JP5155121B2 - Electronic material cleaner and cleaning method - Google Patents

Description

  The present invention relates to a cleaning agent for electronic materials and a cleaning method. More particularly, the present invention relates to a cleaning agent and a cleaning method suitable for a flat panel display, a photomask, a hard disk, or a semiconductor substrate.

  In electronic material cleaning technology, trace amounts of organic contaminants and glass cullet and abrasive impurities remaining on the substrate at the time of manufacturing greatly affect the performance and yield of electronic materials, so their management has become extremely important. Yes. In particular, the impurities to be cleaned are becoming finer (particles), and are more likely to adhere to the interface and remain than before, so the establishment of advanced cleaning technology is an urgent need. For this reason, in order to prevent the contamination by these particles, a method for improving particle removability using a surfactant has been proposed (see Patent Documents 1 to 4).

However, in the manufacturing process of glass or silicon substrate for flat panel displays, photomasks, hard disks and semiconductors, glass chips generated when cutting the glass substrate from mother glass to an appropriate size as required. (Commonly called glass cullet), organic matter stains such as dust and processing oil scattered in the clean room, abrasives and polishing debris used in the process of texturing the substrate surface adhere firmly to the substrate surface, There is a problem that it cannot be removed sufficiently in the cleaning process.
Particles represented by these glass cullet, organic contaminants, abrasives and polishing debris are firmly attached to the substrate surface, so in order to remove them sufficiently, the substrate or abrasive surface is slightly etched. However, it is necessary to disperse the particles in the liquid and to prevent the particles dispersed in the liquid from reattaching to the substrate surface. However, the cleaning agent proposed in Patent Document-1 is a cleaning agent containing alkyl glucoside, glyceryl ether and hydrocarbon, and can be expected to remove organic stains, but the glass cullet removal is insufficient. In addition, it can be expected to remove particles by etching by containing an alkali agent, but there is a problem that the substrate surface after cleaning becomes rough. Patent Document 2 contains a cleaning agent containing a specific nonionic surfactant, a specific glycol ether compound and a hydrocarbon, and a hydrocarbon, a specific glycol ether, an anionic surfactant and dimethyl sulfoxide. The former cleaning agent uses a nonionic surfactant to improve the particle removal performance, and the surfactant component tends to remain on the surface of the electronic material. In addition, there is a problem that the yield rate is lowered, and the latter detergent contains a sulfosuccinic acid type anionic surfactant having an average carbon number of 10 to 20 for the purpose of improving permeability, Although there is an improvement in particle removability, there is a problem in handling properties because the foamability is very high and the foamability is poor. Further, the cleaning agent proposed in Patent Document 3 is a cleaning agent in which hydrogen fluoride and ozone are dissolved, and the effect of removing particles firmly attached to the substrate surface by etching can be expected, but it contains fluorine ions. For this reason, there is a problem that wastewater treatment is very expensive and strong etching properties cannot be controlled, so that the flatness of the substrate is impaired during cleaning. Further, the cleaning agent proposed in Patent Document 4 uses an anionic surfactant, and although the effect of preventing the reattachment of particles can be improved to some extent, there is almost no etching property, so that the particle removability is insufficient. There is a problem that the cleanability is not sufficient.
JP 2007-39627 A JP 2004-26991 A JP 2001-276759 A Japanese Patent Laid-Open No. 2002-212597

  An object of the present invention is to provide a cleaning agent and a cleaning method for an electronic material that realizes excellent particle removability without impairing the flatness of the glass or silicon substrate surface, and has low foaming properties and excellent stability over time. There is to do.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention comprises an anionic surfactant (A) represented by the general formula (1), an alkene (B) having 6 to 18 carbon atoms, and an alkali component (C) . A cleaning agent for electronic materials, wherein the pH at 25 ° C. at an active ingredient concentration of 0.1 to 15% is 10 to 14, and a cleaning method for electronic materials using the cleaning agent.
^{R 1 [- (OA 1)} a -Q -] b (1)
[Wherein, R ¹ is a hydrocarbon group having 4 to 10 carbon atoms, A ¹ is an alkylene group having 2 to 4 carbon atoms, Q ⁻ is —COO ⁻ , —OCH ₂ COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ^- or _{^{-OPO 2 (oR 2) -,}} R 2 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, a is 0 to 20 and an average value, b is an integer of 1 to 6, Q ^- is -COO ^- or -SO ₃ ^- in the case a of zero. ]
Furthermore, it is a cleaning agent for electronic materials of Claim 1 which has an SP value of 6-13 and contains the organic solvent (D) shown by General formula (2).
R ³ [— (OA ² ) _c —OH] _d (2)
[Wherein R ³ is a hydrocarbon group having 6 to 8 carbon atoms, A ² is an alkylene group having 2 to 4 carbon atoms, c is an average value of 0 to 20, and d is an integer of 1 to 6. ]

  The cleaning agent for electronic materials of the present invention has an appropriately controlled etching property without impairing the flatness of the substrate surface in the glass or silicon substrate manufacturing process for flat panel displays, photomasks, hard disks and semiconductors. By applying, the fine particles that adhere firmly are desorbed from the substrate surface, and the desorbed particles are stably dispersed in the cleaning agent, realizing excellent particle removability and low foaming. It is highly efficient and stable over time, improving the yield rate during production and enabling highly efficient advanced cleaning that enables cleaning in a short time.

  The anionic surfactant (A) in the present invention comprises an anionic component and a cationic component, and the anionic component is represented by the general formula (1).

R ¹ in the general formula (1) is a hydrocarbon group having 4 -10 atoms, as R ^1, for example, linear aliphatic hydrocarbon group having 4 -10 carbons, branched number 4 -10 carbon An aliphatic hydrocarbon group and an aromatic hydrocarbon group having 6 to 10 carbon atoms.
Examples of the linear aliphatic hydrocarbon group having 4 to 10 carbon atoms include n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl. Examples thereof include a group and a residue obtained by removing a hydroxyl group from alkylene glycol having 2 to 10 carbon atoms, glycerin, sorbitol and the like.
Examples of the branched aliphatic hydrocarbon group having 4 to 10 carbon atoms include an iso or tert-butyl group, an iso or neopentyl group, an isohexyl group, an isoheptyl group, an isooctyl group, an iso or sec-nonyl group, an iso or sec-decyl group. , 1-ethyloctyl group and a hydrocarbon group represented by the general formula (3).

［式中、Ｒ⁴及びＲ⁵はそれぞれ独立に炭素数１〜６のアルキル基であり、かつＲ⁴とＲ⁵の炭素数の合計は３〜８、ｅは０〜２の整数であり、Ｒ⁴とＲ⁵の炭素数の合計が８の場合ｅは０又は１である。］

[Wherein, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of R ⁴ and R ⁵ is 3 to 8, e is an integer of 0 to 2; When the total number of carbon atoms of R ⁴ and R ⁵ is 8, e is 0 or 1. ]

Specific examples of R ⁴ and R ⁵ in the general formula (3) include, for example, methyl group, ethyl group, n- or isopropyl group, iso or n-butyl group, sec-, iso- or tert-butyl group, n- Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methyl Pentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethyl Butyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1-dimethyl-2-methylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl Examples thereof include a til-1-methylpropyl group and a 1-ethyl-2-methylpropyl group.

［式中、ｆ個のＲ⁶はそれぞれ独立に水素原子又は炭素数１〜４のアルキル基で、かつｆ個のＲ⁶の炭素数の合計は４以下であり、ｆは１〜４の整数である。］
一般式（４）におけるＲ⁶としては、前記一般式（３）におけるＲ⁴及びＲ⁵として例示したアルキル基の内の炭素数１〜４のものが挙げられる。 Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a hydrocarbon group represented by the general formula (4).

[Wherein, f R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the total number of carbon atoms of f R ⁶ is 4 or less, and f is an integer of 1 to 4] It is. ]
Examples of R ⁶ in the general formula (4) include those having 1 to 4 carbon atoms among the alkyl groups exemplified as R ⁴ and R ⁵ in the general formula (3).

Of these R ¹ , hydrocarbon groups represented by the general formula (3) or (4) are preferable from the viewpoint of particle removability and low foaming property.

A ¹ in the general formula (1) is an alkylene group having 2 to 4 carbon atoms, and as A ¹ , ethylene group, 1,2- or 1,3-propylene group and 1,2-, 1,3-, 2,3- or 1,4-butylene group may be mentioned. Of these, ethylene group and 1,2-propylene group are preferable from the viewpoint of stability over time and low foaming property, and A ¹ is a single alkylene group or a combination of two or more alkylene groups. It may be.
As (A ¹ O) is formed by the addition reaction of alkylene oxide (hereinafter abbreviated as AO) whose alkylene is A ¹ as described later, the number of added moles in these adducts has a distribution. Yes. Accordingly, a is represented by an average value, and is usually 0 to 20, preferably 0 to 10, more preferably 0 to 5, particularly preferably 0 from the viewpoint of stability over time.
In addition, when two or more kinds of AO are used together in the formation of (A ¹ O), both block addition (chip type, balance type, active secondary type, etc.) and random addition are mixed systems [chip after random addition. Things: 0 to 50% (preferably 5 to 40%) of oxyethylene chains arbitrarily distributed in the molecule, and 0 to 30% (preferably 5 to 25%) of oxyethylene chains at the end of the molecule It may be].
Unless otherwise specified above and below,% represents% by weight.

