WO2014080917A1 - ガラス基板の洗浄方法 - Google Patents
ガラス基板の洗浄方法 Download PDFInfo
- Publication number
- WO2014080917A1 WO2014080917A1 PCT/JP2013/081203 JP2013081203W WO2014080917A1 WO 2014080917 A1 WO2014080917 A1 WO 2014080917A1 JP 2013081203 W JP2013081203 W JP 2013081203W WO 2014080917 A1 WO2014080917 A1 WO 2014080917A1
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- WO
- WIPO (PCT)
- Prior art keywords
- cleaning
- glass substrate
- acid
- cleaning liquid
- mass
- Prior art date
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- 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
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- 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
- 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
- C11D3/36—Organic compounds containing phosphorus
- C11D3/362—Phosphates or phosphites
-
- C11D2111/18—
-
- C11D2111/20—
-
- C11D2111/44—
Definitions
- the present invention relates to a cleaning method for cleaning a glass substrate polished with an abrasive containing cerium oxide particles, and more particularly to a cleaning method for cleaning a glass substrate for a liquid crystal display device or the like.
- a glass substrate used for an FPD such as a liquid crystal display (LCD) is made by, for example, polishing a glass substrate formed from a molten glass into a plate shape by a rotating and revolving polishing tool to obtain a minute surface. By removing irregularities and undulations, a thin plate having a predetermined thickness (for example, 0.4 to 1.1 mm) that satisfies the flatness required for the glass substrate for FPD is formed.
- an abrasive (slurry) containing cerium oxide particles is used as abrasive grains, and after polishing, abrasives (abrasive grains, etc.) adhering to the glass substrate surface are used. Cleaning with a cleaning solution is performed (see, for example, Patent Document 1).
- an alkaline cleaning liquid containing an inorganic or organic alkali component and a surfactant has insufficient cleaning properties, Abrasive grain residues having a particle size of submicron order could not be sufficiently removed.
- the present inventors use an acidic cleaning liquid containing an organic acid such as organic phosphonic acid, and dissolve abrasive grains on the glass substrate by a method such as dissolving cerium oxide.
- a method for removing the residue was proposed (see Japanese Patent Application No. 2011-115353).
- OH-rich hydrophilic layer a highly hydrophilic layer containing excess OH groups (hereinafter referred to as OH-rich hydrophilic layer) is formed.
- the present invention has been made to solve the above problems, and can remove and remove abrasive grains remaining on and adhered to the surface of the glass substrate without deteriorating the flatness of the glass substrate.
- a glass substrate cleaning method capable of preventing a resin BM film from peeling off by suppressing a decrease in adhesion of a resin black matrix film (hereinafter also referred to as a resin BM film) formed on a substrate surface. The purpose is to do.
- a glass substrate polished with an abrasive containing cerium oxide particles is washed with an acidic aqueous cleaning solution containing an organic acid, and then washed with an alkaline aqueous cleaning solution containing a base. It is characterized by.
- the acidic aqueous cleaning solution preferably has a pH of 5 or less.
- the acidic aqueous cleaning liquid is an aqueous cleaning liquid containing (A) an organic phosphonic acid, (B) a polycarboxylic acid salt, (C) an aromatic sulfonic acid, and (D) an amine-alkylene oxide adduct. It is preferable that In the acidic aqueous cleaning solution, the content ratio of the components (A) to (D) is 0% of (A) organic phosphonic acid with respect to 100% by mass of the total amount of (A) to (D).
- the alkaline aqueous cleaning liquid is preferably an aqueous cleaning liquid having a pH of 10 or more.
- the alkaline aqueous cleaning liquid is preferably an aqueous cleaning liquid containing a base, a chelating agent, and a surfactant.
- the alkaline aqueous cleaning liquid has a mass content ratio of the base, the chelating agent, and the surfactant, and (base) :( chelating agent) :( surfactant) is (1 to 10) :( 1 to 10): (1 to 10) is preferable.
- the glass substrate is a glass substrate made of aluminosilicate glass.
- the aluminosilicate glass is preferably an aluminoborosilicate glass that does not substantially contain an alkali metal component.
- the glass substrate is preferably a glass substrate for a liquid crystal display device on which a resin black matrix film is formed.
- a glass substrate polished with an abrasive containing cerium oxide particles is efficiently cleaned without impairing the flatness of the surface, and the cerium oxide particles remaining on and adhered to the surface, etc.
- the abrasive grains can be removed, and the decrease in the adhesion of the resin BM film formed on the surface of the glass substrate after washing can be suppressed to prevent the resin BM film from peeling off.
- the glass substrate polished with the abrasive is first cleaned with an acidic aqueous cleaning solution containing an organic acid, and abrasive grains such as cerium oxide particles remaining and adhered to the surface of the glass substrate are present.
- the OH-rich hydrophilic layer on the surface of the glass substrate generated by this acid cleaning is removed with an alkaline aqueous cleaning solution containing a base.
- the present invention will be described with reference to a cleaning method for cleaning a glass substrate used for an FPD such as an LCD.
- the present invention is not limited to this embodiment, and other embodiments may belong to the category of the present invention as long as they match the gist of the present invention.
