JP2009263508A - Detergent for electronic material and cleaning method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-bubbling detergent for electronic materials, which has an excellent bubble extinguishing property, and an excellent particle removing property and rinsing property. <P>SOLUTION: The detergent for electronic material contains an anionic surfactant of formula (1) (wherein R<SP>1</SP>and R<SP>2</SP>are each a 1-6C alkyl group, provided that the total number of carbon atoms in R<SP>1</SP>and R<SP>2</SP>is 2-7; R<SP>3</SP>is a 1-3C alkylene group; R<SP>4</SP>is a 2-4C alkylene group; X<SP>-</SP>is -COO<SP>-</SP>, -OCH<SB>2</SB>COO<SP>-</SP>, -OSO<SB>3</SB><SP>-</SP>, -SO<SB>3</SB><SP>-</SP>or -OPO<SB>2</SB>(OR<SP>5</SP>)<SP>-</SP>; R<SP>5</SP>is a hydrogen atom or a group of the formula: R<SP>1</SP>(C=O)<SB>a</SB>-N(R<SP>2</SP>)-R<SP>3</SP>-(OR<SP>4</SP>)<SP>b</SP>-; M<SP>+</SP>is a cation; a is 0 or 1; and b is an average and is 0-10) and shows foaming power of ≤50 mm and foam stability of ≤5 mm in the Ross-Miles test conducted on a 0.2 wt.% aqueous solution at 20°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a cleaning agent for electronic materials and a cleaning method.

  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 more easily adhere to the interface and remain more than before. Therefore, establishment of advanced cleaning technology is urgently required. For this reason, for the purpose of preventing contamination by these particles, a method of improving the particle removability using a surfactant has been proposed (see Patent Document 1).

However, in the process of manufacturing glass or silicon substrates for flat panel displays, hard disks and semiconductors, glass chips (commonly referred to as glass cullet) generated when cutting glass substrates to an appropriate size from mother glass, and clean rooms Ingredients such as dust and processing oil scattered inside, the polishing and polishing debris used in the mirror finishing and texturing processes of the substrate surface adhere firmly to the substrate surface, and the cleaning process There is a problem that it cannot be removed sufficiently.
The cleaning agent proposed in Patent Document 1 is a cleaning solution in which alkyl glucoside, glyceryl ether and hydrocarbon are dissolved, and contains a nonionic surfactant to improve the performance of particle removal. Since the components in the agent tend to remain on the surface of the electronic material, there is a problem that the rinsing property is poor and the yield rate is lowered. Furthermore, Patent Document 1 proposes a sulfosuccinic acid type anionic surfactant having an average carbon number of 10 to 20 to improve particle removal performance by improving penetrating power. Although improvement is observed, the foaming property is very high and the foaming property is poor.
JP 2004-26991 A

  The subject of this invention is providing the cleaning agent for electronic materials which implement | achieves the removal property and the rinse property which were excellent in the low foaming property and excellent foaming property, and the particle | grains.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific cleaning agent can solve the above-mentioned problems, and have reached the present invention. That is, the present invention is a cleaning agent for electronic materials containing the anionic surfactant (A) represented by the general formula (1), wherein a loss of 20 wt. A cleaning agent for electronic materials, wherein the foaming force measured by a Miles test is 50 mm or less and the stability of the foam is 5 mm or less, and a cleaning method for electronic materials using the cleaning agent for electronic materials .
[Wherein R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of R ¹ and R ² is 2 to 7; R ³ is an alkylene having 1 to ³ carbon atoms] R ⁴ is an alkylene group having 2 to ⁴ carbon atoms; X ⁻ is —COO ⁻ , —OCH ₂ COO ⁻ , —OSO ₃ ⁻ , —SO ₃ ^— or —OPO ₂ (OR ⁵ ) ⁻ , ⁵ is a hydrogen atom or _{^{R 1 (C = O) a}} -N (R 2) -R 3 - (oR 4) b - group represented by; M ⁺ is a cation; a is 0 or 1; b is an average value And represents 0-10. ]

The electronic material cleaning agent of the present invention has the following effects in an electronic material manufacturing process, particularly in a flat panel display, hard disk and semiconductor glass or silicon substrate manufacturing process.
(1) Excellent particle removability and rinsing properties.
(2) It has excellent low foaming properties and excellent foaming properties.

In the general formula (1) representing the anionic surfactant (A) in the present invention [hereinafter sometimes simply referred to as (A)], R ¹ and R ² each independently have 1 to 6 carbon atoms. It represents an alkyl group, and the total number of carbon atoms of R ¹ and R ² is 2-7. From the viewpoint of particle removability and low foaming property, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, and the total number of carbon atoms of R ¹ and R ² is preferably 3 to 6. .

Examples of R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and a 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-methylpentyl group, 2-methylpentyl Group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3- Dimethylbutyl group, 3,3-dimethylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-ethyl-1-methyl Examples include a propyl group and a 1-ethyl-2-methylpropyl group.

R ³ is an alkylene group having 1 to ³ carbon atoms, and examples thereof include a methylene group, an ethylene group, a 1,2-propylene group, and a 1,3-propylene group.

R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, specifically, an ethylene group, 1,2- or 1,3-propylene group, and 1,2,1,3-, 2,3- or 1, 4-butylene group is mentioned. Among these, ethylene group and 1,2-propylene group are preferable from the viewpoint of low foamability, and R ⁴ may be a single alkylene group or a combination of two or more alkylene groups. As described below, R ⁴ is formed by an addition reaction of the alkylene oxide whose alkylene group is R ⁴ , and therefore the number of added moles in these adducts has a distribution. Therefore, b is represented by an average value and is usually 0 to 10, and preferably 0 to 5 from the viewpoint of low foaming property. In addition, when two or more kinds of alkylene oxides are used in combination for the formation of R ⁴ , both block addition (chip type, balance type, active secondary type, etc.) and random addition, both mixed systems [chips after random addition: 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 are chipped at the molecular ends Things]. Unless otherwise specified above and below,% represents% by weight.

X ⁻ represents —COO ⁻ , —OCH ₂ COO ⁻ , —OSO ₃ ⁻ , —SO ₃ ^— or —OPO ₂ (OR ⁵ ) ⁻ [R ⁵ represents a hydrogen atom or R ¹ (C═O) _a —N ( R ² ) —R ³ — (OR ⁴ ) _b —], and from the viewpoint of the contact angle of water after washing, —COO ⁻ , —OSO ₃ ⁻ , —SO ₃ ^— and —OPO ₂ (OR ³ ) ⁻ is preferred, and —COO ⁻ , —OSO ₃ ^— and —SO ₃ ^— are more preferred. Incidentally, X ^- is -COO ^- or -SO ₃ ^- in the case of, b is 0.

M ⁺ is a cation, and examples of the cation include an alkali metal cation, an alkaline earth metal cation, an amine cation, an ammonium cation (NH ₄ ⁺ ), and a quaternary ammonium cation.

