine (a) and water (B) forms an azeotropic mixture is determined as follows: fractions having a boiling point of 100 ℃ or lower obtained by subjecting the mixed solution to multistage distillation were analyzed by gas chromatography, and the weight ratio was determined quantitatively by an absolute calibration curve method.
The component (a) is not particularly limited as long as it is a tertiary amine that azeotropes with water and has a boiling point of about 130 to 250 ℃ under 1 atmosphere, and various known components can be used. Specifically, from the viewpoint of particle removability and drying property, a monoamine (a1) represented by the following general formula (2) (hereinafter also referred to as (a1) component) and a polyamine (a2) represented by the following general formula (3) (hereinafter also referred to as (a2) component) are particularly preferable. (A) Component (a) may contain either one of component (a1) and component (a2), or both of them.
General formula (2): (R)2)R3N-CH2-CH(Y)-OH
(in the general formula (2), R2And R3Each represents the same or different alkyl group having 1 to 3 carbon atoms, and Y represents hydrogen or methyl. )
General formula (3): (R)4)R5N-C2H4-Z-C2H4-NR6(R7)
(in the general formula (3), R4、R5、R6And R7Respectively represent the same or different alkyl groups with 1-3 carbon atoms, and Z represents-CH2-、-(CH2)2-, -O-, -NH-or-N (CH)3)-。)
In the general formula (2), with respect to R2And R3The alkyl group of (2) is preferably 2 to 3 carbon atoms, more preferably 2 carbon atoms. Further, Y is preferably hydrogen.
In the general formula (3), with respect to R4、R5、R6And R7The alkyl group of (2) is preferably 1 to 2 carbon atoms, more preferably 1. Furthermore, Z is preferably-CH2-、-(CH2)2-or-O-, more preferably-CH2-or- (CH)2)2-。
Examples of the component (A1) include 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, 2- (diisopropylamino) ethanol, 2- (di-n-propylamino) ethanol, 1-dimethylamino-2-propanol, 1-diethylamino-2-propanol, 1-diisopropylamino-2-propanol, and 1-di-n-propylamino-2-propanol. These components may be used singly or in combination of two or more. Among them, at least one selected from the group consisting of 2- (diethylamino) ethanol, 2- (diisopropylamino) ethanol and 1-diethylamino-2-propanol is preferable, particularly from the viewpoint of low particle removal ability and ignition risk.
Examples of the component (A2) include N, N, N ', N ' -tetramethylpentanediamine, N, N, N ', N ' -tetraethylpentanediamine, N, N, N ', N ' -tetraisopropylpentanediamine, N, N, N ', N ' -tetra-N-propylpentanediamine, N, N, N ', N ' -tetramethylhexanediamine, N, N, N ', N ' -tetraethylhexanediamine, N, N, N ', N ' -tetraisopropylhexanediamine, N, N, N ', N ' -tetra-N-propylhexanediamine, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, bis (2-diisopropylaminoethyl) ether, bis (2-di-N-propylaminoethyl) ether, 1,7,7, -tetramethyldiethylenetriamine, N, N ', N ' -tetramethylethylenediamine, N, N, N ', N ' -tetramethylethylenediamine, N ' -tetramethylhexanediamine, N, N ', N ' -, 1,1,7, 7-tetraethyldiethylenetriamine, 1,7, 7-tetraisopropyldiethylenetriamine, 1,7, 7-tetra-N-propyldiethylenetriamine, N, N, N' -pentamethyldiethylenetriamine, 4-methyl-1, 1,7, 7-tetraethyldiethylenetriamine, 4-methyl-1, 1,7, 7-tetraisopropyldiethylenetriamine and 4-methyl-1, 1,7, 7-tetra-N-propyldiethylenetriamine, and the like. These components may be used singly or in combination of two or more. Among them, at least one selected from the group consisting of N, N '-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, and N, N', N ", N ″ -pentamethyldiethylenetriamine is preferable from the viewpoint of particle removal ability and low ignition risk.
Examples of the component (B) include ultrapure water, pure water, purified water, distilled water, ion-exchanged water, and tap water.