- a glass substrate polished with an abrasive containing cerium oxide particles is washed with an acidic aqueous cleaning solution containing an organic acid (hereinafter also referred to as an acidic cleaning solution), and then a base.
- an acidic aqueous cleaning solution containing an organic acid hereinafter also referred to as an acidic cleaning solution
- cleaning liquid containing this.
- cleaning with an acidic cleaning liquid is also referred to as acid cleaning
- cleaning with an alkaline cleaning liquid is also referred to as alkaline cleaning.
- drying may be performed between the acid cleaning and the alkali cleaning. Furthermore, you may dry after alkali washing. Examples of the drying method include a method of blowing warm air, a method of blowing compressed air, and the like.
- the glass substrate that is an object to be cleaned is a glass substrate for FPD such as LCD, and after polishing with an abrasive containing cerium oxide particles, the residue such as abrasive on the surface is removed.
- the glass constituting the glass substrate is preferably an aluminosilicate glass having a composition containing SiO 2 , Al 2 O 3 , B 2 O 3 and an oxide of an alkaline earth metal, and an alkali metal component is substantially added to the glass composition.
- a so-called alkali-free aluminoborosilicate glass that does not contain is more preferable.
- that an alkali metal component is not included substantially substantially means that content of the alkali metal oxide in a glass composition is 1 mass% or less.
- the surface of such a glass substrate is polished with a polishing agent (slurry) containing cerium oxide particles as abrasive grains using, for example, a polishing pad.
- a polishing agent slurry
- the average particle size of the abrasive grains is preferably in the range of 0.8 to 1.0 ⁇ m, for example.
- the glass substrate polished with the abrasive is washed with an acidic washing solution containing an organic acid (hereinafter, this washing step is referred to as an acid washing step).
- the pH of the acidic cleaning solution is preferably 6 or less, more preferably 5 or less, and particularly preferably 3.5 or less. Further, the pH of the acidic cleaning solution is preferably 1 or more, more preferably 1.5 or more, and particularly preferably 2 or more.
- the organic acid contained in the acidic cleaning liquid include, but are not limited to, organic carboxylic acids such as ascorbic acid and citric acid, and organic phosphonic acids.
- An inorganic acid for example, sulfuric acid, phosphoric acid, nitric acid, hydrofluoric acid, hydrochloric acid, etc.
- an inorganic acid for example, sulfuric acid, phosphoric acid, nitric acid, hydrofluoric acid, hydrochloric acid, etc.
- (A) organic phosphonic acid and (B) polycarboxylic acid are used as acidic cleaning liquid. It is preferable to use a cleaning solution containing an acid salt, (C) an aromatic sulfonic acid, and (D) an amine-alkylene oxide adduct.
- the organic phosphonic acid which is component (A) acts as a chelating agent for cerium oxide, promotes the dispersion of abrasive grains made of cerium oxide and the like adhering to and remaining on the surface of the glass substrate, and from the surface of the glass substrate. It works to peel off and remove.
- the organic phosphonic acid refers to an organic compound having a structure in which a phosphonic acid group represented by the formula: —P ( ⁇ O) (OH) 2 is bonded to a carbon atom.
- the number of phosphonic acid groups per molecule of the organic phosphonic acid is preferably 2 or more, more preferably 2 to 8, and particularly preferably 2 to 4.
- the organic phosphonic acid is a compound having a structure in which a hydrogen atom bonded to carbon of hydrocarbons which may have a substituent is substituted with a phosphonic acid group, or bonded to a nitrogen atom of ammonia or amines.
- a compound having a structure in which a hydrogen atom is substituted with a methylenephosphonic acid group represented by —CH 2 —P ( ⁇ O) (OH) 2 is preferable.
- the hydrocarbons which may have a substituent are preferably aliphatic hydrocarbons or hydroxyl group-containing aliphatic hydrocarbons.
- 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.
- a hydrogen atom bonded to carbon of a hydroxyl group-containing aliphatic hydrocarbon is substituted with a phosphonic acid group.
- Particularly preferred, specifically, 1-hydroxyethane-1,1-diphosphonic acid is most preferred.
- 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 dispersion / removability of the abrasive grains by the (A) organic phosphonic acid and reattach the abrasive grains. It works to prevent.
- 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 that forms the salt is not particularly limited, but salts of alkali metals (sodium and potassium), ammonium salts, primary amines (for example, alkylamines such as methylamine, ethylamine, and butylamine), Salts of secondary amines (eg, dialkylamines such as dimethylamine, diethylamine and dibutylamine, and dialkanolamines such as diethanolamine), tertiary amines (eg, trialkylamines such as trimethylamine, triethylamine and tributylamine, triethanolamine) N-alkyl dialkanolamines such as N-methyldiethanolamine, and 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabisic [4.3.0] -5-Nonene, 1,4-diazabicyclo [2.2.2] octane, 1H imidazole,
- alkali metal (sodium and potassium) salts preferred among these are alkali metal (sodium and potassium) salts, ammonium salts, primary amine salts, secondary amine salts, tertiary amine salts, or quaternary ammonium salts. Particularly preferred are alkali metal (sodium and potassium) salts or ammonium salts.
