Composition for forming glass surface treatment film

Abstract

A composition for forming a glass surface treatment film, which contains a conductive substance and a solvent, and which is used to hold a glass substrate by electrostatic adsorption.

Description

Technical Field

[0001] The present invention relates to a composition for forming a glass surface treatment film that facilitates electrostatic adsorption of a glass substrate. Background Art

[0002] Workpieces such as glass substrates used in the manufacture of semiconductor wafers and displays are conveyed to other processing steps after the specified processing of each workpiece is completed. At this time, a conveying device is used.

[0003] A conveying device having an adsorption head that adsorbs and holds non - contact has been proposed (for example, refer to Patent Document 1). In the proposed technology, the adsorption head jets air toward a plate - shaped glass from air jet holes formed in the head main body, and uses the negative pressure generated by this air flow (that is, utilizes the Bernoulli effect) to attract and suspend the plate - shaped glass as a workpiece non - contact and hold it.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Laid - Open No. 10 - 181879 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] In each process such as conveyance, exposure, film formation (for example, CVD and sputtering, etc.), microfabrication, washing, etching, and cutting of semiconductor wafers, an electrostatic adsorption method is also used to adsorb and hold the semiconductor wafers.

[0009] The so - called electrostatic adsorption method is a method of holding a workpiece by electrostatic force based on the potential difference between the workpiece (for example, a semiconductor wafer) and an electrode (a specimen stage). The electrostatic chuck using the electrostatic adsorption method has advantages over mechanical holding methods such as using jigs, etc., such as no contamination of the wafer caused by contact, and easy temperature control of the wafer because the entire back surface of the workpiece is adsorbed. As electrostatic chucks, there are a Coulomb force type using an insulating material as a dielectric, and a Johnson - Rabek type that induces charge polarization by flowing a very small current between the workpiece and the dielectric interface. In addition, in the electrostatic adsorption method, there are a monopole method of applying an electrostatic adsorption voltage to one electrode and a dipole method of providing two or more electrodes and generally applying electrostatic adsorption voltages of different polarities to each.

[0010] However, if the electrostatic adsorption method is to be applied to the holding of a glass substrate as an insulator, a larger applied voltage is required compared to semiconductors such as silicon wafers, and it is not easy.

[0011] The present invention has been made in view of such circumstances, and an object thereof is to provide a composition for forming a glass surface treatment film capable of facilitating the holding of a glass substrate using an electrostatic adsorption method, a laminate obtained using the composition for forming a glass surface treatment film, a method for manufacturing the laminate using the composition for forming a glass surface treatment film, and a method for removing the glass surface treatment film using the laminate.

[0012] Means for solving the problems

[0013] The present inventors conducted intensive studies to solve the above problems, and as a result, found that the above problems can be solved, and completed the present invention having the following gist.

[0014] That is, the present invention includes the following aspects.

[0015] [1] A composition for forming a glass surface treatment film, which contains a conductive substance and a solvent,

[0016] The composition for forming a glass surface treatment film is used to hold a glass substrate by an electrostatic adsorption method.

[0017] [2] The composition for forming a glass surface treatment film according to claim 1, which further contains a polymer.

[0018] [3] The composition for forming a glass surface treatment film according to [2], wherein the polymer is a water-soluble polymer or an alkali-soluble polymer.

[0019] [4] The composition for forming a glass surface treatment film according to any one of [1] to [3], wherein the conductive substance is at least one selected from surfactants and ionic liquids.

[0020] [5] The composition for forming a glass surface treatment film according to any one of [1] to [3], wherein the conductive substance is a conductive polymer.

[0021] [6] The composition for forming a glass surface treatment film according to any one of [1] to [3], wherein the conductive substance is at least one selected from conductive fillers of carbon-based, metal-based, metal oxide-based, metal-coated, and metal oxide-coated systems.

[0022] [7] The composition for forming a glass surface treatment film according to any one of [1] to [6], wherein the solvent contains at least one selected from alkylene glycol monoalkyl ethers, monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and water.

[0023] [8] The composition for forming a glass surface treatment film according to any one of [1] to [7], which further contains a crosslinking agent.

[0024] [9] A glass surface treatment film is formed from the composition for forming a glass surface treatment film described in any one of [1] to [8].

[0025]

[10] A laminate having a glass substrate and the glass surface treatment film described in [9].

[0026]

[11] A method for manufacturing a laminate, comprising the following step: forming a glass surface treatment film on the surface of a glass substrate using the composition for forming a glass surface treatment film described in any one of [1] to [8].

[0027]

[12] A method for removing a glass surface treatment film, comprising the following step: applying either water or an alkaline aqueous solution as a removal liquid to the laminate described in claim 10 to remove the glass surface treatment film from the glass substrate.

