JPWO2017110885A1 - Cleaning composition for electronic material, cleaning agent stock solution, and cleaning method for electronic material - Google Patents

Abstract

The cleaning composition for electronic materials of the present invention is a cleaning composition containing a tertiary amine (A) and water (B) exhibiting azeotropic properties with water, and has a boiling point of the tertiary amine (A). However, the weight ratio (%) of the tertiary amine (A) in the total of the tertiary amine (A) and the water (B) in the cleaning composition is 130 to 250 ° C under 1 atm. It is below the weight ratio of the tertiary amine (A) in the azeotropic mixture consisting of the tertiary amine (A) and water (B). The cleaning composition can remove particles adhering to the electronic material even in the use of a very small amount (low concentration), and even if there is no rinsing step for washing out the cleaning component, the residue of the cleaning agent It is possible to provide a cleaning method for an electronic material that does not remain, a stock solution thereof, and a cleaning method including a cleaning process for the electronic material.

Description

  The present invention relates to a cleaning composition for electronic materials, a cleaning agent stock solution, and a cleaning method for electronic materials.

  In recent years, in the electronics industry, miniaturization and high performance of electronic components are rapidly progressing with the transition to information society, energy saving, and low carbon society. And in the background, polishing and flattening techniques are greatly involved.

For example, in the field of semiconductors, silicon oxide (SiO ₂ ) formed on a silicon wafer for the purpose of transferring a fine circuit pattern accurately and with high efficiency in a lithography process when manufacturing a digital IC such as CMOS or TTL. Insulating thin films such as silicon nitride (Si ₃ N ₄ ) and phosphide silicate glass (PSG) are polished and planarized. In the field of handling hard disks (Hard Disk Drives, HDDs) and other magnetic disks, the distance between the disk surface and the magnetic head is controlled in the nano order, and the disk surface is polished and flattened to achieve both recording density and reliability. Has been made. Further, in the field of handling optical devices such as semiconductor lighting (LED) and power devices such as high power diodes and transistors, polishing processes include sapphire (Al ₂ O ₃ ), silicon carbide (SiC), gallium nitride (GaN). ) And other irregularities, alterations, and contaminated parts on the substrate surface are removed to improve product performance and yield.

As the polishing method, chemical mechanical polishing (chemical mechanical) using an abrasive (slurry) in which fine particles such as silica (SiO ₂ ), alumina (Al ₂ O ₃ ), or ceria (CeO ₂ ) are dispersed in an aqueous solvent or the like is used. Polishing, CMP) and mechanical polishing with a brush, pad, wheel or the like in which hard particles such as diamond are dispersed.

  However, in any of the methods, a large amount of abrasive grains and polishing debris (hereinafter referred to as particles) adhere to the electronic material after polishing, leading to a decrease in performance and yield. Therefore, a cleaning process for removing them is indispensable, and there is an urgent need to develop a cleaning composition that functionally and efficiently removes particles. As such a cleaning composition, for example, the following cleaning composition is disclosed.

  The cleaning composition described in Patent Document 1 contains a fluorinated anionic surfactant and a quaternary ammonium hydroxide, and contains an alkanolamine as an optional component. According to this document, this cleaning composition is shown to be suitable for removing particles on the surface of a semiconductor wafer. However, this detergent composition contains a non-volatile surfactant and the like, and it is considered that a rinsing step for washing them off is essential after the washing step.

  The cleaning composition described in Patent Document 2 contains alkylamines, aromatic diamines, ureas, thioureas, azo compounds, nitrogen-containing heterocyclic compounds, and specific amino acids. According to this document, this cleaning composition is shown to be suitable for removing copper oxide and particles on the surface of a semiconductor to which copper wiring is applied. However, this cleaning composition contains a non-volatile acid (for example, glycine) and the like, and it is considered that a rinsing step for washing them off is essential after the cleaning step.

  The cleaning composition described in Patent Document 3 contains glycine, an acrylic acid polymer, a specific nonionic compound, and water. According to this document, this cleaning composition is shown to be suitable for removing particles derived from a slurry for chemical mechanical polishing (CMP). However, this cleaning composition contains a non-volatile acid (for example, glycine), a polymer, and the like, and it is considered that a rinsing step for washing them off after the cleaning step is essential.

Japanese Patent No. 3624809 Japanese Patent No. 4821082 JP 2008-147449 A

  The present invention can remove particles adhering to an object to be cleaned even when used in a very small amount (low concentration), and even if there is no rinsing step for washing away the cleaning agent component, a residue of the cleaning agent remains. It is to provide a cleaning composition for electronic materials, a stock solution thereof, and a cleaning method for electronic materials.

  The inventors of the present invention have intensively studied to solve the above problems, and can solve the above problems by using tertiary amines (A) and water (B) that exhibit azeotropic properties with water at a specific ratio. The present invention has been completed by finding out what can be done. That is, this invention is the following items 1-9.

  Item 1. A cleaning composition comprising a tertiary amine (A) and water (B) exhibiting azeotropic properties with water, wherein the tertiary amine (A) has a boiling point of 130 to 250 ° C. under 1 atm. The weight ratio (%) of the tertiary amine (A) in the total of the tertiary amine (A) and the water (B) in the cleaning composition is composed of the tertiary amine (A) and water (B). A cleaning composition for electronic materials, wherein the composition is not more than the weight ratio of the tertiary amine (A) in the azeotropic mixture.