- the aromatic sulfonic acid as component (C) includes alkylbenzene sulfonic acid having 8 to 14 carbon atoms, petroleum sulfonate, toluene sulfonic acid, xylene sulfonic acid (also known as dimethylbenzene sulfonic acid), and cumene sulfonic acid. Etc.
- metaxylene sulfonic acid also known as 2,4-dimethylbenzene sulfonic acid
- the amine-alkylene oxide adduct as the component (D) functions to promote the penetration of the organic phosphoric 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.
- the alkylene oxide is preferably ethylene oxide (hereinafter also referred to as EO) or propylene oxide (hereinafter also referred to as PO), and may be a compound having a structure in which only one of them is added, or both of them are 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. Aromatic monoamines and polyamines having at least one group or aminoalkyl group are 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 (D) amine-alkylene oxide adduct.
- Examples of the PO adducts of aromatic amines include metaxylylenediamine PO adducts.
- D When the PO-EO adduct of ethylenediamine and the PO adduct of aromatic amine are used in combination as the amine-alkylene oxide adduct, the stability of the cleaning / cleaning ability of the cleaning liquid is further improved.
- the content ratio of each component (A) to (D) is 0.01 to 50% by mass of (A) organic phosphonic acid and (B) polycarboxylic acid based on the total amount of (A) to (D). It is preferable that the salt is 0.01 to 10% by mass, (C) the aromatic sulfonic acid is 0.01 to 50% by mass, and (D) the amine-alkylene oxide adduct is 0.02 to 10% by mass.
- the total proportion of (B) polycarboxylate and (C) aromatic sulfonic acid is preferably 0.03 to 60% by mass.
- a preferable acidic cleaning solution used in the present invention is an aqueous cleaning solution obtained by dissolving the components (A) to (D) in water.
- 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 liquid, its content can be appropriately set according to the target cleaning characteristics such as the cleaning speed.
- an aqueous solution containing the components (A) to (D) at a relatively high concentration hereinafter referred to as an acidic cleaning agent stock solution
- an acidic cleaning agent stock solution is diluted with water before use to form an acidic cleaning solution. Used for cleaning.
- the water content can be 55 to 98% by mass.
- the acidic detergent stock solution contains a dispersant, a water-soluble organic solvent, an antioxidant, a rust inhibitor, a pH adjuster, a buffer, and an antifoaming agent. Additives such as preservatives and hydrotropes can be added to the water.
- the surface of the polished glass substrate is cleaned using a diluted solution (acid cleaning solution) obtained by diluting the acidic detergent stock solution with water. It is preferable to wash by a single wafer method.
- the cleaning method is not particularly limited as long as the cleaning liquid is brought into direct contact with the surface of the glass substrate for cleaning. Scrub cleaning, shower cleaning (jet cleaning), dip (immersion) cleaning, and the like can be used.
- the temperature of the cleaning liquid is not particularly limited, and it is used at room temperature (15 ° C.) to 95 ° C. If it exceeds 95 ° C., water may boil, which is inconvenient in the washing operation and is not preferable.
- the acid washing time is preferably 1.5 seconds to 1 hour, more preferably 1.5 seconds to 1 minute, and particularly preferably 1.5 seconds to 15 seconds.
- the cleaning nozzle 4 sprays the upper and lower surfaces of the glass substrate 3 which are continuously transported in the cleaning chamber 2 in the horizontal direction by a mechanism such as a transport roll 1.
- a mechanism such as a transport roll 1.
- a method of scrubbing (rubbing) with the rotating brush 6 disposed on both sides while spraying the acidic cleaning solution 5 can be employed.
- the rotating brush 6 for cleaning a plurality of cylindrical brushes having an outer diameter of 70 to 100 mm made of PVA (polyvinyl alcohol) sponge (foam) are used. Then, these brushes are arranged so 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 at an interval of less than 2 mm. Deploy.
- the rotation speed of the rotary brush 6 is preferably 100 to 500 rpm.
- the acidic cleaning solution 5 a solution obtained by diluting the above-mentioned acidic cleaning agent stock solution with water to a desired concentration is used, and the flow rate (injection amount) of the diluted cleaning solution is 15 to 40 liters / minute. Is preferred.
- the scrub time is preferably 1.5 seconds or longer. Furthermore, the scrub time is preferably 15 seconds or less.
- the glass substrate cleaned with the acidic cleaning solution in the acid cleaning step is then cleaned with an alkaline cleaning solution (that is, an alkaline aqueous cleaning solution containing a base) (hereinafter, this cleaning step is referred to as an alkali cleaning step).
- an alkaline cleaning solution that is, an alkaline aqueous cleaning solution containing a base
- the pH of the alkaline cleaning liquid is preferably 8 or more, more preferably 10 or more, and particularly preferably 12 or more. Further, the pH of the alkaline cleaning liquid is preferably 14 or less.
- the alkaline cleaning liquid can contain a chelating agent and a surfactant in addition to the base. In particular, it is preferable to use a chelating agent and a surfactant in combination.
- Examples of the base contained in the alkaline cleaning liquid include alkali metal compounds such as alkali metal hydroxides and alkali metal carbonates, amines and quaternary ammonium hydroxide.
- alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are preferable.