[0028] Effects of the Invention

[0029] According to the present invention, there can be provided a composition for forming a glass surface treatment film that enables easy holding of a glass substrate using an electrostatic adsorption method, a laminate obtained using the composition for forming a glass surface treatment film, a method for manufacturing a laminate using the composition for forming a glass surface treatment film, and a method for removing a glass surface treatment film using the laminate. Detailed Description

[0030] (Composition for Forming a Glass Surface Treatment Film)

[0031] The composition for forming a glass surface treatment film of the present invention contains a conductive substance and a solvent.

[0032] The composition for forming a glass surface treatment film may further contain a polymer.

[0033] The composition for forming a glass surface treatment film is a composition for forming a glass surface treatment film for holding a glass substrate by an electrostatic adsorption method.

[0034] A glass surface treatment film is formed from the composition for forming a glass surface treatment film of the present invention. By forming this glass surface treatment film on the surface of a glass substrate, the surface resistivity of this surface can be reduced. As a result, it becomes easy to hold a glass substrate using an electrostatic adsorption method.

[0035] The surface resistivity of the glass surface treatment film formed from the composition for forming a glass surface treatment film is, for example, preferably 1.0×10 12 Ω / square or less, more preferably 5.0×10 11 Ω / square or less. The surface resistivity of the glass surface treatment film can be 1.0×10 4 Ω / square or more and can be 1.0×106 Ω / sq or more, and may be 1.0×10 8 Ω / sq or more.

[0036] In addition, the surface resistivity (SR) of the glass surface treatment film formed from the composition for forming a glass surface treatment film is preferably such that the ratio (SR / SR G ) of this surface resistivity (SR) to the surface resistivity (SR G ) of the glass substrate on which the glass surface treatment film is to be disposed becomes a surface resistivity of 1 / 10 or less, and more preferably becomes 1 / 10 2 or less surface resistivity. As the lower limit value of the ratio (SR / SR G ), there is no particular limitation, but the ratio (SR / SR G ) can be 1 / 10 8 or more, can be 1 / 10 6 or more, can be 1 / 10 4 or more.

[0037] The surface resistivity can be measured, for example, using a surface resistance meter (e.g., MEGARESTAII manufactured by Shishido Electrostatic Co., Ltd., measurement voltage: 500 V), by the two-ring electrode method (two-terminal method).

[0038] When the conductive substance contained in the composition for forming a glass surface treatment film has film-forming properties, it is not necessary to contain a non-conductive polymer as a film-forming component.

[0039] For example, when the conductive substance contained in the composition for forming a glass surface treatment film is a conductive polymer and the conductive polymer has film-forming properties, the composition for forming a glass surface treatment film does not need to contain a non-conductive polymer as a film-forming component.

[0040] On the other hand, when the conductive substance contained in the composition for forming a glass surface treatment film is an inorganic substance, generally, since the inorganic substance does not have film-forming properties, the composition for forming a glass surface treatment film preferably contains a non-conductive polymer as a film-forming component.

[0041] <Conductive Substance>

[0042] Regarding the conductivity of the conductive substance, as long as it can make the surface resistivity of the glass surface treatment film formed from the composition for forming a glass surface treatment film less than the surface resistivity of the glass substrate on which the glass surface treatment film is to be disposed, there is no particular limitation.

[0043] As the conductive substance, it can be an organic substance or an inorganic substance.

[0044] Examples of the organic substances include surfactants, ionic liquids, conductive polymers, etc.

[0045] Examples of the surfactants include cationic surfactants, anionic surfactants, zwitterionic surfactants, nonionic surfactants, etc. The surfactant may be a polymeric surfactant. It should be noted that the term "surfactant" is a common name widely used for the compounds shown in the following specific examples. The cationic surfactant may be referred to as a cationic conductive organic compound. The anionic surfactant may be referred to as an anionic conductive organic compound. The zwitterionic surfactant may be referred to as a zwitterionic conductive organic compound. The nonionic surfactant may be referred to as a nonionic conductive organic compound. The polymeric surfactant may be referred to as a polymeric conductive organic compound.

[0046] Examples of the cationic surfactants include, for example, alkylamine salts and quaternary ammonium salts, alkylpyridinium salts, alkylimidazolium salts, etc.

