WO2012161270A1 - Agent de nettoyage et procédé de nettoyage d'un substrat de verre - Google Patents

Agent de nettoyage et procédé de nettoyage d'un substrat de verre Download PDF

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Publication number
WO2012161270A1
WO2012161270A1 PCT/JP2012/063360 JP2012063360W WO2012161270A1 WO 2012161270 A1 WO2012161270 A1 WO 2012161270A1 JP 2012063360 W JP2012063360 W JP 2012063360W WO 2012161270 A1 WO2012161270 A1 WO 2012161270A1
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Prior art keywords
cleaning
glass substrate
cleaning agent
cerium oxide
acid
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PCT/JP2012/063360
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English (en)
Japanese (ja)
Inventor
榎本　久男
幸治 佐原
愛子 金子
智章 石川
哲史 横山
佳孝 前柳
田中　明
Original Assignee
旭硝子株式会社
株式会社パーカーコーポレーション
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Application filed by 旭硝子株式会社, 株式会社パーカーコーポレーション filed Critical 旭硝子株式会社
Priority to KR1020137030821A priority Critical patent/KR20140053003A/ko
Priority to CN201280022749.5A priority patent/CN103562366A/zh
Priority to JP2013516439A priority patent/JPWO2012161270A1/ja
Publication of WO2012161270A1 publication Critical patent/WO2012161270A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0075—Cleaning of glass
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3454—Organic compounds containing sulfur containing sulfone groups, e.g. vinyl sulfones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/362—Phosphates or phosphites

Definitions

  • the present invention relates to a cleaning agent for cleaning a glass substrate polished with a cerium oxide-containing abrasive and a method for cleaning a glass substrate.
  • a glass substrate used for FPD such as a liquid crystal display (LCD) is obtained by forming a molten glass into a plate shape by a manufacturing method called a float method, and cutting the glass substrate, for example, By polishing with a rotating and revolving polishing tool to remove minute irregularities and waviness on the surface, a predetermined thickness satisfying the flatness required for the glass substrate for FPD (for example, 0.4 to 1.. 1 mm) (see, for example, Patent Document 1).
  • polishing abrasive grains containing cerium oxide as a main component and containing a rare earth element such as lanthanum are used.
  • a glass substrate that requires high flatness such as an FPD glass substrate.
  • the remaining abrasive on the substrate surface is a problem.
  • the polishing agent (abrasive grains) adhering to the glass substrate surface is washed and removed (see, for example, Patent Document 2).
  • cleaning agents containing alkali components are used, but for abrasives containing abrasive grains mainly composed of cerium oxide, The detergency was insufficient.
  • a cleaning agent containing an inorganic or organic alkali component and a surfactant is also used. Abrasive grain residues could not be reduced sufficiently.
  • a cleaning agent containing citric acid which is one of organic acids, to dissolve cerium oxide.
  • citric acid which is one of organic acids
  • the cleaning agent using citric acid as the organic acid has good initial cleaning characteristics, but there is a problem that the abrasive residue in the drainage agglomerates with time, resulting in problems in wastewater treatment.
  • the present invention has been made to solve the above-described problems, and for glass substrates that can disperse and remove the abrasive grains remaining and / or adhered to the surface thereof without impairing the flatness of the glass substrate. It aims at providing the cleaning agent and the cleaning method of a glass substrate.
  • a first aspect of the present invention is a cleaning agent for cleaning a glass substrate polished with a cerium oxide-containing polishing agent, wherein (A) an organic phosphonic acid, (B) a polycarboxylate, and (C) A cleaning agent characterized by being a water-based cleaning agent containing an aromatic sulfonic acid and (D) an amine-alkylene oxide adduct.
