JP5410943B2 - Electronic material cleaner - Google Patents

Description

  The present invention relates to a cleaning agent for electronic materials, and more particularly to a cleaning agent for electronic materials such as flat panel display substrates and photomask substrates.

In cleaning technologies for electronic materials such as flat panel display substrates and photomask substrates, trace amounts of organic contaminants and impurities such as glass cullet and abrasive grains remaining on the substrate in the manufacturing process greatly affect the performance and yield of electronic materials. Therefore, its management has become extremely important. In particular, since the impurities to be cleaned are becoming finer (particles) and are more likely to adhere to the interface and remain than before, it is urgently necessary to establish advanced cleaning techniques.
For this reason, in order to prevent contamination by these particles, a method of improving the particle removability by using a surfactant has been proposed (see Patent Documents 1 and 2).
JP 2001-276759 A Japanese Patent Laid-Open No. 2002-212597

  However, in the manufacturing process of flat panel display substrates and photomask substrates, glass chips (commonly referred to as glass cullet) generated when cutting glass substrates to an appropriate size from mother glass as needed, and in clean rooms Organic substances such as scattered processing oil, abrasives (cerium oxide, alumina, colloidal silica, diamond, etc.) and polishing scraps (glass cullet, etc.) used in the process of polishing the substrate surface or end face are firmly attached to the substrate surface. There is a problem that it cannot be removed sufficiently in the cleaning process.

  Particles represented by these abrasives, polishing debris and organic contaminants are firmly attached to the substrate surface. In order to sufficiently remove these particles, the substrate or abrasive surface is slightly etched and the particles are removed. Must be dispersed in the liquid, and the particles dispersed in the liquid need not be reattached to the substrate surface. However, the cleaning agent proposed in Patent Document 1 is a cleaning agent in which hydrogen fluoride and ozone are dissolved, and the effect of removing particles firmly adhered to the substrate surface by etching can be expected, but it contains fluorine ions. For this reason, the wastewater treatment is costly, and the etching property is too strong, so that the flatness of the substrate is impaired during cleaning. In addition, by making the zeta potential of the glass substrate and the surface of the abrasive particles negative, the reattachment of particles is prevented, but the effect is insufficient. Moreover, in the cleaning agent proposed in the above-mentioned Patent Document 2, although the effect of preventing the reattachment of particles can be improved to some extent by using an anionic surfactant, there is almost no etching property, so the particle removability is insufficient. There is insufficient cleanability.

  Accordingly, an object of the present invention is to provide an appropriate etching property without impairing the flatness of the surface of an electronic material substrate such as a flat panel display substrate and a photomask substrate, and to use a surfactant to provide a substrate surface. By improving the dispersibility of particles detached from the surface, excellent particle removability is realized, which enables highly efficient advanced cleaning that improves the yield rate during manufacturing and enables cleaning in a short time. An object of the present invention is to provide a cleaning agent for electronic materials such as flat panel display substrates and photomask substrates.

As a result of intensive studies to solve the above problems, the present inventors have found that there is a preferable redox potential depending on the pH at the time of use of the cleaning agent, and have reached the present invention. That is, the present invention is a cleaning agent for a flat panel display substrate or a photomask substrate containing an anionic surfactant (A-2) and a reducing agent (C), and has an active ingredient concentration of 0.01 to 15% by weight. The flat panel display substrate or photomask substrate , wherein the pH at 25 ° C. in% is 1 to 3, and the pH and redox potential (V) [units are mV, vsSHE] satisfy the following formula (1): use detergents, comprising the step of washing the flat panel display substrate or photomask substrate cleaning method and the cleaning process of a flat panel display substrate or photomask substrate cleaning a flat panel display substrate or photomask substrate in the detergent It is a manufacturing method of a flat panel display substrate or a photomask substrate .
V ≦ −38.7 × pH + 550 (1)

  The cleaning agent of the present invention is excellent in cleaning of fine particles that are a problem in the manufacturing process of electronic materials such as flat panel display substrates and photomask substrates, and is efficient in a short time without damaging the surface of the electronic materials. It has the feature that it can be washed.

As a result of intensive studies on the relationship between various physical property values of the cleaning agent and the cleaning property in order to improve the cleaning property of the electronic material, the present inventors have found that the upper limit value of the pH of the cleaning agent and the oxidation-reduction potential of the cleaning agent. As a result of accumulating and analyzing various data on (upper limit value that can exert the effect), pH and oxidation-reduction potential (V) at 25 ° C. at an active ingredient concentration of the cleaning agent of 0.01 to 15% [at 25 ° C. It has been found that a cleaning agent having a composition satisfying the following formula (1) in terms of values in units of mV and vs SHE exhibits a significantly improved effect as compared with the prior art.
V ≦ −38.7 × pH + 550 (1)
For example, when the pH is 2, the oxidation-reduction potential (V) is 472.6 mV or less, (V) when the pH is 5 is 356.5 mV or less, and (V) when the pH is 10 is 163. The effect of the present invention is exhibited when the pH is 0.0 mV or less and (V) when the pH is 13 is 46.9 mV or less.
If the oxidation-reduction potential (25 ° C.) does not satisfy the formula (1), the substrate surface is remarkably etched, the surface flatness is impaired, and the particle removability is deteriorated.

  The cleaning agent of the present invention contains the surfactant (A) and, if necessary, water (preferably ion-exchanged water or ultrapure water, the same applies to the following water) and other components described later. The active ingredient in means an ingredient other than water. Further, in the above and the following, “%” represents “% by weight” unless otherwise specified.

Among the cleaning agents of the present invention, from the viewpoint of appropriate etching properties for electronic materials and cleaning properties for particles, a cleaning agent satisfying Formula (2) is more preferable, and a cleaning agent satisfying Formula (3) is particularly preferable.
V ≦ −38.7 × pH + 450 (2)
V ≦ −38.7 × pH + 350 (3)

The oxidation-reduction potential (V) in the present invention can be measured by the following known method.
<Measurement method of redox potential>
Using a redox potential (ORP) composite electrode composed of a platinum electrode and a reference electrode (silver chloride electrode) (for example, model number: PST-5421C, Toa DKK Corporation), the potential value of the liquid at 25 ° C. (V1) Measure. The oxidation-reduction potential (mV, vsSHE) of the liquid is obtained by adding the unipolar potential difference (199 mV, 25 ° C.) of the reference electrode (silver chloride electrode) to the potential value (V1). For example, when the potential value (V1) is −100 mV, the oxidation-reduction potential (mV, vsSHE) is −100 + 199 = + 99 mV.

  Further, 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).

  As the surfactant (A) which is an essential component of the cleaning agent of the present invention, a nonionic surfactant (A-1), an anionic surfactant (A-2), a cationic surfactant (A- 3) and amphoteric surfactant (A-4).

  As nonionic surfactant (A-1) used for the cleaning agent of the present invention, alkylene oxide addition type nonionic surfactant (A-1a) and polyhydric alcohol type nonionic surfactant (A-1b) ) And the like.

As (A-1a), higher alcohol (8 to 18 carbon atoms) alkylene (2 to 4 carbon atoms) oxide (1 to 30 added moles per active hydrogen) adduct, alkyl (1 to 12 carbon atoms) ) Phenolethylene oxide (addition moles 1-30 per active hydrogen) adduct, fatty acid (carbon number 8-18) ethylene oxide (addition moles 1-30 per active hydrogen) adduct, aliphatic Alkylene oxide adducts of amines (6 to 24 carbon atoms) (addition moles 1 to 30 per active hydrogen), polypropylene glycol (molecular weight 200 to 4000) ethylene oxide (addition moles 1 to active hydrogen 1 50) Adduct, and polyoxyethylene (1-30 added moles per active hydrogen) alkyl (1-20 carbon atoms) allyl ether, sol Polyhydric (2 to 8 or more) alcohols (carbon number 2) such as tan monolaurate ethylene oxide (addition mole number 1-30) adduct, sorbitan monooleate ethylene oxide (addition mole number 1-30) adduct, etc. To 30) fatty acid (carbon number 8 to 24) ester ethylene oxide adduct (added mole number 1 to 30 per active hydrogen).