[0047] Examples of the anionic surfactants include, for example, alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid and ammonium dodecylbenzenesulfonate and their salts; alkylnaphthalenesulfonic acids such as propylnaphthalenesulfonic acid and triisopropylnaphthalenesulfonic acid and their salts; alkylphenyl ether disulfonic acids such as dodecylphenyl ether disulfonic acid and alkyl diphenyl ether sulfonic acid and their salts; alkyl diphenyl ether disulfonic acids such as dodecyl diphenyl ether disulfonic acid and ammonium dodecyl diphenyl ether disulfonic acid and their salts; dialkylnaphthalene disulfonic acids such as dinonylnaphthalene disulfonic acid and their salts; phenolsulfonic acid-formaldehyde condensates and their salts; arylphenolsulfonic acid-formaldehyde condensates and their salts; carboxylates such as decanoic acid, N-acyl amino acid salts, and polyoxyethylene or polyoxypropylene alkyl ether carboxylates; acylated peptides; sulfonates; sulfate esters such as sulfated oils, alkyl sulfates, alkyl ether sulfates, polyoxyethylene or polyoxypropylene alkyl aryl ether sulfates, and alkylamide sulfates; phosphate esters; alkyl phosphates; polyoxyethylene or polyoxypropylene alkyl aryl ether phosphates; ammonium lauryl sulfate; sodium lauryl sulfate (sodium dodecyl sulfate); sodium lauryl ether sulfate (SLES); sodium myristyl polyoxyethylene ether sulfate; sodium dioctyl sulfosuccinate; octane sulfonates; perfluorooctane sulfonates (PFOS); perfluorobutane sulfonates; alkylbenzene sulfonates; alkyl aryl ether phosphates; alkyl ether phosphates; alkyl carboxylates; fatty acid salts (soaps); sodium stearate; sodium lauroyl sarcosinate; perfluorononanoates; perfluorooctanoates; and mixtures thereof.

[0048] As nonionic surfactants, sugar ester surfactants such as sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters can be cited; fatty acid ester surfactants such as polyoxyethylene resin acid esters and polyoxyethylene fatty acid diethyl esters; ether surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene / polypropylene glycols; aromatic nonionic surfactants such as polyoxyalkylene octyl phenyl ethers, polyoxyalkylene nonyl phenyl ethers, polyoxyalkyl dibutyl phenyl ethers, polyoxyalkyl styryl phenyl ethers, polyoxyalkyl benzyl phenyl ethers, polyoxyalkyl biphenyl ethers, and polyoxyalkyl cumyl phenyl ethers, etc. As the alkyl group, for example, an alkyl group having 1 to 20 carbon atoms can be cited.

[0049] An ionic liquid refers to a molten salt (ionic compound) that is liquid at room temperature (25 °C).

[0050] An ionic liquid is composed of a cationic component and an anionic component. There is no particular limitation on the cationic component and the anionic component, and components used in general ionic liquids can be used.

[0051] As the cationic component, for example, pyridine cation, piperidine cation, pyrrolidine cation, cation having a pyrroline skeleton, cation having a pyrrole skeleton, imidazole cation, 1,3-dimethylimidazole cation, tetrahydropyrimidine cation, dihydropyrimidine cation, pyrazole cation, pyrazoline cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkyl cation, cation, sulfide cation, etc.

[0052] As the anionic component, for example, Cl - , Br - , AlCl4 - , Al2Cl7 - , BF4 - , PF6 - , ClO4 - , NO3 - , CH3COO - , CF3COO - , CH3SO3 - , CH3SO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C- 、AsF6 - 、SbF6 - 、NbF6 - 、TaF6 - 、F(HF) n - 、(CN)2N - 、C4F9SO3 - 、(C2F5SO2)2N - 、C3F7COO - 、(CF3SO2)(CF3CO)N - 、(C n F 2n+1 SO2)2N - (n is an integer from 1 to 10), CF2(C m F 2m SO2)2N - (m is an integer from 1 to 10), - O3S(CF2) l SO3 - (l is an integer from 1 to 10), (C p F 2p+1 SO2)(C q F 2q+1 SO2)N - (p, q are integers from 1 to 10), (FSO2)2N - etc.

[0053] As a conductive polymer, there is no particular limitation. The conductive polymer may be a complex with a dopant.

[0054] Examples of the conductive polymer include, for example, polythiophene, polyaniline, polypyrrole, polyquinoxaline, polyacetylene, polyphenylene vinylene, polynaphthalene, and their derivatives.

[0055] The conductive polymer may also have a hydrophilic functional group. Examples of the hydrophilic functional group include, for example, a sulfone group, an amino group, an amide group, an imino group, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfate group, a phosphate group, and their salts (for example, a quaternary ammonium salt group). When the conductive polymer has a hydrophilic functional group, there is a tendency for the conductive polymer to be easily soluble in water or for the particulate conductive polymer to be easily dispersed in water.