  • the cleaning agent of the first aspect the sum of the (A) organic phosphonic acid, the (B) polycarboxylic acid salt, the (C) aromatic sulfonic acid, and the (D) amine-alkylene oxide adduct
  • the amount of the (A) organic phosphonic acid is 0.01 to 50% by mass
  • the amount of the (B) polycarboxylic acid salt is 0.01 to 10% by mass
  • the amount of the (C) aromatic sulfonic acid is 0.01% by mass. It is preferable that the content of the amine-alkylene oxide adduct is 0.02 to 10% by mass.
  • the organic phosphonic acid (A) is preferably an organic compound having a structure in which a group represented by the formula: —P ( ⁇ O) (OH) 2 is bonded to a carbon atom.
  • the (D) amine-alkylene oxide adduct is preferably a propylene oxide-ethylene oxide adduct of alkylenediamine.
  • (A) an organic phosphonic acid, the (B) polycarboxylate, the (C) aromatic sulfonic acid, the (D) amine-alkylene oxide adduct, and water It is preferable to contain 55 to 98% by mass of water with respect to the total amount of each component of A) to (D) and water.
  • the term “to” indicating the above numerical range is used in the sense that the numerical values described before and after it are used as the lower limit value and the upper limit value, and unless otherwise specified, “to” is the same hereinafter. Used with meaning.
  • a second aspect of the present invention is a method for cleaning a glass substrate, wherein a polishing step of polishing a glass substrate using an abrasive containing cerium oxide, and the glass substrate after the polishing step are combined with the first substrate. And a cleaning step of cleaning with the cleaning agent according to the aspect.
  • the abrasive preferably contains abrasive grains containing cerium oxide as a main component and a rare earth element.
  • the glass substrate can be preferably cleaned by a single wafer type. Furthermore, it is preferable to clean the glass substrate after the polishing step with a diluted cleaning solution obtained by diluting the cleaning agent with water. Furthermore, in the said washing
  • polishing abrasive grains made of cerium oxide or the like remaining on and adhered to the surface of the glass substrate polished with an abrasive containing cerium oxide are dispersed and removed without impairing the flatness of the glass substrate. can do.
  • the glass substrate after polishing with the abrasive containing cerium oxide is efficiently cleaned without impairing the flatness of the surface, and the surface is free of foreign substances such as abrasive grains.
  • a glass substrate with very little residue can be provided.
  • an embodiment of the present invention will be described by taking as an example a cleaning agent for cleaning a glass substrate used for FPD such as an LCD and a cleaning method using the cleaning agent.
  • the FPD glass substrate polished with the cerium oxide-containing polishing agent is cleaned to remove the residue of the polishing agent on the polished glass substrate, and the embodiment of the present invention is a cleaning for this cleaning.
  • Agent and cleaning method The present invention is not limited to these embodiments, and other embodiments may belong to the category of the present invention as long as they match the gist of the present invention.
  • Embodiment of this invention is a cleaning agent of the glass substrate for FPD, (A) organic phosphonic acid, (B) polycarboxylate, (C) aromatic sulfonic acid, (D) amine -An aqueous detergent containing an alkylene oxide adduct.
  • polishing abrasive grains made of cerium oxide or the like remaining on and / or attached to the surface of the polished glass substrate can be well dispersed and removed, thereby impairing the flatness of the glass substrate.
  • the abrasive residue in the cleaning waste liquid does not aggregate over time, and the cleaning drainage can be processed well.
  • the organic phosphonic acid as component (A) acts as a chelating agent for cerium oxide, and remains and / or adheres to the surface of the glass substrate. It promotes the dispersion of abrasive grains composed of, etc., and peels off from the surface of the glass substrate to remove it.
  • the organic phosphonic acid which is the component (A) has a structure in which a group represented by the formula: —P ( ⁇ O) (OH) 2 (hereinafter referred to as a phosphonic acid group) is bonded to a carbon atom.
  • the number of phosphonic acid groups per molecule of organic phosphonic acid is preferably 2 or more, more preferably 2 to 8, and particularly preferably 2 to 4.