As (A-1b), fatty acid (carbon) of polyvalent (2 to 8 or more) alcohols (2 to 30 or more carbon atoms) such as glycerol monostearate, glycerol monooleate, sorbitan monolaurate, sorbitan monooleate, etc. 8-24) Fatty acid alkanolamides, such as ester, lauric acid monoethanolamide, lauric acid diethanolamide, etc. are mentioned.

  Among (A-1), from the viewpoint of detergency, (A-1a) is preferable, and higher alcohol (10 to 16 carbons) alkylene (2 to 3 carbons) oxide (active hydrogen) is more preferable. Addition moles per unit 2 to 20) adducts, alkylphenol ethylene oxide (addition moles 2 to 20 per active hydrogen) adduct, and alkylene oxide adducts of aliphatic amines (8 to 18 carbon atoms) (Number of added moles per active hydrogen 2-20).

  Examples of the anionic surfactant (A-2) include a high molecular weight anionic surfactant (A-2a) and a low molecular weight anionic surfactant (A-2b).

  Polymeric anionic surfactant (A-2a) includes sulfonic acid (salt) group, sulfate ester (salt) group, phosphate ester (salt) group, phosphonic acid (salt) group, and carboxylic acid (salt) Examples thereof include polymeric anionic surfactants having at least one group selected from the group consisting of groups and having a weight average molecular weight of 1,000 to 800,000 (hereinafter abbreviated as Mw). The polymer type anionic surfactant usually has at least two repeating units in one molecule. Specific examples of (A-2a) include the following (A-2a-1) to (A-2a-5).

(A-2a-1) a polymeric anionic surfactant 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 condensate, etc .;

(A-2a-2) Polymer type anionic surfactant having a sulfate (salt) group:
Poly {2-hydroxyethyl (meth) acrylate sulfate}, 2-hydroxyethyl acrylate / 2-hydroxyethyl acrylate sulfate copolymer and 2-hydroxyethyl methacrylate / 2-hydroxyethyl methacrylate sulfate copolymer, poly { 2-hydroxyethyl (meth) acrylate} sulfated ester, poly {(meth) acryloyloxypolyoxyalkylene sulfate}, (meth) acryloyloxypolyoxyalkylene sulfate / acrylic acid copolymer and cellulose, methylcellulose or ethylcellulose Sulfated product of

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

(A-2a-4) Polymeric anionic surfactant having a phosphonic acid (salt) group:
Poly {(meth) acryloyloxyethyl phosphate}, 2-hydroxyethyl acrylate / acryloyloxyethyl phosphate copolymer and 2-hydroxyethyl methacrylate / methacryloyloxyethyl phosphate copolymer, naphthalenephosphonic acid formaldehyde condensate, methylnaphthalenephosphonic acid Formaldehyde condensate, dimethylnaphthalenephosphonic acid formaldehyde condensate, anthracene phosphonic acid formaldehyde condensate, aniline phosphonic acid-phenol-formaldehyde condensate and the like;

(A-2a-5) Polymeric anionic surfactant 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 and 2-hydroxyethyl methacrylate / (meth) acrylic acid copolymer, poly {2-hydroxyethyl (meth) acrylate} carboxymethylated product, carboxymethylcellulose, carboxymethylmethylcellulose, carboxymethylethylcellulose, benzoic acid formaldehyde Condensates and benzoic acid-phenol-formaldehyde condensates and the like.

  The Mw of (A-2a) is preferably from 1,000 to 800,000, more preferably from 1,200 to 400,000, particularly preferably 1, from the viewpoint of preventing reattachment of particles and low foaming properties. 500 to 80,000, most preferably 2,000 to 40,000. Mw in the present invention is measured at 40 ° C. using polyethylene oxide as a reference substance by gel permeation chromatography (hereinafter abbreviated as GPC). Specifically, for example, apparatus main body: HLC-8120 (manufactured by Tosoh Corporation), column: TSKgel α6000, G3000 PWXL, manufactured by Tosoh Corporation, detector: differential refractometer detector built in the apparatus main 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 volume: 200 μl, standard substance : Measured using TSK TANDARD POLYETHYLENE OXIDE manufactured by Tosoh Corporation, data processing software: GPC-8020 model II (manufactured by Tosoh Corporation).

As the low molecular weight type anionic surfactant (A-2b), a low molecular weight type sulfonic acid type surfactant (A-2b-1), a low molecular type sulfate ester type surfactant (A-2b-2), Low molecular weight fatty acid surfactant (A-2b-3) and low molecular phosphate ester surfactant (A-2b-4) etc. have a molecular weight (Mw or calculated molecular weight based on structure) of 1, And anionic surfactants of less than 000.
Among the anionic surfactants, the sulfonic acid-based surfactant (A-2b-1) is a sulfosuccinic acid (mono, di) ester (salt) of an alcohol having 6 to 24 carbon atoms, an 8 to 24 carbon atoms. α-olefin sulfone oxide (salt), alkylbenzene sulfonic acid (salt) having an alkyl group having 8 to 14 carbon atoms, petroleum sulfonate (salt), toluene sulfonic acid (salt), xylene sulfonic acid (salt), and cumene sulfone Examples include acids (salts). Specific examples of (A-2b-1) include dioctylsulfosuccinic acid (salt), paratoluenesulfonic acid (salt), orthotoluenesulfonic acid (salt), metaxylenesulfonic acid (salt), and paraxylenesulfonic acid (salt). ) And the like.

  Examples of the low-molecular-weight sulfate ester surfactant (A-2b-2) include sulfate esters (salts) of aliphatic alcohols having 8 to 18 carbon atoms, and ethylene oxides 1 to 10 of aliphatic alcohols having 8 to 18 carbon atoms. Mole adduct sulfates (salts), sulfated oils (salts), sulfated fatty acid esters (salts), sulfated olefins (salts), and the like. Specific examples of (A-2b-2) include 2-ethylhexanol sulfate (salt), octanol sulfate (salt), 1,10-decandiol disulfate (salt), and ethylene oxide of lauryl alcohol (5 Mol) adduct disulfate (salt) and the like.

  Examples of the low molecular weight fatty acid surfactant (A-2b-3) include fatty acids (salts) having 8 to 18 carbon atoms and ether carboxylic acids (salts) of aliphatic alcohols having 8 to 18 carbon atoms. Specific examples of (A-2b-3) include n-octanoic acid (salt), 2-ethylhexanoic acid (salt), n-nonanoic acid (salt), isononanoic acid (salt), oleic acid (salt) and Examples include stearic acid (salt).

  Examples of the low molecular phosphate ester surfactant (A-2b-4) include phosphoric acid (mono, di) esters (salts) of higher alcohols having 8 to 24 carbon atoms and higher alcohols having 8 to 24 carbon atoms. Examples include phosphoric acid (mono, di) esters (salts) of alkylene oxide adducts. Specific examples of (A-2b-4) include lauryl alcohol monophosphate (salt), phosphate monoester (salt) of ethylene oxide (5 mol) adduct of lauryl alcohol, and octyl alcohol diphosphate (salt). Etc.

  The counter ion when (A-2) forms a salt is not particularly limited. Usually, alkali metal (sodium and potassium) salts, ammonium salts, primary amines (alkylamines such as methylamine, ethylamine and butylamine, Monoethanolamine and guanidine etc.) salt, secondary amine (dialkylamine such as dimethylamine, diethylamine and dibutylamine and diethanolamine etc.) salt, tertiary amine {trialkylamine such as trimethylamine, triethylamine and tributylamine, triethanolamine, N-methyldiethanolamine and 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) or 1,4- Diazabicyclo [2.2.2] O Tan (DABCO), 1H imidazole, 2-methyl-1H-imidazole, 2-ethyl-1H-imidazole, 4,5-dihydro-1H imidazole, 2-methyl-4,5-dihydro-1H imidazole, 1,4 5,6-tetrahydro-pyrimidine, 1,6 (4) -dihydropyrimidine etc.} salt and quaternary ammonium salt (tetraalkyl ammonium etc.) salt. Of these, ammonium salts, primary amine salts, secondary amine salts, tertiary amine salts and quaternary ammonium salts are preferred from the viewpoint of metal contamination on the substrate, and tertiary amines are particularly preferred. Salts and quaternary ammonium salts, most preferred are DBU, DBN, DABCO, N-methyldiethanolamine, 1H-imidazole, 2-methyl-1H-imidazole and 2-ethyl-1H-imidazole.