Q ⁻ in the general formula (1) is —COO ⁻ , —OCH ₂ COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ^— or —OPO ₂ (OR ² ) ⁻ , and from the viewpoint of detergent rinsing properties, —OSO ₃ ^- and -OPO ^₂ (oR ₂₎ ^- it is preferred.
Incidentally, Q ^- is -COO ^- or -SO ₃ ^- in the case of the a is 0.
R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and examples of the hydrocarbon group having 1 to 10 carbon atoms include the same as those exemplified for R ¹ in the general formula (1), From the viewpoint of dispersion stability of the particles, a hydrocarbon group having 4 to 10 carbon atoms is preferable, and a hydrocarbon group represented by the general formula (3) or (4) is more preferable.
In the general formula (1), b is an integer of 1 to 6, preferably 1 to 3, more preferably 1, from the viewpoint of surface flatness after washing.

Specific examples of anionic components constituting the anionic surfactant (A), 1-, 2- or tert- butanol, 1-, 2- or 3-pentanol, 2-methyl-1-butanol, 3- Methyl-2-butanol, 1-, 2- or 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-2-pentanol, 3,3-dimethyl-2 -Butanol, 3-methyl-2-pentanol, 1-, 2-, 3- or 4-heptanol, 2,4-dimethyl-3-pentanol, 3-methyl-1-hexanol, 5-methyl-2- Hexanol, 1-, 2-, 3- or 4-octanol, 6-methyl-2-heptanol, 2,2-dimethyl-3-hexanol, 2,5-dimethyl-3-hexanol, 2-ethyl-1 − Hexanol, 5-methyl-2-heptanol, 5-methyl-3-heptanol, 6-methyl-3-heptanol, 2,2-dimethyl-3-heptanol, 1-, 2-, 3-, 4- or 5- Nonanol, 2-methyl-3-octanol, 1-, 2-, 3-, 4- or 5-decanol, 3,7-dimethyl-1-octanol, ethylene glycol, 1,6-hexanediol, 1,10- Alcohols such as decanediol, glycerin and sorbitol and AO having 2 to 4 carbon atoms (ethylene oxide, 1,2- or 1,3-propylene oxide and 1,2-, 1,3-, 2,3- or 1,4-butylene oxide, etc.) anion obtained by removing proton from sulfate or phosphate ester of an adduct (addition mole number 1 to 20) ; Panic acid, 2,2-dimethylpropanoic acid, butanoic acid, 2-methyl or 3-methylbutanoic acid, 2-ethylbutanoic acid, 2,3-dimethyl or 3,3-dimethylbutanoic acid, 2-ethyl-3-methylbutanoic acid , Pentanoic acid, 2-, 3- or 4-methylpentanoic acid, 2- or 3-ethylpentanoic acid, 2-n-propyl or isopropylpentanoic acid, 2,4-dimethylpentanoic acid, 2,4,4- or 3,4,4-trimethylpentanoic acid, hexanoic acid, 2-, 3-, 4- or 5-methylhexanoic acid, 2-, 3- or 4-ethylhexanoic acid, 2- or 3-n-propylhexanoic acid 2-, 3-isopropylhexanoic acid, 2,5- or 3,5-dimethylhexanoic acid, 2,5,5- or 3,5,5-trimethylhexanoic acid, heptanoic acid, 2-, 3--4 -, 5- or 6-methylheptanoic acid, 2-, 3-, 4- or 5-ethylheptanoic acid, 2-, 3- or 4-n-propylheptanoic acid, 2-, -3 or 4-isopropylheptanoic acid, 2, 6- or 3,6-dimethylheptanoic acid, 2,6,6-, 2,4,6- or 3,6,6-trimethylheptanoic acid, octanoic acid, 2-, 3-, 4-, 5-, 6- or 7-methyloctanoic acid, 2-, 3-, 4-, 5- or 6-ethyloctanoic acid, 2,7- or 3,7-dimethyloctanoic acid, nonanoic acid and 2-, 3-, 4 -, 5-, 6-, 7- or 8-methylnonanoic acid with anion removed; proton with 1-methylpropanesulfonic acid, 1-methylpentanesulfonic acid and 1-ethylbutanesulfonic acid with proton removed; Alcohols or their C 2-4 A Anion in alkyl ether carboxylate obtained by reaction of adduct (addition mole number 1-20) with 2-chloroacetate (potassium salt or sodium salt); benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, cumene Examples include anions obtained by removing protons from sulfonic acid and benzoic acid.

  Among the anionic components constituting these anionic surfactants (A), 1-butanol, 2-ethyl-1-hexanol, 3-methyl-1 are preferable from the viewpoint of particle removability and low foaming property. -Hexanol, 3,7-dimethyl-1-octanol and their C2-4 AO (ethylene oxide, 1,2- or 1,3-propylene oxide and 1,2-, 1,3-, 2, 3- or 1,4-butylene oxide, etc.) an anion obtained by removing a proton from a sulfate ester or phosphate ester of an adduct (addition mole number 1 to 20), 2-ethylpentanoic acid, 2-n-propylpentanoic acid, 2 -Isopropylpentanoic acid, 2,4,4- or 3,4,4-trimethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 2-n-propyl Xanic acid, 2-isopropylhexanoic acid, 2-methylheptanoic acid, 2-ethylheptanoic acid, 2-methyloctanoic acid, benzenesulfonic acid, toluenesulfonic acid and xylenesulfonic acid are anions obtained by removing protons, and more preferable. Is an anion obtained by removing a proton from 2-ethyl-1-hexanol, 3-methyl-1-hexanol and sulfate ester or phosphate ester of 3,7-dimethyl-1-octanol and 2-n-propylpentanoic acid, 2 -Isopropylpentanoic acid, 2,4,4- or 3,4,4-trimethylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, paratoluenesulfonic acid, orthotoluenesulfonic acid, metaxylenesulfonic acid and para An anion obtained by removing a proton from xylene sulfonic acid, Preferred is an anion obtained by removing a proton from 2-ethyl-1-hexanol sulfate or phosphate, and an anion obtained by removing a proton from octanoic acid, paratoluenesulfonic acid and metaxylenesulfonic acid. Is an anion obtained by removing protons from 2-ethyl-1-hexanol sulfate, paratoluenesulfonic acid and metaxylenesulfonic acid.

  As the cation component constituting the anionic surfactant (A) in the present invention, an alkali metal cation, an alkaline earth metal cation, an ammonium cation having 0 to 25 carbon atoms, a cation obtained by adding a proton to hydroxylamine, 1 carbon atom. A cation having a proton added to an aliphatic amine having ˜36, a cation having a proton added to an amidine compound having 4 to 10 carbon atoms, a cation having a proton added to an alkanolamine having 1 to 23 carbon atoms, and a fragrance having 6 to 20 carbon atoms And cations obtained by adding protons to aliphatic or araliphatic amines. These may be used alone or in combination of two or more.

Examples of the alkali metal cation include a sodium cation and a potassium cation.
Examples of alkaline earth metal cations include calcium cations and magnesium cations.

  Examples of the ammonium cation having 0 to 25 carbon atoms include ammonium, tetramethylammonium, trimethylvinylammonium, trimethylphenylammonium, benzyltriethylammonium, dodecyltrimethylammonium, tetrabutylammonium, trimethyltetradecylammonium, benzyltributylammonium, tetrapentylammonium, Examples include ethyl hexadecyldimethylammonium and octadecyltrimethylammonium.

As a C1-C36 aliphatic amine in the cation which added the proton to the C1-C36 aliphatic amine, C1-C12 alkylamine, C2-C6 alkylenediamine, C3-C3 7 cyclic amines, poly (n = 2-6) alkylene (2-6 carbon atoms) poly (n = 3-7) amines and their C2-4 AO (ethylene oxide, 1,2- or 1) , 3-propylene oxide and 1,2-, 1,3-, 2,3- or 1,4-butylene oxide) and the like.
Examples of the alkylamine having 1 to 12 carbon atoms include monoalkylamines having 1 to 6 carbon atoms (such as methylamine, ethylamine, propylamine, isopropylamine, butylamine and hexylamine) and dialkylamines having 2 to 12 carbon atoms (dimethylamine). Ethylmethylamine, propylmethylamine, butylmethylamine, diethylamine, propylethylamine, diisopropylamine and dihexylamine).
Examples of the alkylene diamine having 2 to 6 carbon atoms include ethylene diamine, 1,2- or 1,3-propylene diamine, tetramethylene diamine, pentamethylene diamine and hexamethylene diamine.
Examples of the cyclic amine having 3 to 7 carbon atoms include cyclopropylamine, cyclohexylamine, piperidine, piperazine, quinuclidine, 2-pyridineamine, cis-3-methylcyclohexylamine and 1,4-diazabicyclo [2.2.2] octane. (DABCO).
As poly (n = 2-6) alkylene (2-6 carbon atoms) poly (n = 3-7) amine, diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine And hexaethyleneheptamine.