  • organic phosphonic acid in the present invention a compound having a structure in which a hydrogen atom bonded to carbon of a hydrocarbon which may have a substituent is substituted with a phosphonic acid group, and a nitrogen atom of ammonia or amines
  • a compound having a structure in which a hydrogen atom bonded to is substituted with a methylenephosphonic acid group represented by —CH 2 —P ( ⁇ O) (OH) 2 is preferable.
  • the hydrocarbon which may have a substituent is preferably an aliphatic hydrocarbon or a hydroxyl group-containing aliphatic hydrocarbon.
  • the number of carbon atoms is preferably 1 to 6, and the number of hydroxyl groups is preferably 2 or less.
  • Specific examples of the organic phosphonic acid having this structure include methyl diphosphonic acid and 1-hydroxyethane-1,1-diphosphonic acid.
  • the organic phosphonic acid in the present invention includes a compound having a structure in which a hydrogen atom bonded to carbon of a hydroxyl group-containing aliphatic hydrocarbon is substituted with a phosphonic acid group.
  • organic phosphonic acid having the latter structure a compound having a structure in which all hydrogen atoms bonded to nitrogen atoms of ammonia or aliphatic amines are substituted with methylenephosphonic acid groups is preferable.
  • a part of hydrogen atoms bonded to amine nitrogen atoms may be substituted with an organic group such as an alkyl group.
  • an alkylene diamine or a polyalkylene polyamine which is a multimer thereof is preferable.
  • the alkylenediamine preferably has 2 to 4 carbon atoms.
  • the number of hydrogen atoms bonded to nitrogen atoms of these amines (hydrogen atoms substituted for methylenephosphonic acid groups) is preferably 2 to 8, and more preferably 2 to 4.
  • organic phosphonic acids having this structure include aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), propylenediaminetetra (methylenephosphonic acid), and diethylenetriamine.
  • Penta methylenephosphonic acid
  • triethylenetetraminehexa methylenephosphonic acid
  • tris (2-aminoethyl) aminehexa (methylenephosphonic acid)
  • trans-1,2-cyclohexanediaminetetra methylenephosphonic acid
  • glycol etherdiaminetetra Methylene phosphonic acid
  • tetraethylene pentamine hepta methylene phosphonic acid
  • the (B) component polycarboxylate and the (C) component aromatic sulfonic acid improve the dispersibility and / or removability of the abrasive grains by the (A) organic phosphonic acid, and polish the abrasive. It works to prevent the reattachment of grains.
  • the polycarboxylic acid salt as the component (B) include poly (meth) acrylates and salts of (meth) acrylic acid-maleic acid copolymers.
  • the notation (meth) acrylic acid means both acrylic acid and methacrylic acid.
  • the weight average molecular weight (hereinafter abbreviated as Mw) of the polycarboxylic acid is preferably in the range of 2,000 to 50,000 from the viewpoint of preventing reattachment of abrasive grains and low foaming properties.
  • Mw is a value measured by gel permeation chromatography (hereinafter abbreviated as GPC).
  • the counter ion forming the salt is not particularly limited, but alkali metal (for example, sodium and potassium) salts, ammonium salts, primary amines (for example, alkylamines such as methylamine, ethylamine, and butylamine).
  • alkali metal for example, sodium and potassium
  • ammonium salts for example, ammonium salts
  • primary amines for example, alkylamines such as methylamine, ethylamine, and butylamine.
  • secondary amines eg, dialkylamines such as dimethylamine, diethylamine and dibutylamine, and diethanolamine
  • tertiary amines eg, trialkylamines such as trimethylamine, triethylamine and tributylamine, triethanolamine, N-methyl
  • 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) salts
  • DBU 1,8
  • alkali metal for example, sodium and potassium
  • ammonium salts for example, sodium and potassium
  • primary amine salts secondary amine salts
  • secondary amine salts tertiary amine salts
  • quaternary ammonium salts particularly preferred are salts of alkali metals (for example, sodium and potassium) and ammonium salts.