[0056] From the viewpoints of conductivity and chemical stability, the conductive polymer is preferably poly(3,4-disubstituted thiophene). Examples of poly(3,4-disubstituted thiophene) include, for example, poly(3,4-alkylenedioxythiophene) and poly(3,4-dialkoxythiophene), and poly(3,4-alkylenedioxythiophene) is preferred. Poly(3,4-alkylenedioxythiophene) has a structural unit represented by the following formula (I), for example.

[0057]

[0058] In formula (I), R 1 is, for example, an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear or branched. Examples of the alkylene group include, for example, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1-methyl-1,2-ethylene, 1-ethyl-1,2-ethylene, 1-methyl-1,3-propylene, and 2-methyl-1,3-propylene, and methylene, 1,2-ethylene, and 1,3-propylene are preferred, and 1,2-ethylene is more preferred.

[0059] The conductive polymer is preferably poly(3,4-ethylenedioxythiophene) (PEDOT).

[0060] Examples of the dopant include, for example, polyanions. In the case where the conductive polymer is polythiophene (or its derivative), the polyanion can form an ion pair with polythiophene (or its derivative) to stably disperse polythiophene (or its derivative) in water.

[0061] There is no particular limitation on the polyanion, and examples thereof include carboxylic acid polymers such as polyacrylic acid, polymaleic acid, and polymethacrylic acid; sulfonic acid polymers such as polystyrene sulfonic acid, polyvinyl sulfonic acid, and polyisoprene sulfonic acid, and the like.

[0062] The polyanion may also be a copolymer of a vinyl carboxylic acid or a vinyl sulfonic acid and other monomer classes. Examples of the other monomer classes include, for example, (meth)acrylate compounds; aromatic vinyl compounds such as styrene and vinylnaphthalene.

[0063] The polyanion is particularly preferably polystyrene sulfonic acid (PSS).

[0064] Examples of the conductive polymer as a complex with the dopant include, for example, a complex of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (PEDOT / PSS).

[0065] Examples of the inorganic substance include, for example, inorganic conductive fillers.

[0066] Examples of the inorganic conductive filler include conductive fillers of a carbon type, a metal type, a metal oxide type, a metal-coated type, and a metal oxide-coated type.

[0067] Examples of the carbon type conductive filler include Ketjen black, acetylene black, and oil furnace black.

[0068] Examples of the metal constituting the metal type conductive filler include Ag, Ni, Cu, Zn, Al, and stainless steel.

[0069] Examples of the metal oxide constituting the metal oxide type conductive filler include SnO2, In2O3, and ZnO.

[0070] Examples of the metal-coated type conductive filler include fillers using Ni, Al, etc. as the coating material and using a base filler.

[0071] Examples of the metal oxide-coated type conductive filler include fillers using SnO2, In2O3, ZnO, etc. as the coating material and using a base filler.

[0072] Examples of the base filler include mica, glass beads, glass fibers, carbon fibers, calcium carbonate, zinc oxide, and titanium oxide.

[0073] The content of the conductive substance in the composition for forming the glass surface treatment film is not particularly limited, but is preferably 1% by mass to 100% by mass, more preferably 2% by mass to 100% by mass, and particularly preferably 5% by mass to 100% by mass with respect to the film constituent components.

[0074] The so-called film constituent components refer to the components constituting the glass surface treatment film. In other words, the so-called film constituent components refer to the components obtained by removing the solvent from all the components of the composition for forming the glass surface treatment film.

[0075] When the composition for forming the glass surface treatment film contains a polymer (non-conductive polymer), the content of the conductive substance in the composition for forming the glass surface treatment film is not particularly limited, but is preferably 1% by mass to 90% by mass, more preferably 2% by mass to 50% by mass, and particularly preferably 5% by mass to 35% by mass with respect to the film constituent components.

[0076] When the composition for forming the glass surface treatment film contains a polymer (non-conductive polymer), the content of the conductive substance in the composition for forming the glass surface treatment film is not particularly limited, but is preferably 1% by mass to 1000% by mass, more preferably 2% by mass to 100% by mass, and particularly preferably 5% by mass to 50% by mass with respect to the polymer.

[0077] When the composition for forming a glass surface treatment film does not contain a polymer (non-conductive polymer), the content of the conductive substance in the composition for forming a glass surface treatment film is not particularly limited, but is preferably 75% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and particularly preferably 85% by mass to 100% by mass, relative to the film constituent components.

[0078] <Polymer>

[0079] The polymer is used, for example, to impart film-forming properties to the glass surface treatment film.

[0080] The polymer is not particularly limited, but from the viewpoint of excellent removability of the glass surface treatment film, a water-soluble polymer or an alkali-soluble polymer is preferred.

[0081] It should be noted that, among the components contained in the composition for forming a glass surface treatment film, a component that is a conductive substance and a polymer belongs to the conductive substance in the present invention. Therefore, the polymer described here is, for example, a non-conductive polymer.