Item 2. Moreover, the general formula shown water and azeotropic _^(1): in R 1 -O- [CH 2 -CH ( X) -O] n -H ( Formula (1), ^{R 1} is from 1 to 4 carbon atoms An alkyl group, n represents 1 to 3, and X represents hydrogen or a methyl group.), And the boiling point of the glycol solvent (C) is 1 atm. 120 to 275 ° C., and the weight ratio (%) of the glycol solvent (C) in the total of the glycol solvent (C) and the water (B) in the cleaning composition is a glycol solvent (C ) And water (B) in the azeotrope, the weight ratio of the glycol solvent (C) is not more than the weight ratio of the cleaning composition for electronic materials as described in the preceding item 1.

Item 3. The tertiary amine (A) is represented by the general formula (2): (R ² ) R ³ N—CH ₂ —CH (Y) —OH (in the formula (2), R ² and R ³ are the same or different carbons, respectively. And a monoamine (A1) represented by formula (3) :( R ⁴ ) R ⁵ N—C ₂ H ₄ —Z. —C ₂ H ₄ —NR ⁶ (R ⁷ ) (wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different alkyl groups having 1 to 3 carbon atoms, and Z represents —CH ₂ -,-(CH ₂ ) _2- , -O-, -NH-, or -N (CH ₃ )-)), or any one or more of polyamines (A2) represented by The cleaning composition for electronic materials according to the preceding item 1 or 2.

  Item 4. Any of the preceding items 1 to 3, wherein a weight ratio (A / (A + B)) of the tertiary amine (A) in the total of the tertiary amine (A) and the water (B) is 1/100000 or more. The cleaning composition for electronic materials as described.

  Item 5. The total weight ratio of the tertiary amine (A) and the glycol solvent (C) in the total of the tertiary amine (A), the water (B) and the glycol solvent (C) ((A + C) / (A + B + C)) is 1 / 100,000 or more, The cleaning composition for electronic materials in any one of the preceding clauses 2-4.

  Item 6. A detergent stock solution comprising the tertiary amine (A) and the water (B) for preparing the detergent composition for electronic materials according to any one of items 1 to 5.

  Item 7. 6. A method for cleaning an electronic material, comprising a step of cleaning the electronic material using the electronic material cleaning composition according to any one of 1 to 5 above.

  Item 8. 8. The method for cleaning an electronic material according to item 7, wherein the rinsing step is not included.

  Item 9. 9. The method for cleaning an electronic material as described in 7 or 8 above, further comprising a step of removing particles of the electronic material.

  According to the present invention, even when a very small amount (low concentration) is used, particles adhering to the electronic material can be removed, and even if there is no rinsing step for washing away the detergent component, the residue of the detergent is removed. It is possible to provide a cleaning composition for an electronic material that does not remain, a stock solution thereof, and a cleaning method for the electronic material.

  The cleaning composition of the present invention comprises a tertiary amine (A) and water (B) exhibiting azeotropic properties with water, and the tertiary amine (A) and the water (B) in the cleaning composition. Since the weight ratio (%) of the tertiary amine (A) in the total is not more than the weight ratio of the tertiary amine (A) in the azeotrope composed of the tertiary amine (A) and water (B), for example, In the case of drying in a short time of several minutes to several tens of minutes under conditions of about 50 ° C. to 150 ° C., there is an effect that the residue of the cleaning agent does not remain, so that safety and productivity are excellent.

Further, the cleaning composition of the present invention further has a general formula (1) exhibiting an azeotropic property with water: R ¹ —O— [CH ₂ —CH (X) —O] _n —H (formula (1)) Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, n represents 1 to 3, and X represents hydrogen or a methyl group. An azeotrope in which the weight ratio (%) of the glycol solvent (C) in the total of the glycol solvent (C) and the water (B) in the agent composition is composed of the glycol solvent (C) and water (B). Since it is less than the weight ratio of the glycol solvent (C) in the mixture, for example, no residue of the cleaning agent remains even when drying in a short time of several minutes to several tens of minutes under conditions of about 50 ° C to 150 ° C. As a result, it has excellent safety and productivity.

It is explanatory drawing by an example which showed the particle removal method of the cleaning composition.

  The cleaning composition of the present invention comprises tertiary amine (A) (hereinafter also referred to as component (A)) and water (B) (hereinafter also referred to as component (B)) exhibiting azeotropic properties with water. And the boiling point of the tertiary amine is 130 to 250 ° C. under 1 atmosphere (under normal pressure and standard atmospheric pressure), and the tertiary amine (A) in the total of the tertiary amine (A) and the water (B) ) Is less than or equal to the weight proportion of the tertiary amine (A) in the azeotropic mixture composed of the tertiary amine (A) and water (B) (the proportion of the tertiary amine is azeotropic with water). Less than the composition ratio of the mixture). When the boiling point of the tertiary amine (A) is less than 130 ° C. under 1 atm, there is a risk of ignition in the stock solution of the cleaning composition, and handling such as transportation and storage becomes difficult. On the other hand, when the boiling point of the tertiary amine (A) exceeds 250 ° C. under 1 atm, it is difficult to form an azeotrope with water and the drying property is deteriorated. Therefore, it is preferably about 140 to 240 ° C, more preferably about 150 to 230 ° C in terms of flammability and drying properties.