  Examples of the alkali metal cation include sodium cation, potassium cation and lithium cation. Examples of alkaline earth metal cations include calcium cations and magnesium cations. Examples of the amine cation include those obtained by adding a proton to an amine having 1 to 15 carbon atoms. Examples of the amine having 1 to 15 carbon atoms include methylamine, ethylamine, isopropylamine, dimethylamine, trimethylamine, diethanolamine, 2- Pyridineamine, cis-3-methylcyclohexylamine, benzylamine and 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter abbreviated as DBU), 1,5-diazabicyclo [4.3.0] Cations of monovalent amines such as amidine such as -5-nonene (hereinafter abbreviated as DBN), 2-methylimidazole, 2-butylbenzimidazole and 2- (4-thiazolyl) benzimidazole, and ethylenediamine, 1,5- Pentanediamine, diethylenetriamine, triethylenetet Amine, tetraethylene pentamine, pentaethylene hexamine, hexaethyleneheptamine, polyethyleneimine, paraphenylenediamine, cationic 2-7 monovalent amines such as tri-aminonaphthalene and triamino anthracene.

  The quaternary ammonium cation includes a quaternary ammonium cation having a hydrocarbon group having 1 to 25 carbon atoms [tetramethylammonium, trimethylvinylammonium, trimethylphenylammonium, benzyltriethylammonium, dodecyltrimethylammonium, tetrabutylammonium, trimethyltetradecyl. Ammonium, benzyltributylammonium, tetrapentylammonium, ethylhexadecyldimethylammonium, octadecyltrimethylammonium, etc.].

  Among the cations, alkali metal cations, amine cations and combinations thereof are preferable from the viewpoint of particle removability, and potassium cations, trimethylamine cations, diethanolamine cations, DBU cations and DBN cations are particularly preferable. Are potassium cation, diethanolamine cation and DBU cation.

As a manufacturing method of an anionic surfactant (A), the following method is mentioned, for example.
(1) Production of X- is —OSO ₃ ^— or —OPO ₂ (OR5) ^— ;
The alkylene oxide adduct of dialkylamine or dialkylamino alcohol is sulfated or phosphated and neutralized with an alkali.
(2) Production of X- is —SO ₃ ^— ;
Monoalkyl taurine and carboxylic acid halide are reacted to form monoalkyl monoacylated taurine and neutralized with alkali.
(3) Production of X- is —COO 2 ^—
An amino acid and a carboxylic acid halide are reacted to form an acylated amino acid and neutralized with an alkali.
(4) X- is -OCH ₂ COO ^- production of things;
An alkylene oxide adduct of dialkylamino alcohol or dialkylamine is carboxymethylated in the presence of an alkali metal monohalogenated acetic acid salt and an alkali (such as sodium hydroxide or potassium hydroxide).

  The production of the alkylene oxide adduct is carried out in the usual manner. A dialkylamine, dialkylamino alcohol, acylalkylamine or acylalkylamino alcohol is charged into a pressure reaction vessel, and the alkylene oxide is added without a catalyst or in the presence of a catalyst. The reaction is carried out in one stage or in multiple stages under blowing, normal pressure or pressure. Examples of the catalyst include alkali catalysts [for example, hydroxides of alkali metals (lithium, sodium, potassium, cesium, etc.), acids [perhalogen acids (perchloric acid, perbromic acid, periodic acid, etc.), sulfuric acid, phosphoric acid, and 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 alkylene oxide addition reaction, the catalyst can be neutralized and treated with an adsorbent as necessary to remove and purify the catalyst.

  Examples of the sulfate esterification method include (a) a method using chlorosulfonic acid, (b) a method using sulfane, (c) a method using sulfamic acid, and (d) a method using sulfuric acid. In the case of (i) and (b), the reaction temperature is usually −10 to 70 ° C., preferably −5 to 40 ° C. In the case of (c) and (d), the temperature is usually 50 to 150 ° C, preferably 60 to 130 ° C. The end point of the sulfuric 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%. is there. Examples of the phosphoric acid esterification method include a method of reacting at a reaction temperature of 50 to 150 ° C. using phosphoric acid.

  Specific examples of the anionic surfactant (A) include N-methyl-Nn-butylamine ethylene oxide 1 mol addition product sulfate potassium salt, N-methyl-Nn-butylamine ethylene oxide 1 mol addition. Sulfuric acid ester DBU salt, N-methyl-Nn-butylamine ethylene oxide 1 mol adduct sulfate diethanolamine salt, N-methyl-Nn-butylamine ethylene oxide 1 mol adduct phosphate potassium salt, N -Valeryl sarcosine potassium salt, N-methyl-N-valeryl taurine potassium salt, N, N-dimethylamino-1-propanol sulfate potassium salt, N-propyl-N-sec-butylamine ethylene oxide 1 mol adduct Sulfate ester potassium salt, N-methyl-Nn-buty Ethylene oxide 11 mol adduct sulfuric acid ester potassium salt of an amine, and N- methyl -N-n-butylamine ethylene oxide 1 mol / 1,2-propylene oxide 5 mol block adduct sulfuric acid ester potassium salt and the like.

  The foaming power at 20 ° C. according to the Ross Miles test in the present invention can be measured according to JIS K3362 (1998), and the surface activity is adjusted using ion-exchanged water as an apparatus and test solution defined in JIS. This is a value obtained by visual observation of the height of the foam immediately after all the test solutions flow out in a test using a 0.2% aqueous solution of the agent.

  Further, the foam stability in the present invention refers to the height of the foam 1 minute after all of the test liquid has flowed out in the Loss-Miles test, and the lower the foam height after 1 minute, the lower the foam stability. The stability of the foam is low, that is, the foaming property is good, which is preferable for the cleaning agent of the present invention.

Specifically, for example, foaming power and foam stability can be determined as follows.
(1) The inner cylinder of the foaming force measuring device for Los Miles test specified in JIS K3362 (1998) is set up vertically, and predetermined water is circulated to the outer cylinder by a pump to keep it at a constant temperature (20 ° C.). .
(2) While maintaining the test solution (0.2% aqueous solution of surfactant) at the same temperature (20 ° C.), pour 50 ml of the test solution along the tube wall of the inner cylinder so as to moisten the entire side surface.
(3) Take 200 ml of the test solution in a pipette, set it on the top of the foaming force measuring device for Ross Miles test, open the top cock, let the test solution flow out in about 30 seconds, and drop Is allowed to flow down so as to fall to the center of the inner cylinder liquid surface.
(4) Immediately after all the test solution has flowed out, the height (mm) (foaming force) of the foam is visually measured.
(5) Further, after 1 minute, the height (mm) of foam (the stability of foam) is measured visually.
(6) This operation is performed twice, and the average of each measured value is obtained up to an integer, and the foaming power and the stability of the foam are obtained.

  The foaming power of the 0.2% aqueous solution of the anionic surfactant (A) of the present invention is usually 50 mm or less, preferably 40 mm or less, more preferably 30 mm or less, particularly preferably from the viewpoint of suppressing foaming during use. Is 20 mm or less, most preferably 10 mm or less. In addition, the lower limit of said foaming force is 0 mm.

  The stability of the foam of the 0.2% aqueous solution of the anionic surfactant (A) of the present invention is usually 5 mm or less, preferably 4 mm or less, more preferably 3 mm or less from the viewpoint of suppressing foaming during use. Particularly preferably, it is 2 mm or less, and most preferably 1 mm or less. In addition, the lower limit of the stability of the foam is 0 mm.

  The cleaning agent for electronic materials of the present invention can contain the following organic solvent (B) [hereinafter sometimes simply referred to as (B)]. By containing (B), the organic dirt removal property, low foaming property and foaming property are further improved. Examples of (B) include the following.