As the amidine compound having 4 to 10 carbon atoms in the cation obtained by adding a proton to the amidine compound having 4 to 10 carbon atoms, 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter abbreviated as DBU), Examples include 1,5-diazabicyclo [4.3.0] -5-nonene (hereinafter abbreviated as DBN), 2-methylimidazole, 2-butylbenzimidazole, and 2- (4-thiazolyl) benzimidazole.

  Examples of the alkanolamine having 1 to 23 carbon atoms in the cation obtained by adding a proton to the alkanolamine having 1 to 23 carbon atoms include monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, N , N-diethylethanolamine, 2-amino-2-methyl-1-propanol, N- (aminoethyl) ethanolamine, 2- (2-aminoethoxy) ethanol and their C2-4 AO (ethylene oxide) 1,2- or 1,3-propylene oxide and 1,2-, 1,3-, 2,3- or 1,4-butylene oxide) and the like.

  Examples of the aromatic or araliphatic amine having 6 to 20 carbon atoms in the cation obtained by adding a proton to an aromatic or araliphatic amine having 6 to 20 carbon atoms include aniline, phenylenediamine, tolylenediamine, methylenedianiline, and diphenyl ether. Diamine, naphthalenediamine, anthracenediamine, benzylamine, xylylenediamine and their C2-4 AO (ethylene oxide, 1,2- or 1,3-propylene oxide and 1,2-, 1,3-, 2,3- or 1,4-butylene oxide and the like).

  Among these cation components, from the viewpoint of particle removability, an alkali metal cation, a monovalent cation obtained by adding a proton to an aliphatic amine having 1 to 15 carbon atoms, or a proton added to an amidine compound having 4 to 10 carbon atoms. A cation and a monovalent cation in which a proton is added to an alkanolamine having 1 to 15 carbon atoms are preferable, and a sodium cation, a potassium cation, and a cation in which a proton is added to trimethylamine, DBU, DBN, and diethanolamine are particularly preferable. Are a cation in which a proton is added to sodium cation, potassium cation, DBU, and a cation in which a proton is added to diethanolamine.

In the general formula (1), the anionic surfactant (A) is, for example, when Q ⁻ is —COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ^— or —OPO ₂ (OR ² ) ⁻ , And an alkali compound composed of an acid consisting of an alkali metal cation, an alkaline earth metal cation or an ammonium cation having 0 to 25 carbon atoms and a hydroxyl anion, or an amine having 1 to 15 carbon atoms or a polyvalent having 2 to 36 carbon atoms ( It can be produced by a neutralization reaction with (2-7 valent) amine. The temperature of the neutralization reaction is usually 10 to 60 ° C., and the time is usually 30 to 200 minutes. The neutralization degree is usually 95 to 100%, and the pH of the neutralized product (5% aqueous solution of the neutralized product) is usually 7 to 12.

In the general formula (1), when Q ⁻ is —OSO ₃ ^— or —OPO ₂ (OR ² ) ^— , an acid composed of an anionic component and a proton can be produced by, for example, the following reactions (1) and (2): .
(1) Addition reaction of AO AO having 2 to 4 carbon atoms is added to the hydroxyl group of the compound in which R ¹ in R ¹ in the general formula (1) is substituted by a usual method. Specifically, the hydroxyl group-containing compound is charged into a pressurized reaction vessel, AO is blown in the presence of no catalyst or catalyst (particularly in the latter half of the AO addition), and one or more stages under normal pressure or pressure. Perform the reaction at Examples of the catalyst include alkali catalysts such as alkali metal (lithium, sodium, potassium, cesium, etc.); acids [perhalogen acids (perchloric acid, perbromic acid and periodic acid), sulfuric acid, phosphoric acid, nitric acid, etc. (Preferably perchloric acid)] and salts thereof [preferably salts of divalent or trivalent metals (Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu, Al, etc.)].
The reaction temperature is usually 50 to 150 ° C., and the reaction time is usually 2 to 20 hours.
After completion of the AO addition reaction, if necessary, the catalyst can be neutralized and treated with an adsorbent to remove and purify the catalyst.

(2) Sulfate esterification reaction or phosphoric acid esterification reaction The terminal hydroxyl group of the compound in which R ¹ in the general formula (1) is substituted with a hydroxyl group or the AO adduct obtained in the above (1) is sulfated or phosphoric acid. By esterification, a sulfated ester or a phosphate esterified product is obtained.
Examples of the esterification method include (i) a method using chlorosulfonic acid, (ii) a method using sulfane, (iii) a method using sulfamic acid, (iv) a method using sulfuric acid, and (v) phosphoric acid. The method to use etc. are mentioned. The sulfan (ii) is diluted with dry nitrogen or the like.
In the case of (i) and (ii), the reaction temperature is usually −10 to 70 ° C., preferably −5 to 40 ° C. In the case of (iii), (iv) and (v), it is usually 50 to 150 ° C, preferably 60 to 130 ° C.
The end point of the esterification reaction is that the acid value (AV) represented by 56100 / (molecular weight of the ester compound) is 70 to 110% of the theoretical value, preferably 80 to 105%. .

In the general formula (1), when Q ⁻ is —SO ₃ ^— , an acid composed of an anionic component and a proton is obtained by reacting a hydrocarbon using, for example, a method of reacting an alkyl halide or alkyl sulfate with an alkali sulfite, or using fuming sulfuric acid. It can be produced by a direct sulfonation method and a method of reacting hydrocarbons with sulfur dioxide and chlorine under ultraviolet irradiation.

In the general formula (1), when Q ⁻ is —COO ⁻ , an acid composed of an anionic component and a proton is, for example, a high pressure decomposition method (8 to 50 atm) or a Toichel decomposition method (a Toichel decomposition agent and a small amount of sulfuric acid are added). To remove the fatty acid pitch) by hydrolysis of natural fats and oils.

When Q ⁻ is —OCH ₂ COO ^{— in} the general formula (1), the anionic surfactant (A) is obtained, for example, from the compound in which R ¹ in the general formula (1) is substituted with a hydroxyl group or the above (1). The obtained AO adduct and monochloroacetate (such as sodium salt and potassium salt) can be produced by carboxymethylation in the presence of alkali (such as sodium hydroxide and potassium hydroxide).

The alkene (B) in the present invention include alkenyl emissions having 6 to 18 carbon atoms.

  Examples of the alkene having 6 to 18 carbon atoms include linear or branched alkenes having 6 to 18 carbon atoms, and specifically include 1-hexene, 2-heptene, 3-octene, 4-nonene, and 5-decene. 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, butylene dimer, butylene trimer, butylene tetramer, isobutylene trimer, propylene dimer, propylene trimer , Propylene tetramer, propylene pentamer and the like.

R ³ in the general formula (2) is preferably hydrogen or a hydrocarbon group having 6 to 8 carbon atoms from the viewpoint of organic dirt removing performance.
Examples of the hydrocarbon group having 6 to 8 carbon atoms include hydrocarbon groups having 6 to 8 carbon atoms among the hydrocarbon groups exemplified as R ¹ in the general formula (1).

A ² in the general formula (2) is an alkylene group having 2 to 4 carbon atoms (ethylene group, 1,2- or 1,3-propylene group and 1,2-, 1,3-, 2,3- or 1, 4-butylene group and the like, and from the viewpoint of stability over time and low foaming property, ethylene group and 1,2-propylene group are preferable, and A ² is a single type of alkylene group or two types of A group. A combination of the above alkylene groups may be used.
Since (A ² O) is formed in the same manner as (A ¹ O) in general formula (1), the number of added moles has a distribution. Therefore, c is represented by an average value and is usually 0 to 20, and preferably 0 to 10 from the viewpoint of stability over time.

  D in the general formula (2) is an integer of 1 to 6, and is preferably 1 to 3, and more preferably 1 from the viewpoint of rinsing properties after washing.

Specific examples of the organic solvent represented by the general formula (2) include 2-ethylhexanol and hexyl carbitol.

Among the organic solvents (B), preferred from the viewpoint of particle removability are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, isobutylene trimer, propylene tetramer, propylene pentamer, 2-ethylhexanol, hexyl. Carbitol, and more preferred are 1-dodecene, isobutylene trimer, propylene tetramer, propylene pentamer, and hexyl carbitol.

One of the alkene (B) having 6 to 18 carbon atoms and the organic solvent (D) represented by the general formula (2) may be used alone, or two or more thereof may be used in combination.