  • aromatic sulfonic acid (C) examples include alkylbenzene sulfonic acid having 8 to 14 carbon atoms, petroleum sulfonate, toluene sulfonic acid, xylene sulfonic acid, and cumene sulfonic acid.
  • alkylbenzene sulfonic acid having 8 to 14 carbon atoms petroleum sulfonate, toluene sulfonic acid, xylene sulfonic acid, and cumene sulfonic acid.
  • metaxylene sulfonic acid (2,4-dimethylbenzene sulfonic acid) is preferable.
  • the amine-alkylene oxide adduct as the component (D) functions to promote the penetration of the organic phosphonic acid (A) into the interface between the abrasive grains and the glass substrate.
  • the amine-alkylene oxide adduct is preferably a compound known as an alkylene oxide addition type nonionic surfactant.
  • an alkylene oxide addition type nonionic surfactant As the alkylene oxide, ethylene oxide (hereinafter also referred to as EO) and propylene oxide (hereinafter also referred to as PO) are preferable, and a compound having a structure in which only one of them is added may be added. It may be a compound having the above structure.
  • the EO unit that is, oxyethylene group
  • the PO unit that is, oxypropylene group
  • the former is obtained by sequentially adding EO and PO separately to the amine, and the latter is obtained by adding a mixture of EO and PO to the amine.
  • the PO-EO adduct refers to an adduct obtained by any of these addition methods.
  • amines to which alkylene oxide is added amines having 2 to 8 hydrogen atoms bonded to nitrogen atoms and 1 to 4 amino groups are preferred. Moreover, 16 or less are preferable and, as for carbon number of amines, 10 or less are more preferable.
  • examples of such amines include aliphatic monoamines and polyamines, alicyclic monoamines and polyamines, and aromatic monoamines and polyamines. More specifically, alkyl monoamines, alkylene diamines and polyalkylene polyamines that are multimers thereof, alicyclic monoamines and polyamines having at least one amino group or aminoalkyl group bonded to an alicyclic ring, and amino groups bonded to an aromatic ring. An alicyclic monoamine or polyamine having at least one group or aminoalkyl group is preferred.
  • the amine-alkylene oxide adduct as the component (D) is a PO-EO adduct of alkylenediamine.
  • alkylene diamine an alkylene diamine having 2 to 4 carbon atoms is preferable, and ethylene diamine is particularly preferable.
  • the PO—EO adduct of ethylenediamine include a compound in which PO and EO are added to four hydrogen atoms bonded to the nitrogen atom of ethylenediamine. It is also preferable to use an aromatic amine PO adduct together with the ethylenediamine PO-EO adduct as the amine-alkylene oxide adduct as the component (D).
  • Examples of the PO adducts of aromatic amines include metaxylylenediamine PO adducts.
  • D When an amine-alkylene oxide adduct is used in combination with a PO-EO adduct of ethylenediamine and a PO adduct of aromatic amine, the stability of the cleaning / removing ability of the cleaning agent is further improved.
  • the content ratio of each component of (A) to (D) with respect to the total amount of each component of (A) to (D) including water is 0.01 to 50% by mass of organic phosphonic acid, 0.01 to 10% by mass of (B) polycarboxylate, 0.01 to 50% by mass of (C) aromatic sulfonic acid, (D) amine-alkylene
  • the oxide adduct is preferably 0.02 to 10% by mass.
  • the mass% of the total of (B) polycarboxylate and (C) aromatic sulfonic acid with respect to the total amount of (A) to (D) including water is 0.03 to 60 mass%. Is preferred.
  • (D) When an amine-alkylene oxide adduct is used in combination with an alkylenediamine PO-EO adduct and an aromatic amine PO adduct, 0.01 to 5% by mass of an alkylenediamine PO-EO adduct The PO group adduct of the aromatic amine is 0.01 to 5% by mass, and the total mass% of the total amount of (A) to (D) including water is 0.02 to 10% by mass. It is preferable.