In the cleaning agent composition of the present invention, from the viewpoint of particle removability, the weight ratio (a/(a + B)) of the tertiary amine (a) to the total of the components (a) and (B) is preferably 1/100000 or more. More preferably 1/80000 or more, still more preferably 1/20000 or more, and still more preferably 1/5000 or more.
From the viewpoint of particle removability, the cleaning agent composition of the present invention preferably contains a glycol-based solvent (C) represented by the general formula (1) (hereinafter also referred to as component (C)) azeotropic with water, the general formula (1): r1-O-[CH2-CH(X)-O]n-H, (in the general formula (1), R1The cleaning agent composition is characterized by representing an alkyl group with 1-4 carbon atoms, n represents 1-3, X represents hydrogen or methyl), the boiling point of the dihydric alcohol solvent (C) is 120-275 ℃ under 1 atmospheric pressure, the weight ratio (%) of the dihydric alcohol solvent (C) in the total amount of the dihydric alcohol solvent (C) and the water (B) in the cleaning agent composition is less than or equal to the weight ratio of the dihydric alcohol solvent (C) in an azeotropic mixture formed by the dihydric alcohol solvent (C) and the water (B).
The azeotropic mixture composed of the glycol solvent (C) and water (B) is a composition in which the mixture composed of (C) and (B) forms an azeotropic mixture (constant boiling point mixture). The weight ratio of (C) in the azeotropic mixture when the mixture of the glycol solvent (C) and water (B) forms an azeotropic mixture is determined as follows: fractions having a boiling point of 100 ℃ or lower obtained by subjecting the mixed solution to multistage distillation were analyzed by gas chromatography, and the weight ratio was determined quantitatively by an absolute calibration curve method.
In the general formula (1), with respect to R1The alkyl group of (2) preferably has 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms. Furthermore, X is preferably methyl. In addition, n is preferably 2 to 3, and more preferably 3.
Examples of the component (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-sec-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-sec-butyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, diethylene glycol mono-sec-butyl ether, diethylene glycol mono-tert-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-, Dipropylene glycol mono-sec-butyl ether, dipropylene glycol mono-tert-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol monoisopropyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol monoisobutyl ether, triethylene glycol sec-butyl ether, triethylene glycol mono-tert-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol mono-n-butyl ether, tripropylene glycol mono-isobutyl ether, tripropylene glycol mono-sec-butyl ether, tripropylene glycol mono-tert-butyl ether, and the like. These components may be used singly or in combination of two or more. Among them, at least one selected from the group consisting of diethylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether is preferable, particularly from the viewpoint of low particle removal ability and low ignition risk.
The boiling point of the component (C) is about 120 to 275 ℃, preferably about 130 to 260 ℃, and more preferably about 140 to 250 ℃ under 1 atmosphere, from the viewpoint of improving the drying property and suppressing the ignition of the cleaning agent stock solution.
In addition, when the component (C) is added, the cleaning agent composition of the present invention is preferably such that the weight ratio of the component (a) to the component (C) to the total of the component (a), the component (B), and the component (C) ((a + C)/(a + B + C)) is 1/100000 or more from the viewpoint of particle removability. More preferably 1/80000 or more, still more preferably 1/20000 or more, and still more preferably 1/5000 or more.
The total proportion of the component (a) and the component (B) or the total proportion of the component (a), the component (B) and the component (C) in the detergent composition of the present invention is preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, still more preferably 98% by weight or more, and most preferably 100% by weight.
The cleaning agent composition of the present invention is prepared by mixing the component (A) and the component (B) and, if necessary, the component (C) by various known means.
The cleaning agent composition of the present invention is used as a cleaning agent for electronic materials. The electronic material includes: glass processed products such as photomasks, optical lenses, vacuum discharge tubes, touch panels, and glass for display devices; metal processing products such as metal masks, trays, lead frames, magnetic disks, heat sinks, and the like; epoxy glass substrates, polyimide substrates, phenolic paper substrates, plastic mold parts and other resin processing products; silicon (Si) and sapphire (Al)2O3) Wafers such as silicon carbide (SiC), diamond (C), gallium nitride (GaN), gallium phosphide (GaP), gallium arsenide (GaAs), indium phosphide (InP), and the like, and processed products thereof subjected to cutting (slicing, cutting, etc.), grinding (back grinding, sand blasting, etc.), chamfering (chamfer, roller, etc.), grinding (grinding, polishing, buffing, etc.); and jigs, carriers, boxes, and the like used for processing, mounting, welding, cleaning, and transporting these articles.