Among the anionic surfactants (A-2), the polymer type anionic surfactant (A-2a) and the low molecular weight sulfonic acid type surfactant (A) are preferred from the viewpoint of preventing the reattachment of particles. -2b-1), low molecular weight sulfate ester surfactant (A-2b-2) and low molecular weight fatty acid surfactant (A-2b-3), more preferably (A-2a) , (A-2b-1) and (A-2b-2), particularly preferably polyacrylic acid (salt), polystyrene sulfonic acid (salt), salt of naphthalene sulfonic acid formalin condensate, acrylamide-2-methylpropane Salt of sulfonic acid / acrylic acid copolymer, salt of methacryloyloxypolyoxyalkylene sulfate / acrylic acid copolymer, octylbenzenesulfonic acid (salt), paratoluenesulfonic acid (salt) Meta-xylene sulfonic acid (salt) and 2-ethylhexanol sulfate (salt).
(A-2) may be used alone or in combination of two or more. From the viewpoint of particle dispersibility, it is more preferable to use two or more kinds in combination.

  As the cationic surfactant (A-3), a quaternary ammonium salt type surfactant (A-3a) {for example, alkyl (C1-30) trimethylammonium salt, dialkyl (C1-30) Dimethyl ammonium salt, nitrogen ring-containing quaternary ammonium salt, poly (addition mole number 2 to 15) oxyalkylene (carbon number 2 to 4) chain-containing quaternary ammonium salt, alkyl (carbon number 1 to 30) amidoalkyl ( C1-C10) dialkyl (C1-C4) methylammonium salt, etc., and amine surfactant (A-3b) {for example, an aliphatic tertiary amine having 3 to 90 carbon atoms, 3 to 3 carbon atoms 90 alicyclic (including nitrogen-containing heterocycle) tertiary amines and C3-90 hydroxyalkyl group-containing tertiary amine inorganic acid salts or organic acid salts, etc.}.

  As amphoteric surfactant (A-4); betaine-type amphoteric surfactant (A-4a) {for example, alkyl (C1-30) dimethylbetaine, alkyl (C1-30) amide alkyl (carbon number) 1-4) Dimethylbetaine, alkyl (C1-30) dihydroxyalkyl (C1-30) betaine, sulfobetaine type, etc.}; amino acid type amphoteric surfactant (A-4b) {for example, alanine type [ Alkyl (C1-C30) aminopropionic acid type, alkyl (C1-C30) iminodipropionic acid type, etc.], glycine type [alkyl (C1-C30) aminoacetic acid type, etc.]}; and aminosulfone Acid salt type amphoteric surfactant (A-4c) {for example, alkyl (C1-30) taurine type amphoteric surfactant, etc.};

  Of the surfactants (A), anionic surfactants (A-2), and nonionic surfactants (A-1) and (A-2) are preferable from the viewpoint of preventing reattachment of particles. The combination of (A-1) and (A-2) is more preferable. In the case of combined use, the content ratio [(A-1) / (A-2)] of (A-1) and (A-2) is preferably 6 or less, more preferably from the viewpoint of detergency and foamability. Is 0.1 to 5, particularly preferably 0.2 to 0.8.

  The content of the surfactant (A) in the cleaning agent of the present invention is preferably 1.5 to 100%, more preferably 2 to 90%, particularly preferably based on the weight of the active ingredient of the cleaning agent of the present invention. Is 3 to 80%.

  In addition to the surfactant (A), the cleaning agent of the present invention further contains one or more components selected from the group consisting of the following chelating agents (B), reducing agents (C) and alkali components (D). be able to.

  It is more preferable that the cleaning agent of the present invention contains the chelating agent (B) from the viewpoint of improving the cleaning property of the surface of the electronic material and controlling the etching property. Moreover, since the cleaning agent of this invention can control the etching property with respect to the electronic material surface by containing a reducing agent (C), it is still more preferable to contain a reducing agent (C). The cleaning agent of the present invention further improves the cleaning properties for particles by containing the alkali component (D).

As the chelating agent (B), aminopolycarboxylic acid (salt) (B-1) {for example, ethylenediaminetetraacetic acid (EDTA) (salt), diethylenetriaminepentaacetic acid (DTPA) (salt), triethylenetetraminehexaacetic acid (TTHA) ) (Salt), hydroxyethylethylenediaminetriacetic acid (HEDTA) (salt), dihydroxyethylethylenediaminetetraacetic acid (DHEDDA) (salt), nitriloacetic acid (NTA) (salt), hydroxyethyliminodiacetic acid (HIDA) (salt) , Β-alanine diacetate (salt), aspartate diacetate (salt), methylglycine diacetate (salt), iminodisuccinate (salt), serine diacetate (salt), hydroxyiminodisuccinate (salt), dihydroxyethyl glycine (salt) Salt), aspartic acid (salt), glutamic acid (salt), etc.};
Hydroxycarboxylic acid (salt) (B-2) {eg, hydroxyacetic acid (salt), tartaric acid (salt), citric acid (salt), gluconic acid (salt), etc.};
Cyclocarboxylic acid (salt) (B-3) {eg, pyromellitic acid (salt), benzopolycarboxylic acid (salt), cyclopentanetetracarboxylic acid (salt), etc.};
Ether carboxylic acid (salt) (B-4) (for example, carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid monosuccinate, tartaric acid disuccinate, etc.);
Other carboxylic acid (salt) (B-5) {eg, maleic acid derivative, oxalic acid (salt), etc.};
Phosphonic acid (salt) (B-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), triaminotriethylamine hexa (methylenephosphonic acid) (salt), trans-1,2-cyclohexanediaminetetra (methylenephosphonic acid) (salt), glycol etherdiaminetetra (methylenephosphonic acid) (salt) and Tetraethylenepentamine hepta Methylene phosphonic acid) (salt), etc.};
Condensed phosphoric acid (salt) (B-7) {eg, metaphosphoric acid (salt), tripolyphosphoric acid (salt), hexametaphosphoric acid (salt), etc.};
Etc.

In addition, as these salts, what was illustrated by the above-mentioned anionic surfactant (A-2) is mentioned. These may be used alone or in combination of two or more.
Of these, (B-1), (B-2), (B-6), (B-7), and salts thereof are preferable from the viewpoints of etching control and cleaning performance of the substrate. Preferred are (B-1), (B-6), (B-7) and their salts, particularly preferred are ethylenediaminetetraacetic acid (EDTA) (salt), diethylenetriaminepentaacetic acid (DTPA) (salt), dihydroxy Ethylethylenediaminetetraacetic acid (DHEDDA) (salt), aspartic acid diacetic acid (salt), aspartic acid (salt), glutamic acid (salt), 1-hydroxyethylidene-1, 1-diphosphonic acid (salt), ethylenediaminetetra (methylenephosphone) Acid) (salt), metaphosphoric acid (salt), hexametaphosphoric acid (salt), most preferably ethylenediaminetetraacetic acid (EDTA) (salt) 1-hydroxyethylidene-1,1-diphosphonic acid (salt), a hexametaphosphate (salt).

  In the case of using the chelating agent (B), from the viewpoint of substrate etching control and cleaning performance, the content of (B) is preferably 30% or less based on the weight of the active ingredient of the cleaning agent of the present invention. More preferably, it is 0.1-20%, Most preferably, it is 0.3-20%.

  Examples of the reducing agent (C) include an organic reducing agent (C-1) and an inorganic reducing agent (C-2). Examples of the organic reducing agent (C-1) include aliphatic organic reducing agents (C-1a), aromatic organic reducing agents (C-1b) and other organic reducing agents (C-1c). Can be illustrated.