C1-C8 monohydric alcohol solvent (B-1):
Methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, diacetone alcohol, 1-octanol, 2-ethylhexanol and the like;

C2-C9 glycol solvent (B-2):
Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butylene glycol and the like;

C3-60 glycol ether solvent (B-3):
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, methyl alcohol ethylene oxide (10 mol) adduct and allyl alcohol ethylene oxide (5 mol) propylene oxide (15 mol) block adduct, etc .;

C6-C12 saturated hydrocarbon solvent (B-4):
n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane and the like;
C6-C18 unsaturated aliphatic hydrocarbon solvent (B-5):
1-hexene, 1- or 2-heptene, 1- or 3-octene, 1- or 4-nonene, 1-decene, 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 and propylene pentamer, etc .;

C4-10 ether solvent (B-6):
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and tetrahydrofuran, tetrahydropyran, etc .;
C3-C10 ketone solvent (B-7):
Acetone, diethyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, acetophenone, benzyl ethyl ketone, etc .;

C3-C6 amide solvent (B-8):
N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-hydroxymethyl-2- Pyrrolidone, etc .;
C2-C6 ester solvent (B-9):
β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-methyl-γ-valerolactone, ethylene carbonate, propylene carbonate, and the like;

C2-C10 sulfur-containing solvent (B-10):
Dimethylsulfoxide, dimethylsulfone, diethylsulfone, di-n-butylsulfone, diisobutylsulfone, di-tert-butylsulfone, butylphenylsulfone, bis (2-hydroxyethyl) sulfone, sulfolane, 3-methylsulfolane and 2,4- Dimethyl sulfolane and the like;
C3-C4 oxazolidinone solvent (B-11):
N-methyl-2-oxazolidinone, 3,5-dimethyl-2-oxazolidinone and the like;
C2-C7 nitrile solvent (B-12):
Acetonitrile, propionitrile, butyronitrile, acrylonitrile, methacrylonitrile, benzonitrile and the like;

  Among (B), preferred are (B-1), (B-2), (B-3), and (B-4) from the viewpoints of removal of organic matter stains, low foaming property and foaming property. And (B-5), more preferred are (B-2), (B-3), (B-4) and (B-5), and particularly preferred are (B-3) and (B-4). And (B-5), particularly preferred are ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, n-hexane, n-heptane, n-octane, n-nonane. N-decane, n-undecane, n-dodecane, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, -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 and propylene penta Diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, butylene dimer, butylene trimer, butylene tetramer, isobutylene trimer , Propylene dimer, propylene trimer, propylene tetramer and propylene pentamer. (B) may be used independently and may use 2 or more types together.

  The electronic material cleaning agent of the present invention may contain the following alkali component (C) [hereinafter sometimes simply referred to as (C)]. By containing (C), the particle removability is further improved.

  As (C), ammonia (C-1), quaternary ammonium salt (C-2), aliphatic amine (C-3) having 1 to 36 carbon atoms, inorganic alkali (C-4), carbon number 1 -23 alkanolamines (C-5) and mixtures thereof.

  (C-2) 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.

  (C-3) includes an alkylamine having 1 to 12 carbon atoms, an alkylenediamine having 2 to 6 carbon atoms, a cyclic amine having 4 to 6 carbon atoms, an amidine compound having 5 to 10 carbon atoms, and a poly (n = 2 to 2). 6) Alkylene (having 2 to 6 carbon atoms) poly (n = 3 to 7) amine and the like.

  Examples of the alkylamine having 1 to 12 carbon atoms include monoalkylamines having 1 to 6 carbon atoms [methylamine, ethylamine, propylamine, isopropylamine, butylamine, hexylamine and the like] and dialkylamines having 2 to 12 carbon atoms [dimethylamine. , Ethyl methylamine, propylmethylamine, butylmethylamine, diethylamine, propylethylamine, diisopropylamine, dihexylamine, etc.].

  Examples of the alkylene diamine having 2 to 6 carbon atoms include ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine and hexamethylene diamine.

  Examples of the cyclic amine having 4 to 6 carbon atoms include piperidine, piperazine, quinuclidine, and 1,4-diazabicyclo [2.2.2] octane (DABCO).

  Examples of the amidine compound having 5 to 10 carbon atoms include DBU and DBN.

  Poly (n = 2-5) alkylene poly (n = 3-7) amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethyleneheptamine, iminobispropylamine, bis (hexamethylene) triamine and pentane. Ethylenehexamine etc. are mentioned.

  Examples of (C-4) include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide.

  (C-5) includes monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, 2-amino-2-methyl-1-propanol N- (aminoethyl) ethanolamine, 2- (2-aminoethoxy) ethanol, ethylenediamine ethylene oxide adduct (addition mole number 10), hydroxylamine and the like.

  Among (C), (C-3), (C-4), (C-5) and a mixture thereof are preferable and more preferable from the viewpoint of etching property and contact angle (rinsing property) of water after washing. Is potassium hydroxide, sodium hydroxide, DBU, N-methyldiethanolamine and mixtures thereof.

  The electronic material cleaning agent of the present invention may contain the following chelating agent (D) [hereinafter sometimes simply referred to as (D)]. By containing (D), the dispersion stability of the particles is further improved.

(D) includes aminocarboxylic acid (salt) (D-1) [for example, ethylenediaminetetraacetic acid (hereinafter abbreviated as EDTA) (salt), diethylenetriaminepentaacetic acid (hereinafter abbreviated as DTPA) (salt), triethylene Tetramine hexaacetic acid (salt), hydroxyethylethylenediaminetriacetic acid (salt), dihydroxyethylethylenediaminediacetic acid (hereinafter abbreviated as DHEDDA) (salt), nitrilolic acid acetic acid (salt), N-2-hydroxyethyliminodiacetic acid (salt) ), 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) (D-2) [eg, hydroxyacetic acid (salt), tartaric acid (salt), citric acid (salt) and gluconic acid (salt)];
Cyclocarboxylic acid (salt) (D-3) [for example, benzene polycarboxylic acid (salt) such as pyromellitic acid (salt) and cyclopentanetetracarboxylic acid (salt)];
Ether carboxylic acid (salt) (D-4) [for example, 2-oxapropane-1,1,3-tricarboxylic acid, (carboxymethoxy) succinic acid, 2,2′-oxybissuccinic acid, 2- (1, 2-dicarboxyethoxy) -3-hydroxybutanedioic acid and 2,3-bis (1,2-dicarboxyethoxy) butanedioic acid];
Other carboxylic acids (salts) (D-5) [eg maleic acid derivatives and oxalic acid (salts)];
Phosphonic acid (salt) (D-6) [for example, methyldiphosphonic 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), tris (2-aminoethyl) amine, hexa (methylenephosphonic acid) (salt), trans-1,2-cyclohexanediaminetetra (methylenephosphonic acid) (salt), glycol etherdiaminetetra (methylenephosphone) Acid) (salt) and tetraethylenepentami Hepta (methylene phosphonic acid) (salt)];
Condensed phosphoric acid (salt) (D-7) [e.g., metaphosphoric acid (salt), tripolyphosphoric acid (salt) and hexametaphosphoric acid (salt)];
Etc.

  Although there is no limitation in particular as a counter ion in case (D) forms a salt, For example, the cation illustrated by the above-mentioned anionic surfactant (A) is mentioned, These are combining 1 type (s) or 2 or more types. May be used. Moreover, (D) may be used independently and may use 2 or more types together.