Examples of the electronic material include electronic components such as printed circuit boards, flexible wiring boards, ceramic wiring boards, semiconductor elements, semiconductor packages, magnetic media, power modules, and camera modules; and jigs, carriers, boxes, and the like used for processing, mounting, welding, cleaning, and transporting these articles.
Various known additives may be mixed in the detergent composition of the present invention within a range not affecting the drying property. Specifically, examples of the additive include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a polymeric surfactant, a chelating agent, an antioxidant, an antirust agent, a pore-sealing agent, a pH adjuster, and an antifoaming agent.
A detergent stock solution which can be diluted with water to prepare the above detergent composition for electronic materials is also one aspect of the present invention. The cleaning agent stock solution of the present invention concentrates the effective components for cleaning particles, and thus can be efficiently transported and stored. Further, since the stock solution of the cleaning agent has excellent cleaning performance even in a small amount, the weight ratio of water can be increased when diluted with water at the time of use, and the stock solution of the cleaning agent is excellent from the viewpoint of reducing the cost and the environmental load.
A cleaning method comprising a cleaning step of an electronic material using the cleaning agent composition of the present invention is also one aspect of the present invention. The cleaning step is a step of bringing the cleaning agent composition of the present invention into contact with the electronic material to which the particles are attached, and washing away the particles. The cleaning method may not include a rinsing step for washing away the cleaning agent component from the electronic material by various known detergents. This can reduce the cost and time required for the rinsing step. The particles to be cleaned are not particularly limited, but typical particles include, for example, silicon dioxide (SiO) used in Chemical Mechanical Polishing (CMP) and mechanical polishing2) Alumina (Al)2O3) Cerium oxide (CeO)2) And the like; cutting powder, chips, and abrasive dust generated when cutting (slicing, cutting, etc.), grinding (back grinding, sand blasting, etc.), chamfering (chamfering), rolling, etc.), and grinding (buffing, polishing, buffing, etc.) hard particles such as diamond, garnet, stainless steel, iron, copper, zinc, aluminum, ceramics, glass, silica sand, plastic, etc., and the electronic material are processed; and organic matter residues and inorganic matter residues generated when the electronic materials and electronic parts are processed, mounted, welded, cleaned, and transported.
Examples of the other particles include dust and dirt adhering to an article in the entire production process of the electronic material and the electronic component.
The method of contacting the cleaning agent composition of the present invention with an article to which particles are attached and cleaning the article is not limited, and examples of the cleaning method include immersion cleaning, spray cleaning, ultrasonic cleaning, liquid jet cleaning, direct cleaning (directpa (registered trademark)), and the like. Further, examples of known cleaning apparatuses include Japanese patent laid-open Nos. 7-328565, 2000-189912, 2001-932, and 2005-144441. In addition, the cleaner compositions and cleaner stock solutions of the present invention are not flammable because they are not hazardous materials. Thus, since explosion-proof equipment is not required, it is also suitable for spray cleaning and spray cleaning.
Since the cleaning agent composition of the present invention can be easily volatilized in the drying step, the residue does not remain on the cleaned article. Thus, the rinsing process for the article can be omitted. However, rinsing with the same cleaning agent as in the present invention or various known detergents may be carried out as necessary. Examples of the detergent include water such as pure water and ion-exchanged water; alcohols such as methanol, ethanol and isopropanol.
Examples
The method of the present invention will be described in more detail below by referring to examples and comparative examples, but the present invention is not limited thereto. Further, in the examples, parts or% are on a weight basis. The structures of the various tertiary amines (a) and the glycol solvents (C) used in the cleaning agent stock solutions below, the boiling points at 1 atm, and the composition ratios (weight ratios) of azeotropic mixtures with water are shown in tables 2 and 3.