[0082] <<Water-soluble polymer>>

[0083] As the water-soluble polymer, it is a high molecular compound that dissolves 1 g or more in 100 g of water at 25°C, preferably a high molecular compound that dissolves 5 g or more in 100 g of water at 25°C, and more preferably a high molecular compound that dissolves 10 g or more in 100 g of water at 25°C.

[0084] The water-soluble polymer is not particularly limited, and examples thereof include polyvinyl alcohol, water-soluble cellulose, polyethylene glycol (PEG), polyethylene oxide (PEO), polyvinylpyrrolidone, polyacrylic acid, polystyrene sulfonic acid, polyvinylacetamide, and the like.

[0085] Polyvinyl alcohol is a polymer obtained by hydrolyzing polyvinyl acetate to convert the acetyl groups in the polyvinyl acetate molecules into hydroxyl groups. The value representing the proportion of the hydroxyl groups in mole % is called the saponification degree. It is known that polyvinyl alcohol has various properties depending on its saponification degree. For example, generally, polyvinyl acetate (saponification degree 0 mole %) is water-insoluble, and polyvinyl alcohol with a saponification degree of 100 mole % is water-soluble. In polyvinyl alcohol, if the saponification degree is 60 mole % or less, the solubility in water is poor, and if the saponification degree is 30 mole % or less, it is substantially completely insoluble. In addition, conversely, even if the saponification degree is too high, the solubility also becomes low, and the solubility is highest for substances with a saponification degree of 85 - 90 mole %. It is preferable to use polyvinyl alcohol with a saponification degree of 70 mole % or more. Generally, when the saponification degree is high, the water solubility becomes good, so it is preferable to use polyvinyl alcohol with a saponification degree of 75 mole % or more. However, conversely, if the saponification degree is too high, there is a tendency for the storage stability of the composition (generation of insoluble foreign matters) to deteriorate. Therefore, the saponification degree of polyvinyl alcohol is preferably 99 mole % or less, and more preferably 98 mole % or less.

[0086] The degree of polymerization of polyvinyl alcohol is usually represented by the viscosity (20 °C) of a 4 mass % aqueous solution, and is generally about 1 - 80 cps (mPa·s). Polyvinyl alcohol particularly preferably has a viscosity of 1 cps or more, and more preferably 2 cps or more. In addition, the upper limit of the viscosity is preferably 70 cps, and the upper limit of the viscosity is more preferably 65 cps, 50 cps, 40 cps, 30 cps, 20 cps, 10 cps, 8 cps, or 5 cps. The viscosity range is, for example, 1 - 20 cps, 2 - 10 cps, 3 - 8 cps.

[0087] Polyvinyl alcohol may also be a substance modified by substituting a part of its hydroxyl groups with an alkyl ether group, an alkoxymethyl group, an acetoacetate group, or the like.

[0088] There is no particular limitation on the water-soluble cellulose, but examples thereof include alkyl celluloses such as methyl cellulose and ethyl cellulose; hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; and hydroxyalkylalkyl celluloses such as hydroxyethylmethyl cellulose and hydroxypropylmethyl cellulose.

[0089] Among them, hydroxypropyl cellulose is more preferable.

[0090] Regarding hydroxypropyl cellulose, various products with different viscosities are commercially available from various companies and can all be used in the present invention. There is no particular limitation on the viscosity of a 2 mass % aqueous solution (20 °C) of hydroxypropyl cellulose, and it can be appropriately selected according to the purpose, but it is preferably 2.0 mPa·s (centipoise, cps) or more and 4,000 mPa·s (centipoise, cps) or less.

[0091] In addition, it is considered that the viscosity of hydroxypropyl cellulose depends on the weight-average molecular weight, degree of substitution, and molecular weight of hydroxypropyl cellulose.

[0092] There is no particular limitation on the weight-average molecular weight of hydroxypropyl cellulose, and it can be appropriately selected according to the purpose, but it is preferably 15,000 or more and 400,000 or less. It should be noted that the weight-average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

[0093] There is no particular limitation on commercially available products of hydroxypropyl cellulose, and they can be appropriately selected according to the purpose. Examples of commercially available products include the following.