  In the cleaning composition of the present invention, the weight ratio (%) of the tertiary amine (A) in the total of the tertiary amine (A) and the water (B) is such that the tertiary amine (A) and water (B Or less than the weight proportion of the tertiary amine (A) in the azeotropic mixture. 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). . When the mixture of the tertiary amine (A) and water (B) forms an azeotrope, the weight ratio of (A) in the azeotrope is obtained by, for example, multistage distillation of the mixture solution. The fraction having a boiling point of 100 ° C. or less is determined by analyzing by gas chromatography and quantifying according to the absolute calibration curve method.

  As the component (A), various known amines can be used without particular limitation as long as they are tertiary amines having an azeotropic property with water and having a boiling point of about 130 to 250 ° C. under 1 atm. Specifically, from the viewpoint of particle removal power and drying properties, the monoamine (A1) (hereinafter also referred to as the (A1) component) represented by the following general formula (2) and the following general formula (3): Polyamine (A2) represented (hereinafter also referred to as component (A2)) is particularly preferable. The component (A) may be either one of the component (A1) or the component (A2), or may include both components.

Formula _{^{(2) :( R 2) R}} 3 N-CH 2 -CH (Y) -OH
(In Formula (2), R ² and R ³ each represent the same or different alkyl group having 1 to 3 carbon atoms, and Y represents hydrogen or a methyl group.)

Formula (3): (R ⁴ ) R ⁵ N—C ₂ H ₄ —Z—C ₂ H ₄ —NR ⁶ (R ⁷ )
(In Formula (3), R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different alkyl groups having 1 to 3 carbon atoms, and Z is —CH ₂ —, — (CH ₂ ) ₂ —, -O -, - NH-, or -N (CH ₃₎ - indicates a).

In the general formula (2), the alkyl group represented by R ² and R ³ preferably has 2 to 3 carbon atoms, and more preferably 2 carbon atoms. Y is preferably hydrogen.

In the general formula (3), the alkyl group of R ⁴ , R ⁵ , R ⁶ , and R ⁷ preferably has 1 to 2 carbon atoms, and more preferably 1. Z is preferably —CH ₂ —, — (CH ₂ ) ₂ —, or —O—, and more preferably —CH ₂ — 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- Examples include 2-propanol, 1-diethylamino-2-propanol, 1-diisopropylamino-2-propanol, and 1-di-n-propylamino-2-propanol. These can be used individually by 1 type or in combination of 2 or more types. Among these, especially from the point of the removal power of particles and the low risk of ignition, it is selected from the group consisting of 2- (diethylamino) ethanol, 2- (diisopropylamino) ethanol and 1-diethylamino-2-propanol. At least one selected from the above is preferred.

  Examples of the component (A2) include N, N, N ′, N′-tetramethylpentamethylenediamine, N, N, N ′, N′-tetraethylpentamethylenediamine, N, N, N ′, N ′. -Tetraisopropylpentamethylenediamine, N, N, N ', N'-tetra-n-propylpentamethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N, N ', N '-Tetraethylhexamethylenediamine, N, N, N', N'-tetraisopropylhexamethylenediamine, N, N, N ', N'-tetra-n-propylhexamethylenediamine, bis (2-dimethylaminoethyl) Ether, bis (2-diethylaminoethyl) ether, bis (2-diisopropylaminoethyl) ether, bis (2-di-n-propylene) Aminoethyl) ether, 1,1,7,7-tetramethyldiethylenetriamine, 1,1,7,7-tetraethyldiethylenetriamine, 1,1,7,7-tetraisopropyldiethylenetriamine, 1,1,7,7-tetra- n-propyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 4-methyl-1,1,7,7-tetraethyldiethylenetriamine, 4-methyl-1,1,7,7 -Tetraisopropyldiethylenetriamine, 4-methyl-1,1,7,7-tetra-n-propyldiethylenetriamine and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, N, N, N ′, N′-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, and N are particularly preferred from the viewpoint of particle removal ability and low risk of ignition. , N, N ′, N ″, N ″ -Pentamethyldiethylenetriamine is preferably at least one selected from the group consisting of

  Examples of the component (B) include ultrapure water, pure water, purified water, distilled water, ion exchange water, and tap water.

  In the cleaning composition of the present invention, the weight ratio (A / (A + B)) of the tertiary amine (A) in the total of the components (A) and (B) is 1/100000 or more. It is preferable in terms of particle removability. More preferably, it is 1/80000 or more, More preferably, it is 1/20000 or more, More preferably, it is 1/5000 or more.

The cleaning composition of the present invention has a general formula (1) that exhibits azeotropicity with water in terms of particle removability: R ¹ —O— [CH ₂ —CH (X) —O] _n —H (formula In (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, n represents 1 to 3, and X represents hydrogen or a methyl group). The glycol solvent (C) has a boiling point of 120 to 275 ° C. under 1 atm, and the glycol solvent (C) and the water (in the cleaning composition) The weight ratio (%) of the glycol solvent (C) in the total of B) is not more than the weight ratio of the glycol solvent (C) in the azeotropic mixture composed of the glycol solvent (C) and water (B). Is preferred.