[ composition ratio of azeotropic mixture ]
In a 200ml round bottom flask, 25 parts by weight of component (a) and 100 parts by weight of ion-exchanged water were placed and sufficiently mixed by a magnetic stirrer to prepare an aqueous solution containing component (a). Then, a distillation column having a theoretical plate number N of 10, a distillation head, a thermometer, and a liebig condenser were connected to the eggplant-shaped flask. Thereafter, the eggplant-shaped flask was heated by an oil bath under 1 atmosphere, and the mixed solution was boiled, whereby only a fraction having a boiling point of 100 ℃ or lower was collected.
Then, the component (a) in the fraction was quantified by an absolute calibration curve method in a gas chromatograph 6850Network GC System (Agilent Technologies). Further, the component (C) was also quantified by the same method as that of the component (A).
1. Preparation of stock solution of cleaning agent
Preparation example 1
100 parts by weight of ion-exchanged water, 20 parts by weight of 2- (diethylamino) ethanol (DEAE) as the component (A), 80 parts by weight of dipropylene glycol monomethyl ether (DPGMME) as the component (C), and a stirrer were placed in a beaker and sufficiently stirred with a magnetic stirrer, thereby preparing a stock solution of a cleaning agent.
Preparation example 2
100 parts by weight of ion-exchanged water, 20 parts by weight of DEAE as the component (A), 80 parts by weight of tripropylene glycol monomethyl ether (TPGMME) as the component (C) and a stirrer were placed in a beaker and sufficiently stirred with a magnetic stirrer to prepare a stock solution of a cleaning agent.
Preparation example 3
100 parts by weight of ion-exchanged water, 20 parts by weight of N, N' -Tetramethylhexamethylenediamine (TMHMDA) as the component (a), 80 parts by weight of TPGMME as the component (C), and a stirrer were placed in a beaker and sufficiently stirred with a magnetic stirrer to prepare a stock solution of a cleaning agent.
Preparation example 4
100 parts by weight of ion exchange water, 20 parts by weight of TMHMDA as the component (A), 80 parts by weight of diethylene glycol mono-n-butyl ether (DEGMBE) as the component (C) and a stirrer were placed in a beaker and sufficiently stirred with a magnetic stirrer, thereby preparing a stock solution of a cleaning agent.
Preparation example 5
100 parts by weight of ion-exchanged water, 20 parts by weight of bis (2-dimethylaminoethyl) ether (BDMAEE) as the component (A), 80 parts by weight of DEGMBE as the component (C) and a stirrer were placed in a beaker and sufficiently stirred by a magnetic stirrer, thereby preparing a stock solution of a cleaning agent.
Preparation example 6
100 parts by weight of ion-exchanged water, 100 parts by weight of DEAE as the component (A) and a stirrer were placed in a beaker, and sufficiently stirred with a magnetic stirrer to prepare a stock solution of a cleaning agent.
Preparation example 7
100 parts by weight of ion-exchanged water, 100 parts by weight of TMHMDA as the component (a), and a stirrer were placed in a beaker, and sufficiently stirred with a magnetic stirrer, thereby preparing a stock solution of a cleaning agent.
Preparation example 8
100 parts by weight of ion-exchanged water, 100 parts by weight of BDMAEE as the component (A) and a stirrer were placed in a beaker and sufficiently stirred with a magnetic stirrer to prepare a stock solution of a cleaning agent.
Comparative preparation example 1
100 parts by weight of ion exchange water, 20 parts by weight of N-Butyldiethanolamine (BDEA) as the component (a), 80 parts by weight of tetraethyleneglycol monomethyl ether (teggmme) as the component (C), and a stirring bar were put into a beaker and sufficiently stirred with a magnetic stirrer, thereby preparing a stock solution of a cleaning agent.
Comparative preparation example 2
100 parts by weight of ion-exchanged water, 100 parts by weight of BDEA as the component (A) and a stirrer were placed in a beaker and sufficiently stirred with a magnetic stirrer, thereby preparing a stock solution of a cleaning agent.
Comparative preparation example 3
100 parts by weight of ion-exchanged water, 100 parts by weight of 2- (2-aminoethylamino) ethanol (AEAE) as the component (A), and a stirring bar were placed in a beaker, and sufficiently stirred with a magnetic stirrer to prepare a stock solution of a cleaning agent.
Comparative preparation example 4
100 parts by weight of ion-exchanged water, 100 parts by weight of polyoxyethylene alkyl ether (POEAE) as the component (C), and a stirrer were placed in a beaker, and sufficiently stirred with a magnetic stirrer, thereby preparing a stock solution of a cleaning agent.