[0094] · HPC-SSL, etc. (manufactured by Nippon Soda Co., Ltd.) with a molecular weight of 15,000 or more and 30,000 or less, and a viscosity of 2.0 mPa·s or more and 2.9 mPa·s or less

[0095] · HPC-SL, etc. (manufactured by Nippon Soda Co., Ltd.) with a molecular weight of 30,000 or more and 50,000 or less, and a viscosity of 3.0 mPa·s or more and 5.9 mPa·s or less

[0096] · HPC-L, etc. (manufactured by Nippon Soda Co., Ltd.) with a molecular weight of 55,000 or more and 70,000 or less, and a viscosity of 6.0 mPa·s or more and 10.0 mPa·s or less

[0097] · HPC-M, etc. (manufactured by Nippon Soda Co., Ltd.) with a molecular weight of 110,000 or more and 150,000 or less, and a viscosity of 150 mPa·s or more and 400 mPa·s or less

[0098] · HPC-H, etc. (manufactured by Nippon Soda Co., Ltd.) with a molecular weight of 250,000 or more and 400,000 or less, and a viscosity of 1,000 mPa·s or more and 4,000 mPa·s or less

[0099] Among them, HPC-SSL with a molecular weight of 15,000 or more and 30,000 or less, and a viscosity of 2.0 mPa·s or more and 2.9 mPa·s or less is preferred.

[0100] It should be noted that in the above commercially available products, the molecular weight is measured by gel permeation chromatography (GPC), and the viscosity is measured using a 2 mass% aqueous solution (20 °C).

[0101] The water-soluble polymer can be used alone or in combination of two or more.

[0102] <<Alkali-soluble polymer>>

[0103] The so-called alkali-soluble polymer is a polymer having an alkali-soluble group (for example, carboxyl group, sulfonic acid group, phenolic hydroxyl group, alcoholic hydroxyl group, amino group, etc.), and it is sufficient that it can be dissolved in an alkaline aqueous solution.

[0104] As the alkaline aqueous solution, for example, a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution can be cited.

[0105] As the alkali-soluble polymer, an addition polymer of a monomer containing a polymerizable unsaturated compound having an alkali-soluble group can be cited.

[0106] The addition polymer can be a homopolymer or a copolymer.

[0107] As the polymerizable unsaturated compound having an alkali-soluble group, for example, a polymerizable unsaturated compound having a carboxyl group, a polymerizable unsaturated compound having an alcoholic hydroxyl group, a polymerizable unsaturated compound having a phenolic hydroxyl group, etc. can be cited.

[0108] As the polymerizable unsaturated compound having a carboxyl group, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc.; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc.; (meth)acrylic acid derivatives having a carboxyl group and an ester bond such as 2-succinylethyl (meth)acrylate, 2-maleylethyl (meth)acrylate, 2-hexahydrophthaloylethyl (meth)acrylate, etc. can be used.

[0109] As the polymerizable unsaturated compound having an alcoholic hydroxyl group, for example, aliphatic (meth)acrylate esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, etc.; aromatic (meth)acrylate esters such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl (meth)acrylate, 2-hydroxy-3-(1-naphthyloxy)propyl (meth)acrylate, 2-hydroxy-3-(2-naphthyloxy)propyl (meth)acrylate, etc. can be cited.

[0110] As the polymerizable unsaturated compound having a phenolic hydroxyl group, for example, hydroxystyrene, etc. can be cited.

[0111] As the alkali-soluble polymer, polyhydroxystyrene is preferred.

[0112] The polyhydroxystyrene may be a homopolymer of hydroxystyrene or a copolymer of hydroxystyrene and other monomers, and may be a branched polyhydroxystyrene or a modified polyhydroxystyrene. Examples of the branched polyhydroxystyrene include, for example, the branched polyhydroxystyrene described in WO2009 / 038126. Examples of the modified polyhydroxystyrene include, for example, the modified polyhydroxystyrene resin described in Japanese Patent Application Laid-Open No. 2013-227364.

[0113] The alkali-soluble polymer may be used alone or in combination of two or more.

[0114] The content of the polymer in the composition for forming a glass surface treatment film is not particularly limited, but is preferably 10% by mass to 99% by mass, more preferably 50% by mass to 98% by mass, and particularly preferably 65% by mass to 95% by mass relative to the film constituent components.

[0115] <Solvent>

[0116] The solvent is not particularly limited and may be water or an organic solvent.

[0117] Examples of the organic solvent include alkylene glycol monoalkyl ethers and mono-carboxylic acid esters of alkylene glycol monoalkyl ethers.

[0118] Examples of the alkylene of the alkylene glycol monoalkyl ether include alkylene having 2 to 4 carbon atoms.

[0119] Examples of the alkyl of the alkylene glycol monoalkyl ether include alkyl having 1 to 4 carbon atoms.

[0120] Examples of the number of carbon atoms of the alkylene glycol monoalkyl ether include 3 to 8.

[0121] Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.

[0122] Examples of the alkylene of the mono-carboxylic acid ester of alkylene glycol monoalkyl ether include alkylene having 2 to 4 carbon atoms.