The SP value of the organic solvent (D) is usually 6 to 13, preferably 7 to 12, and more preferably 8 to 11. When the SP value is less than 6 or exceeds 13, the organic soil removability deteriorates.
The SP value is a value calculated by the Fedors method described in “Polymer Engineering and Science, Vol. 14, No. 2, p 147 to 154 (1974)”.

  As the alkali component (C), ammonia, hydroxylamine, quaternary ammonium hydroxide (C-1), aliphatic amine (C-2) having 1 to 36 carbon atoms, inorganic alkali (C-3), carbon A C1-C23 alkanolamine (C-4), C4-C10 amidine compound (C-5), and these mixtures are mentioned.

  (C-1) includes tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, tetraethylammonium hydroxide, triethylmethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetra Examples include pentylammonium hydroxide, tetrahexylammonium hydroxide, hydroxyethyltrimethylammonium hydroxide, triethylhydroxyethylammonium hydroxide, dihydroxyethyldimethylammonium hydroxide, and trihydroxyethylmethylammonium hydroxide.

  As (C-2), the same thing as the C1-C36 aliphatic amine illustrated in description of the cation component which comprises the said anionic surfactant (A) is mentioned.

  Examples of (C-3) include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide.

  As (C-4), the same thing as the C1-C23 alkanolamine illustrated in the description of the cation component which comprises the said anionic surfactant (A) is mentioned.

  As (C-5), the same thing as the C4-C10 amidine compound illustrated in the description of the cation component which comprises the said anionic surfactant (A) is mentioned.

  Among (C), (C-2), (C-3), (C-4), (C-5), and these from the viewpoint of the etching property and the contact angle (rinse property) of water after cleaning. Mixtures are preferred, and potassium hydroxide, sodium hydroxide, DBU, butylamine, hexylamine, cyclohexylamine, triethanolamine, N-methyldiethanolamine, cyclohexylamine ethylene oxide (2 mol) adduct, cyclohexylamine propylene oxide are more preferred. (2 mol) adduct, N, N-dimethylethanolamine, triethanolamine ethylene oxide (5 mol) adduct, triethanolamine propylene oxide (5 mol) adduct, N, N-dimethylethanolamine ethylene oxide (3 Mol) Adduct, N, N-dimethylethanol Emissions of ethylene oxide (3 mol) adducts, and mixtures thereof.

  The electronic material cleaning agent of the present invention may further contain one or more selected from the group consisting of the following polymer dispersant (D) and chelating agent (E).

  The detergent for electronic materials of this invention contains a polymer type dispersing agent (D), and further improves the dispersibility of particles and the prevention of recontamination.

(D) is a polymer type anionic surfactant (D-1) having a sulfonic acid (salt) group having a weight average molecular weight (hereinafter abbreviated as Mw) of 2,500 to 800,000, sulfate ester A polymeric anionic surfactant (D-2) having a (salt) group, a polymeric anionic surfactant (D-3) having a phosphate ester (salt) group, and a phosphonic acid (salt) group. Polymer type anionic surfactant (D-4), polymer type anionic surfactant (D-5) having a carboxylic acid (salt) group, polysaccharides and derivatives thereof (D-6), and the like. Raru.
Specific examples of (D) include the following.

Polymeric anionic surfactant (D-1) having a sulfonic acid (salt) group:
Polystyrene sulfonic acid, styrene / styrene sulfonic acid copolymer, poly [2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid], 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / Styrene copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / acrylamide copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / (meth) acrylic acid co Polymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / (meth) acrylic acid / acrylamide copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / styrene / Acrylamide copolymer, 2- (meth) acryloylamino-2,2-dimethyl eta Sulfonic acid / styrene / (meth) acrylic acid copolymer, naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, dimethyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate And aniline sulfonic acid-phenol-formaldehyde condensates and the like and salts thereof;

Polymer type anionic surfactant (D-2) having a sulfate (salt) group:
Poly [2-hydroxyethyl (meth) acrylate sulfate], 2-hydroxyethyl acrylate / 2-hydroxyethyl acrylate sulfate copolymer, 2-hydroxyethyl methacrylate / 2-hydroxyethyl methacrylate sulfate copolymer, poly [ 2-hydroxyethyl (meth) acrylate] sulfated product, poly [(meth) acryloyloxypolyoxyalkylene sulfate], (meth) acryloyloxypolyoxyalkylene sulfate / acrylic acid copolymer and cellulose, methylcellulose or ethylcellulose Sulfates of these and their salts;

Polymeric anionic surfactant (D-3) having a phosphate ester (salt) group:
Poly [2-hydroxyethyl (meth) acrylate phosphate ester], 2-hydroxyethyl acrylate / 2-hydroxyethyl acrylate phosphate ester copolymer, 2-hydroxyethyl methacrylate / 2-hydroxyethyl methacrylate phosphate ester copolymer , Poly [2-hydroxyethyl (meth) acrylate] phosphoric acid ester, poly [(meth) acryloyloxypolyoxyalkylene phosphoric acid ester], (meth) acryloyloxy polyoxyalkylene phosphoric acid ester / acrylic acid copolymer And phosphoric acid ester of cellulose, methylcellulose or ethylcellulose, and salts thereof;

Polymer type anionic surfactant (D-4) having a phosphonic acid (salt) group:
Poly [(meth) acryloyloxyethylphosphonic acid], 2-hydroxyethyl acrylate / acryloyloxyethylphosphonic acid copolymer and 2-hydroxyethyl methacrylate / methacryloyloxyethylphosphonic acid copolymer, naphthalenephosphonic acid formaldehyde condensate, methyl Naphthalene phosphonic acid formaldehyde condensate, dimethyl naphthalene phosphonic acid formaldehyde condensate, anthracene phosphonic acid formaldehyde condensate, aniline phosphonic acid-phenol-formaldehyde condensate and the like, and salts thereof;

Polymeric anionic surfactant (D-5) having a carboxylic acid (salt) group:
Poly (meth) acrylic acid, (meth) acrylic acid-maleic acid copolymer, (meth) acrylic acid-itaconic acid copolymer, (meth) acrylic acid-fumaric acid copolymer, (meth) acrylic acid / acetic acid Vinyl copolymer, 2-hydroxyethyl methacrylate / (meth) acrylic acid copolymer, carboxymethylated product of poly [2-hydroxyethyl (meth) acrylate], carboxymethylcellulose, carboxymethylmethylcellulose, carboxymethylethylcellulose, formaldehyde benzoate Condensates and benzoic acid-phenol-formaldehyde condensates and the like and salts thereof;

Polysaccharides and their derivatives (D-6):
Hydroxyethylcellulose, cationized cellulose, hydroxymethylcellulose, hydroxypropylcellulose, guar gum, cationized guar gum, xanthan gum, alginate, cationized starch, etc., poval and phosphate esters [phytic acid, di (polyoxyethylene) alkyl ether phosphate and Tri (polyoxyethylene) alkyl ether phosphoric acid etc.] etc .;
Etc.

  The counter ion when (D) forms a salt is not particularly limited, and examples thereof include alkali metal salts (sodium salt and potassium salt), ammonium salts, primary amine salts (alkylamines such as methylamine, ethylamine and butylamine). , Monoethanolamine and guanidine, etc.) Secondary amine salts (dialkylamines such as dimethylamine, diethylamine and dibutylamine, and diethanolamine) Tertiary amine salts (trialkylamines such as trimethylamine, triethylamine and tributylamine, triethanolamine) , DBU, DBN, DABCO, etc.) and quaternary ammonium salts (tetraalkylammonium salts, etc.).

  Among (D), (D-1) and (D-5) are preferable from the viewpoint of particle dispersibility, and polystyrene sulfonic acid, styrene / styrene sulfonic acid copolymer, and poly (meth) acrylic are more preferable. Acid and (meth) acrylic acid-maleic acid copolymers and salts thereof, particularly preferred are poly (meth) acrylic acid and (meth) acrylic acid-maleic acid copolymers and salts thereof.

(D) Mw is preferably from 3,000 to 400,000, more preferably from 4,000 to 80,000, particularly preferably 5,000, from the viewpoint of preventing reattachment of particles and low foaming property. ~ 40,000.
Mw in the present invention is measured by gel permeation chromatography at 40 ° C. using polyethylene oxide as a reference material [for example, apparatus main body: HLC-8120 (manufactured by Tosoh Corporation), column: TSKgel α6000 manufactured by Tosoh Corporation, G3000 PWXL, detector: differential refractometer detector built in the apparatus body, eluent: 0.5% sodium acetate / water / methanol (volume ratio 70/30), eluent flow rate: 1.0 ml / min, column temperature: 40 ° C., sample: 0.25% eluent solution, injection amount: 200 μl, standard material: TSK TANDARD POLYETHYLENE OXIDE manufactured by Tosoh Corporation, data processing software: GPC-8020 model II (manufactured by Tosoh Corporation)].

  By containing the chelating agent (E), the cleaning material for electronic materials of the present invention can further control the etching property of the substrate and further improve the dispersion stability of the particles.