Comparative preparation example 5
100 parts by weight of ion-exchanged water, 100 parts by weight of Diethylamine (DEA) as the component (A), and a stirrer were placed in a beaker and sufficiently stirred with a magnetic stirrer, to prepare a stock solution of a cleaning agent.
Comparative preparation example 6
Ion-exchanged water itself was used as a stock solution of the cleaning agent.
2. Flammability of detergent stock solution
[ method for evaluating flammability ]
The flash point of each detergent stock solution was measured according to the Cleveland open cup method (JIS K2265-4), and the flammability was evaluated according to the following criteria. The results are shown in Table 1.
[ evaluation criteria for flammability ]
O: no flash point, or flash point of more than 100 DEG C
X: flash point less than 100 DEG C
[ Table 1]
Stock solution of detergent (unit: wt%) Flammability of
Preparation example 1 DEAE (10)/DPGMME (40)/water (50) ○
Preparation example 2 DEAE (10)/TPGMME (40)/water (50) ○
Preparation example 3 TMHMDA (10)/TPGMME (40)/Water (50) ○
Preparation example 4 TMHMDA (10)/DEGMBE (40)/water (50) ○
Preparation example 5 BDMAEE (10)/DEGMBE (40)/water (50) ○
Preparation example 6 DEAE (50)/water (50) ○
Preparation example 7 TMHMDA (50)/Water (50) ○
Preparation example 8 BDMAEE (50)/Water (50) ○
Comparative preparation example 1 BDEA (10)/TEGMME (40)/water (50) ○
Comparative preparation example 2 BDEA (50)/water (50) ○
Comparative preparation example 3 AEAE (50)/water (50) ○
Comparative preparation example 4 POEAE (50)/Water (50) ○
Comparative preparation example 5 DEA (50)/Water (50) ×
[ Table 2]
Figure GDA0001683754910000111
[ Table 3]
Figure GDA0001683754910000121
3. Particulate removal of cleaner compositions
[ preparation of contaminated liquid ]
9.9g of acetone (having a purity of 99.5% or more, manufactured by Wako pure chemical industries, Ltd.) and 0.1g of a crystalline silica filler (having an average particle diameter of 5 μm, manufactured by Lonson K.K.) were put into a threaded tube (having a capacity of 20mL) (A) and sufficiently shaken to prepare 10g of a contaminated liquid (A) having a concentration of 1%. Then, in another threaded tube (A '), 1g of the contaminated liquid (A) and 9g of acetone were placed and sufficiently shaken to prepare 10g of the contaminated liquid (A') having a concentration of 0.1%.
Similarly, 9.9g of acetone and 0.1g of spherical silica (trade name "Sciqas", made by Sakai chemical industry Co., Ltd., average particle diameter: 1 μm) were put into the threaded pipe (B) and sufficiently shaken to prepare 10g of a contaminated liquid (B) having a concentration of 1%. Then, in another threaded tube (B '), 1g of the contaminated liquid (B) and 9g of acetone were placed and sufficiently shaken to prepare 10g of the contaminated liquid (B') having a concentration of 0.1%.
Similarly, 9.9g of acetone and 0.1g of alumina particles (trade name "α -alumina for precision polishing", manufactured by Wako pure chemical industries, Ltd., average particle diameter of 0.5 μm) were put into the threaded pipe (C) and sufficiently shaken to prepare 10g of a contaminated liquid (C) having a concentration of 1%. Then, in another threaded tube (C '), 1g of the contaminated liquid (C) and 9g of acetone were put and sufficiently shaken to prepare 10g of the contaminated liquid (C') having a concentration of 0.1%.
[ production of test wafer ]
Then, 0.02g of the contaminated liquid (A) was dropped onto the center of a high purity silicon wafer (manufactured by AS ONE, Inc., having a diameter of 4 inches), and the wafer was naturally dried to prepare a test wafer (A). In the same manner, the contaminated liquids (B), (C) and (A ') to (C') were dropped onto a high-purity silicon wafer and naturally dried to prepare test wafers (B), (C) and (A ') to (C'), respectively.