Examples of the aliphatic organic reducing agent (C-1a) include organic acids having 1 to 12 carbon atoms, aldehydes having 1 to 12 carbon atoms, reductones having 6 to 9 carbon atoms, and aliphatic amines having 1 to 30 carbon atoms. Is mentioned.
Examples of the organic acids having 1 to 12 carbon atoms include formic acid, acetic acid, succinic acid, lactic acid, malic acid, butyric acid, maleic acid, 2-oxopropanoic acid, malonic acid, gallic acid, and salts thereof.
The (B-2) and (B-5) also have an effect as a reducing agent.
Examples of aldehydes having 1 to 12 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, and vinyl aldehyde.
Examples of reductones having 6 to 9 carbon atoms include L-ascorbic acid, isoascorbic acid, L-ascorbic acid sulfate, L-ascorbic acid phosphate, L-ascorbic acid 2-glucoside, and L-ascorbyl palmitate , Tetraisopalmitic acid L-ascorbyl, ascorbic acid isopalmitate, erythorbic acid, erythorbic acid phosphate ester, erythorbic acid palmitic acid ester, tetraisopalmitic acid erythovir, and salts thereof.

  As an aliphatic amine having 1 to 30 carbon atoms, an alkylamine having 1 to 6 carbon atoms, an alkanolamine having 2 to 6 carbon atoms, an alkylenediamine having 2 to 5 carbon atoms, a cyclic amine having 4 to 10 carbon atoms, and a carbon number Examples thereof include 3-15 amidine compounds and poly (n = 2-5) alkylene (2-6 carbon atoms) poly (n = 3-6) amines having 4-30 carbon atoms.

  Examples of the alkylamine having 1 to 6 carbon atoms include monoalkylamines {methylamine, ethylamine, propylamine, isopropylamine, butylamine, hexylamine, etc.} and dialkylamines having 2 to 6 carbon atoms {dimethylamine, ethylmethylamine, propyl Methylamine, butylmethylamine, diethylamine, propylethylamine, diisopropylamine, etc.}.

  Examples of the alkanolamine having 2 to 6 carbon atoms include monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, N-methyl-diethanolamine, 2-amino-2-methyl-1-propanol, N- (amino And ethyl) ethanolamine, N, N-dimethyl-2-aminoethanol, and 2- (2-aminoethoxy) ethanol.

  Examples of the alkylene diamine having 2 to 5 carbon atoms include ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, and hexamethylene diamine.

Examples of the cyclic amine having 4 to 10 carbon atoms include piperidine, piperazine, and 1,4-diazabicyclo [2.2.2] octane (DABCO).
Examples of the amidine compound having 3 to 15 carbon atoms include 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) and 1,5-diazabicyclo [4.3.0] -5-nonene (DBN). Etc.
Examples of the poly (n = 2 to 5) alkylene (2 to 6 carbon) poly (n = 3 to 6) amine having 4 to 30 carbon atoms include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, Examples include iminobispropylamine, bis (hexamethylene) triamine, and pentaethylenehexamine.

Examples of the aromatic organic reducing agent (C-1b) include an aromatic aldehyde having 7 to 12 carbon atoms, an aromatic amine having 6 to 9 carbon atoms, and a phenol compound having 6 to 30 carbon atoms.
Examples of the aromatic aldehyde having 7 to 12 carbon atoms include benzaldehyde and cinnamaldehyde.
Examples of the aromatic amine having 6 to 9 carbon atoms include p-phenylenediamine and p-aminophenol.

  Examples of the phenol compound having 6 to 30 carbon atoms include monohydric phenol and polyphenol. Examples of the monohydric phenol include 3-hydroxyflavone and tocopherol (such as α-, β-, γ-, δ-, ε-, or η-tocopherol). Examples of the polyphenol include 3,4,5-trihydroxybenzoic acid, pyrocatechol, resorcinol, hydroquinone, naphthoresorcinol, pyrogallol and phloroglucinol.

  Examples of other organic reducing agents (C-1c) include phosphorus reducing agents (eg, tris-2-carboxyethylphosphine), borane complexes (eg, borane-tert-butylamine complex, borane-N, N-diethyl). Aniline complexes and borane-trimethylamine complexes), thiol-based reducing agents (such as L-cysteine and aminoethanethiol), and hydroxylamine-based reducing agents (such as hydroxylamine and diethylhydroxylamine). In addition, the saccharides and sugar alcohols exemplified as (F3) and (F4) described later also have an effect as an organic reducing agent.

As the inorganic reducing agent (C-2), sulfur oxo acids {for example, sulfurous acid (salt), disulfurous acid (salt), dithionic acid (salt), thiosulfuric acid (salt), dithionic acid (salt), polythionic acid (Salts, etc.), phosphorus oxo acids {eg, phosphorous acid (salt), hydrophosphorous acid (salt), hypophosphorous acid (salt), etc.}, other inorganic reducing agents (ferrous sulfate, Stannic chloride, sodium cyanoborohydride, sodium borohydride, etc.).
As a salt which forms these reducing agents (C), the thing similar to what was illustrated by said (A-2) can be used.

Among these reducing agents (C), from the viewpoint of etching control of the cleaning agent and recontamination of the substrate with ions in the cleaning agent, aldehydes having 1 to 12 carbon atoms, reductones having 6 to 9 carbon atoms, carbon An aliphatic amine having a number of 1 to 30, a thiol-based reducing agent, a sulfur oxo acid and a phosphorus oxo acid are preferable, and more preferable are formaldehyde, L-ascorbic acid (salt), isoascorbic acid (salt), erythorbic acid ( Salt), monoethanolamine, diethanolamine, N-methyl-diethanolamine, L-cysteine, aminoethanethiol, sulfurous acid (salt), disulfite (salt), dithionite (salt), thiosulfuric acid (salt), phosphorous acid (Salt), hydrophosphorous acid (salt) and hypophosphorous acid (salt), particularly preferred are L-ascorbic acid (salt), L-cysteine, Sulfuric acid (salt), dithionite (salt), phosphorous acid (salt), a hydrogen phosphite acid (salt) and hypophosphorous acid (salt).
The counter ion when (C) forms a salt is not particularly limited, but those similar to those exemplified in the above (A-2) can be used.
Moreover, (C) may be used independently and may be used in combination of 2 or more types.

  When the reducing agent (C) is contained, the content of the reducing agent (C) is preferably 60% or less, more preferably 1 to 50%, particularly preferably 2 to 40 based on the weight of the active ingredient of the cleaning agent. %. This range is preferable from the viewpoint of controlling the etching property of the substrate.

  As an alkali component (D), C1-C30 illustrated by the quaternary ammonium salt (D-1) represented by General formula (1), ammonia (D-2), and the above-mentioned (C-1a). Aliphatic amines (D-3), inorganic alkalis (D-4) and mixtures thereof. In addition, a C1-C10 aliphatic amine (D-3) has both the effect as a reducing agent and the effect as an alkali component.

In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 24 carbon atoms or a group represented by — (R ⁵ O) r—H, and R ⁵ is a carbon number. 2-4 alkylene group, r represents the integer of 1-6.
Examples of the alkyl group having 1 to 24 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl , Hexosyl, docosyl, tricosyl, and tetracosyl groups. Examples of the alkylene group having 2 to 4 carbon atoms include ethylene, propylene and butylene. r is preferably 1 to 3.

  Specific examples of (D-1) include tetramethylammonium hydroxide, trimethylethylammonium hydroxide, tetraethylammonium hydroxide, triethylmethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide. Side, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, trimethylethylammonium hydroxide and tetraethylammonium hydroxide, hydroxyethyltrimethylammonium hydroxide, hydroxyethyltriethylammonium hydroxide, dihydroxyethyldimethylammonium hydro Xide, trihydroxyethyl methylan Chloride hydro-key side or the like.

  Examples of the inorganic alkali (D-4) include lithium hydroxide, sodium hydroxide and potassium hydroxide.

  Among (D), from the viewpoint of detergency, a quaternary ammonium salt (D-1) and an aliphatic amine (D-3) having 1 to 30 carbon atoms are preferable, and tetramethylammonium hydroxide is more preferable. Side, trimethylethylammonium hydroxide, tetraethylammonium hydroxide, triethylmethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, N-methyl-diethanolamine, DBU, DBN and combinations thereof.

  When the alkali component (D) is contained, from the viewpoint of detergency, the content of (D) is preferably 40% or less, more preferably 2 to 30 based on the weight of the active ingredient of the cleaning agent of the present invention. %, Particularly preferably 3 to 25%.