  Of these, (D-1), (D-2), (D-5), (D-6) and (D) are preferred from the viewpoints of particle dispersion stability and substrate etching control. -7), more preferred are (D-1), (D-2), (D-6) and (D-7), and particularly preferred are EDTA (salt), DTPA (salt), DHEDDA ( Salt), aspartic acid diacetic acid (salt), aspartic acid (salt), glutamic acid (salt), citric acid (salt), 1-hydroxyethylidene-1,1-diphosphonic acid (salt), ethylenediaminetetra (methylenephosphonic acid) (Salt), metaphosphoric acid (salt) and hexametaphosphoric acid (salt), most preferred are EDTA (salt), citric acid (salt) and hexametaphosphoric acid (salt).

  The electronic material cleaning agent of the present invention may contain the following dispersant (E) [hereinafter sometimes simply referred to as (E)]. By containing (E), the dispersibility of particles and the anti-recontamination property are further improved.

  As (E), a polymeric anionic surfactant (E-1) having a sulfonic acid (salt) group, a polymeric anionic surfactant (E-2) having a sulfate (salt) group, Polymer type anionic surfactant (E-3) having phosphate ester (salt) group, polymer type anionic surfactant (E-4) having phosphonic acid (salt) group, carboxylic acid (salt) And a polymer type anionic surfactant (E-5) having a group and a compound (E-6) having 3 or more hydroxyl groups. Specific examples of (E) include the following.

Polymer type anionic surfactant (E-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;

Polymeric anionic surfactant (E-2) having a sulfate (salt) group:
Poly [2-hydroxyethyl (meth) acrylate sulfate], 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate sulfate copolymer, sulfuric acid of poly [2-hydroxyethyl (meth) acrylate] Esterified products, poly [(meth) acryloyloxypolyoxyalkylene sulfate], (meth) acryloyloxypolyoxyalkylene sulfate / acrylic acid copolymers and sulfates of cellulose, methylcellulose or ethylcellulose, and salts thereof;

Polymer type anionic surfactant (E-3) having a phosphate ester (salt) group:
Poly [2-hydroxyethyl (meth) acrylate phosphate ester], 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate phosphate ester copolymer, poly [2-hydroxyethyl (meth) acrylate] Phosphoric acid ester, poly [(meth) acryloyloxypolyoxyalkylene phosphoric acid ester], (meth) acryloyloxypolyoxyalkylene phosphoric acid ester / acrylic acid copolymer, cellulose, methyl cellulose or ethyl cellulose phosphoric acid ester and Monoalkyldi (polyoxyethylene) phosphates and their salts;

Polymer type anionic surfactant (E-4) having a phosphonic acid (salt) group:
Poly [(meth) acryloyloxyethanephosphonic acid], 2-hydroxyethyl (meth) acrylate / (meth) acryloyloxyethanephosphonic acid copolymer, naphthalenephosphonic acid formaldehyde condensate, methylnaphthalenephosphonic acid formaldehyde condensate, dimethylnaphthalene Phosphonic acid formaldehyde condensate, anthracene phosphonic acid formaldehyde condensate, aniline phosphonic acid-phenol-formaldehyde condensate and the like and salts thereof;

Polymer type anionic surfactant (E-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 (meth) acrylate / (meth) acrylic acid copolymer, carboxymethylated product of poly [2-hydroxyethyl (meth) acrylate], carboxymethylcellulose, carboxymethylmethylcellulose, carboxymethylethylcellulose, Benzoic acid formaldehyde condensate, benzoic acid-phenol-formaldehyde condensate and the like and salts thereof;

Compound (E-6) having 3 or more hydroxyl groups:
Trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, glycerine alkylene (2 to 4 carbon atoms) oxide adduct (added moles of 1 to 30), sorbitol, sorbitol alkylene (C2-C4) oxide adduct (addition mole number 1-60), monosaccharide (arabinose, xylose, ribose, xylulose, ribulose, glucose, mannose, galactose, fructose, sorbose, tagatose, cedoheptulose, etc.), disaccharide (Trehalose, saccharose, maltose, cellobiose, gentiobiose, lactose, etc.) and trisaccharides (raffinose, maltotriose, etc.), polysaccharides more than tetrasaccharide and derivatives thereof (hydride) Carboxymethyl cellulose, cationized cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, guar gum, cationized guar gum, xanthan gum, alginates and cationized starch) and Poval like.

  In addition, as a counter ion in case (E) forms a salt, the cation illustrated by the above-mentioned anionic surfactant (A) is mentioned, These may be used 1 type or in combination of 2 or more types. Good. Moreover, (E) may be used independently and may use 2 or more types together.

  Among (E), (E-5) is preferable from the viewpoint of dispersibility of particles, and poly (meth) acrylic acid, (meth) acrylic acid-maleic acid copolymers, and salts thereof are more preferable.

  The polymer type in (E-1) to (E-5) means that the weight average molecular weight (hereinafter abbreviated as Mw) is 300 to 800,000. Mw of (E-1) to (E-5) is preferably 600 to 400,000, more preferably 1,000 to 80,000, from the viewpoint of preventing reattachment of particles and low foaming property. Most preferably, it is 2,000-40,000. Mw in the present invention is measured by gel permeation chromatography at 40 ° C. using polyethylene oxide as a reference substance [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 substance: TSK STANDARD POLYETHLENE OXIDE manufactured by Tosoh Corporation, data processing software: GPC-8020 model II (manufactured by Tosoh Corporation)].

  The electronic material cleaning agent of the present invention can contain the following reducing agent (F) [hereinafter, it may be simply expressed as (F)]. By containing (F), the flatness of the substrate surface is further improved.

  Examples of (F) include an organic reducing agent (F-1) and an inorganic reducing agent (F-2). Examples of the organic reducing agent (F-1) include aliphatic organic reducing agents, aromatic organic reducing agents, and other organic reducing agents.

  Examples of the aliphatic organic reducing agent include ascorbic acid (salt) having 6 to 12 carbon atoms and derivatives thereof [L-ascorbic acid, isoascorbic acid, 5,6-alkylidene-L-ascorbic acid {5,6-O-isopropylidene. Redene-L-ascorbic acid, 5,6-O- (butane-2-ylidene) -L-ascorbic acid and 5,6-O- (pentane-3-ylidene) -L-ascorbic acid, etc.}, sulfuric acid ascorbic acid Ester, ascorbic acid phosphate ester, ascorbic acid glucoside and salts thereof] and the like.

  Examples of the aromatic organic reducing agent include aromatic amines having 6 to 9 carbon atoms (such as p-phenylenediamine and p-hydroxyaniline) and phenolic compounds having 6 to 30 carbon atoms (3-hydroxyflavone, α-, β-, γ-, δ-, ε- or η-tocopherol, 3,4,5-trihydroxybenzoic acid, pyrocatechol, resorcinol, hydroquinone, naphthoresorcinol, pyrogallol and phloroglucinol).

  Other organic reducing agents include phosphorus-based reducing agents (such as tris-2-carboxyethylphosphine), aldehydes (such as formaldehyde and acetaldehyde), borane-based complexes (borane-tert-butylamine complex, borane-N, N-diethylaniline). Complexes and borane-trimethylamine complexes), thiol-based reducing agents (such as cysteine and aminoethanethiol), hydroxylamine-based reducing agents (such as hydroxylamine and diethylhydroxylamine), and the like.