  • the cleaning agent of the present invention is an aqueous cleaning agent obtained by dissolving the components (A) to (D) in water.
  • the water in the cleaning agent dissolves the above-mentioned (A) organic phosphonic acid, (B) polycarboxylic acid salt, (C) aromatic sulfonic acid, and (D) amine-alkylene oxide adduct. It is a solvent.
  • this water deionized water, ultrapure water, charged ion water, hydrogen water, ozone water, or the like can be used. Since water has a function of controlling the fluidity of the cleaning agent of the present invention, the content thereof can be appropriately set according to the target cleaning characteristics such as the cleaning speed.
  • the content ratio of water to the total amount of the components (A) to (D) and water is 55 to 98% by mass.
  • a cleaning agent containing the components (A) to (D) and water in the above ranges is also referred to as a “cleaning agent stock solution”.
  • additives can be added to water.
  • examples of other additives include a dispersant, a water-soluble organic solvent, an antioxidant, a rust inhibitor, a pH adjuster, a buffer, an antifoaming agent, an antiseptic, and a hydrotrope.
  • the cleaning agent of the present invention configured as described above cleans a glass substrate using a polishing agent containing abrasive grains mainly composed of cerium oxide, and a glass substrate after the polishing step.
  • a polishing agent containing abrasive grains mainly composed of cerium oxide In the manufacturing method of the glass substrate including at least 2 process with a washing
  • the cleaning agent stock solution is further diluted with water so that the content (concentration) of the cleaning agent stock solution is 0.5 to 2.5% by mass. Are preferably used. By diluting with water as described above, it is possible to satisfactorily remove the abrasive grains made of cerium oxide and the like that remain and adhere without roughening the surface of the glass substrate.
  • the surface of the glass substrate is polished using a polishing pad and containing abrasive grains containing cerium oxide as a main component and rare earth elements, for example, abrasive grains having an average grain size of 0.5 to 3.0 ⁇ m. It can be set as the process grind
  • the above average particle diameter is a value obtained by measuring the abrasive grains by the air permeation method (Blaine method).
  • the average particle diameter is expressed in the present specification, the value obtained by this measurement method. Say.
  • the abrasive grains containing cerium oxide as a main component and containing a rare earth element include 45% by mass or more of cerium oxide and 0% of a rare earth element compound (for example, rare earth element oxide). This refers to those containing from 55% to 55% by weight.
  • rare earth elements include La, Pr, and Nd.
  • the cleaning step can be carried out by a method in which the cleaning agent of the present invention is brought into direct contact with the polished glass substrate and cleaned by a single wafer method.
  • the cleaning nozzle 4 is provided on both upper and lower surfaces of the glass substrate 3 that is continuously transported in the cleaning chamber 2 in the horizontal direction by a mechanism such as a transport roll 1.
  • a method of scribing with the rotating brush 6 disposed on both sides while spraying the sprayed cleaning agent 5 is employed.
  • the temperature of the cleaning agent 5 is not particularly limited, and is used at room temperature (15 ° C.) to 95 ° C. If the temperature exceeds 95 ° C., water may be boiled, which is inconvenient in the washing operation and is not preferable.
  • the rotating brush 6 for cleaning for example, a plurality of cylindrical brushes made of PVA (polyvinyl alcohol) sponge and having an outer diameter of 70 to 100 mm can be used. In this case, for example, these brushes are arranged such that the rotation axis is perpendicular to the surface to be cleaned of the glass substrate 3 and the tip part is in contact with the surface to be cleaned of the glass substrate 3 or less than 2 mm. Arrange them at intervals.
  • the rotation speed of the rotary brush 6 is preferably 100 to 500 rpm.
  • the cleaning agent 5 a solution obtained by diluting the above-described cleaning agent stock solution of the present invention with water so as to have a desired concentration can be used.
  • the injection amount can be 15 to 40 liters / minute.