The cleaning agent of the present invention preferably contains one or more selected from the group consisting of a chelating agent (B), a reducing agent (C) and an alkali component (D), and more preferably (B) and (C ), Or (B), (C) and (D).
When the cleaning agent of the present invention usually contains a chelating agent (B) and a reducing agent (C), the preferred range is 0.1 to 60% based on the weight of (A), and (C) is 0.1% to 60%. 0.1 to 20%, more preferably (B) is 1 to 33%, (C) is 0.5 to 13%, particularly preferably (B) is 3 to 27%, and (C) is 1 to 8%. It is.

  The cleaning agent of the present invention includes the surfactant (A) as an essential component, water as an optional component, a chelating agent (B), a reducing agent (C), and an alkaline component (D). As long as the effect is not impaired, the dispersant (E), a trihydric or higher polyhydric alcohol (F), a water-soluble organic solvent (G), and other additives (H) are further selected. Ingredients may also be included.

As the dispersant (E), those conventionally used as fine particle dispersants such as polysaccharides and derivatives thereof (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, tri (polyoxyethylene) alkyl ether phosphate, etc.}. The (A-2a) also has an effect as a dispersant.
When these dispersants (E) are contained, the content of these dispersants (E) is preferably 10% or less, more preferably 8% or less, based on the weight of the active ingredient of the cleaning agent of the present invention. Particularly preferably, it is 5% or less.

Examples of the trihydric or higher polyhydric alcohol (F) include the following (F1) to (F5).
(F1) aliphatic polyhydric alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc.);
(F2) Dehydration condensate of (F1) (diglycerin, triglycerin, tetraglycerin, pentaglycerin, etc.);
(F3) Saccharides such as monosaccharides {pentose (arabinose, xylose, ribose, xylulose, ribulose, etc.), hexose (glucose, mannose, galactose, fructose, sorbose, tagatose, etc.), heptose (sedheptulose etc.)}, disaccharide ( Trehalose, saccharose, maltose, cellobiose, gentiobiose, lactose, etc.) and trisaccharides (raffinose, maltotriose, etc.);
(F4) sugar alcohol (arabitol, adonitol, xylitol, sorbitol, mannitol, dulcitol, etc.);
(F5) Trisphenol (such as trisphenol PA);
In addition, these alkylene oxide (carbon number 2 to 4) adducts (addition mole number 1 to 7 mol) and the like.
Moreover, (F) may be used independently or may be used together 2 or more types.

  Among (F), (F1), (F2), (F3) and (F4) are preferable from the viewpoint of high effect of preventing corrosion of the substrate, and glycerin, saccharose and sorbitol are more preferable.

  When (F) is contained, the content is preferably 30% or less, more preferably 20% or less, and particularly preferably 10% or less, based on the weight of the active ingredient of the cleaning agent.

Examples of the water-soluble organic solvent (G) include organic solvents having a solubility in water (g / 100 gH ₂ O) at 20 ° C. of 3 or more, preferably 10 or more.
For example, sulfoxide {dimethyl sulfoxide, sulfolane, butyl sulfone, 3-methyl sulfolane, 2,4-dimethyl sulfolane, etc.}; sulfone {dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, etc.}; amide {N, N -Dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide and the like}; lactam {N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxymethyl-2 -Pyrrolidone, etc.}; Lactones {β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, etc.}; alcohols {methanol, ethanol, isopropanol, etc.}; glycol And glycol ether Recall, ethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol, propylene glycol monomethyl ether, dipropylene glycol Monomethyl ether, 1,3-butylene glycol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, etc.}; oxazolidinone (N-methyl-2-oxazolidinone, 3,5-di- Nitr-2-oxazolidinone, etc.); nitrile (acetonitrile, propionitrile, butyronitrile, acrylonitrile, methacrylonitrile, benzonitrile, etc.); carbonate (ethylene carbonate, propion carbonate, etc.); ketone (acetone, diethyl ketone, acetophenone, methyl ethyl ketone, cyclohexanone) , Cyclopentanone, diacetone alcohol, etc.); cyclic ethers (tetrahydrofuran, tetrahydropyran, etc.) and the like.
(G) may be used alone or in combination of two or more.

  Among (G), glycols and glycol ethers are preferable from the viewpoint of cleaning properties and preventing components in the cleaning agent from remaining on the surface of the electronic material, and more preferable are ethylene glycol monomethyl ether and diethylene glycol monomethyl ether. , Triethylene glycol monomethyl ether, diethylene glycol monobutyl ether and diethylene glycol monohexyl ether.

  When (G) is contained, its content is 80% or less, more preferably 50% or less, and particularly preferably 20% or less, based on the weight of the active ingredient of the cleaning agent.

  Examples of the other additive (H) include an antioxidant, a rust inhibitor, a pH adjuster, a buffer agent, an antifoaming agent, a preservative, and a hydrotrope agent.

As antioxidant, phenolic antioxidant {2,6-di-t-butylphenol, 2-t-butyl-4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, etc.}; amine-based oxidation Inhibitors {monoalkyl diphenylamines such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamines such as 4,4′-dibutyldiphenylamine and 4,4′-dipentyldiphenylamine; polyalkyldiphenylamines such as tetrabutyldiphenylamine and tetrahexyldiphenylamine; α -Naphtylamine such as naphthylamine, phenyl-α-naphthylamine, etc.}; sulfur compounds {phenothiazine, pentaerythritol-tetrakis- (3-laurylthiopropionate), bis (3,5-tert- Til-4-hydroxybenzyl) sulfide and the like}; phosphorus antioxidant {bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, phenyldiisodecylphosphite, diphenyldiisooctylphosphite, triphenyl Phosphite, etc.};
These may be used alone or in combination of two or more.

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 acid such as dodecenyl succinic acid half ester, octadecenyl succinic anhydride, dodecenyl succinic acid amide; sorbitan monooleate, glycerin monoole And polyhydric alcohol partial esters such as 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, phosphoric acid and the like), the inorganic alkalis (D-4) exemplified above, and the like. You may use together.

As the buffering agent, an organic acid or inorganic acid having a buffering action and / or a salt thereof can be used.
Examples of the organic acid include organic acids having 1 to 12 carbon atoms exemplified in the above (C-1a), and examples of the inorganic acid include phosphoric acid and boric acid. Moreover, as a salt of these acids, the thing similar to the salt illustrated by the above-mentioned anionic surfactant (A-2) is mentioned. These may be used alone or in combination of two or more.

  Examples of the antifoaming agent include silicone antifoaming agents {antifoaming agents containing dimethyl silicone, fluorosilicone, polyether silicone and the like as constituents}. 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, 5-chloro-2-methyl-4-isothiazolin-3-one etc.}, pyridine derivative {pyridine 2-pyridinethiol-1-oxide (salt) etc.}, morpholine derivative {4- (2- Nitrobutyl) morpholine, 4,4- (2-ethyl-2-nitrotrimethylene) -dimorpholine, etc.}, benzimidazole derivatives {2- (4-thiazolyl) benzimidazole, etc.}, other preservatives {poly [oxyethylene ( Dimethylimino) ethylene (dimethylimino) ethylene] dichloride, p-chloro-m-xyleno , Phenoxyethanol, phenoxypropanol, acetoxydimethyldioxane, isopropylmethylphenol, tetrachloroisophthalonitrile, bisbromoacetoxyethane, 3-iodo-2-propynylbutylcarbamate, 2-bromo-2-nitropropane-1,3-diol Etc.}. These may be used alone or in combination of two or more.

  Examples of the hydrotrope include resorcin and salicylic acid (salt). Moreover, as a salt of these acids, the thing similar to the salt illustrated by the above-mentioned anionic surfactant (A-2) is mentioned. These may be used alone or in combination of two or more. In addition, toluenesulfonic acid (salt), xylenesulfonic acid (salt), and cumenesulfonic acid (salt) exemplified as the sulfonic acid surfactant (A-2b-1) also have an effect as a hydrotrope agent.