- Examples of chelating agents include ethylenediaminetetraacetic acid chelating agents, gluconic acid chelating agents, nitrilotriacetic acid chelating agents, and iminosuccinic acid chelating agents. In particular, an ethylenediaminetetraacetic acid chelating agent is preferred.
- As the surfactant a nonionic surfactant is preferable.
- Nonionic surfactants include amine-alkylene oxide adducts that are component (D) of the acidic detergent, polyoxyalkylene ether-based nonionic surfactants such as polyoxyethylene dodecyl ether, and polyoxyethylene sorbitan fatty acids. Examples thereof include polyoxyalkylene ether ester-based nonionic surfactants such as esters and ester-based nonionic surfactants such as glycerin fatty acid esters.
- the alkaline cleaning liquid used in the present invention is an aqueous cleaning liquid obtained by dissolving the above-described base or the like in water.
- 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 liquid, its content can be appropriately set according to the target cleaning characteristics such as the cleaning speed.
- an aqueous solution containing the above-mentioned base or the like at a relatively high concentration hereinafter referred to as an alkaline detergent stock solution
- the water content can be 55 to 98% by mass.
- the alkaline detergent stock solution includes a dispersant, a water-soluble organic solvent, an antioxidant, a rust inhibitor, a pH adjuster, a buffer, Additives such as foaming agents, preservatives, hydrotropes and the like can be incorporated into the water.
- the content of each component in the alkaline detergent stock solution is preferably 1 to 10% by mass for the base, the chelating agent, and the nonionic surfactant, and the balance is preferably water.
- an alkaline detergent stock solution containing each component in the above range is diluted with water so that the content ratio (concentration) of the stock solution is 1 to 5% by mass to obtain an alkaline cleaning solution. It is preferable to use it.
- diluting with water in this way, only the OH-rich hydrophilic layer generated on the surface of the glass substrate in the acid cleaning step is removed without excessively roughening the surface of the glass substrate, and a highly adhesive resin BM film It is possible to obtain a glass substrate surface capable of forming
- the glass substrate cleaned with the acidic cleaning solution in the acid cleaning step is cleaned with an alkaline cleaning solution obtained by diluting the alkaline cleaning agent stock solution with water. It is preferable to wash by a single wafer method.
- the cleaning method is not particularly limited as long as it is a method in which the alkaline cleaning liquid is cleaned by directly contacting the surface of the glass substrate. Similar to the cleaning with the acidic cleaning liquid described above, scrub cleaning, shower cleaning (jet cleaning), dip (immersion) cleaning, and the like can be used.
- the temperature of the alkaline cleaning liquid is not particularly limited as in the case of the acidic cleaning liquid, and the alkaline cleaning liquid is used at room temperature (15 ° C.) to 95 ° C. If it exceeds 95 ° C., water may boil, which is inconvenient in the washing operation and is not preferable.
- the alkali cleaning time is preferably 1.5 seconds to 1 hour, more preferably 1.5 seconds to 1 minute, and particularly preferably 1.5 seconds to 15 seconds.
- cleaning can be performed using the cleaning apparatus shown in FIG. As shown in FIG. 1, the glass substrate after the acid cleaning is further transported continuously in the cleaning chamber 2 in the horizontal direction by a mechanism such as a transport roll 1, and the upper and lower surfaces of the glass substrate 3 are downstream in the acid cleaning process.
- a method of scrubbing both surfaces of the glass substrate with the rotating brush 6 disposed on both sides while spraying the alkaline cleaning liquid 7 ejected from the cleaning nozzle 4 can be employed.
- an alkaline cleaning liquid obtained by diluting the above-mentioned alkaline cleaning agent stock solution with water to a desired concentration is used, and the flow rate (injection amount) of the alkaline cleaning liquid is 15 to 40 liters / liter. Minutes are preferred.
- the scrub time is preferably 1.5 seconds or longer. Furthermore, the scrub time is preferably 15 seconds or less.
- a glass substrate polished with an abrasive containing cerium oxide particles is first cleaned with an acidic cleaning solution containing an organic acid in an acid cleaning step, and the cerium oxide particles remaining on and adhered to the surface thereof.
- the OH-rich hydrophilic layer on the surface of the glass substrate generated by the acid cleaning is removed by cleaning with an alkaline cleaning liquid containing a base in an alkaline cleaning step.
- a glass substrate for LCD made of aluminosilicate glass (product name: AN100, manufactured by Asahi Glass Co., Ltd.) is used, and the surface of this glass substrate is used with a polishing pad and a particle size of 0.8 to 1.0 ⁇ m Polishing was performed using an abrasive slurry containing cerium oxide particles (manufactured by Showa Denko KK, trade name: SHOROX A10).
- Alkaline cleaning is performed by applying an alkaline detergent stock solution (manufactured by Parker Corporation, trade name: PK-LCG211) on the surface of the glass substrate after acid cleaning so that the concentration of the stock solution (including water) is 1.5%.
- the alkaline cleaning solution (pH 11 to 12) diluted with 1 was scrubbed while sprayed at a flow rate of 25 L per minute.
- the temperature of each cleaning solution in acid cleaning and alkali cleaning was 25 ° C. in Example 1 and 35 ° C. in Example 2.
- the average scrub time in the acid cleaning step and the alkali cleaning step was 2.94 seconds. No residual abrasive grains are observed on the glass substrates after cleaning in Examples 1 and 2.