  • a test piece was prepared. That is, a known polishing cerium oxide (CeO 2 ) on one side of a glass substrate (product name: AN100; manufactured by Asahi Glass Co., Ltd., hereinafter the same) having a length of 5.0 cm ⁇ width of 4.0 cm ⁇ thickness of 0.07 cm. A 4% by mass aqueous solution of particles (average particle size 0.8 to 1.0 ⁇ m) was added dropwise and dried at room temperature for 20 minutes. Thus, as a test piece, a glass substrate (hereinafter, referred to as a particle-attached glass substrate) having white cerium oxide (CeO 2 ) particles attached on one side was produced.
  • a glass substrate hereinafter, referred to as a particle-attached glass substrate having white cerium oxide (CeO 2 ) particles attached on one side was produced.
  • ⁇ Preliminary test 2 for cleaning performance of cerium oxide> A 4% by mass aqueous solution of a known polishing cerium oxide (CeO 2 ) particle (average particle size 0.8 to 1.0 ⁇ m) is dropped on one side of the same glass substrate (trade name: AN100) for 60 minutes at room temperature. It was made to dry and the cerium oxide particle adhesion glass substrate was produced.
  • a known polishing cerium oxide (CeO 2 ) particle average particle size 0.8 to 1.0 ⁇ m
  • each component shown in Table 3 was blended with the composition shown in the same table to prepare a detergent stock solution.
  • the cleaning property of the cleaning agent stock solution thus obtained was examined as follows. That is, after the obtained cleaning agent stock solution (including water) was diluted by adding water so that the concentration became 2% by mass, the above-mentioned particle-attached glass substrate was immersed in this cleaning dilution solution at room temperature for 9 hours. did. And the surface state of the glass substrate after immersion was observed with the naked eye, and the detergency was evaluated according to the following criteria. The evaluation results are shown in Table 3. (Evaluation criteria) ⁇ : The cerium oxide particles on the glass substrate surface are completely removed. ⁇ : Some cerium oxide particles remain on the glass substrate surface. X: The cerium oxide particle is hardly removed and remains on the glass substrate surface.
  • Example 3 The glass substrate after the polishing step was cleaned by the method shown in FIG.
  • the concentration of the stock solution (concentration of the stock solution containing water) of the cleaning agent stock solution obtained in Example 1 (hereinafter referred to as organic acid system 1) is 0.5% by mass.
  • the detergent stock solution obtained in Example 2 (hereinafter referred to as “organic acid system 2”) was used as the concentration of the stock solution (the concentration of the stock solution containing water).
  • a diluted washing solution diluted with water so as to be 0.5% by mass was used.
  • the alkaline detergent is a detergent comprising potassium hydroxide and sodium hydroxide as inorganic alkali, ethylenediaminetetraacetate as a chelating agent, and polyoxyethylene dodecyl ether as a surfactant, and the balance water.
  • AN100 (trade name) is used, and in the polishing step, the surface of the glass substrate is polished mainly using known cerium oxide particles having an average particle diameter of 0.8 to 1.0 ⁇ m as an abrasive.
  • An abrasive slurry containing abrasive grains (trade name SHOROX A10; manufactured by Showa Denko KK) was used, and the polishing was performed using a polishing pad.
  • the various diluted cleaning solutions described above are sprayed onto the surface of the polished glass substrate at a rate of 250 to 700 mL per second, and a PVA brush rotating at a speed of 100 to 500 rpm for 6 to 10 seconds. Scrub.
  • Examples 5 to 8, Comparative Examples 7 and 8 In Examples 5 to 8, as shown in Table 5, a diluted cleaning solution in which the organic acid system 1 or the organic acid system 2 was diluted with water to the concentration shown in the same table was used, and the polishing process was performed by the method shown in FIG. The glass substrate was cleaned. In Comparative Examples 7 and 8, a conventional alkaline cleaning agent diluted to the concentration shown in Table 5 was used, and cleaning was performed in the same manner. The alkaline cleaning agent is the same cleaning agent used in Comparative Example 6.