  When other additives (H) are contained, the content of each additive is based on the weight of the active ingredient of the cleaning agent, antioxidant, rust inhibitor, buffer, preservative and hydrotrope. Preferably it is 10% or less, More preferably, it is 8% or less, Most preferably, it is 5% or less. The amount of antifoaming agent added is preferably 2% or less, more preferably 1.5% or less, and particularly preferably 1% or less. Further, the pH adjuster is preferably 90% or less, more preferably 85% or less, and particularly preferably 80% or less based on the weight of the active ingredient of the cleaning agent. The total content of other additives (H) is 90% or less, more preferably 85% or less, and particularly preferably 80% or less, based on the weight of the active ingredient of the cleaning agent.

  In addition, when the composition is the same and overlaps between (B) to (H), the amount of each component exerting the corresponding addition effect is not used regardless of the effect as the other component, Considering that the effects as other components can be obtained at the same time, the amount used is adjusted according to the purpose of use.

The concentration of the active ingredient of the cleaning agent of the present invention is preferably 0.1 to 100%, more preferably 0.2 to 90%, particularly preferably 0.5 to 70% from the viewpoint of transport efficiency. Most preferably, it is 1.0 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). The active ingredient concentration is preferably 0.01 to 15%, particularly 0.05 to 10%, from the viewpoint of workability and cost during use.

  When the cleaning agent for electronic materials of the present invention is diluted with dilution water, the pH at 25 ° C. at an active ingredient concentration of 0.01 to 15% is preferably 1 to 13, more preferably 1 to 5 or 8. To 13, particularly preferably 1 to 4 or 9 to 13, most preferably 1 to 3 or 10 to 13. When the pH is within this range, it becomes easy to exert an effect of having an appropriate etching property and preventing the reattachment of fine particles without impairing the flatness of the substrate.

Each metal content of Na, K, Ca, Fe, Cu, Al, Pb, Ni and Zn atoms in the cleaning agent of the present invention is 20 ppm based on the weight of the active ingredient of the cleaning agent from the viewpoint of preventing metal contamination. The following is preferable, more preferably 10 ppm or less, and particularly preferably 5 ppm or less.
As a method for measuring the content of these metal atoms, known methods such as atomic absorption spectrometry, ICP emission analysis, and ICP mass spectrometry can be used.

  The surface tension (25 ° C.) of the cleaning agent of the present invention is preferably 65 mN / m or less, more preferably 50 mN / m or less, particularly preferably 40 mN / m, from the viewpoint of the wettability of the cleaning agent to an electronic material. It is as follows. The surface tension in the present invention can be measured in accordance with JIS K3362: 1998 Annulus Method: Corresponding ISO 304.

  The electrical conductivity (mS / cm) of the cleaning agent is preferably 0.2 to 10.0, more preferably 0.5 to 5.0, and particularly preferably from the viewpoint of preventing re-adhesion of particles and etching properties. 1.0 to 3.5.

  The cleaning agent of the present invention is a mixture of (A) and at least one component selected from the group consisting of (B) to (H) and water, except for the case where the surfactant (A) is used alone. However, in order to obtain a cleaning agent that satisfies the above mathematical formula (1), it is preferable to manufacture by the following method.

(1) Take a part of surfactant (A) or (A) and, if necessary, at least one component selected from the group consisting of (B) to (H) and water mixed at room temperature to 80 ° C. Measure the pH and oxidation-reduction potential at 25 ° C. of the diluted solution diluted with water to the active ingredient concentration when used as a cleaning agent, and the pH and oxidation-reduction potential (V) satisfy Equation (1) Confirm.
(2) When the oxidation-reduction potential does not satisfy the formula (1), a component that lowers the oxidation-reduction potential, for example, a chelating agent (B), a reducing agent (C), and / or an alkali component (D) is added. The redox potential is adjusted so that the pH and redox potential satisfy Equation (1).
In addition, when obtaining the cleaning agent which has pH of a specific range, in addition to the said operation, pH adjustment is performed with the following method.
When the pH in the above operation (1) or (2) is lower than the desired pH range, for example, an alkaline component (D), a pH adjuster among other additives (H), / Or Surfactant (A-2) etc. are added and pH is adjusted to the desired range.
When the pH in the above operation (1) or (2) is higher than the desired pH range, for example, a chelating agent (B), a reducing agent (C), or other additives (H) The pH adjuster and / or buffering agent is added to adjust the pH to a desired range.
The mixing / dissolving device in the production of the cleaning agent of the present invention is not particularly limited, and a stirring / mixing device equipped with a saddle type blade, a stirring / mixing device equipped with a spiral blade, and the like can be used.

The cleaning agent of the present invention is a cleaning agent for cleaning an electronic material. As an electronic material to be cleaned, flat panel display substrates (glass substrates for liquid crystal panels, color filter substrates, array substrates, plasmas) Display substrate and organic EL substrate), photomask substrate, magnetic disk substrate (glass substrate, aluminum substrate and Ni-P plated aluminum substrate), semiconductor substrate (semiconductor element, silicon wafer, etc.), compound Semiconductor substrates (SiC substrates, GaAs substrates, GaN substrates, AlGaAs substrates, etc.), sapphire substrates (LEDs, etc.), solar cell substrates (silicon substrates, glass substrates for thin film solar cells, etc.), optical lenses, printed wiring boards, light Communication cables, micro electro mechanical systems (MEMS), crystal units, etc. It is.
Among these, suitable electronic materials include flat panel display substrates, photomask substrates, sapphire substrates, solar cell substrates, optical lenses, printed circuit boards, crystal resonators, and the like, particularly preferred electronic materials. Flat panel display substrates and photomask substrates are raised.

  The electronic material cleaning method of the present invention is a cleaning method for cleaning an electronic material using the above-described cleaning agent, and is suitable as a cleaning method for flat panel display substrates, photomask substrates, and the like. Objects to be cleaned (dirt) include oils (coolant, etc.), dirt from human bodies (fingerprints, sebum, etc.), plasticizers (dioctyl phthalate, etc.), organic particles and other organic substances and inorganic particles [abrasives (for example, cerium oxide) , Alumina, colloidal silica, diamond, etc.) and polishing scraps (glass cullet, etc.)].

Since the cleaning method of the present invention is extremely excellent in particle removability, it aims at removing particles such as abrasives, polishing debris and grinding debris in the manufacturing process of flat panel display substrates and photomask substrates. It is preferably performed in the cleaning step, and more specifically, it is preferably applied as a cleaning method in the cleaning step after the grinding step, the cleaning step after the polishing step, or the cleaning step after the texturing step.
Further, in order to prevent dirt (particles and organic matter dirt, etc.) floating in the atmosphere from firmly attaching to the substrate surface, the substrate may be immersed in the cleaning agent of the present invention before and after the cleaning step. .
When the polishing step is a polishing step using any one of cerium oxide, alumina, colloidal silica or diamond as an abrasive, the effect of the cleaning method of the present invention is particularly easily exhibited.

  The cleaning method in the cleaning method of the present invention includes 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. In any case, the effect of the cleaning method of the present invention is easily exhibited.

  The washing temperature (° C.) when washing using the cleaning agent of the present invention is preferably 10 to 80 ° C., more preferably 15 to 70, and particularly preferably 20 to 60 from the viewpoint of detergency.

  The contact angle of water (25 ° C.) with respect to the electronic material cleaned by the cleaning method of the present invention is preferably 20 ° or less, more preferably 1 to 15 °, and particularly preferably 2 to 10 °. If the contact angle is within this range, the occurrence rate of defective products relating to electrical characteristics when paneled is further reduced. In addition, the measurement of a contact angle can be measured using a fully automatic contact angle meter [Kyowa Interface Science Co., Ltd. product, PD-W], for example.

The surface roughness (Ra) of the surface of the electronic material after being cleaned by the cleaning method of the present invention is preferably 0.5 nm or less, more preferably 0.001 to 0.3 nm, from the viewpoint of surface flatness of the electronic material. Especially preferably, it is 0.05-0.25 nm.
In addition, surface roughness (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

A method for manufacturing an electronic material according to a fourth aspect of the present invention is a method for manufacturing an electronic material including a step of cleaning the electronic material by the cleaning method described above, and includes a flat panel display substrate, a photomask substrate, a magnetic disk substrate, It is a manufacturing method of a semiconductor substrate, a compound semiconductor substrate, a sapphire substrate, a solar cell substrate, an optical lens, a printed wiring board, an optical communication cable, a micro electromechanical system, a crystal resonator, and the like.
It is particularly suitable as a method for producing a flat panel display substrate and a photomask substrate.