  As the inorganic reducing agent (F-2), sulfurous acid (salt), thiosulfuric acid (salt), phosphorous acid (salt), hypophosphorous acid (salt), ferrous sulfate, stannic chloride, hydrogenated cyano Examples include sodium borohydride and sodium borohydride.

  Examples of the counter ion when these reducing agents (F) form a salt include the cations exemplified in the above-mentioned anionic surfactant (A). These cations are used alone or in combination of two or more. May be. Moreover, (F) may be used independently and may use 2 or more types together.

  Among (F), (F-1) is preferable from the viewpoint of etching property control of the cleaning agent and recontamination of the substrate with ions in the cleaning agent, and more preferably aliphatic organic reducing agents and other organic reducing agents. Among them, thiol-based reducing agents, particularly preferably ascorbic acid (salt) and cysteine are preferred.

  The electronic material cleaning agent of the present invention may contain the following nonionic surfactant (G) [hereinafter sometimes simply referred to as (G)]. By containing (G), the solubility of (B-4) and (B-5) in the cleaning liquid is further improved.

  As (G), fatty acid (carbon number 8 to 18) ethylene oxide adduct (addition mole number 1 to 60), polypropylene glycol (Mw 200 to 4000) ethylene oxide adduct (addition mole number 1 to 100), polyoxyethylene (Repeating unit number 3 to 60) alkyl (carbon number 6 to 20) allyl ether, polyvalent (2 to 8 valence or more) alcohol (carbon number 2 to 30) fatty acid (carbon number 8 to 24) ester ethylene oxide Addition (addition mole number 1-60) [Sorbitan monolaurate ethylene oxide addition product (addition mole number 1-60), sorbitan monooleate ethylene oxide addition product (addition mole number 1-60), etc.]], alkyl (carbon number) 8-24) Amine ethylene oxide adduct (addition mole number 1 to 100), polyvalent (2 to 8 or more) Top) Fatty acid (carbon number 8-24) ester [glycerin monostearate, glycerin monooleate, sorbitan monolaurate, sorbitan monooleate, etc.] of alcohol (carbon number 2-30) and fatty acid (carbon number 8-24) alkanol (C2-C6) amide [lauric acid monoethanolamide, lauric acid diethanolamide and lauric acid-1-tert-butylethanolamide] and the like. (G) may be used alone or in combination of two or more.

  The electronic material cleaning agent of the present invention can contain other additives (H) [hereinafter sometimes simply referred to as (H)] as long as the effects of the cleaning agent are not impaired. Examples of (H) include antioxidants, rust inhibitors, pH adjusters, buffers, antifoaming agents, preservatives, and hydrotropes.

  Examples of the antioxidant include phenolic antioxidants, amine antioxidants, sulfur compounds, and phosphorus antioxidants. These may be used alone or in combination of two or more.

  Examples of the rust preventive include nitrogen-containing organic rust preventives, alkyl or alkenyl succinic acids, and polyhydric alcohol partial esters. These may be used alone or in combination of two or more.

  Examples of pH adjusters include inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, etc.), organic acids (citric acid, oxalic acid, lactic acid, etc.), quaternary ammonium salts, ammonia, aliphatic amines having 1 to 10 carbon atoms. And inorganic alkali (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.) and the like. These may be used alone or in combination of two or more.

  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 their salts. In addition, as a counter ion in case a buffer forms a salt, the cation illustrated by the above-mentioned anionic surfactant (A) is mentioned, These may be used 1 type or in combination of 2 or more types. Moreover, a buffering agent may be used independently and may use 2 or more types together.

  Examples of the antifoaming agent include silicone antifoaming agents [antifoaming agents containing dimethyl silicone, fluorosilicone, polyether silicone and the like as constituents] and the like. These may be used alone or in combination of two or more.

  Examples of the preservative include triazine derivatives, isothiazoline derivatives, pyridine and pyridine derivatives, morpholine derivatives, and benzimidazole derivatives. These may be used alone or in combination of two or more.

  Examples of the hydrotrope include toluene sulfonic acid (salt), xylene sulfonic acid (salt), cumene sulfonic acid (salt), and the like. In addition, as a counter ion in the case of forming a salt, cations similar to those exemplified in the above-mentioned anionic surfactant (A) can be mentioned, and these may be used alone or in combination of two or more. Good. Moreover, a hydrotrope agent may be used independently and may use 2 or more types together.

  The electronic material cleaning agent of the present invention 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).

  The contact angle of water with respect to the glass cleaned with the electronic material cleaning agent in the present invention is 20 ° or less, preferably 15 ° or less. In the present invention, the contact angle is measured with respect to glass by a contact angle meter [apparatus body: PD-W (manufactured by Kyowa Interface Chemical Co., Ltd.), glass plate: glass plate # 1737 (manufactured by Corning), detection condition: automatic detection Measurement conditions: Measure contact angle 10 seconds after landing].

  The content of (A) is usually 1 to 100%, preferably 2 to 98%, more preferably 3 based on the weight of the active ingredient of the electronic material cleaning agent from the viewpoint of particle removability and low foamability. -95%, particularly preferably 4-90%. In the present invention, the active ingredient means an ingredient other than water.

  The content of (B) is usually from 0 to 99%, preferably from 1 to 99%, based on the weight of the active ingredient of the electronic material cleaning agent, from the viewpoints of organic soil removability, low foaming and foaming properties. 90%, more preferably 2 to 80%, particularly preferably 5 to 70%.

  The content of (C) is 0 to 55%, preferably 0.01 to 50%, more preferably 0.05 to 45, based on the weight of the active ingredient of the electronic material cleaning agent from the viewpoint of particle removability. %, Particularly preferably 0.1 to 40%.

  The content of (D) is usually 0 to 10%, preferably 0.01 to 7%, more preferably 0. 0% based on the weight of the active ingredient of the electronic material cleaning agent from the viewpoint of particle dispersion stability. 05 to 5%, particularly preferably 0.1 to 3%.

  The content of (E) is usually from 0 to 25%, preferably from 0.1 to 20%, based on the weight of the active ingredient of the cleaning material for electronic materials, from the viewpoints of particle dispersibility and re-contamination prevention. Preferably it is 0.5 to 15%, particularly preferably 1 to 10%.

  The content of (F) is usually from 0 to 20%, preferably from 0.1 to 15%, more preferably from 0.1 to 20% based on the weight of the active ingredient of the electronic material cleaning agent from the viewpoint of the flatness of the substrate surface. 5 to 10%, particularly preferably 1 to 5%.

  The content of (G) is usually from 0 to 30%, preferably from 0 to 30% based on the weight of the active ingredient of the electronic material cleaning agent from the viewpoint of the solubility of (B-4) and (B-5) in the cleaning liquid. It is 0.5 to 25%, more preferably 1 to 20%, and particularly preferably 1.5 to 15%.

  The content of each additive in (H) is usually based on the weight of the active ingredient of the cleaning agent for electronic materials, which is an antioxidant, rust inhibitor, pH adjuster, buffer, preservative, and hydrotrope. It is 0 to 20%, preferably 0 to 15%, more preferably 0 to 10%, and particularly preferably 0 to 5%. The content of the antifoaming agent is usually 0 to 2%, preferably 0 to 1.5%, more preferably 0 to 1%, particularly preferably 0 to 0.5%.