[ method for evaluating particle removability ]
Example 1
As shown in FIG. 1, 40.0g of the stock solution of the cleaning agent (2) of production example 1, 960.0g of ion-exchanged water (3) and a stirrer (4) were placed in a beaker (1) (having a capacity of 1000mL, a bottle diameter. phi. of 110mm and a height of 150mm) and sufficiently stirred by a magnetic stirrer (5), thereby producing a cleaning agent composition having a mixing ratio of the components (A), (B) and (C) [ (A + C)/(A + B + C) ] of 1/50. Then, the rotation speed of the magnetic stirrer was adjusted to 800rpm, and the wafers (a) (6) for test were put into the solution, and were cleaned at room temperature for 10 minutes while being fixed with a stainless clip (7) and a stainless bar (8). Thereafter, the test wafer (a) was taken out of the solution and dried in a circulation dryer with a temperature set to 80 ℃ for 10 minutes. In addition, the test wafers (B), (C), and (a ') to (C') were washed and dried in the same procedure.
Next, five contaminated portions of the test wafer (a) after completion of the cleaning and drying were randomly observed using an optical microscope (1000 × magnification), and the total number of remaining particles was determined. On the other hand, the total number of particles adhering to the wafer surface immediately after being contaminated with the above-mentioned contaminated liquid (a) was also determined in advance by the same method as described above, and the particle removal rate was calculated by the following equation. This evaluation was performed five times for each example, and the average value of the particle removal rate was determined, and the particle removal performance was evaluated according to the following evaluation criteria. The results are shown in Table 4 (the same applies hereinafter).
Particle removal rate (%) (total number of particles immediately after contamination-total number of particles remaining after cleaning)/total number of particles immediately after contamination × 100
[ evaluation criteria for particle removal ]
Very good: the particle removal rate is more than or equal to 90 percent
O: the particle removal rate is more than or equal to 70 percent and less than 90 percent
And (delta): the particle removal rate is more than or equal to 50 percent and less than 70 percent
X: the particle removal rate is less than 50 percent
In addition, the test wafers (B), (C), and (a ') to (C') after completion of the washing and drying were evaluated for particle removability in the same procedure.
Example 2
As shown in FIG. 1, 20.0g of the stock solution of the cleaning agent (2) of production example 1, 980.0g of ion-exchanged water (3), and a stirrer (4) were placed in a beaker (1) (having a capacity of 1000mL, a bottle diameter. phi. of 110mm, and a height of 150mm) and sufficiently stirred by a magnetic stirrer (5) to prepare a cleaning agent composition in which the mixing ratio of the component (A), the component (B), and the component (C) [ (A + C)/(A + B + C) ] was 1/100. Then, the rotation speed of the magnetic stirrer was adjusted to 800rpm, and the wafers (a) (6) for test were put into the solution, and were cleaned at room temperature for 10 minutes while being fixed with a stainless clip (7) and a stainless bar (8). Thereafter, the test wafer (a) was taken out of the solution and dried in a circulation dryer with a temperature set to 80 ℃ for 10 minutes. In addition, the test wafers (B), (C), and (a ') to (C') were washed and dried in the same procedure.
The test wafers (a) to (C) and (a ') to (C') after completion of the washing and drying were evaluated for particle removal on the basis of the same evaluation criteria as in example 1.
Example 3
As shown in FIG. 1, a detergent composition having a mixing ratio of the above-mentioned component (A), component (B) and component (C) [ (A + C)/(A + B + C) ] of 1/2000 was prepared by charging 1.0g of the detergent stock solution (2) of preparation example 1, 999.0g of ion-exchanged water (3) and a stirrer (4) into a beaker (1) (having a capacity of 1000mL, a bottle diameter. phi. of 110mm and a height of 150mm) and sufficiently stirring the mixture with a magnetic stirrer (5). Then, the rotation speed of the magnetic stirrer was adjusted to 800rpm, and the wafers (a) (6) for test were put into the solution, and were cleaned at room temperature for 10 minutes while being fixed with a stainless clip (7) and a stainless bar (8). Thereafter, the test wafer (a) was taken out of the solution and dried in a circulation dryer with a temperature set to 80 ℃ for 10 minutes. In addition, the test wafers (B), (C), and (a ') to (C') were washed and dried in the same procedure.