  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. The measurement conditions of the molecular weight of the polymer by GPC were measured by the method described above. The ultrapure water used in the examples and comparative examples had a specific resistance value of 18 MΩ or more.

[Production Example 1]
In a 1 liter stainless steel autoclave equipped with a stirrer and a temperature controller, 10 parts of a 25% aqueous solution of 200 parts (1.1 mole parts) of lauryl alcohol and tetramethylammonium hydroxide (hereinafter abbreviated as TMAH) (0 .027 mol parts) and dehydrated at 100 ° C. under reduced pressure of 4 kPa or less for 30 minutes. 430 parts (9.8 mole parts) of ethylene oxide (hereinafter abbreviated as EO) was added dropwise over 3 hours while controlling the reaction temperature at 100 ° C., and then aged at 100 ° C. for 3 hours to obtain a crude product. Obtained. This crude product was kept under reduced pressure of 2.6 kPa or less at 150 ° C. for 2 hours to decompose and remove the remaining TMAH, and a nonionic surfactant lauryl alcohol EO 9 mol adduct (A-1- 1) 630 parts were obtained.

[Production Example 2]
In a 1 liter stainless steel autoclave equipped with a stirrer and a temperature controller, 185 parts (1.0 mole part) of laurylamine and 3.6 parts (0.01 mole part) of 25% TMAH aqueous solution were charged at 100 ° C., It dehydrated under reduced pressure of 4 kPa or less for 30 minutes. 264 parts (6.0 mol parts) of EO was added dropwise over 3 hours while controlling the reaction temperature at 100 ° C., and then aged at 100 ° C. for 3 hours to obtain a crude product. This crude product was maintained at 150 ° C. under a reduced pressure of 2.6 kPa or less for 2 hours to decompose and remove the remaining TMAH, and a nonionic surfactant laurylamine EO 6 mol adduct (A-1-2) 445 parts were obtained.

[Production Example 3]
A 1 liter stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 212 parts (1.0 mole part) of cumylphenol and 2.9 parts (0.008 mole part) of 25% TMAH aqueous solution at 100 ° C. It dehydrated for 30 minutes under reduced pressure of 4 kPa or less. 352 parts (8.0 mole parts) of EO was added dropwise over 3 hours while controlling the reaction temperature at 100 ° C., and then aged at 100 ° C. for 3 hours to obtain a crude product. This crude product was maintained at 150 ° C. under a reduced pressure of 2.6 kPa or less for 2 hours to decompose and remove the remaining TMAH, and a nonionic surfactant cumylphenol EO 8 mol adduct (A-1- 3) 560 parts were obtained.

[Production Example 4]
In a reaction vessel capable of temperature control and stirring, 300 parts of isopropyl alcohol and 100 parts of ultrapure water were charged, and the temperature was raised to 75 ° C. after purging with nitrogen. Under stirring, 407 parts of a 75% aqueous solution of acrylic acid and 95 parts of a 15% isopropyl alcohol solution of dimethyl 2,2′-azobisisobutyrate were simultaneously added dropwise over 3.5 hours. After completion of the dropwise addition, the mixture was stirred at 75 ° C. for 5 hours, and then ultrapure water was intermittently added so that the system did not solidify, and the mixture of water and isopropyl alcohol was distilled off until isopropyl alcohol could not be detected. The obtained polyacrylic acid aqueous solution is neutralized with DBU (about 450 parts) until the pH becomes 7, and the concentration is adjusted with ultrapure water, whereby the polyacrylic acid DBU salt (A- A 40% aqueous solution of 2-1) was obtained. In addition, Mw of (A-2-1) was 10,000.

[Production Example 5]
100 parts of ethylene dichloride was charged into a reaction vessel equipped with a stirrer capable of temperature control and refluxing, and after purging with nitrogen under stirring, the temperature was raised to 90 ° C. to reflux ethylene dichloride. 120 parts of styrene and an initiator solution prepared by previously dissolving 1.7 parts of 2,2′-azobisisobutyronitrile in 20 parts of ethylene dichloride are separately added dropwise to the reaction vessel separately over 6 hours. Polymerization was carried out for another hour after completion. After the polymerization, the mixture was cooled to 20 ° C. under a nitrogen seal, 105 parts of anhydrous sulfuric acid was added dropwise over 10 hours while controlling the temperature at 20 ° C., and a sulfonation reaction was further carried out for 3 hours after the completion of the addition. After the reaction, the solvent was distilled off and solidified, and then 345 parts of ultrapure water was added and dissolved to obtain a polystyrenesulfonic acid aqueous solution. The resulting polystyrene sulfonic acid aqueous solution is neutralized with a 25% TMAH aqueous solution (about 400 parts) until the pH becomes 7, and the concentration is adjusted with ultrapure water, whereby polystyrene sulfonic acid TMAH salt which is an anionic surfactant is obtained. A 40% aqueous solution of (A-2-2) was obtained. In addition, Mw of (A-2-2) was 40,000, and the sulfonation rate was 97%.

[Production Example 6]
A reaction vessel with stirring was charged with 21 parts of naphthalenesulfonic acid and 10 parts of ultrapure water, and 8 parts of 37% formaldehyde was added dropwise at 80 ° C. over 3 hours. After completion of the dropwise addition, the temperature was raised to 105 ° C. and reacted for 25 hours, then cooled to room temperature (about 25 ° C.), DBU was gradually added while adjusting to 25 ° C. in a water bath, and adjusted to pH 6.5 (DBU). Use about 15 parts). Ultrapure water was added to adjust the solid content to 40% to obtain a 40% aqueous solution of a DBU salt (A-2-3) of naphthalenesulfonic acid formalin condensate which is an anionic surfactant. In addition, Mw of (A-2-3) was 5,000.

[Production Example 7]
Production Example except that 407 parts of 70% monomer aqueous solution consisting of 227 parts of acrylamido-2-methylpropanesulfonic acid, 78 parts of acrylic acid and 131 parts of ultrapure water was used instead of 407 parts of 75% aqueous solution of acrylic acid. In the same manner as in No. 4, the mixture of water and isopropyl alcohol was distilled off until isopropyl alcohol could not be detected after polymerization to obtain an aqueous acrylamide-2-methylpropanesulfonic acid / acrylic acid copolymer solution. While adjusting the obtained acrylamide-2-methylpropanesulfonic acid / acrylic acid copolymer aqueous solution to 25 ° C., DBU was gradually added to adjust the pH to 6.5 (using about 280 parts of DBU), and the concentration was adjusted with ultrapure water. As a result, a 40% aqueous solution of acrylamide-2-methylpropanesulfonic acid / acrylic acid copolymer DBU salt (A-2-4), which is an anionic surfactant, was obtained. In addition, Mw of (A-2-4) was 8,000.

[Production Example 8]
Instead of 407 parts of 75% aqueous solution of acrylic acid, 65% of 50% aqueous solution of sodium methacryloyloxypolyoxyalkylenesulfate (manufactured by Sanyo Chemical Co., Ltd., Eleminol RS-30) and 145 parts of acrylic acid Except that 465 parts of the monomer aqueous solution was used, the mixture of water and isopropyl alcohol was distilled off until isopropyl alcohol could not be detected after polymerization in the same manner as in Production Example 4, and methacryloyloxypolyoxyalkylene sulfate sodium salt / An aqueous acrylic acid copolymer solution was obtained. After diluting the obtained aqueous copolymer solution with ultrapure water so that the solid content concentration becomes 10%, using a cation exchange resin “Amberlite IR-120B” (manufactured by Organo Corporation), Sodium ions were removed until the concentration became 1 ppm or less. The sodium content was measured using an ICP emission analyzer (Varian730-ES, manufactured by VARIAN). The resulting methacryloyloxypolyoxyalkylene sulfate / acrylic acid copolymer is neutralized with 25% TMAH aqueous solution (about 600 parts) while adjusting the temperature to 25 ° C., and the concentration is adjusted with ultrapure water. As a result, a 10% aqueous solution of methacryloyloxypolyoxyalkylene sulfate / acrylic acid copolymer TMAH salt (A-2-5), which is an anionic surfactant, was obtained. In addition, Mw of (A-2-5) was 9,000.