- Comparative Example 1 only alkali cleaning was performed on the surface of the polished glass substrate.
- an alkaline cleaning solution at 25 ° C. obtained by diluting an alkaline detergent stock solution (manufactured by Parker Corporation, trade name: PK-LCG211) with water so that the concentration of the stock solution becomes 1.5% is applied to the surface of the glass substrate.
- PK-LCG211 an alkaline detergent stock solution
- spraying at a flow rate of 25 L per minute scrubbing with a rotating PVA brush was performed.
- the average scrub time was 2.94 seconds. Remaining abrasive grains were observed on the glass substrate after cleaning in Comparative Example 1.
- the adhesion of the resin BM film was evaluated by the following method. Further, the Al concentration (Al / Si ratio) and contact angle of the glass substrate surface were measured.
- this BM-forming resin composition was applied (spin coated) for 10 seconds at 200 rpm using a spin coater (manufactured by Mikasa, device name: MS-A100) on the surface of the glass substrate after washing. Using a hot plate (manufactured by AS ONE, apparatus name: HI-1000), the coating film was formed by heating and drying at 90 ° C. for 60 seconds.
- a spin coater manufactured by Mikasa, device name: MS-A100
- the photomask had four types of pattern shapes L1 to L4 shown below, and a total of 110 types of patterns in which the line width was changed by 1 ⁇ m for each type.
- L1 .
- 25 linear patterns in one block 2835 ⁇ m ⁇ 2000 ⁇ m
- a pattern spacing of 100 ⁇ m the line width is variable in the range of 1 to 25 ⁇ m
- L2 .
- 30 linear patterns in one block (2952.6 ⁇ m ⁇ 2000 ⁇ m) with a pattern spacing of 50 ⁇ m (the line width is variable in the range of 1 to 30 ⁇ m) L3 .
- the developed glass substrate is observed with a laser microscope (manufactured by Keyence Corporation, apparatus name: VK-9510), and the line width of the mask in which the pattern of the resin BM film remains on the glass substrate is represented by four types of pattern shapes L1 to L4. Each was examined.
- the line width value with the largest line width hereinafter referred to as the maximum remaining resolution value
- the minimum remaining resolution value the line width value with the minimum line width
- the average value hereinafter referred to as the average remaining resolution. Value.
- the remaining resolution refers to the line width of the mask remaining after development (Line width of the mask why remains after developing).
- cleaning is so high that all of the residual resolution maximum value, the residual resolution minimum value, and the residual resolution average value are small.
- the surface Al concentration and the Al / Si ratio can be one of the indicators of the wettability (hydrophilicity) of the substrate surface. That is, the higher the surface Al concentration and the Al / Si ratio, the less leaching of the Al component on the glass substrate surface (surface layer), and the hydrophilicity (wetting property) caused by the OH-rich hydrophilic layer on the glass substrate surface. It is low.
- Example 1 and Example 2 in which the polished glass substrate surface was cleaned with an acidic cleaning solution (acid cleaning) and then cleaned with an alkaline cleaning solution (alkali cleaning), the maximum resolution value of the remaining resin BM film was left.
- the minimum resolution value and the average remaining resolution value are smaller than those of the comparative example in which only the acid cleaning is performed, and are similar to those in the comparative example 1 in which only the alkali cleaning is performed, and the resin BM film adheres to the glass substrate surface. The properties were found to be good.
- Example 2 in which the temperature of the cleaning liquid in acid cleaning and alkaline cleaning was 35 ° C., the maximum remaining resolution and the remaining resolution were compared with Example 1 in which acid cleaning and alkaline cleaning were performed using a cleaning liquid of 25 ° C. It was found that the difference from the minimum value was small, and that the variation in the adhesion of the resin BM film was reduced by raising the temperature of the cleaning solution.
- Example 1 and Example 2 the Al / Si ratio is higher than that in Comparative Example 2 and is about the same as that in Comparative Example 1, and after washing with an acidic washing liquid, washing with an alkaline washing liquid, The hydrophilicity (wettability) of the glass substrate surface is as low as that of Comparative Example 1 in which only alkali cleaning is performed without acid cleaning, and a glass substrate surface with good adhesion of the resin BM film is obtained. I understood it.
- ⁇ Measurement of contact angle> About 1 ⁇ L of pure water was deposited on the surface of the glass substrate immediately after washing, and the contact angle with water was measured using a contact angle meter (manufactured by FACE, apparatus name: CA-X). Further, after 7 days, 14 days, 21 days and 28 days from the cleaning, the contact angle of the glass substrate surface with water was measured in the same manner as described above. The measurement results are shown in Table 2 and the graph of FIG. Note that the contact angle with water can also be one of the indicators of the wettability (hydrophilicity) of the substrate surface. The larger the contact angle of the glass substrate surface with water, the lower the hydrophilicity (wetting property).