The total content of (H) is usually 0 to 25%, preferably 0 to 20%, more preferably 0 to 15%, particularly preferably 0 to 0% based on the weight of the active ingredient of the electronic material cleaner. 10%.
In addition, between the above arbitrary components (C) to (H), 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 cleaning agent for electronic materials of the present invention is usually 1 to 100%, preferably 2 to 99%, more preferably 5 to 98%, particularly preferably from the viewpoint of workability and transport efficiency during use. 10 to 95%.

  The electronic material cleaning agent of the present invention can be produced, for example, by mixing and dissolving the anionic surfactant (A) and, if necessary, optional components (B) to (H) and water at 10 to 40 ° C. 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.

  When the electronic material cleaner is used as a cleaning liquid, it is usually diluted with water, particularly ion-exchanged water (conductivity: 0.2 μS / cm or less) or ultrapure water (electric resistivity: 18 MΩ · cm or more). From the viewpoint of workability and cost, the active ingredient concentration of the electronic material cleaning agent in the cleaning liquid is preferably 0.1 to 90%, more preferably 0.5 to 80%, and particularly preferably 1 to 70%.

  The contact angle of the cleaning liquid with respect to the glass is preferably 10 ° or less, more preferably 8 ° or less, from the viewpoint of wettability to the substrate.

  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 uses the above-described electronic material cleaning agent, ultrasonic cleaning (a cleaning method using a cavitation effect due to ultrasonic radiation into the cleaning liquid and a destructive effect of core particles), shower cleaning (cleaning liquid) Cleaning method that continuously flows down to the substrate surface as a film shower), spray cleaning (cleaning method in which cleaning liquid is sprayed at high pressure toward the substrate surface), brush cleaning (rotating disk brush etc. are pressed against the substrate surface) Cleaning method), immersion cleaning (usually batch method soaking the substrate in the cleaning solution, mainly cleaning method by dissolving power), immersion rocking cleaning (soaking the immersed substrate up / down or left / right or rotating it) A cleaning method that improves the cleaning effect by stirring) and single wafer cleaning (a cleaning method in which a substrate is gripped and rotated one by one and sprayed onto the substrate surface). A method of cleaning by at least one method of cleaning selected et. 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.

<Example>
Hereinafter, although an example and a manufacture example explain the present invention still in detail, the present invention is not limited to this. Unless otherwise specified, “parts” means “parts by weight” below. In the following, ion-exchanged water having an electric conductivity of 0.2 μS / cm or less and ultrapure water having an electric resistivity of 18 MΩ · cm or more were used.

[Production Example 1]
A stainless steel autoclave equipped with a stirrer and a temperature control function was charged with 66.5 parts of N-methyl-Nn-butylamine, and the gas phase part in the system was replaced with nitrogen at room temperature (20 ° C.) under stirring. Under reduced pressure (gauge pressure: -0.05 MPa), blowing of 33.5 parts of ethylene oxide was started at a reaction temperature of 90 ° C, and the gauge pressure was controlled to be 0.1 to 0.3 MPa. It was made to react until a pressure change was lost, and 100 parts of ethylene oxide 1 mol adducts of N-methyl-Nn-butylamine were obtained. Subsequently, 100 parts of N-methyl-Nn-butylamine ethylene oxide 1-mole adduct was charged into a glass reactor equipped with a stirrer and temperature control, cooled to 0 ° C. with stirring, and the system temperature was reduced to 0 ° C. 88.8 parts of chlorosulfonic acid was added dropwise over 3 hours while keeping the pH of the mixture to obtain a sulfuric ester. Further, 88.9 parts of 48% potassium hydroxide aqueous solution and 224.9 parts of ion-exchanged water were gradually added, mixed and neutralized by mixing at 20 ° C. for 60 minutes, and an anionic surfactant (A -1) 474.8 parts were obtained. (A-1) is N-methyl-Nn-butylamine ethylene oxide 1 mol adduct sulfate potassium salt.

[Production Example 2]
Anionicity with an active ingredient concentration of 40% in the same manner as in Production Example 1 except that 88.9 parts of 48% aqueous potassium hydroxide solution was changed to 115.9 parts of DBU and 415.2 parts of ion-exchanged water. 692.1 parts of surfactant (A-2) was obtained. (A-2) is an ethylene oxide 1 mol adduct sulfate DBU salt of N-methyl-Nn-butylamine.

[Production Example 3]
An anion having an active ingredient concentration of 40% in the same manner as in Production Example 1 except that 88.9 parts of 48% aqueous potassium hydroxide solution was changed to 80.0 parts of diethanolamine and the number of parts of ion-exchanged water was changed to 361.5 parts. 602.5 parts of a surfactant (A-3) was obtained. (A-3) is N-methyl-Nn-butylamine ethylene oxide 1 mol adduct sulfate diethanolamine salt.

[Production Example 4]
100 parts of an ethylene oxide 1 mol adduct of N-methyl-N-butylamine was charged into a glass reactor equipped with a stirrer and temperature control, and the temperature was adjusted to 70 ° C. with stirring, while maintaining the system temperature at 70 ° C. After 37.3 parts of phosphoric acid was added dropwise over 2 hours, the mixture was further stirred at 70 ° C. for 4 hours to obtain a phosphate ester. Further, the system was cooled to 30 ° C., and 44.5 parts of 48% potassium hydroxide aqueous solution and 163.5 parts of ion-exchanged water were gradually added, and mixed at 20 ° C. for 60 minutes for neutralization. 405.3% of anionic surfactant (A-4) 345.3 parts was obtained. (A-4) is N-methyl-Nn-butylamine ethylene oxide 1 mol adduct phosphate ester potassium salt.

[Production Example 5]
Charge 89.0 parts of sarcosine and 117.3 parts of ion-exchanged water to a glass reactor equipped with a stirrer and temperature control, and gradually add 116.7 parts of 48% potassium hydroxide aqueous solution to 25 ° C. with stirring. The temperature was controlled, 120.6 parts of valeryl chloride and 116.7 parts of 48% aqueous potassium hydroxide solution were added dropwise over 5 hours while maintaining the system temperature at 25 ° C., and stirring was further continued at 50 ° C. for 2 hours. Further, 153.6 parts of ion-exchanged water was added to obtain 713.8 parts of an anionic surfactant (A-5) having an active ingredient concentration of 40%. (A-5) is N-valeryl sarcosine potassium salt.

[Production Example 6]
139.2 parts of methyl taurine and 217.7 parts of ion-exchanged water were charged into a glass reactor equipped with a stirrer and temperature control, and 116.7 parts of 48% potassium hydroxide aqueous solution was gradually charged, and the mixture was stirred at 25 ° C. Then, 120.6 parts of valeryl chloride and 116.7 parts of 48% aqueous potassium hydroxide solution were added dropwise over 5 hours while maintaining the system temperature at 25 ° C., and stirring was further continued at 50 ° C. for 2 hours. Thereafter, 128.6 parts of ion-exchanged water was further added to obtain 839.5 parts of an anionic surfactant (A-6) having an active ingredient concentration of 40%. (A-6) is N-methyl-N-valeryl taurine potassium salt.

[Production Example 7]
A glass reactor equipped with a stirrer and temperature control was charged with 100.0 parts of 3-dimethylamino-1-propanol, cooled to 0 ° C. with stirring, and chlorosulfonic acid 99. 4 parts were dripped over 3 hours, and the sulfate ester was obtained. Further, 99.5 parts of a 48% potassium hydroxide aqueous solution and 233.9 parts of ion-exchanged water were gradually added, mixed and neutralized by mixing at 20 ° C. for 60 minutes, and an anionic surfactant (A -7) 501.7 parts were obtained. (A-7) is N, N-dimethylamino-1-propanol sulfate potassium salt.