  • AN100 As a glass substrate, AN100 (trade name) is used, and in the polishing step, the surface of the glass substrate is composed mainly of known cerium oxide particles for polishing having an average particle size of 0.8 to 1.0 ⁇ m as an abrasive.
  • a polishing agent slurry (trade name SHOROX A10) containing polishing abrasive grains to be used was used, and a polishing pad was used.
  • the diluted cleaning solution was sprayed onto the surface of the polished glass substrate at a rate of 250 to 700 mL per second, and scrubbed with a PVA brush rotating at a speed of 100 to 500 rpm for 6 to 10 seconds.
  • the number of particles such as abrasive grains remaining on the surface of the glass substrate was measured separately for each particle slice level.
  • the slice level is one of the classification methods.
  • the particle size is classified based on the intensity of the scattered light by irradiating the particles with laser light.
  • the measurement was performed by a laser scattering imaging method (HS830E; manufactured by Toray Engineering Co., Ltd.). Table 5 shows the measurement results.
  • Examples 5 to 8 where cleaning was performed using a diluted cleaning solution diluted to a concentration particles (particles) residue on the surface of the glass substrate compared to Comparative Examples 7 and 8 using an alkaline cleaning agent
  • the residual of fine particles of abrasive grains having a size (slice level) of about 0.3 ⁇ m was extremely small.
  • the cleaning agent of the present invention can be used for FPD because it can disperse and remove abrasive grains made of cerium oxide or the like remaining on or adhered to the surface of the glass substrate after polishing without impairing the flatness of the glass substrate after polishing. It can be effectively applied to a glass substrate cleaning method.

Abstract

Pour disperser et enlever des grains abrasifs laissés ou déposés sur une surface sans compromettre la planéité d'un substrat de verre, poli à l'aide d'un agent de polissage contenant de l'oxyde de cérium, la présente invention concerne un agent de nettoyage à base aqueuse qui contient (A) un acide phosphonique organique, (B) un polycarboxylate, (C) un acide sulfonique aromatique et (D) un produit d'addition amine-oxyde d'alkylène, de façon à nettoyer un substrat de verre poli à l'aide d'un agent de polissage contenant de l'oxyde de cérium. Le procédé de nettoyage d'un substrat de verre comporte une étape de polissage pour polir un substrat de verre à l'aide d'un agent de polissage contenant de l'oxyde de cérium, et une étape de nettoyage pour nettoyer le substrat de verre à l'aide de l'agent de nettoyage après l'étape de polissage.
PCT/JP2012/063360 2011-05-24 2012-05-24 Agent de nettoyage et procédé de nettoyage d'un substrat de verre WO2012161270A1 (fr)

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KR1020137030821A KR20140053003A (ko) 2011-05-24 2012-05-24 세정제 및 유리 기판의 세정 방법
CN201280022749.5A CN103562366A (zh) 2011-05-24 2012-05-24 清洗剂及玻璃基板的清洗方法
JP2013516439A JPWO2012161270A1 (ja) 2011-05-24 2012-05-24 洗浄剤およびガラス基板の洗浄方法

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JP2011-115353 2011-05-24

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CN112602175A (zh) * 2018-08-30 2021-04-02 三菱化学株式会社 清洗液、清洗方法和半导体晶片的制造方法

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CN106694416A (zh) * 2016-12-30 2017-05-24 武汉华星光电技术有限公司 一种湿式设备背面毛刷
WO2018168207A1 (fr) * 2017-03-14 2018-09-20 株式会社フジミインコーポレーテッド Composition de traitement de surface ainsi que procédé de fabrication de celle-ci, et procédé de traitement de surface mettant en œuvre cette composition
CN107214162A (zh) * 2017-07-18 2017-09-29 合肥余塝电子商务有限公司 一种玻璃制品用清洁装置
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