- Table 2 shows the following. That is, there is almost no difference between Example 1 and Comparative Example 1 and Comparative Example 2 in the contact angle immediately after cleaning, but the contact angle after exposing the substrate for one week or more is in Comparative Example 1 in Example 1. Although it was lower than 1, it was significantly higher than Comparative Example 2. From this, the contact angle is higher in Example 1 after exposing the glass substrate for one week or more than in Comparative Example 2 in which only the acid cleaning was performed by cleaning with an acidic cleaning solution and then with alkali cleaning. It was found that the hydrophilicity (wetting property) was lowered and a glass substrate surface with good adhesion of the resin BM film was obtained.
- the glass substrate after being polished with the abrasive containing cerium oxide is efficiently cleaned without impairing the flatness of the surface, and the abrasive grains remaining on and adhered to the surface are removed.
- the cleaning method of the present invention can be effectively applied to cleaning glass substrates used for FPDs such as LCDs.
Abstract
Description
さらにまた、前記ガラス基板は、アルミノケイ酸ガラスからなるガラス基板であることが好ましい。そして、前記アルミノケイ酸ガラスは、アルカリ金属成分を実質的に含有しないアルミノホウケイ酸ガラスであることが好ましい。さらに、前記ガラス基板は、その上に樹脂系ブラックマトリックス膜が形成される液晶表示装置用のガラス基板であることが好ましい。
また、本発明の洗浄方法において、酸洗浄とアルカリ洗浄との間に乾燥を行ってもよい。さらに、アルカリ洗浄の後に乾燥を行ってもよい。乾燥方法としては、温風を吹き付ける方法や、圧縮した空気を吹き付ける方法等が挙げられる。
本発明において、洗浄対象物であるガラス基板は、LCDのようなFPD用のガラス基板であり、酸化セリウム粒子を含有する研磨剤で研磨された後、表面の研磨剤等の残さを除去するために洗浄される。このガラス基板を構成するガラスは、SiO2とAl2O3とB2O3およびアルカリ土類金属の酸化物を含む組成を有するアルミノケイ酸ガラスが好ましく、ガラス組成にアルカリ金属成分を実質的に含まない、いわゆる無アルカリのアルミノホウケイ酸ガラスがより好ましい。なお、アルカリ金属成分を実質的に含まないとは、ガラス組成中におけるアルカリ金属酸化物の含有量が1質量%以下であることをいう。
本発明においては、前記研磨剤により研磨されたガラス基板を、有機酸を含む酸性の洗浄液によって洗浄する(以下、この洗浄工程を酸洗浄工程という。)。酸性洗浄液のpHは、6以下が好ましく、5以下がより好ましく、3.5以下が特に好ましい。また、酸性洗浄液のpHは、1以上が好ましく、1.5以上がより好ましく、2以上が特に好ましい。酸性洗浄液に含有される有機酸としては、例えば、アスコルビン酸、クエン酸のような有機カルボン酸や、有機ホスホン酸等が挙げられるが、これらに限定されない。これらの有機酸とともに、無機酸(例えば、硫酸、リン酸、硝酸、フッ酸、塩酸など)を加えることができる。また、pHの変動を抑制するために、前記無機酸とともにこれらの酸の塩を加えることも可能である。
下記メチレンホスホン酸基を有する構造の有機ホスホン酸も含めて、本発明における有機ホスホン酸としては、水酸基含有脂肪族炭化水素の炭素に結合した水素原子をホスホン酸基に置換した構造を有する化合物が特に好ましく、具体的には、1-ヒドロキシエタン-1,1-ジホスホン酸が最も好ましい。
ここで、(メタ)アクリル酸という表記は、アクリル酸とメタクリル酸の両方を意味する。ポリカルボン酸の重量平均分子量(以下、Mwと略記。)は、砥粒の再付着防止および低泡性の観点から、2,000~50,000の範囲であることが好ましい。なお、Mwは、ゲルパーミエーションクロマトグラフィー(以下、GPCと略記。)によって、測定された値である。
本発明の酸洗浄においては、前記酸性洗浄剤原液を水で希釈した希釈液(酸性洗浄液)を使用して、研磨後のガラス基板の表面を洗浄する。枚葉方式で洗浄することが好ましい。洗浄液をガラス基板の表面に直接接触させて洗浄する方法であれは、洗浄方法は特に限定されない。スクラブ洗浄、シャワー洗浄(噴射洗浄)、ディップ(浸漬)洗浄等を用いることができる。洗浄液の温度は特に限定されることはなく、室温(15℃)~95℃で使用される。95℃を超える場合には、水が沸騰するおそれがあり、洗浄操作上不便であり好ましくない。酸洗浄時間は、1.5秒~1時間が好ましく、1.5秒~1分がさらに好ましく、1.5秒~15秒が特に好ましい。