[Production Example 8]
N-methyl-Nn-butylamine 66.5 parts to Nn-propyl-N-sec-butylamine 72.4 parts, ethylene oxide 33.5 parts to 27.6 parts, chlorosulfonic acid 88.8 In the same manner as in Production Example 1, except that the amount was changed to 73.2 parts, 88.9 parts of 48% potassium hydroxide aqueous solution to 73.3 parts, and 224.9 parts of ion-exchanged water to 211.8 parts. Then, 435.3 parts of an anionic surfactant (A-8) having an active ingredient concentration of 40% was obtained. (A-8) is Nn-propyl-N-sec-butylamine ethylene oxide 1 mol adduct sulfate potassium salt.

[Production Example 9]
N-methyl-Nn-butylamine 66.5 parts to 15.3 parts, ethylene oxide 33.5 parts to 84.7 parts, chlorosulfonic acid 88.8 parts to 20.4 parts, 48% water An anionic interface having an active ingredient concentration of 40% in the same manner as in Production Example 1, except that 88.9 parts of the potassium oxide aqueous solution was changed to 20.4 parts and 224.9 parts of ion-exchanged water were changed to 167.2 parts. 301.6 parts of activator (A-9) was obtained. (A-9) is an ethylene oxide 11 mol adduct sulfate potassium salt of N-methyl-Nn-butylamine.

[Production Example 10]
A stainless steel autoclave equipped with a stirrer and a temperature control function was charged with 20.7 parts of N-methyl-Nn-butylamine, and the gas phase part in the system was replaced with nitrogen at room temperature (20 ° C.) under stirring. Under reduced pressure (gauge pressure: -0.05 MPa), blowing of 10.4 parts of ethylene oxide was started at a reaction temperature of 90 ° C., while controlling the gauge pressure to be 0.1 to 0.3 MPa. After reacting until there is no change in pressure, the mixture is cooled to 30 ° C., 0.3 parts of potassium hydroxide is further added, and the gas phase in the system is replaced with nitrogen at room temperature (20 ° C.) under stirring again, and the pressure is reduced. Under the pressure (gauge pressure: -0.05 MPa), starting to blow 68.9 parts of 1,2-propylene oxide at a reaction temperature of 110 ° C., and controlling the gauge pressure to be 0.1 to 0.3 MPa, No pressure change in the system In reacted to give ethylene oxide 1 mol / 1,2-propylene oxide 5-mol adduct, 100 parts of N- methyl -N-n-butylamine. Subsequently, 100 parts of an ethylene oxide 1 mol / 1,2-propylene oxide 5 mol adduct of N-methyl-Nn-butylamine was charged in a glass reactor with a stirrer and temperature control, and the mixture was stirred to 0 ° C. The mixture was cooled, and 27.7 parts of chlorosulfonic acid was added dropwise over 3 hours while maintaining the internal temperature at 0 ° C. to obtain a sulfate ester. Further, 88.9 parts of a 48% potassium hydroxide aqueous solution and 173.3 parts of ion-exchanged water were gradually added, mixed and neutralized by mixing at 20 ° C. for 60 minutes, and an anionic surfactant (A -10) 320.0 parts were obtained. (A-10) is N-methyl-Nn-butylamine ethylene oxide 1 mol / 1,2-propylene oxide 5 mol block adduct sulfate potassium salt.

[Comparative Production Example 1]
N-methyl-Nn-butylamine ethylene oxide 1 mol adduct is 2- (dibutylamino) ethanol, 88.8 parts chlorosulfonic acid is 67.2 parts, 88.9 parts 48% aqueous potassium hydroxide solution In the same manner as in Production Example 1 except that 67.3 parts and 224.9 parts of ion-exchanged water were changed to 206.7 parts, an anionic surfactant (A-11) having an active ingredient concentration of 40% ) 420.2 parts were obtained. (A-11) is 2- (n-dibutylamino) ethanol sulfate potassium salt.

[Examples 1 to 38] and [Comparative Examples 1 to 5]
Each component listed in Tables 1 to 4 is uniformly mixed at 20 ° C. using a beaker with the number of blending parts listed in Tables 1 to 4 (where the number of parts listed in Tables 1 to 4 is the number of parts of the active ingredient). The cleaning agent of Examples 1-38 and Comparative Examples 1-5 was produced. The components of the abbreviations in Tables 1 to 4 are as follows.
CMTNa: N-cocoyl-N-methyltaurine Na salt [manufactured by NOF Corporation, Diapon K-SF] (anionic surfactant for comparison)
D2eHNa: di-2-ethylhexyl sulfosuccinate (Tokyo Chemical Industry Co., Ltd.) (anionic surfactant for comparison)
SDS: sodium lauryl sulfate [manufactured by Nacalai Tesque Co., Ltd.] (anionic surfactant for comparison)
PELSNa: Polyoxyethylene lauryl ether sulfate sodium salt [Sandet EN, manufactured by Sanyo Chemical Industries, Ltd.] (Anionic surfactant for comparison)
DE-Bu: Diethylene glycol monobutyl ether HEDP: 1-hydroxyethylidene-1,1-diphosphonic acid [manufactured by Kirest Co., Ltd., Kirest PH-210 (60% aqueous solution)]
PANH3: polyacrylic acid ammonium salt [manufactured by Sannopco, SN Tisper Santo 5468 (40% aqueous solution)]
Cys: L-cysteine

  The measurement results of the foaming power and foam stability of the cleaning agents of Examples 1 to 38 and Comparative Examples 1 to 5 are shown in Tables 5 to 8. Moreover, the cleaning agents of Examples 1 to 38 and Comparative Examples 1 to 5 were used as cleaning liquids at the same concentrations, and cleaning properties-1, cleaning properties-2, cleaning properties-3, cleaning properties-4, and cleaning properties-5. Tables 5 to 8 show the results of evaluating or measuring the pH of the cleaning liquid, the contact angle of water after cleaning, the contact angle of the cleaning liquid, and the surface roughness.

  In addition, foaming power, foam stability, detergency-1, detergency-2, detergency-3, detergency-4, detergency-5, pH of the cleaning liquid, contact angle of water after cleaning, cleaning liquid The contact angle and surface roughness were measured or evaluated by the following method.

<Foaming power and foam stability>
(1) The inner cylinder of the foaming force measuring device for Los Miles test specified in JIS K3362 (1998) is set up vertically, and a predetermined amount of water is circulated through the outer cylinder by a pump to maintain a constant temperature (20 ° C.). It was.
(2) While maintaining the test liquid (0.2% aqueous solution of surfactant) at the same temperature (20 ° C.), 50 ml of the test liquid was poured along the tube wall of the inner cylinder so as to moisten the entire side surface.
(3) Take 200 ml of the test solution in a pipette, set it on the top of the foaming force measuring device for Ross Miles test, open the top cock, let the test solution flow out in about 30 seconds, and drop Was allowed to flow down to the center of the inner cylinder liquid surface.
(4) Immediately after all the test liquids flowed out, the height (mm) (foaming power) of the foam was visually measured.
(5) Further, after 1 minute, the height (mm) (stability of the foam) of the foam was visually measured.
(6) This operation was performed twice, and the average of the respective measured values was obtained up to an integer, which was defined as foaming power and foam stability.