[0123] Examples of the alkyl of the mono-carboxylic acid ester of alkylene glycol monoalkyl ether include alkyl having 1 to 4 carbon atoms.

[0124] Examples of the mono-carboxylic acid of the mono-carboxylic acid ester of alkylene glycol monoalkyl ether include saturated mono-carboxylic acids having 2 to 4 carbon atoms.

[0125] Examples of the saturated mono-carboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid.

[0126] The number of carbon atoms of the mono-carboxylic acid ester of alkylene glycol mono-alkyl ether is, for example, 5 to 10.

[0127] Examples of the mono-carboxylic acid ester of alkylene glycol mono-alkyl ether include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.

[0128] Examples of other organic solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0129] Among these solvents, alkylene glycol mono-alkyl ether, mono-carboxylic acid ester of alkylene glycol mono-alkyl ether, and water are preferred.

[0130] These solvents can be used alone or in combination of two or more.

[0131] The mass ratio of the organic solvent in the solvent is not particularly limited, but is preferably 50% by mass to 100% by mass.

[0132] The content of the solvent in the glass surface treatment film-forming composition is not particularly limited, but is preferably 50% by mass to 99.9% by mass, more preferably 75% by mass to 99.5% by mass, and particularly preferably 90% by mass to 99% by mass.

[0133] <Crosslinking agent>

[0134] In order to improve the solvent resistance of the formed glass surface treatment film, the glass surface treatment film-forming composition may contain a crosslinking agent.

[0135] It should be noted that the crosslinking agent is a substance different from the above-mentioned conductive substance and polymer.

[0136] There is no particular limitation on the crosslinking agent.

[0137] Examples of the crosslinking agent include compounds having two or more of the following structures.

[0138]

[0139] (In the structure, R 101represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bonding site.)

[0140] The bonding site binds to, for example, a nitrogen atom, a carbon atom constituting an aromatic hydrocarbon ring, etc.

[0141] As R 101 , a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure is preferred.

[0142]

[0143] (In the structure, R 102 represents a hydrogen atom, a methyl group or an ethyl group. * represents a bonding site.)

[0144] As the crosslinking agent, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a compound having a phenolic hydroxyl group is preferred. They can be used alone or in combination of two or more.

[0145] As the melamine compound, there is no particular limitation as long as it is a melamine compound having a group capable of reacting with a hydroxyl group.

[0146] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound or a mixture thereof in which 1 to 6 hydroxymethyl groups of hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound or a mixture thereof in which 1 to 6 hydroxymethyl groups of hexamethylol melamine are acyloxymethylated, etc.

[0147] As the guanamine compound, there is no particular limitation as long as it is a guanamine compound having a group capable of reacting with a hydroxyl group.

[0148] Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound or a mixture thereof in which 1 to 4 hydroxymethyl groups of tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxy guanamine, a compound or a mixture thereof in which 1 to 4 hydroxymethyl groups of tetramethylol guanamine are acyloxymethylated, etc.

[0149] As the glycoluril compound, there is no particular limitation as long as it is a glycoluril compound having a group capable of reacting with a hydroxyl group.

[0150] Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound or a mixture thereof in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are methoxymethylated, a compound or a mixture thereof in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are acyloxymethylated, etc.

[0151] In addition, as the glycoluril compound, for example, a glycoluril derivative represented by the following formula (1E) can be used.

[0152]

[0153] (In formula (1E), each of the four R1 independently represents a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0154] As the glycoluril derivative represented by the above formula (1E), for example, compounds represented by the following formulas (1E-1) to (1E-6) can be cited.

[0155]

[0156] The glycoluril derivative represented by formula (1E) is obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0157]

[0158] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and each R4 independently represents an alkyl group having 1 to 4 carbon atoms.)

[0159]

[0160] (In formula (3d), R1 represents a methyl group or an ethyl group.)

[0161] As the glycoluril derivative represented by the above formula (2E), for example, compounds represented by the following formulas (2E-1) to (2E-4) can be cited. Further, as the compound represented by the above formula (3d), for example, compounds represented by the following formulas (3d-1) and (3d-2) can be cited.

[0162]

[0163] As the urea compound, there is no particular limitation as long as it is a urea compound having a group capable of reacting with a hydroxyl group.

[0164] As the urea compound, for example, tetrahydroxymethylurea, tetramethoxymethylurea, a compound or a mixture in which 1 to 4 hydroxymethyl groups of tetrahydroxymethylurea are methoxymethylated, tetramethoxyethylurea, etc. can be cited.

[0165] As the compound having a phenolic hydroxyl group, for example, compounds represented by the following formula (111) or formula (112) can be cited.