本発明においては、前記酸洗浄工程で酸性洗浄液により洗浄されたガラス基板を、次いで、アルカリ性洗浄液(すなわち、塩基を含むアルカリ性の水系洗浄液)により洗浄する(以下、この洗浄工程をアルカリ洗浄工程という。)。アルカリ性洗浄液のpHは、8以上が好ましく、10以上がより好ましく、12以上が特に好ましい。また、アルカリ性洗浄液のpHは、14以下が好ましい。また、このアルカリ性洗浄液は、塩基以外にキレート剤や界面活性剤を含有することができる。特に、キレート剤と界面活性剤を併用することが好ましい。
アルカリ洗浄工程においては、酸洗浄工程で酸性洗浄液により洗浄されたガラス基板を、前記アルカリ性洗浄剤原液を水で希釈したアルカリ性洗浄液により洗浄する。枚葉方式で洗浄することが好ましい。アルカリ性洗浄液をガラス基板の表面に直接接触させて洗浄する方法であれは、洗浄方法は特に限定されない。前記した酸性洗浄液による洗浄と同様に、スクラブ洗浄、シャワー洗浄(噴射洗浄)、ディップ(浸漬)洗浄等を用いることができる。また、アルカリ性洗浄液の温度も、前記酸性洗浄液と同様に特に限定されることはなく、室温(15℃)~95℃で使用される。95℃を超える場合には、水が沸騰するおそれがあり、洗浄操作上不便であり好ましくない。アルカリ洗浄時間は、1.5秒~1時間が好ましく、1.5秒~1分がさらに好ましく、1.5秒~15秒が特に好ましい。
図1に示す洗浄装置を使用し、以下に示すようにして、表面を研磨されたガラス基板の洗浄を行った。
まず、以下に示す各成分を以下の組成で配合し、均一に混合して、固形分濃度15%の感光性BM形成用樹脂組成物を調製した。
[BM形成用樹脂組成物の組成]
・バインダ樹脂(日本化薬社製、商品名;ZCR1569H)28.4部
・光活性剤(光重合開始剤)
(チバ・スペシャルティ・ケミカル社製、商品名;イルガキュアOXE02)6.1部
・コロイダルシリカ微粒子(日産化学社製、商品名;PMAST)20.3部
・カーボンブラック32.5部
・界面活性剤(ビックケミー・ジャパン社製、商品名;BYK306)0.3部
・架橋剤(日本化薬社製、商品名;UX5002D)6.1部
(日本化薬社製、商品名;NC3000H)3.0部
・シランカップリング剤(信越化学社製、商品名;KBM403)3.0部
・リン酸化合物(リン酸とモノメタクリロイルオキシエチルフォスフェート、ジメタクリロイルオキシエチルフォスフェートの2:1(質量比)混合物)0.3部
L1………パターン間隔100μmで1ブロック(2835μm×2000μm)に25本の線状パターン(線幅は1~25μmの範囲で可変)
L2………パターン間隔50μmで1ブロック(2952.6μm×2000μm)に30本の線状パターン(線幅は1~30μmの範囲で可変)
L3………パターン間隔200μmで1ブロック(2682.5μm×2000μm)に25本の線状パターン(線幅は1~25μmの範囲で可変)
L4………パターン間隔200μmで1ブロック(2682.5μm×2000μm)に25本の短い線状パターン(線幅は1~25μmの範囲で可変)
なお、残し解像度最大値、残し解像度最小値および残し解像度平均値は、いずれも小さいほど、洗浄後のガラス基板上に形成された樹脂BM膜の密着性が高いことを示している。
洗浄後のガラス基板表面のAl濃度およびSi濃度を、X線光電子分光法を用いて測定し、Al濃度とSi濃度の比(Al/Si比)を求めた。ESCA(Electron Spectroscopy for Chemical Analysis)の測定には、アルバック・ファイ社製のESCA5500を使用し、Si(2p)およびAl(2p)のピークを用い、パスエネルギー117.4eV、エネルギーステップ0.5eV/step、取り出し角(試料表面と検出器のなす角度)15°の条件で測定を行った。スペクトルの解析には、解析ソフトMultiPak Ver.8.2を使用した。得られた結果を、表1に示す。
なお、表面Al濃度およびAl/Si比は、基板表面の濡れ性(親水性)の指標の一つとすることができる。すなわち、表面Al濃度およびAl/Si比が高いほど、ガラス基板表面(表層)のAl成分の浸出が少ないことを意味し、ガラス基板表面のOHリッチ親水層に起因する親水性(濡れ性)が低いことを示している。
洗浄直後のガラス基板の表面に、約1μLの純水の水滴を着滴させ、接触角計(FACE社製、装置名;CA-X)を用いて、水に対する接触角を測定した。また、洗浄から7日、14日、21日および28日経過後において、ガラス基板の表面の水に対する接触角を、前記と同様にして測定した。測定結果を、表2および図3のグラフに示す。
なお、水に対する接触角も、基板表面の濡れ性(親水性)の指標の一つとすることができる。ガラス基板表面の水に対する接触角が大きいほど、親水性(濡れ性)が低いことを示している。
Claims (10)
- 酸化セリウム粒子を含有する研磨剤により研磨されたガラス基板を、有機酸を含む酸性の水系洗浄液により洗浄し、次いで塩基を含むアルカリ性の水系洗浄液により洗浄することを特徴とするガラス基板の洗浄方法。
- 前記酸性の水系洗浄液が、pH5以下の水系洗浄液である請求項1に記載のガラス基板の洗浄方法。
- 前記酸性の水系洗浄液が、(A)有機ホスホン酸と、(B)ポリカルボン酸塩と、(C)芳香族スルホン酸と、(D)アミン-アルキレンオキサイド付加物とを含有する水系洗浄液である、請求項1または2に記載のガラス基板の洗浄方法。
- 前記酸性の水系洗浄液中の前記(A)~(D)の各成分の含有割合が、(A)~(D)の合計量100質量%に対して、(A)有機ホスホン酸が0.01~50質量%、(B)ポリカルボン酸塩が0.01~10質量%、(C)芳香族スルホン酸が0.01~50質量%、および(D)アミン-アルキレンオキサイド付加物が0.02~10質量%である
請求項3に記載のガラス基板の洗浄方法。 - 前記アルカリ性の水系洗浄液が、pH10以上の水系洗浄液である、請求項1ないし4のいずれか1項に記載のガラス基板の洗浄方法。
- 前記アルカリ性の水系洗浄液が、塩基とキレート剤と界面活性剤とを含有する水系洗浄液である、請求項1ないし5のいずれか1項に記載のガラス基板の洗浄方法。
- 前記アルカリ性の水系洗浄液中の前記塩基と前記キレート剤と前記界面活性剤との質量含有比率である、(塩基):(キレート剤):(界面活性剤)が、(1~10):(1~10):(1~10)である請求項6に記載のガラス基板の洗浄方法。