(E) includes aminopolycarboxylic acid (salt) (E-1) [for example, ethylenediaminetetraacetic acid (salt) (EDTA), diethylenetriaminepentaacetic acid (salt) (DTPA), triethylenetetraminehexaacetic acid (salt) ( TTHA), hydroxyethylethylenediaminetriacetic acid (salt) (HEDTA), dihydroxyethylethylenediaminetetraacetic acid (salt) (DHEDDA), nitrilolic acid acetic acid (salt) (NTA), hydroxyethyliminodiacetic acid (salt) (HIDA), β -Alanine diacetate (salt), aspartate diacetate (salt), methylglycine diacetate (salt), iminodisuccinate (salt), serine diacetate (salt), hydroxyiminodisuccinate (salt), dihydroxyethylglycine (salt) , Aspartic acid (salt) and glutamic acid (salt)];
Hydroxycarboxylic acid (salt) (E-2) [e.g. hydroxyacetic acid (salt), tartaric acid (salt), citric acid (salt) and gluconic acid (salt)];
Ether carboxylic acids (salts) (E-3) [e.g. carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid monosuccinate and tartaric acid disuccinate];
Other carboxylic acids (salts) (E-4) [for example, maleic acid derivatives and oxalic acid (salts)];
Phosphonic acid (salt) (E-5) [for example, methanediphosphonic acid (salt), aminotri (methylenephosphonic acid) (salt), 1-hydroxyethylidene-1, 1-diphosphonic acid (salt), ethylenediaminetetra (methylene Phosphonic acid) (salt), hexamethylenediaminetetra (methylenephosphonic acid) (salt), propylenediaminetetra (methylenephosphonic acid) (salt), diethylenetriaminepenta (methylenephosphonic acid) (salt), triethylenetetramine hexa (methylenephosphone) Acid) (salt), triaminotriethylamine hexa (methylenephosphonic acid) (salt), trans-1,2-cyclohexanediaminetetra (methylenephosphonic acid) (salt), glycol etherdiaminetetra (methylenephosphonic acid) (salt) and Tetraethylenepentamine hepta Methylene phosphonic acid) (salt)];
Condensed phosphoric acid (salt) (E-6) [e.g., metaphosphoric acid (salt), tripolyphosphoric acid (salt) and hexametaphosphoric acid (salt)];
Etc.
In addition, what was illustrated by the above-mentioned polymeric dispersing agent (D) as a counter ion in case (E) forms a salt is mentioned. Moreover, these may be used independently and may use 2 or more types together.

  Of these, (E-1), (E-2), (E-4), (E-5) and (E-6) are preferable from the viewpoints of etching control and cleaning performance of the substrate. More preferred are (E-1), (E-2), (E-5) and (E-6), and particularly preferred are ethylenediaminetetraacetic acid (salt) (EDTA) and diethylenetriaminepentaacetic acid (salt). ) (DTPA), dihydroxyethylethylenediaminetetraacetic acid (salt) (DHEDDA), aspartic acid diacetic acid (salt), aspartic acid (salt), glutamic acid (salt), citric acid (salt), aminotri (methylenephosphonic acid) (salt) ), 1-hydroxyethylidene-1,1-diphosphonic acid (salt), ethylenediaminetetra (methylenephosphonic acid) (salt), metaphosphoric acid (salt) and hexametaphosphoric acid (salt), and Particularly preferred are citric acid (salt), aminotri (methylenephosphonic acid) (salt), 1-hydroxyethylidene-1, 1-diphosphonic acid (salt), ethylenediaminetetra (methylenephosphonic acid) (salt), and hexametaphosphoric acid (salt). ).

  Of the anionic surfactants (A) of the present invention, cyclocarboxylic acids (salts) [for example, pyromellitic acid (salt), benzopolycarboxylic acid (salt) and cyclopentanetetracarboxylic acid (salt)] are also included. Has an effect as a chelating agent.

  The electronic material cleaning agent of the present invention may further contain other additives (F) as long as the effect of the cleaning agent is not impaired. Examples of (F) include a reducing agent, an antioxidant, a rust inhibitor, a pH adjuster, a buffer agent, an antifoaming agent, a preservative, and a hydrotrope agent.

  Examples of the reducing agent include reductones having 6 to 70 carbon atoms [for example, L-ascorbic acid (salt), isoascorbic acid (salt), 5,6-alkylidene-L-ascorbic acid {5,6-isopropylidene-L -Ascorbic acid, 5,6- (butan-2-ylidene) -L-ascorbic acid and 5,6- (pentane-3-ylidene) -L-ascorbic acid etc.} (salt), L-ascorbic acid-6 Carboxylic acid ester (L-ascorbic acid-6-acetic acid ester and L-ascorbic acid-6-propanoic acid ester etc.) (salt), ascorbic acid sulfuric acid ester (salt), ascorbic acid phosphoric acid ester (salt), ascorbic acid glucoside (Salt), ascorbic acid isopalmitate (salt), erythorbic acid (salt), erythorbic acid phosphate (salt), eryso Binic acid palmitic acid ester (salt) and tetraisopalmitic acid erythovir (salt)]; aromatic amines having 6 to 9 carbon atoms (such as p-phenylenediamine and p-aminophenol); phenol compounds having 6 to 30 carbon atoms [ Monohydric phenol compounds {3-hydroxyflavones and tocopherols (α-, β-, γ-, δ-, ε- or η-tocopherols)} and polyphenols (3,4,5-trihydroxybenzoic acid, pyrocatechol, Resorcinol, hydroquinone, naphthoresorcinol, pyrogallol, phloroglucinol, etc.]]; Phosphorus-based reducing agents (Tris-2-carboxyethylphosphine, etc.); Aldehydes (formaldehyde, acetaldehyde, propionaldehyde, vinylaldehyde, etc.); Borane complexes ( Boran-tert-buchi Amine complexes, borane-N, N-diethylaniline complexes and borane-trimethylamine complexes, etc.); thiol-based reducing agents (such as L-cysteine and aminoethanethiol); hydroxylamine-based reducing agents (such as hydroxylamine and diethylhydroxylamine); Inorganic reducing agent [sulfurous acid (salt), disulfurous acid (salt), dithionic acid (salt), thiosulfuric acid (salt), dithionic acid (salt), polythionic acid (salt), phosphorous acid (salt), phosphorous acid Hydroacid (salt), hypophosphorous acid (salt), ferrous sulfate, stannic chloride, sodium cyanoborohydride, sodium borohydride, and the like].

  As the counter ion in the case where the reducing agent forms a salt, the same ions as those exemplified for the polymer dispersant (D) can be used. A reducing agent may be used independently and may use 2 or more types together. In addition, (C-2), (C-4) and (C-5) exemplified as the above-mentioned alkali component (C) also have an effect as a reducing agent.

  Antioxidants include phenolic antioxidants (2,6-di-t-butylphenol, 2-t-butyl-4-methoxyphenol and 2,4-dimethyl-6-t-butylphenol), amine-based oxidation Inhibitors (monoalkyldiphenylamines such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamines such as 4,4′-dibutyldiphenylamine and 4,4′-dipentyldiphenylamine; polyalkyldiphenylamines such as tetrabutyldiphenylamine and tetrahexyldiphenylamine; α Naphthylamine such as naphthylamine and phenyl-α-naphthylamine), sulfur compounds [phenothiazine, pentaerythritol-tetrakis- (3-laurylthiopropionate) and bis (3,5-t ert-butyl-4-hydroxybenzyl) sulfide etc.] and phosphorus antioxidants [bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, phenyldiisodecylphosphite, diphenyldiisooctylphosphite and Triphenyl phosphite etc.] and the like.

  Examples of the rust preventive include benzotriazole, tolyltriazole, benzotriazole having 2 to 10 carbon atoms, benzimidazole, imidazole having 2 to 20 carbon atoms, and 2 to 20 hydrocarbon groups. Nitrogen-containing organic rust preventives such as thiazole and 2-mercaptobenzothiazole; alkyl or alkenyl succinic acids such as dodecenyl succinic acid half ester, octadecenyl succinic anhydride and dodecenyl succinic acid amide; sorbitan monooleate, glycerin monoole And polyhydric alcohol partial esters such as acrylate and pentaerythritol monooleate. These may be used alone or in combination of two or more.

  Examples of the pH adjuster include inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, etc.), organic acids (citric acid, oxalic acid, lactic acid, etc.), and the alkali components (C) exemplified above, and these are used alone. It may be used in combination, or two or more may be used in combination.

  Examples of the buffer include organic acids having 1 to 10 carbon atoms having a buffering action (such as acetic acid, formic acid, gluconic acid, glycolic acid, tartaric acid, fumaric acid, levulinic acid, valeric acid, maleic acid and mandelic acid), inorganic acids ( Phosphoric acid and boric acid) and salts thereof. In addition, as a counter ion in case a buffer forms a salt, the thing similar to what was illustrated by the above-mentioned polymeric dispersing agent (D) is mentioned. These may be used alone or in combination of two or more.