  The azeotrope composed of the glycol solvent (C) and water (B) means a composition in which the mixture composed of (C) and (B) forms an azeotrope (constant boiling point mixture). When the mixture of the glycol solvent (C) and water (B) forms an azeotrope, the weight ratio of (C) in the azeotrope is obtained, for example, by subjecting the mixture solution to multistage distillation. The fraction having a boiling point of 100 ° C. or less is determined by analyzing by gas chromatography and quantifying according to the absolute calibration curve method.

In the general formula (1), the alkyl group for ^{R 1} is preferably 1 to 3 carbon atoms, 1 to 2 is more preferred. X is preferably a methyl group. Further, 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 monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl 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 monoisopropyl ether, propylene glycol mono-n-butyl ether, Propylene glycol monoisobutyl ether, propylene glycol No-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 monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl 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-propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-n-butyl Ether, dipropylene glycol monoisobutyl ether, 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 mono-sec-butyl ether, triethylene glycol mono-tert-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol Monoethyl ether, tripropylene glycol mono-n- Examples include propyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol mono-n-butyl ether, tripropylene glycol monoisobutyl ether, tripropylene glycol mono-sec-butyl ether, and tripropylene glycol mono-tert-butyl ether. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of diethylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether, in terms of particle removal power and low risk of ignition. Is preferred.

  In addition, the component (C) has a boiling point of about 120 to 275 ° C., preferably about 130 to 260 ° C., more preferably about 1 to 1 atm in terms of good drying properties and suppression of ignition of the detergent stock solution. It is about 140-250 degreeC.

  In addition, when adding (C) component, the cleaning composition of this invention is the weight ratio of (A) component and (C) component in the sum total of the said (A) component, (B) component, and (C) component. ((A + C) / (A + B + C)) is preferably 1/100000 or more from the viewpoint of particle removability. More preferably, it is 1/80000 or more, More preferably, it is 1/20000 or more, More preferably, it is 1/5000 or more.

  The total proportion of the component (A) and the component (B) in the cleaning composition of the present invention, or the total proportion of the component (A), the component (B) and the component (C) is preferably 80% by weight or more, 90% by weight or more is more preferable, 95% by weight or more is further preferable, 98% by weight or more is further more preferable, and 100% by weight is further more preferable.

  The cleaning 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 composition of the present invention is used as a cleaning agent for electronic materials. Examples of electronic materials include glass processed products such as photomasks, optical lenses, vacuum discharge tubes, touch panels, glass for display devices, metal processed products such as metal masks, pallets, lead frames, magnetic disks, heat sinks, and glass epoxy substrates. Resin processed products such as polyimide substrate, paper phenol substrate, plastic mold parts, silicon (Si), sapphire (Al ₂ O ₃ ), silicon carbide (SiC), diamond (C), gallium nitride (GaN), gallium phosphide (GaP), gallium arsenide (GaAs), indium phosphide (InP), and the like, and cutting (slicing, dicing, etc.), grinding (back grinding, blasting, etc.), chamfering (beveling, barrel, etc.), polishing ( Wrapping, polishing, buffing, etc.) These items include jigs, carriers, magazines, and the like used when processing, mounting, welding, cleaning, and transporting these articles.

  Electronic materials include printed circuit boards, flexible wiring boards, ceramic wiring boards, semiconductor elements, semiconductor packages, magnetic media, power modules, camera modules, and other electronic parts, as well as processing, mounting, and welding of these articles. , Jigs, carriers, magazines and the like used for cleaning and transporting.

  The cleaning composition of the present invention may contain various known additives as long as it does not affect the drying property. Specific examples of additives include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants, chelating agents, antioxidants, and rust inhibitors. , Sealing agents, pH adjusters and antifoaming agents.

  A cleaning agent stock solution capable of preparing the cleaning composition for electronic materials by diluting with water is also one aspect of the present invention. In the cleaning agent stock solution of the present invention, components effective for cleaning particles are concentrated, and efficient transportation and storage are possible. In addition, since this detergent stock solution exhibits excellent detergency even in a small amount, when diluted with water at the time of use, the weight ratio of water can be increased, and this is also excellent in terms of reducing cost and environmental burden.

A cleaning method including a cleaning step of an electronic material using the cleaning composition of the present invention is also one aspect of the present invention. The cleaning step is a step in which the cleaning composition according to the present invention is brought into contact with the electronic material to which the particles adhere to wash off the particles. The cleaning method may not include a rinsing step for washing away the cleaning agent component from the electronic material with various known rinse agents. Thereby, the cost and time required for the rinsing process can be reduced. The particles to be cleaned are not particularly limited, but representative examples include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), ceria (used for chemical mechanical polishing (CMP) and mechanical polishing, for example. Cutting (slicing, dicing, etc.) and grinding of hard particles such as fine particles such as CeO ₂ ), diamond, garnet, stainless steel, steel, iron, copper, zinc, aluminum, ceramic, glass, silica sand, plastic, and the above electronic materials ( Back grinding, blasting, etc.), chamfering (beveling, barreling, etc.), polishing (lapping, polishing, buffing, etc.), cutting chips, debris, polishing debris, and the above electronic materials and electronic parts are processed. , Organic residue, inorganic residue and the like generated during mounting, welding, cleaning, and transportation.

  Examples of the other particles include dust, dust, and the like attached to articles in the entire manufacturing process of the electronic material and electronic component.