[Production Example 9]
136 parts of octylbenzenesulfonic acid and 245 parts of ultrapure water were charged into a 1 L beaker and dissolved until uniform. The obtained octylbenzenesulfonic acid aqueous solution was neutralized with DBN (about 65 parts) until the pH became 7, and the concentration was adjusted with ultrapure water, whereby octylbenzenesulfonic acid DBN salt (anionic surfactant) ( A 40% aqueous solution of A-2-6) was obtained.

[Production Example 10]
144 parts of 2-ethylhexanoic acid and 300 parts of ultrapure water were charged into a 1 L beaker and dissolved until uniform. The obtained 2-ethylhexanoic acid aqueous solution is neutralized with diethanolamine (about 105 parts) until the pH becomes 7, and the concentration is adjusted with ultrapure water, whereby 2-ethylhexanoic acid diethanolamine which is an anionic surfactant is obtained. A 40% aqueous solution of salt (A-2-7) was obtained.

[Production Example 11]
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, neutralization with a 48% aqueous potassium hydroxide solution (about 230 parts) until the pH becomes 7, and adjusting the concentration with ultrapure water, 2-ethylhexanol sulfate potassium salt (A A 40% aqueous solution of 2-8) was obtained.

[Examples 1 to 30], [Comparative Examples 1 to 3]
Examples 1 to 30 and Comparative Example 1 were prepared by uniformly stirring and mixing the components shown in Tables 1 and 2 at the room temperature (about 20 ° C.) in a 1 L beaker with the number of parts shown in Tables 1 and 2. Tables 1 and 2 show the results of producing the cleaning agents of ˜3 and evaluating them based on the following evaluation methods.
In addition, the compounding part number of each component other than the ultrapure water described in a table | surface is the value of an active ingredient, and the quantity of the ultrapure water described in a table | surface is surfactant obtained in manufacture examples 1-11 The amount of ultrapure water in the aqueous solution.

Moreover, the abbreviations of chelating agent (B), reducing agent (C), alkali component (D) and water-soluble organic solvent (G) in Tables 1 and 2 are as follows.
HEDP: 1-hydroxyethylidene-1,1-diphosphonic acid HMP: sodium hexametaphosphate AA: ascorbic acid Cys: L-cysteine hypophosphorous acid 1Na: hypophosphorous acid monosodium salt MDEA: N-methyldiethanolamine DBU: 1, 8-diazabicyclo [5.4.0] -7-undecene DEG-B: diethylene glycol monobutyl ether

  The pH of the obtained cleaning agent at 25 ° C. was measured with a pH meter (H-12, M-12). The oxidation-reduction potential and the surface tension were measured by the methods described above. Moreover, the following methods evaluated washability-1 and 2, surface flatness, etching property, and a contact angle.

<Detergency evaluation-1>
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, A contaminated substrate was prepared by heating on a digital hot plate series 730) for 1 hour. 1000 g of the cleaning agent was put in a 2 L glass beaker, the produced contaminated substrate was immersed, and washed in an ultrasonic cleaner (200 kHz) at 30 ° C. for 5 minutes. 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 evaluation-2>
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, 10 cm × 10 cm) at 70 ° C. hot plate (manufactured by PMC Industries, digital hot plate Evaluation was carried out in the same manner as in the cleaning property evaluation-1, except that a contaminated substrate was prepared by fusing for 1 minute on the series 730).

<Surface flatness>
A substrate obtained by taking 10 ml of each cleaning agent in a 20 ml glass container and adjusting the temperature to 30 ° C., and then cutting a commercially available glass substrate (Corning, glass plate # 1737, 10 cm × 10 cm) into a size of 1 cm × 1 cm. And was immersed and washed at 30 ° C. for 20 minutes. After cleaning, the substrate was taken out using tweezers, thoroughly rinsed with ultrapure water to remove the cleaning agent, and then dried at room temperature (25 ° C.) by blowing with nitrogen. The surface roughness (Ra) of the dried substrate surface was measured using an atomic force microscope (S-I Nano Technology Co., Ltd., E-Sweep) to evaluate the surface flatness. The surface roughness (Ra) of the substrate before the test was 0.50 nm.

<Etching property>
A substrate obtained by taking 10 parts of a cleaning agent in a 50 ml polypropylene container, adjusting the temperature to 50 ° C., and then cutting a commercially available glass substrate (Corning, glass plate # 1737, 10 cm × 10 cm) into a size of 2 cm × 2 cm. After being immersed and allowed to stand 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 measurement>
The contact angle of water (25 ° C., after 1 second) with the substrate immediately after the evaluation in the cleaning property test-1 was measured using a fully automatic contact angle meter [Kyowa Interface Science Co., Ltd., PD-W]. .

  From the results of Tables 1 and 2, it was found that the cleaning agent of the present invention is extremely excellent in the removability of particles adhering to various substrate surfaces. Further, from the results of the etching property test, the cleaning agent of the present invention has an appropriate etching property, but hardly changes the flatness of the substrate surface after cleaning, so there is a concern that the substrate surface may be roughened during cleaning. It was also found that particles adhered to the substrate surface were very effective. Furthermore, since the cleaning agent of the present invention can reduce the contact angle of water on the substrate surface after cleaning, it has been found that there is an effect that an extremely clean substrate surface can be realized.

  Since the cleaning agent of the present invention is excellent in particle cleaning properties, a flat panel display substrate, a photomask substrate, a magnetic disk substrate, a semiconductor substrate, a compound semiconductor substrate, a sapphire substrate, a solar cell substrate, an optical lens, a print It can be suitably used as a cleaning agent for electronic materials such as wiring boards, optical communication cables, MEMS, and crystal resonators.

Claims (11)

A cleaning agent for a flat panel display substrate or a photomask substrate comprising an anionic surfactant (A-2) and a reducing agent (C) , at an active ingredient concentration of 0.01 to 15% by weight at 25 ° C. The cleaning agent for a flat panel display substrate or photomask substrate , wherein the pH is 1 to 3, and the pH and oxidation-reduction potential (V) [unit: mV, vsSHE] satisfy the following formula (1).
V ≦ −38.7 × pH + 550 (1) The cleaning agent according to claim 1, wherein the anionic surfactant (A-2) is a polymer type anionic surfactant (A-2a). Furthermore, the cleaning agent of Claim 1 or 2 containing a nonionic surfactant (A-1) . Cleaning agent according to any one of claims 1 to 3 containing one or more selected from the group consisting of further chelating agent (B) 及 Beauty alkaline component (D).   The chelating agent (B) is composed of aminopolycarboxylic acid (B-1), hydroxycarboxylic acid (B-2), phosphonic acid (B-6), condensed phosphoric acid (B-7), and salts thereof. The cleaning agent according to claim 4, which is one or more chelating agents selected from the group consisting of: The reducing agent (C) is an aldehyde having 1 to 12 carbon atoms, Redakuto emissions of 6 to 9 carbon atoms, aliphatic amine having 1 to 30 carbon atoms, thiol reducing agents, oxo sulfur oxo San及 beauty phosphorus cleaning agent according to any of claims 1 to 5 is one or more reducing agents selected from acid or Ranaru group. A method for cleaning a flat panel display substrate or photomask substrate , wherein the flat panel display substrate or photomask substrate is cleaned using the cleaning agent according to claim 1. The cleaning method according to claim 7 , wherein the polishing step is a polishing step or a texturing step using any one of cerium oxide, alumina, colloidal silica, or diamond as an abrasive. The method according to claim 7 or 8, wherein the cleaning is performed 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. The cleaning method according to any one of claims 7 to 9 , wherein a contact angle (25 ° C) of water with respect to the substrate after cleaning is 20 ° or less. The manufacturing method of a flat panel display substrate or a photomask substrate including the process of wash | cleaning a flat panel display substrate or a photomask substrate with the cleaning method in any one of Claims 7-10 .