<Detergency-1>
10 mg of n-triacontane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a model pollutant on a commercially available glass substrate (Corning, glass plate # 1737, 10 cm × 10 cm × thickness 0.1 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). 100 g of the cleaning solution was put in a 200 ml glass beaker, the prepared contaminated substrate was immersed, and cleaning was performed at 30 ° C. for 5 minutes in an ultrasonic cleaner (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: 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 (Tokyo Chemical Industry Co., Ltd.) was applied as a model contaminant.

<Cleanability-3>
On a commercially available glass substrate (Corning, glass plate # 1737, 10 cm × 10 cm × thickness 0.1 cm), 5 mg of glass powder obtained by cutting (breaking) the glass plate was sprayed, and a 105 ° C. hot plate (PMC Evaluation was carried out in the same manner as in Detergency-1, except that a contaminated substrate was prepared by heating on an industry, digital hot plate series 730) for 1 hour.

<Detergency-4>
A commercially available glass substrate (Corning, glass plate # 1737, 10 cm × 10 cm × 0.1 cm thick) is polished using a commercially available colloidal silica slurry (KEMIRA, VI-80) and a polishing cloth as an abrasive. 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.

<Detergency-5>
Using a commercially available cerium oxide slurry (manufactured by Fujimi Incorporated, CEPOL-120) and a polishing cloth as an abrasive, a commercially available glass substrate (manufactured by Corning, glass plate # 1737, 10 cm × 10 cm × thickness 0.1 cm) After polishing the surface, the surface was rinsed with ultrapure water and blown with nitrogen to evaluate the same as the detergency-1 except that a contaminated substrate was prepared.

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

<Contact angle of water after washing>
The contact angle (25 ° C., 10 seconds later) with respect to water was measured on the substrate immediately after evaluating the detergency-1 using a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DM-700).

<Contact angle of cleaning solution>
After thoroughly rinsing a commercially available glass substrate (manufactured by Corning, glass plate # 1737, 10 cm × 10 cm × thickness 0.1 cm) with ultrapure water, the substrate immediately after being blown with nitrogen and dried at 25 ° C. Using a fully automatic contact angle meter (PD-W, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle with respect to the cleaning liquid (at 25 ° C., after 10 seconds) was measured.

<Surface roughness>
After taking 10 g of the cleaning solution in a 20 ml glass container and adjusting the temperature to 50 ° C., a commercially available glass substrate (manufactured by Corning, glass plate # 1737, 10 cm × 10 cm × thickness 0.1 cm) is 2 cm × 2 cm × thickness. A substrate cut to a size of 0.1 cm is put in, immersed and left at 50 ° C. for 5 hours, taken out using tweezers, rinsed thoroughly with ultrapure water to remove the cleaning solution, and then at 25 ° C. Then, the surface roughness (Ra) of the substrate surface, which was blown with nitrogen and dried, was measured using an atomic force microscope (E-Sweep, manufactured by SII Nanotechnology Co., Ltd.). The smaller the Ra, the better the surface flatness.

  From Tables 5-8, the cleaning agent for electronic materials of the present invention has low foaming properties and excellent foaming properties, and is capable of removing particles such as organic matter stains, glass cullet and abrasives, preventing recontamination, and glass. It can be seen that the flatness of the substrate surface is excellent. The electronic material cleaning agent of the present invention having such excellent effects also has an effect of improving the yield rate of the product and an effect of shortening the process time.

  The cleaning material for electronic materials of the present invention includes oil, dirt from human bodies (fingerprints, etc.), organic substances such as resin, plasticizer (dioctyl phthalate, etc.) and organic particles, and inorganic particles (glass powder, abrasive grains, ceramic powder and metal). Excellent cleaning properties for inorganic substances such as powder, etc., and 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. ), Hard disk substrates (substrate substrates, magnetic disks, magnetic heads, etc.), semiconductor substrates (semiconductor elements, silicon wafers, etc.), optical lenses, printed wiring boards, optical communication cables, LEDs, and photomasks] Can be suitably used in the washing step. The electronic material cleaning method of the present invention is particularly suitable when the electronic material is a flat panel display substrate, a hard disk substrate, a semiconductor substrate, or an optical lens.

Claims (11)

A cleaning agent for electronic materials containing an anionic surfactant (A) represented by the general formula (1), which is measured by a Ross Miles test at 20 ° C. of a 0.2 wt% aqueous solution of (A). A cleaning agent for electronic materials, wherein the foaming power is 50 mm or less and the stability of the foam is 5 mm or less.
[Wherein R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of R ¹ and R ² is 2 to 7; R ³ is an alkylene having 1 to ³ carbon atoms] R ⁴ is an alkylene group having 2 to ⁴ carbon atoms; X ⁻ is —COO ⁻ , —OCH ₂ COO ⁻ , —OSO ₃ ⁻ , —SO ₃ ^— or —OPO ₂ (OR ⁵ ) ⁻ , ⁵ is a hydrogen atom or _{^{R 1 (C = O) a}} -N (R 2) -R 3 - (oR 4) b - group represented by; M ⁺ is a cation; a is 0 or 1; b is an average value And represents 0-10. ] The cleaning agent for electronic materials according to claim 1, wherein M ⁺ in the general formula (1) is an alkali metal cation and / or an amine cation. In formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, the total number of carbon atoms of R ¹ and R ² is 3 to 6, and X ⁻ is —COO ^−. The cleaning agent for electronic materials according to claim 1, which is —OSO ₃ ^— or —SO ₃ ^— .   Furthermore, the cleaning agent for electronic materials in any one of Claims 1-3 containing an organic solvent (B).   The organic solvent (B) is a monohydric alcohol solvent (B-1) having 1 to 8 carbon atoms, a glycol solvent (B-2) having 2 to 9 carbon atoms, or a glycol ether system having 3 to 60 carbon atoms. 1 selected from the group consisting of a solvent (B-3), a saturated hydrocarbon solvent having 6 to 12 carbon atoms (B-4), and an unsaturated aliphatic hydrocarbon solvent having 6 to 18 carbon atoms (B-5) The electronic material cleaning agent according to claim 4, wherein the cleaning agent is an organic solvent of at least one species.   Furthermore, the washing | cleaning agent for electronic materials in any one of Claims 1-5 containing an alkali component (C) and / or a chelating agent (D).   The alkali component (C) is ammonia (C-1), a quaternary ammonium salt (C-2), an aliphatic amine (C-3) having 1 to 36 carbon atoms, an inorganic alkali (C-4) and carbon. The cleaning agent for electronic materials according to claim 6, wherein the cleaning material is one or more selected from the group consisting of alkanolamines (C-5) of formulas 1 to 23. Furthermore, the cleaning agent for electronic materials in any one of Claims 1-7 containing a polymer type dispersing agent (E) and / or a reducing agent (F).   The cleaning agent for electronic materials according to any one of claims 1 to 8, wherein an active ingredient concentration when used as a cleaning liquid is 0.1 to 90% by weight.   The cleaning method of the electronic material using the cleaning agent for electronic materials in any one of Claims 1-9. The electronic material according to claim 10, wherein the electronic material is cleaned using at least one cleaning method selected from the group consisting of ultrasonic cleaning, shower cleaning, spray cleaning, brush cleaning, immersion cleaning, immersion rocking cleaning, and single wafer cleaning. Cleaning method.