  The means for cleaning the article by bringing the cleaning composition of the present invention into contact with the article to which particles are attached is not limited. Examples of the cleaning means include immersion cleaning, shower cleaning, spray cleaning, ultrasonic cleaning, and submerged jet. Cleaning, direct cleaning (Direct Pass (registered trademark)) and the like can be mentioned. Moreover, as a well-known washing | cleaning apparatus, Unexamined-Japanese-Patent No. 7-328565, Unexamined-Japanese-Patent No. 2000-189912, Unexamined-Japanese-Patent No. 2001-932, Unexamined-Japanese-Patent No. 2005-144441 etc. are mentioned, for example. In addition, since the cleaning composition and the cleaning agent stock solution of the present invention are non-hazardous materials, they do not burn. Therefore, explosion-proof equipment is not necessary, and it is suitable for shower cleaning and spray cleaning.

  Since the cleaning composition of the present invention can be easily volatilized in the drying step, no residue remains in the cleaned article. Therefore, the article rinsing step can be omitted. However, if necessary, it can be rinsed with the same cleaning agent or various known rinsing agents as in the present invention. Examples of the rinse agent include water such as pure water and ion exchange water, and alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention method is demonstrated in more detail, it cannot be overemphasized that this invention is not limited to these. In the examples, parts or% is based on weight. Regarding the various tertiary amines (A) and glycol solvents (C) used in the following detergent stock solutions, the structure, boiling point under 1 atmosphere, composition ratio (weight ratio) of azeotrope with water Table 2 and Table 3 show.

[Composition ratio of azeotropic mixture]
A 200 ml eggplant-shaped flask was charged with 25 parts by weight of component (A) and 100 parts by weight of ion-exchanged water, and thoroughly mixed with a magnetic stirrer to prepare an aqueous solution containing component (A). Next, a distillation column, a T-tube, a thermometer, and a Liebig condenser corresponding to the theoretical plate number N = 10 were connected to the eggplant-shaped flask. Subsequently, the eggplant-shaped flask was heated with an oil bath under 1 atm to boil the mixed solution, whereby only a fraction having a boiling point of 100 ° C. or less was collected.

  Next, the component (A) in the fraction was quantified in a gas chromatography 6850 Network GC System (manufactured by Agilent Technologies) according to an absolute calibration curve method. The component (C) was also quantified by the same method in place of the component (A).

1. Preparation of detergent stock solution Preparation Example 1
In a beaker, 100 parts by weight of ion-exchange water, 20 parts by weight of 2- (diethylamino) ethanol (DEAE) as the component (A), 80 parts by weight of dipropylene glycol monomethyl ether (DPGMME) and the stirrer piece as the component (C) Then, the mixture was sufficiently stirred with a magnetic stirrer to prepare a detergent stock solution.

Preparation Example 2
In a beaker, 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) and a stirrer piece as the component (C) are sufficiently stirred with a magnetic stirrer. A stock detergent solution was prepared.

Preparation Example 3
100 parts by weight of ion-exchanged water in a beaker, 20 parts by weight of N, N, N ′, N ′,-tetramethylhexamethylenediamine (TMHMDA) as the component (A), 80 parts by weight of TPGMME and the stirrer piece as the component (C) And thoroughly stirred with a magnetic stirrer to prepare a stock solution of cleaning agent.

Preparation Example 4
In a beaker, 100 parts by weight of ion-exchanged water, 20 parts by weight of TMHMDA as the component (A), 80 parts by weight of diethylene glycol mono-n-butyl ether (DEGMBE) and a stirrer piece as the component (C) are sufficiently stirred with a magnetic stirrer. A detergent stock solution was prepared.

Preparation Example 5
In a beaker, 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 and the stirrer piece as the component (C) were added. The mixture was thoroughly stirred to prepare a detergent stock solution.

Preparation Example 6
In a beaker, 100 parts by weight of ion-exchanged water, 100 parts by weight of DEAE and the stirrer piece as the component (A) were placed, and sufficiently stirred with a magnetic stirrer to prepare a detergent stock solution.

Preparation Example 7
In a beaker, 100 parts by weight of ion-exchanged water, 100 parts by weight of TMHMDA and a stirrer piece as the component (A) were placed, and sufficiently stirred with a magnetic stirrer to prepare a detergent stock solution.

Preparation Example 8
A beaker was charged with 100 parts by weight of ion-exchanged water, 100 parts by weight of BDMAEE as the component (A) and a stirrer piece, and sufficiently stirred with a magnetic stirrer to prepare a detergent stock solution.

Comparative Preparation Example 1
In a beaker, 100 parts by weight of ion-exchanged water, 20 parts by weight of N-butyldiethanolamine (BDEA) as the component (A), 80 parts by weight of tetraethylene glycol monomethyl ether (TEGMME) and the stirrer piece as the component (C) were added. The mixture was sufficiently stirred with a tic stirrer to prepare a stock detergent solution.

Comparative Preparation Example 2
In a beaker, 100 parts by weight of ion-exchanged water, 100 parts by weight of BDEA and the stirrer piece as the component (A) were placed, and sufficiently stirred with a magnetic stirrer to prepare a detergent stock solution.