The test wafers (a) to (C) and (a ') to (C') after completion of the washing and drying were evaluated for particle removal on the basis of the same evaluation criteria as in example 1.
Example 4
As shown in FIG. 1, a detergent composition having a mixing ratio of the above-mentioned component (A), component (B) and component (C) [ (A + C)/(A + B + C) ] of 1/10000 was prepared by charging 0.2g of the detergent stock solution (2) of preparation example 1, 999.8g of ion-exchanged water (3) and a stirrer (4) into a beaker (1) (having a capacity of 1000mL, a bottle diameter. phi. of 110mm and a height of 150mm) and sufficiently stirring the mixture with a magnetic stirrer (5). Then, the rotation speed of the magnetic stirrer was adjusted to 800rpm, and the wafers (a) (6) for test were put into the solution, and were cleaned at room temperature for 10 minutes while being fixed with a stainless clip (7) and a stainless bar (8). Thereafter, the test wafer (a) was taken out of the solution and dried in a circulation dryer with a temperature set to 80 ℃ for 10 minutes. In addition, the test wafers (B), (C), and (a ') to (C') were washed and dried in the same procedure.
The test wafers (a) to (C) and (a ') to (C') after completion of the washing and drying were evaluated for particle removal on the basis of the same evaluation criteria as in example 1.
Examples 5 to 18 and comparative examples 1 to 8
As shown in table 4, each of the detergent stock solutions was diluted so that the mixing ratio [ (a + C)/(a + B + C) ] was 1/2000 or 1/10000 in the same manner as in example 1, and the particle removability of each of the detergent compositions was evaluated.
Comparative example 9
Since the flash point of the cleaning agent stock solution of comparative preparation example 5 was less than 100 ℃, it was not evaluated.
Comparative example 10
As shown in FIG. 1, 1000g of ion-exchanged water (3) and a stirrer (4) were placed in a beaker (1) (capacity 1000mL, bottle diameter. phi. 110mm, height 150mm), and the rotation speed of the magnetic stirrer was adjusted to 800 rpm. Next, the test wafers (a) and (6) were put in the solution, fixed by a stainless clip (7) and a stainless bar (8), and washed at room temperature for 10 minutes. Thereafter, the test wafer (a) was taken out of the solution and dried in a circulation dryer with a temperature set to 80 ℃ for 10 minutes. In addition, the test wafers (a ') to (C') were washed and dried in the same manner.
The test wafers (a) to (C) and (a ') to (C') after completion of the washing and drying were evaluated for particle removal on the basis of the same evaluation criteria as in example 1.
4. Drying Property of detergent composition
[ evaluation method of drying Property ]
Example 1
A threaded pipe (capacity: 100mL) was charged with 4.0g of the stock solution of the cleaning agent of preparation example 1 and 96.0g of ion-exchanged water, and sufficiently shaken to prepare a cleaning agent composition having a mixing ratio of the component (A), the component (B) and the component (C) [ (A + C)/(A + B + C) ] of 1/50. Next, 0.05g of the cleaning agent composition was dropped onto the center of a high purity silicon wafer (manufactured by AS ONE, Inc., having a diameter. phi. of 4 inches), and the wafer was allowed to stand in a circulation dryer with a temperature adjusted to 80 ℃ for 20 minutes. The dried wafer surface was visually observed, and the drying property of the cleaning agent composition was evaluated according to the following evaluation criteria.
[ evaluation criteria for drying Properties ]
O: residue of detergent-free composition
X: residue with detergent composition
Example 2
A threaded pipe (capacity: 100mL) was charged with 2.0g of the stock solution of the cleaning agent of preparation example 1 and 98.0g of ion-exchanged water, and sufficiently shaken to prepare a cleaning agent composition having a mixing ratio of the component (A), the component (B) and the component (C) [ (A + C)/(A + B + C) ] of 1/100. The drying property of the cleaning agent composition was evaluated by the same procedure as in example 1.
Example 3
A threaded pipe (capacity: 100mL) was charged with 0.1g of the stock solution of the cleaning agent of preparation example 1 and 99.9g of ion-exchanged water, and sufficiently shaken to prepare a cleaning agent composition having a mixing ratio of the component (A), the component (B) and the component (C) [ (A + C)/(A + B + C) ] of 1/2000. The drying property of the cleaning agent composition was evaluated by the same procedure as in example 1.