  Examples of the antifoaming agent include silicone antifoaming agents (such as antifoaming agents containing dimethyl silicone, fluorosilicone, polyether silicone, etc.). These may be used alone or in combination of two or more.

  Examples of preservatives include triazine derivatives [hexahydro-1,3,5-tris (2-hydroxyethyl) -S-triazine and the like], isothiazoline derivatives (1,2-benzisothiazolin-3-one, 2-methyl-4- Isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one), pyridine derivatives [pyridine 2-pyridinethiol-1-oxide (salts, etc.)], morpholine derivatives [4- (2- Nitrobutyl) morpholine and 4,4- (2-ethyl-2-nitrotrimethylene) -dimorpholine etc.], benzimidazole derivatives [2- (4-thiazolyl) benzimidazole etc.], poly [oxyethylene (dimethylimino) ethylene ( Dimethylimino) ethylene] dichloride, p-chloro-m-xylenol, phenol Siethanol, phenoxypropanol, acetoxydimethyldioxane, isopropylmethylphenol, tetrachloroisophthalonitrile, bisbromoacetoxyethane, 3-iodo-2-propynylbutylcarbamate, 2-bromo-2-nitropropane-1,3-diol, etc. Is mentioned. These may be used alone or in combination of two or more.

  Examples of the hydrotrope include resorcin and salicylic acid (salt). In addition, as a counter ion in case a hydrotrope agent forms a salt, the thing similar to what was illustrated by the above-mentioned (D) is mentioned. These may be used alone or in combination of two or more. In addition, toluenesulfonic acid (salt), xylenesulfonic acid (salt), cumenesulfonic acid (salt) and benzoic acid (salt) exemplified as the anionic surfactant (A) also have an effect as a hydrotrope agent.

As described above, the detergent for electronic materials of the present invention comprises an anionic surfactant (A), an alkene (B), and, if necessary, an alkali component (C), a polymeric dispersant (D), a chelating agent (E ) And other additives (F), but may further contain water, particularly ion-exchanged water (conductivity: 0.2 μS / cm or less) or ultrapure water (electric resistivity: 18 MΩ · cm or more). .
In the present invention, the active ingredient means an ingredient other than water.

  The content of (A) is preferably 0.5 to 80%, more preferably 1 to 70% based on the weight of the active ingredient of the electronic material cleaning agent from the viewpoint of particle removability and low foaming property. Particularly preferred is 2 to 60%, and most preferred is 5 to 50%.

  The content of (B) is preferably 1 to 90%, more preferably 2 to 80%, and particularly preferably 5 to 70, based on the weight of the active ingredient of the electronic material cleaning agent, from the viewpoint of particle removability. %, Most preferably 10-60%.

  The content of (C) is preferably from 1 to 55%, more preferably from 2 to 50%, particularly preferably from 5 to 50% based on the weight of the active ingredient of the electronic material cleaning agent from the viewpoints of etching properties and rinsing properties. 45%, most preferably 10-40%.

  The content of (D) is preferably 0 to 25%, more preferably 0.1 to 20 based on the weight of the active ingredient of the electronic material cleaning agent from the viewpoints of particle dispersibility and recontamination prevention. %, Particularly preferably 0.5 to 15%, most preferably 1 to 10%.

  The content of (E) is preferably 0 to 10%, more preferably 0.01 to 7 based on the weight of the active ingredient of the electronic material cleaning agent, from the viewpoints of substrate etching control and dispersion stability. %, Particularly preferably 0.05 to 5%, most preferably 0.1 to 3%.

The content of each additive in (F) is preferably 0-20, based on the weight of the active ingredient of the electronic material cleaner, in which the reducing agent, antioxidant, rust inhibitor, buffering agent and hydrotrope agent are used. %, More preferably 0.1 to 15%, particularly preferably 0.5 to 10%, most preferably 1 to 5%. The content of the antifoaming agent is preferably 0 to 2%, more preferably 0.01 to 1.5%, particularly preferably 0.02 to 1%, most preferably 0.05 to 0.5%. is there.
The total content of (F) is preferably 0 to 25%, more preferably 0.5 to 20%, particularly preferably 1 to 15%, most preferably, based on the weight of the active ingredient of the electronic material cleaner. Preferably it is 2 to 10%.

  In addition, between the above arbitrary components (D) to (F), when the composition is the same and overlaps, the content of each arbitrary component is not simply the total, but each other arbitrary component In consideration of the fact that the effects are also produced at the same time, it is adjusted according to the purpose of use.

The active ingredient concentration of the electronic material cleaning agent of the present invention is preferably 1 to 100%, more preferably 2 to 90%, particularly preferably 5 to 70%, and most preferably from the viewpoint of transportation efficiency. 10 to 50%.
When using the electronic material cleaning agent of the present invention, if necessary, diluted water, particularly ion-exchanged water (conductivity: 0.2 μS / cm or less) or ultrapure water (electric resistivity: 18 MΩ · cm or more). It is preferable from the viewpoint of workability and cost during use that the active ingredient concentration is 0.1 to 15%, particularly 0.5 to 10%.
When diluted with water and using an alkene having 6 to 18 carbon atoms as the organic solvent (B), the presence of the alkene in a dispersed state in the cleaning agent is from the viewpoint of removability from organic contaminants. preferable.

The pH of the cleaning agent at 25 ° C. in an active ingredient concentration of 0.1 to 15% when the electronic material cleaning agent of the present invention is diluted with water is usually 10 to 14, preferably from the viewpoint of etching property and rinsing property. Is 11-13.
The pH in the present invention is measured at a measurement temperature of 25 ° C. using a pH meter (manufactured by Horiba, Ltd., M-12).
In this case, the contact angle of the cleaning agent with respect to the glass is preferably 10 ° or less, more preferably 8 ° or less, particularly preferably 5 ° or less, and most preferably 1 ° or less from the viewpoint of wettability to the substrate. is there.
In the present invention, the contact angle is measured on a glass with a contact angle meter [device main body: PD-W (manufactured by Kyowa Interface Chemical Co., Ltd.), glass plate: glass plate # 1737 (manufactured by Corning), detection condition: automatic. Detection and measurement conditions: Measure contact angle 10 seconds after landing].

The cleaning agent for electronic materials of the present invention contains, for example, an anionic surfactant (A), an alkene (B), an alkali component (C), and optionally components (D) to (F) and water at 10 to 40 ° C. It can be produced by mixing and dissolving for 30 to 300 minutes.
Although the apparatus for mixing and dissolving is not particularly limited, for example, a stirring and mixing apparatus equipped with a bowl-shaped blade or a stirring and mixing apparatus equipped with a spiral blade can be used.

  The method of diluting the electronic material cleaning agent with water is not particularly limited. For example, the electronic material cleaning agent and the water can be mixed with a stirring and mixing device equipped with a saddle type blade or a stirring and mixing device equipped with a spiral blade. Can be mixed and dissolved at 10 to 40 ° C. for 30 to 300 minutes.

The electronic material cleaning method of the present invention is at least one selected from the group consisting of ultrasonic cleaning, shower cleaning, spray cleaning, brush cleaning, immersion cleaning, immersion oscillation, and single wafer cleaning using the above-described cleaning agent. It is a method of cleaning by a seed cleaning method.
The washing temperature is preferably 10 to 80 ° C., more preferably 15 to 60 ° C., particularly preferably 20 to 50 ° C. from the viewpoint of detergency.

The surface roughness (Ra) of the glass surface after being cleaned by the cleaning method of the present invention is preferably 1.0 nm or less, more preferably 0.75 nm, and particularly preferably 0.5 nm or less. When Ra is 1.0 nm or less, a uniform film can be formed when the film is formed by sputtering or the like in the subsequent process, and the yield rate is improved.
In addition, Ra is measured on condition of the following using the SII nanotechnology company make and E-sweep.
Measurement mode: DFM (tapping mode)
Scan area: 10 μm × 10 μm
Number of scan lines: 256 (Y-direction scan)
Correction: Flat correction in X and Y directions

  The contact angle of water with respect to the glass cleaned using the electronic material cleaning agent in the present invention is preferably 20 ° or less, and more preferably 15 ° or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, “parts” means “parts by weight” below. In the following, ultrapure water having a specific resistance value of 18 MΩ · cm or more was used.

[Production Example 1]
A glass reactor equipped with a stirrer and a temperature controller was charged with 256 parts of 2-ethylhexanol, cooled to 0 ° C. with stirring, and 229 parts of chlorosulfonic acid was added over 3 hours while maintaining the system temperature at 0 ° C. Dropped to obtain a sulfate ester. Further, 252 parts of 48% potassium hydroxide aqueous solution and 583 parts of ion-exchanged water are gradually added, mixed and neutralized at 20 ° C. for 60 minutes, and an anionic surfactant (A-1) having an active ingredient concentration of 40%. 1248 parts were obtained.