Comparative Preparation Example 3
Place 100 parts by weight of ion-exchanged water in a beaker, 100 parts by weight of 2- (2-aminoethylamino) ethanol (AEAE) as a component (A) and a stirrer piece, and stir well with a magnetic stirrer. Prepared.

Comparative Preparation Example 4
A beaker was charged with 100 parts by weight of ion-exchanged water, 100 parts by weight of polyoxyethylene alkyl ether (POEAE) as a component (C) and a stirrer piece, and sufficiently stirred with a magnetic stirrer to prepare a detergent stock solution.

Comparative Preparation Example 5
A beaker was charged with 100 parts by weight of ion-exchanged water, 100 parts by weight of diethylamine (DEA) as a component (A) and a stirrer piece, and sufficiently stirred with a magnetic stirrer to prepare a detergent stock solution.

Comparative Preparation Example 6
Ion exchange water itself was used as a detergent stock solution.

2. Flammability of cleaning agent stock solution [Flammability evaluation method]
The flash point of each detergent stock solution was measured according to the Cleveland Opening Method (JIS K2265-4), and the flammability was evaluated according to the following criteria. Table 1 shows the results.

[Flammability evaluation criteria]
○: No flash point or flash point is 100 ° C or higher ×: Flash point is lower than 100 ° C

3. Particle removal property of cleaning composition [Preparation of contaminated liquid]
9.9 g of acetone (made by Wako Pure Chemical Industries, Ltd., purity 99.5% or more) and crystalline silica filler (trade name “Crystallite VX-S2”, Co., Ltd.) 0.1 g (manufactured by Tatsumori, average particle size 5 μm) was added and shaken well to prepare 10 g of a contaminated liquid (A) having a concentration of 1%. Subsequently, 1 g of the contaminated liquid (A) and 9 g of acetone were put into another screw tube (A ′), and shaken well to prepare 10 g of a contaminated liquid (A ′) having a concentration of 0.1%.

  Similarly, 9.9 g of acetone and 0.1 g of spherical silica (trade name “Sciqas”, manufactured by Sakai Chemical Industry Co., Ltd., average particle size 1 μm) are placed in the screw tube (B), and shaken well, with a concentration of 1%. 10 g of the contaminated liquid (B) was prepared. Subsequently, 1 g of the contaminated liquid (B) and 9 g of acetone were put into another screw tube (B ′), and shaken well to prepare 10 g of a contaminated liquid (B ′) having a concentration of 0.1%.

  Similarly, 9.9 g of acetone and 0.1 g of alumina particles (trade name “α-alumina for precision polishing”, manufactured by Wako Pure Chemical Industries, Ltd., average particle size 0.5 μm) are put into the screw tube (C), The mixture was shaken well to prepare 10 g of a contaminated liquid (C) having a concentration of 1%. Subsequently, 1 g of the contaminated liquid (C) and 9 g of acetone were put into another screw tube (C ′), and shaken well to prepare 10 g of 0.1% of the contaminated liquid (C ′).

[Production of test wafers]
Next, 0.02 g of the contaminated liquid (A) was dropped on the center of a high-purity silicon wafer (manufactured by ASONE Co., Ltd., diameter φ4 inch) and allowed to dry naturally to prepare a test wafer (A). Similarly, the contaminated liquids (B), (C) and (A ′) to (C ′) are dropped on a high-purity silicon wafer and dried naturally, and the test wafers (B), (C) and ( A ′) to (C ′) were prepared.

[Evaluation method of particle removability]
Example 1
As shown in FIG. 1, 40.0 g (2) of the cleaning agent stock solution of Preparation Example 1, 960.0 g (3) of ion-exchanged water and a stirrer piece in a beaker (1) (capacity 1000 mL, trunk diameter φ110 mm, height 150 mm) (4) is added and sufficiently stirred with a magnetic stirrer (5), and the blending ratio [(A + C) / (A + B + C)] of the components (A), (B) and (C) is 1/50. A cleaning composition was prepared. Subsequently, the rotational speed of the magnetic stirrer was adjusted to 800 rpm, the test wafer (A) (6) was put in the solution, and fixed with the stainless steel clip (7) and the stainless steel rod (8) at room temperature. Washing was performed for 10 minutes. Thereafter, the test wafer (A) was taken out from the solution and dried for 10 minutes in a circulating drier set at a temperature of 80 ° C. The test wafers (B), (C) and (A ′) to (C ′) were also washed and dried in the same procedure.

  Next, using an optical microscope (1000 magnifications), five contaminated spots on the test wafer (A) that had been cleaned and dried were randomly observed to determine the total number of remaining particles. On the other hand, by the same method as this, the total number of particles adhering to the wafer surface immediately after being contaminated with the contamination liquid (A) was also obtained, and the particle removal rate was calculated by the following equation. This evaluation was performed five times for each example, the average value of the particle removal rate was determined, and the particle removability was evaluated based on the following evaluation criteria. Table 4 shows the results (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 removability]
A: Particle removal rate is 90% or more B: Particle removal rate is 70% or more and less than 90% Δ: Particle removal rate is 50% or more and less than 70% ×: Particle removal rate is less than 50%

  The test wafers (B), (C), and (A ′) to (C ′) that had been cleaned and dried were evaluated for particle removability in the same procedure.