Example 4
A threaded pipe (capacity: 100mL) was charged with 0.02g of the stock solution of the cleanser in preparation example 1 and 99.98g of ion-exchanged water, and sufficiently shaken to prepare a cleanser composition having a mixing ratio of the component (A), the component (B) and the component (C) [ (A + C)/(A + B + C) ] of 1/10000. The drying property of the cleaning agent composition was evaluated by the same procedure as in example 1.
Examples 5 to 18 and comparative examples 1 to 8
As shown in table 4, each stock solution of the cleaning agent was diluted so that the mixing ratio [ (a + C)/(a + B + C) ] was 1/2000 or 1/10000 in the same manner as in example 1, and the drying property of each cleaning agent composition was evaluated.
Comparative example 10
The drying property was evaluated by the same procedure as in example 1 using ion-exchanged water.
[ Table 4]
Figure GDA0001683754910000161
Figure GDA0001683754910000171
Description of reference numerals
1 beaker
2 stock solution of cleaning agent
3 ion exchange water
4 stirrer
5 magnetic stirrer
6 test wafer
7 stainless steel clip
8 stainless steel bar

Claims (7)

1. A cleaning agent composition for electronic materials, characterized in that,
the cleaning agent composition contains tertiary amine A and water B which are azeotroped with water,
the boiling point of the tertiary amine A is 130-250 ℃ under 1 atmospheric pressure,
the weight ratio of the tertiary amine A to the total amount of the tertiary amine A and the water B in the cleaning agent composition is not more than the weight ratio of the tertiary amine A to an azeotropic mixture composed of the tertiary amine A and the water B, and the weight ratio is expressed by percent,
the tertiary amine A is a polyamine A2 represented by the general formula (3):
general formula (3): (R)4)R5N-C2H4-Z-C2H4-NR6(R7) In the general formula (3), R4、R5、R6And R7Respectively represent the same or different alkyl groups with 1-3 carbon atoms, and Z represents-CH2-、-(CH2)2-, -O-, -NH-or-N (CH)3)-，
The polyamine A2 is at least one selected from the group consisting of N, N, N ', N ' -tetramethylhexamethylenediamine, N, N, N ', N ' -tetraethylhexamethylenediamine, 1,7,7, -tetramethyldiethylenetriamine, 1,7,7, -tetraethyldiethylenetriamine and N, N, N ', N ", N" -pentamethyldiethylenetriamine,
the cleaning agent composition further contains a glycol solvent C represented by the general formula (1) which azeotropes with water,
general formula (1): r1-O-[CH2-CH(X)-O]n-H, in formula (1), R1Represents an alkyl group having 1 to 4 carbon atoms, n represents 1 to 3, X represents hydrogen or methyl,
the boiling point of the dihydric alcohol solvent C is 120-275 ℃ under 1 atmospheric pressure,
the weight ratio of the glycol solvent C in the total amount of the glycol solvent C and the water B in the cleaning agent composition is not more than the weight ratio of the glycol solvent C in an azeotropic mixture composed of the glycol solvent C and the water B, and the weight ratio is expressed by%.
2. The cleaning agent composition for electronic materials according to claim 1,
the weight ratio of the tertiary amine A to the total of the tertiary amine A and the water B, namely A/(A + B), is 1/100000 or more.
3. The cleaning agent composition for electronic materials according to claim 1,
the weight ratio of the total amount of the tertiary amine A and the glycol solvent C to the total amount of the tertiary amine A, the water B and the glycol solvent C, that is, (A + C)/(A + B + C), is 1/100000 or more.
4. A detergent stock solution containing the tertiary amine A and the water B for producing the detergent composition for electronic materials described in any one of claims 1 to 3.
5. A method for cleaning electronic material is characterized in that,
the method comprises a step of cleaning an electronic material using the cleaning agent composition for an electronic material according to any one of claims 1 to 3.
6. The method for cleaning electronic material according to claim 5,
the method does not include a rinsing process.
7. The method for cleaning electronic material according to claim 5 or 6,
the method includes a particle removal process for the electronic material.
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