- 前記ガラス基板が、アルミノケイ酸ガラスからなるガラス基板である、請求項1ないし7のいずれか1項に記載のガラス基板の洗浄方法。
- 前記アルミノケイ酸ガラスが、アルカリ金属成分を実質的に含有しないアルミノホウケイ酸ガラスである、請求項8に記載のガラス基板の洗浄方法。
- 前記ガラス基板が、その上に樹脂系ブラックマトリックス膜が形成される液晶表示装置用のガラス基板である、請求項1ないし9のいずれか1項に記載のガラス基板の洗浄方法。
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US9884782B2 (en) | 2014-04-04 | 2018-02-06 | Corning Incorporated | Treatment of glass surfaces for improved adhesion |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001206737A (ja) * | 1999-11-18 | 2001-07-31 | Nippon Sheet Glass Co Ltd | ガラス基板及びその洗浄方法 |
JP2001229531A (ja) * | 2000-02-08 | 2001-08-24 | Fuji Electric Co Ltd | ガラス基板の洗浄方法 |
JP2004059419A (ja) * | 2002-05-31 | 2004-02-26 | Nippon Sheet Glass Co Ltd | ガラス基材の製造方法及びその製造方法で得られたガラス基材 |
JP2004145958A (ja) * | 2002-10-23 | 2004-05-20 | Nippon Sheet Glass Co Ltd | 情報記録媒体用ガラス基板及びその製造方法 |
JP2009087523A (ja) * | 2007-09-14 | 2009-04-23 | Sanyo Chem Ind Ltd | 磁気ディスク用ガラス基板洗浄剤 |
JP2011105824A (ja) * | 2009-11-16 | 2011-06-02 | Dai Ichi Kogyo Seiyaku Co Ltd | 硬質表面用洗浄剤組成物 |
JP2012219186A (ja) * | 2011-04-08 | 2012-11-12 | Lion Corp | ハードディスク基板用洗浄剤 |
JP2012248247A (ja) * | 2011-05-26 | 2012-12-13 | Kao Corp | ハードディスク製造方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1277775C (zh) * | 2001-06-04 | 2006-10-04 | 日本板硝子株式会社 | 玻璃基板的制造方法及玻璃基板、以及具有此玻璃基板的有机场致发光元件 |
TWI302950B (en) * | 2002-01-28 | 2008-11-11 | Mitsubishi Chem Corp | Cleaning solution and method of cleanimg board of semiconductor device |
MY156414A (en) * | 2007-09-14 | 2016-02-26 | Sanyo Chemical Ind Ltd | Cleaning agent for electronic material |
JP5177087B2 (ja) * | 2009-07-09 | 2013-04-03 | 旭硝子株式会社 | 情報記録媒体用ガラス基板及びその製造方法、磁気記録媒体 |
-
2013
- 2013-11-19 JP JP2014548586A patent/JPWO2014080917A1/ja active Pending
- 2013-11-19 CN CN201380059747.8A patent/CN104781204A/zh active Pending
- 2013-11-19 KR KR1020157012506A patent/KR20150087224A/ko not_active Application Discontinuation
- 2013-11-19 WO PCT/JP2013/081203 patent/WO2014080917A1/ja active Application Filing
- 2013-11-21 TW TW102142432A patent/TW201433373A/zh unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001206737A (ja) * | 1999-11-18 | 2001-07-31 | Nippon Sheet Glass Co Ltd | ガラス基板及びその洗浄方法 |
JP2001229531A (ja) * | 2000-02-08 | 2001-08-24 | Fuji Electric Co Ltd | ガラス基板の洗浄方法 |
JP2004059419A (ja) * | 2002-05-31 | 2004-02-26 | Nippon Sheet Glass Co Ltd | ガラス基材の製造方法及びその製造方法で得られたガラス基材 |
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WO2021193477A1 (ja) * | 2020-03-25 | 2021-09-30 | 日本電気硝子株式会社 | ガラス板の製造方法 |
Also Published As
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TW201433373A (zh) | 2014-09-01 |
KR20150087224A (ko) | 2015-07-29 |
CN104781204A (zh) | 2015-07-15 |
JPWO2014080917A1 (ja) | 2017-01-05 |
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