Example 2
As shown in FIG. 1, 20.0 g (2) of the detergent stock solution of Preparation Example 1, 980.0 g (3) of ion-exchanged water and a stirrer piece in a beaker (1) (capacity 1000 mL, trunk diameter φ110 mm, height 150 mm) (4) is added and sufficiently stirred with a magnetic stirrer (5), and the blending ratio [(A + C) / (A + B + C)] of the components (A), (B) and (C) is 1/100. A cleaning composition was prepared. Subsequently, the rotational speed of the magnetic stirrer was adjusted to 800 rpm, the test wafer (A) (6) was put in the solution, and fixed with the stainless steel clip (7) and the stainless steel rod (8) at room temperature. Washing was performed for 10 minutes. Thereafter, the test wafer (A) was taken out from the solution and dried for 10 minutes in a circulating drier set at a temperature of 80 ° C. The test wafers (B), (C) and (A ′) to (C ′) were also washed and dried in the same procedure.

  The test wafers (A) to (C) and (A ′) to (C ′) that had been cleaned and dried were evaluated for particle removability based on the same evaluation criteria as in Example 1.

Example 3
As shown in FIG. 1, in a beaker (1) (capacity 1000 mL, trunk diameter φ110 mm, height 150 mm), 1.0 g (2) of the stock detergent solution of Preparation Example 1, 999.0 g (3) of ion-exchanged water, and a stirrer piece (4) was added, and the mixture was sufficiently stirred with a magnetic stirrer (5), and the blending ratio [(A + C) / (A + B + C)] of the above components (A), (B) and (C) was 1/2000. A cleaning composition was prepared. Subsequently, the rotational speed of the magnetic stirrer was adjusted to 800 rpm, the test wafer (A) (6) was put in the solution, and fixed with the stainless steel clip (7) and the stainless steel rod (8) at room temperature. Washing was performed for 10 minutes. Thereafter, the test wafer (A) was taken out from the solution and dried for 10 minutes in a circulating drier set at a temperature of 80 ° C. The test wafers (B), (C) and (A ′) to (C ′) were also washed and dried in the same procedure.

  The test wafers (A) to (C) and (A ′) to (C ′) that had been cleaned and dried were evaluated for particle removability based on the same evaluation criteria as in Example 1.

Example 4
As shown in FIG. 1, 0.2 g (2) of the detergent stock solution of Preparation Example 1, 999.8 g (3) of ion-exchanged water, and a stirrer piece in a beaker (1) (capacity 1000 mL, trunk diameter φ110 mm, height 150 mm) (4) is added and sufficiently stirred with a magnetic stirrer (5), and the blending ratio [(A + C) / (A + B + C)] of the components (A), (B) and (C) is 1/10000. A cleaning composition was prepared. Subsequently, the rotational speed of the magnetic stirrer was adjusted to 800 rpm, the test wafer (A) (6) was put in the solution, and fixed with the stainless steel clip (7) and the stainless steel rod (8) at room temperature. Washing was performed for 10 minutes. Thereafter, the test wafer (A) was taken out from the solution and dried for 10 minutes in a circulating drier set at a temperature of 80 ° C. The test wafers (B), (C) and (A ′) to (C ′) were also washed and dried in the same procedure.

  The test wafers (A) to (C) and (A ′) to (C ′) that had been cleaned and dried were evaluated for particle removability based on the same evaluation criteria as in Example 1.

Examples 5-18, Comparative Examples 1-8
In the same manner as in Example 1, as shown in Table 4, each detergent stock solution was diluted so that the blending ratio [(A + C) / (A + B + C)] was 1/2000 or 1/10000, The particle removability of the cleaning composition was evaluated.

Comparative Example 9
The detergent stock solution of Comparative Preparation Example 5 was not evaluated because its flash point was less than 100 ° C.

Comparative Example 10
As shown in FIG. 1, 1000 g (3) of ion-exchanged water and a stirrer piece (4) are placed in a beaker (1) (capacity 1000 mL, trunk diameter φ110 mm, height 150 mm), and the rotational speed of the magnetic stirrer is adjusted to 800 rpm. did. Subsequently, the test wafer (A) (6) was placed in the solution and washed for 10 minutes at room temperature while being fixed with the stainless steel clip (7) and the stainless steel rod (8). Thereafter, the test wafer (A) was taken out from the solution and dried for 10 minutes in a circulating drier set at a temperature of 80 ° C. The test wafers (A ′) to (C ′) were also washed and dried in the same procedure.

  The test wafers (A) to (C) and (A ′) to (C ′) that had been cleaned and dried were evaluated for particle removability based on the same evaluation criteria as in Example 1.

4). Dryability of cleaning composition [Dryability evaluation method]
Example 1
Add 4.0 g of the cleaning agent stock solution of Preparation Example 1 and 96.0 g of ion-exchanged water to a screw tube (capacity 100 mL), shake well, and blend ratio of the above components (A), (B) and (C) [ A cleaning composition in which (A + C) / (A + B + C)] was 1/50 was prepared. Next, 0.05 g of this cleaning composition was dropped at the center of a high-purity silicon wafer (manufactured by AS ONE, diameter φ4 inch) and allowed to stand for 20 minutes in a circulating drier adjusted to 80 ° C. . And the wafer surface after drying was visually observed, and the drying property of the cleaning composition was evaluated based on the following evaluation criteria.