[Production Example 2]
148 parts of n-butanol was charged into a glass reactor equipped with a stirrer and a temperature controller, and the temperature was adjusted to 70 ° C. with stirring, and 98 parts of phosphoric acid was added dropwise over 2 hours while maintaining the system temperature at 70 ° C. Thereafter, the mixture was further stirred at 70 ° C. for 4 hours to obtain a phosphate ester. Furthermore, the inside of the system is cooled to 30 ° C., 133 parts of 30% sodium hydroxide aqueous solution and 201 parts of ion-exchanged water are gradually added, mixed and neutralized at 20 ° C. for 60 minutes, and an active ingredient concentration of 40% 580 parts of a surfactant (A-2) was obtained.

[Production Example 3]
Except for replacing 2-ethylhexanol with 3,7-dimethyl-1-octanol, 189 parts of chlorosulfonic acid, 253 parts of 48% potassium hydroxide aqueous solution with 271 parts of DBU, and 912 parts of ion-exchanged water. Produced 1568 parts of an anionic surfactant (A-3) having an active ingredient concentration of 40% in the same manner as in Production Example 1.

[Production Example 4]
First, 144 parts of 2-ethylhexanoic acid and 395 parts of ion-exchanged water are charged into a beaker and stirred at 20 ° C. for 15 minutes to uniformly mix, then 119 parts of N-methyldiethanolamine is gradually added and mixed at 20 ° C. for 60 minutes. Neutralization gave 658 parts of an anionic surfactant (A-4) having an active ingredient concentration of 40%.

[Production Example 5]
A stainless steel autoclave equipped with a stirrer and temperature controller was charged with 130 parts of 1-octanol and 8 parts of 28% sodium methylate methanol solution, and the gas phase part in the system was replaced with nitrogen at room temperature (20 ° C.) under stirring. Then, after methanol removal at 120 ° C. for 2 hours under reduced pressure (gauge pressure: −0.0025 MPa), 88 parts of ethylene oxide at a reaction temperature of 120 ° C. under reduced pressure (gauge pressure: −0.05 MPa). Blowing was started, and the reaction was continued until the pressure in the system disappeared while controlling the gauge pressure to be 0.1 to 0.3 MPa to obtain 218 parts of 1-octanol ethylene oxide 2-mol adduct. A glass reactor equipped with a stirring and temperature controller was charged with 164 parts of the 1-octanol ethylene oxide 2-mol adduct, 96 parts of sodium monochloroacetate and 200 parts of toluene, and gradually reduced the pressure while maintaining the temperature at 50 ° C. After increasing the pressure to -0.01 MPa, 38 parts of granular sodium hydroxide was charged over 2 hours while dehydrating under reduced pressure, and further aging was performed for 6 hours. Then, 300 parts of ion-exchanged water was added and acidified with hydrochloric acid. , Standing, and after desalting by liquid separation, toluene removal was performed to obtain an ether carboxylic acid having a structural formula represented by C ₈ H ₁₇ O (CH ₂ CH ₂ O) ₂ CH ₂ COOH. Charge 323 parts of water into a glass reactor equipped with stirring and temperature controller, gradually add 30 parts of granular sodium hydroxide and dissolve, add 208 parts of ether carboxylic acid at 60 ° C. Was 561 parts of 40% of anionic surfactant (A-5).

[Production Example 6]
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 113 parts of 2-ethylhexanol and 3 parts of potassium hydroxide, and the gas phase part in the system was replaced with nitrogen at room temperature (20 ° C.) under stirring. (Gauge pressure: -0.05 MPa) At a reaction temperature of 120 ° C., 384 parts of ethylene oxide was started to be blown, and the pressure change in the system disappeared while controlling the gauge pressure to be 0.1 to 0.3 MPa. To give 497 parts of 2-ethylhexanol ethylene oxide 10 mol adduct.
256 parts of 2-ethylhexanol is added to 497 parts of the ethylene oxide 10 mol adduct of 2-ethylhexanol, 102 parts of chlorosulfonic acid, 112 parts of 48% potassium hydroxide aqueous solution, and ion-exchanged water. 1512 parts of anionic surfactant (A-6) having an active ingredient concentration of 40% was obtained in the same manner as in Production Example 1 except that the number of parts was changed to 833 parts.

[Production Example 7]
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 297 parts of cyclohexylamine, and the gas phase in the system was replaced with nitrogen at room temperature (20 ° C.) under stirring, and under reduced pressure (gauge pressure: −0.05 MPa) ) At a reaction temperature of 100 ° C., 264 parts of ethylene oxide was started to be blown, and the reaction was continued until there was no pressure change in the system while controlling the gauge pressure to be 0.1 to 0.3 MPa. (2 mol) 561 parts of an adduct were obtained.

[Examples 1 to 25 and Comparative Examples 1 to 5]
The components in Tables 1 and 2 were mixed uniformly at 20 ° C. using the beaker in the number of parts shown in Tables 1 and 2, and the detergents of Examples 1 to 25 and Comparative Examples 1 to 5 were mixed. Produced. However, the number of parts (A) to (F) shown in Tables 1 and 2 is the number of parts of the active ingredient, and the number of parts of ultrapure water is (A-1) to (A-6) and (D) described later. Water in PANA.
In addition, the symbol of the component in Table 1 and Table 2 is as follows.
・ MeXSNa: Meta-xylenesulfonic acid sodium salt (manufactured by Hokusei Kogyo Co., Ltd.)
SDS: sodium lauryl sulfate (manufactured by Nacalai Tesque, Inc .: comparative anionic surfactant)
PELSNa: polyoxyethylene lauryl ether sulfate sodium salt (Sandet EN, manufactured by Sanyo Chemical Industries, Ltd .: comparative anionic surfactant)
D2ehNa: sulfosuccinic acid di-2-ethylhexyl sodium salt (manufactured by Tokyo Chemical Industry Co., Ltd .: comparative anionic surfactant)
HC: hexyl carbitol (SP value 10.2)
PP-15: propylene pentamer (SP value 7.6)
TEG-M: triethylene glycol monomethyl ether (SP value 10.8)
FA: formamide (SP value 19.2: solvent for comparison)
-KOH: Potassium hydroxide-DBU: 1,8-diazabicyclo [5.4.0] -7-undecene [manufactured by San Apro Co., Ltd.]
MDEA: N-methyldiethanolamine CHNEG: cyclohexylamine ethylene oxide (2 mol) adduct obtained in Preparation Example 7 PANa: polyacrylic acid sodium salt [Carribbon L-400, 43% aqueous solution, Sanyo Chemical Industries Ltd. Made by company]
EDTA: ethylenediaminetetraacetic acid Cys: L-cysteine

  Using the cleaning agents of Examples 1 to 25 and Comparative Examples 1 to 5, pH, detergency-1, detergency-2, detergency-3, detergency-4, detergency-5, etching property, after cleaning Tables 3 and 4 show the results of measuring or evaluating the contact angle of water, the contact angle of the cleaning agent, the surface roughness, the foaming property and the stability over time.

  In addition, pH, detergency-1, detergency-2, detergency-3, detergency-4, detergency-5, etching property, contact angle of water after cleaning, contact angle of cleaning agent, surface roughness, The measurement or evaluation of foamability and stability over time was performed by the following method.

<Measurement of pH>
The measurement was performed at a measurement temperature of 25 ° C. using a pH meter (manufactured by Horiba, Ltd., M-12).

<Detergency-1>
10 mg of n-triacontane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a model contaminant on a commercially available glass substrate (manufactured by Corning, glass plate # 1737, length 10 cm × width 10 cm) at 70 ° C. hot plate (PMC Industries, A contaminated substrate was prepared by fusing for 1 minute on a digital hot plate series 730). 1000 g of the cleaning agent was put in a 2000 ml glass beaker, the produced contaminated substrate was immersed, and cleaning was performed at 30 ° C. for 5 minutes in an ultrasonic cleaning machine (200 kHz). After cleaning, the substrate was taken out, thoroughly rinsed with ultrapure water, then blown with nitrogen gas and dried, and the substrate surface was cleaned according to the following evaluation points using a differential interference microscope (manufactured by Nikon, OPTIPHOT- 2 and 400 times magnification). This evaluation was performed in a clean room of class 1,000 (FED-STD-209D, US Federal Standard, 1988) to prevent contamination from the atmosphere.
A: Almost completely removed.
○: Almost cleaned.
Δ: Some particles remain.
X: Almost no washing

<Detergency-2>
Evaluation was conducted in the same manner as in Detergency-1 except that 10 mg of dioctyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) was applied as a model contaminant.

<Detergency evaluation-3>
5 mg of glass powder obtained by cutting (breaking) the glass plate on a commercially available glass substrate (Corning, glass plate # 1737, length 10 cm × width 10 cm) was sprayed, and a 105 ° C. hot plate (PMC Industries, Evaluation was performed in the same manner as in Detergency-1 except that a contaminated substrate was prepared by heating on a digital hot plate series 730) for 1 hour.

<Detergency-4>
After polishing a commercially available glass substrate (Corning, glass plate # 1737, length 10 cm × width 10 cm) using a commercially available colloidal silica slurry (KEMIRA, VI-80) and a polishing cloth as an abrasive, The surface was rinsed with ultrapure water and blown with nitrogen to evaluate the same as in Detergency-1 except that a contaminated substrate was produced.

<Detergency evaluation-5>
Using a commercially available cerium oxide slurry (manufactured by Fujimi Incorporated, CEPOL-120) as a polishing agent and a polishing cloth, a commercially available glass substrate (manufactured by Corning, glass plate # 1737, length 10 cm × width 10 cm) is polished. Then, the surface was rinsed with ultrapure water and blown with nitrogen to evaluate the same as in the cleaning property-1, except that a contaminated substrate was produced.

<Etching evaluation>
After taking 10 g of cleaning agent into a 50 ml polypropylene container and adjusting the temperature to 50 ° C., put a substrate obtained by cutting a commercially available glass substrate (Corning, glass plate # 1737) into a size of 2 cm long × 2 cm wide, After immersion and standing at 50 ° C. for 24 hours, the cleaning agent was collected, and the Si content in the cleaning agent was measured with an ICP emission spectrometer (Varian730-ES, manufactured by VARIAN). In addition, the Si content (ppb) eluted during a test was calculated | required similarly about the cleaning agent before a test previously by measuring the Si content previously, and calculating | requiring the difference. The higher the eluted Si content, the higher the etching property.

<Contact angle of water after washing>
The substrate immediately after evaluating the detergency-1 was measured for a contact angle with water (at 25 ° C., after 10 seconds) using a fully automatic contact angle meter [PD-W, manufactured by Kyowa Interface Science Co., Ltd.].

<Contact angle of cleaning agent>
A commercially available glass substrate (Corning Corp., glass plate # 1737, length 10 cm × width 10 cm) was thoroughly rinsed with ultrapure water, and then the substrate immediately after being blown with nitrogen and dried at 25 ° C. was fully automatic contact angle The contact angle (25 ° C., 10 seconds later) with respect to the cleaning agent was measured using a total [PD-W manufactured by Kyowa Interface Science Co., Ltd.]

<Surface roughness>
After taking 10 g of the cleaning agent in a 20 ml glass container and adjusting the temperature to 50 ° C., put a substrate obtained by cutting a commercially available glass substrate (Corning, glass plate # 1737) into a size of 2 cm long × 2 cm wide, After dipping and leaving at 50 ° C. for 5 hours, the substrate is taken out using tweezers, rinsed thoroughly with ultrapure water to remove the cleaning agent, and then blown with nitrogen at 25 ° C. to dry the substrate. The surface roughness (Ra) was measured using an atomic force microscope (S-I Nano Technology Co., Ltd., E-Sweep). The smaller the Ra, the better the surface flatness.

<Foamability>
20 ml of detergent is put into a 100 ml glass-equipped graduated cylinder (size specified as a graduated cylinder of JIS R3504 “Chemical Volumetric Glass Material”), and the temperature is adjusted to 25 ° C. in a constant temperature bath. The lid of the closed graduated cylinder was closed and shaken vigorously up and down 60 times in 30 seconds, and the amount of foam (ml) immediately after shaking and after 1 minute was measured. The smaller the amount of foam immediately after shaking, the lower the foaming property, and the smaller the amount of foam after 1 minute, the higher the defoaming property.

<Stability over time>
Into a 50 ml glass container, 45 ml of the cleaning agent was taken and allowed to stand for 6 months under conditions of 5 ° C. and 50 ° C., and stability over time was evaluated according to the following evaluation points.
A: No change in appearance at 5 ° C. and 50 ° C.
○: Slightly separated at either 5 ° C or 50 ° C, but uniform when shaken lightly.
Δ: Separated considerably at either 5 ° C. or 50 ° C., but becomes uniform when shaken lightly.
X: Both 5 degreeC and 50 degreeC isolate | separate, Even if it shakes lightly, it does not become uniform.

  From the results described in Table 3 and Table 4, the electronic material cleaning agent of the present invention has a moderately controlled etching property without impairing the flatness of the substrate surface, organic matter stains, glass cullet, abrasives, etc. It can be seen that the particles are excellent in particle removability and recontamination prevention.

The cleaning agent for electronic materials of the present invention includes oil, dirt from human bodies (fingerprints, etc.), resin, plasticizer (dioctyl phthalate, etc.), organic substances such as organic particles, and inorganic particles (glass powder, abrasive grains, ceramic powder and metal). It is suitably used for cleaning in which powder or the like is to be cleaned.
Therefore, the cleaning agent for electronic materials of the present invention can be used for various electronic materials [for example, flat panel display substrates (glass substrates for liquid crystal panels, color filter substrates, array substrates, plasma display substrates, organic EL substrates, etc.), Photomask substrate, hard disk substrate (aluminum substrate, NiP substrate, glass substrate, magnetic disk, magnetic head, etc.), semiconductor substrate (semiconductor element, silicon wafer, etc.), optical lens, printed wiring board, optical communication cable, LED, solar cell substrate and quartz crystal resonator] can be suitably used in a cleaning process in the manufacturing process.
The electronic material cleaning method of the present invention is particularly suitable when the electronic material is a flat panel display substrate, a photomask substrate, a hard disk substrate, or a semiconductor substrate.

Claims (12)

The anionic component contains an anionic surfactant (A) represented by the general formula (1), an alkene (B) having 6 to 18 carbon atoms, and an alkaline component (C). A cleaning agent for electronic materials having an SP value of 6 to 13 and a pH at 25 ° C of 10 to 14 at an active ingredient concentration of 0.1 to 15%.
^{R 1 [- (OA 1)} a -Q -] b (1)
[Wherein, R ¹ is a hydrocarbon group having 4 to 10 carbon atoms, A ¹ is an alkylene group having 2 to 4 carbon atoms, Q ⁻ is —COO ⁻ , —OCH ₂ COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ^- or _{^{-OPO 2 (oR 2) -,}} R 2 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, a is 0 to 20 and an average value, b is an integer of 1 to 6, Q ^- is -COO ^- or -SO ₃ ^- in the case a of zero. ] Furthermore, the cleaning agent for electronic materials of Claim 1 which has an SP value of 6-13 and contains the organic solvent (D) shown by General formula (2).
R ^Three [-(OA ² ) _c -OH] _d                       (2)
[Wherein R ^Three Is a hydrocarbon group having 6 to 8 carbon atoms, A ² Is an alkylene group having 2 to 4 carbon atoms, c is an average value of 0 to 20, and d is an integer of 1 to 6. ] The cation component of the anionic surfactant (A) is an alkali metal cation, a monovalent cation obtained by adding a proton to an aliphatic amine having 1 to 15 carbon atoms, or a proton added to an amidine compound having 4 to 10 carbon atoms. The cleaning agent for electronic materials according to claim 1 or 2, which is at least one cation selected from the group consisting of a cation and a monovalent cation obtained by adding a proton to an alkanolamine having 1 to 15 carbon atoms. The cleaning agent for electronic materials according to any one of claims 1 to 3 , wherein, in the general formula (1), R ¹ is a hydrocarbon group represented by the general formula (3) or the general formula (4).

[Wherein, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of R ⁴ and R ⁵ is 3 to 8, e is an integer of 0 to 2; When the total number of carbon atoms of R ⁴ and R ⁵ is 8, e is 0 or 1. ]

[Wherein, f R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the total number of carbon atoms of f R ⁶ is 4 or less, and f is an integer of 1 to 4] It is. ] In general formula (1), a is 0 and b is 1, and the alkali component (C) is an aliphatic amine (C-2) having 1 to 36 carbon atoms, an inorganic alkali (C-3), or 1 to C carbon atoms. The electronic material according to any one of claims 1 to 4 , which is one or more alkali components selected from the group consisting of 23 alkanolamines (C-4) and amidine compounds (C-5) having 4 to 10 carbon atoms. Washing soap. Based on the weight of the active ingredient of the electronic material cleaning agent, the content of (A) is 0.5 to 80% by weight, the content of (B) is 1 to 90% by weight, and the content of (C) The cleaning agent for electronic materials according to any one of claims 1 to 5 , wherein the amount is 1 to 55% by weight.   The cleaning agent for electronic materials according to any one of claims 1 to 6, wherein a contact angle of the cleaning agent with respect to glass at an active ingredient concentration of 0.1 to 15% by weight of the cleaning agent is 10 ° or less.   The cleaning agent for electronic materials according to claim 1, wherein a contact angle of water with respect to the glass cleaned using the cleaning agent is 20 ° or less.   The said electronic material is a glass-made electronic material board | substrate, The cleaning agent for electronic materials in any one of Claims 1-8. The electronic material cleaning agent according to any one of claims 1 to 9 , wherein the electronic material is a flat panel display, a photomask, a hard disk, or a semiconductor substrate. The cleaning method of the electronic material using the cleaning agent in any one of Claims 1-10 . The cleaning method according to claim 11 , wherein the electronic material is an electronic material substrate made of glass .