[Evaluation criteria for drying properties]
○: No residue of detergent composition ×: There is residue of detergent composition

Example 2
Add 2.0 g of the detergent stock solution of Preparation Example 1 and 98.0 g of ion-exchanged water to a screw tube (capacity: 100 mL), shake well, and blend ratio of the above components (A), (B) and (C) [ A cleaning composition in which (A + C) / (A + B + C)] was 1/100 was prepared. Hereafter, the drying property of the cleaning composition was evaluated by the same procedure as in Example 1.

Example 3
Add 0.1 g of the detergent stock solution of Preparation Example 1 and 99.9 g of ion-exchanged water to a screw tube (capacity: 100 mL), shake well, and blend ratio of the above components (A), (B) and (C) [ A cleaning composition having (A + C) / (A + B + C)] of 1/2000 was prepared. Hereafter, the drying property of the cleaning composition was evaluated by the same procedure as in Example 1.

Example 4
Put 0.02 g of the detergent stock solution of Preparation Example 1 and 99.98 g of ion-exchanged water in a screw tube (capacity 100 mL), shake well, and blend ratio of the above components (A), (B) and (C) [ A cleaning composition in which (A + C) / (A + B + C)] was 1/10000 was prepared. Hereafter, the drying property of the cleaning composition was evaluated by the same procedure as in Example 1.

Examples 5-18, Comparative Examples 1-8
In the same manner as in Example 1, as shown in Table 4, each detergent stock solution was diluted so that the blending ratio [(A + C) / (A + B + C)] was 1/2000 or 1/10000, The drying property of the cleaning composition was evaluated.

Comparative Example 10
Dryness was evaluated by the same procedure as in Example 1 using ion-exchanged water.

DESCRIPTION OF SYMBOLS 1 Beaker 2 Detergent stock solution 3 Ion exchange water 4 Stirrer piece 5 Magnetic stirrer 6 Test wafer 7 Stainless clip 8 Stainless bar

［符号の説明］
［０１０１］
１ ビーカー[0024]
The drying property of the cleaning composition was evaluated.
[0098]
Examples 5-18, Comparative Examples 1-8
In the same manner as in Example 1, as shown in Table 4, each detergent stock solution was diluted so that the blending ratio [(A + C) / (A + B + C)] was 1/2000 or 1/10000, The drying property of the cleaning composition was evaluated.
[0099]
Comparative Example 10
Dryness was evaluated by the same procedure as in Example 1 using ion-exchanged water.
[0100]
[Table 4]

[Explanation of symbols]
[0101]
1 Beaker

Claims (9)

A detergent composition comprising a tertiary amine (A) and water (B) exhibiting azeotropic properties with water,
The boiling point of the tertiary amine (A) is 130 to 250 ° C. under 1 atm,
The weight ratio (%) of the tertiary amine (A) in the total of the tertiary amine (A) and the water (B) in the cleaning composition is composed of the tertiary amine (A) and water (B). A cleaning composition for electronic materials, wherein the composition is not more than the weight ratio of the tertiary amine (A) in the azeotropic mixture. Furthermore, general formula (1) showing azeotropic properties with water:
R ¹ —O— [CH ₂ —CH (X) —O] _n —H
(In Formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, n represents 1 to 3, and X represents hydrogen or a methyl group.) A glycol solvent (C) represented by Including
The glycol solvent (C) has a boiling point of 120 to 275 ° C. under 1 atm,
The weight ratio (%) of the glycol solvent (C) in the total of the glycol solvent (C) and the water (B) in the cleaning composition is composed of the glycol solvent (C) and water (B). The cleaning composition for an electronic material according to claim 1, wherein the composition is not more than the weight ratio of the glycol solvent (C) in the azeotropic mixture. The tertiary amine (A) is represented by the general formula (2):
_{^{(R 2) R 3 N-}} CH 2 -CH (Y) -OH
(In formula (2), R ² and R ³ each represent the same or different alkyl group having 1 to 3 carbon atoms, and Y represents hydrogen or a methyl group), and a general formula (3):
_{^{(R 4) R 5 N-}} C 2 H 4 -Z-C 2 H 4 -NR 6 (R 7)
(In the formula (3), R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different alkyl groups having 1 to 3 carbon atoms, and Z is —CH ₂ —, — (CH ₂ ) ₂ —, — It is any one or more of polyamines (A2) represented by O-, -NH-, or -N (CH ₃ )-). Cleaning composition.   The weight ratio (A / (A + B)) of the tertiary amine (A) in the total of the tertiary amine (A) and the water (B) is 1/100000 or more. The cleaning composition for electronic materials as described in above.   The total weight ratio of the tertiary amine (A) and the glycol solvent (C) in the total of the tertiary amine (A), the water (B) and the glycol solvent (C) ((A + C) / (A + B + C)) is 1/100000 or more, The cleaning composition for electronic materials in any one of Claims 2-4.   A detergent stock solution comprising the tertiary amine (A) and the water (B) for preparing the detergent composition for electronic materials according to any one of claims 1 to 5.   A cleaning method for an electronic material, comprising a cleaning step for the electronic material using the cleaning composition for an electronic material according to any one of claims 1 to 5.   8. The method for cleaning an electronic material according to claim 7, wherein a rinsing step is not included.   The method for cleaning an electronic material according to claim 7 or 8, further comprising a step of removing particles of the electronic material.

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