[0166]

[0167] (In formulas (111) and (112), Q 2 represents a single bond or an m2-valent organic group.

[0168] R 8 、R 9 、R 11 and R 12 each represent a hydrogen atom or a methyl group.

[0169] R 7 and R 10 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0170] n9 represents an integer of 1 ≤ n9 ≤ 3, n 10 represents an integer of 2 ≤ n 10 ≤ 5, n 11 represents an integer of 0 ≤ n 11 ≤ 3, n 12 represents an integer of 0 ≤ n 12 ≤ 3, and n9, n 10 、n 11 、n 12 represent an integer of 3 ≤ (n9 + n 10 + n 11 + n 12 ) ≤ 6.

[0171] n 13 represents an integer of 1 ≤ n 13 ≤ 3, n 14 represents an integer of 1 ≤ n 14 ≤ 4, n 15 represents an integer of 0 ≤ n 15 ≤ 3, n 16 represents an integer of 0 ≤ n 16 ≤ 3, and n 13 、n 14 、n 15 、n 16 represent an integer of 2 ≤ (n 13 + n 14 + n 15 + n 16 ) ≤ 5.

[0172] m2 represents an integer of 2 to 10.)

[0173] As the m2-valent organic group in Q 2 , for example, an m2-valent organic group having 1 to 4 carbon atoms can be cited.

[0174] As the compound represented by formula (111) or formula (112), for example, the following compounds can be cited.

[0175]

[0176] The above-mentioned compounds can be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Industry Co., Ltd. Examples of products include TMOM-BP, the trade name of Asahi Organic Materials Co., Ltd.

[0177] Among them, glycoluril compounds are preferred. Specifically, tetrahydroxymethylglycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, compounds in which 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycoluril are methoxymethylated or their mixtures, compounds in which 1 to 4 hydroxymethyl groups of tetrahydroxymethylglycoluril are acyloxymethylated or their mixtures are preferred, and tetramethoxymethylglycoluril is more preferred.

[0178] There is no particular limitation on the molecular weight of the crosslinking agent, but it is preferably 500 or less.

[0179] There is no particular limitation on the content of the crosslinking agent in the composition for forming a glass surface treatment film, but it is, for example, 1% by mass to 50% by mass, preferably 5% by mass to 40% by mass, relative to the film constituent components.

[0180] <Acid generator>

[0181] Regarding the acid generator included as an optional component in the composition for forming a glass surface treatment film, both thermal acid generators and photoacid generators can be used, but thermal acid generators are preferably used.

[0182] Examples of the thermal acid generator include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine -p-toluenesulfonate (pyridine -p-toluenesulfonic acid), pyridine phenolsulfonic acid, pyridine -p-hydroxybenzenesulfonic acid (pyridine p-phenolsulfonate salt), pyridine -trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid and other sulfonic acid compounds and carboxylic acid compounds.

[0183] Examples of the photoacid generator include salt compounds, sulfimide compounds, disulfonyldiazomethane compounds and the like.

[0184] As salt compounds, examples include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium perfluorooctanesulfonate, diphenyliodonium Camphorsulfonate, bis(4-tert-butylphenyl)iodonium Camphorsulfonate and bis(4-tert-butylphenyl)iodonium Iodonium salts such as trifluoromethanesulfonate Salt compounds, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate, etc.

[0185] Examples of the sulfimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalenedicarboximide, etc.

[0186] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane, etc.

[0187] The acid generator may be used alone, or two or more kinds may be used in combination.

[0188] When using an acid generator, the content ratio of the acid generator relative to the crosslinking agent is, for example, 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass.

[0189] <Light absorber>

[0190] The composition for forming a glass surface treatment film may contain a light absorber.

[0191] By containing a light absorber in the composition for forming a glass surface treatment film, light (light corresponding to the light absorber) can be irradiated onto the glass substrate on which the glass surface treatment film is disposed, and the position of the glass substrate can be confirmed. Therefore, the positioning (alignment) of the glass substrate becomes easy.

[0192] As the light absorber, it preferably has a maximum absorbance at 450 to 750 nm, more preferably at 620 to 750 nm.

[0193] Examples of the light absorber include black dyes, red dyes, yellow dyes, blue dyes, etc. They can be used, for example, the following commercially available products, etc.

[0194] Titanium black: 12S, 13M, 13M-C (manufactured by Mitsubishi Materials Corporation).

[0195] Black dyes: VALIFAST BLACK 1807, 1821, 3804, 3810, 3820, 2830, 2840, 3866, 3870, Oil Black 803, 830, 860, BS, HBB, NO5 (manufactured by Orient Chemical Industries, Ltd.), Aizen Spilon Black MHS-Liquid (manufactured by Hodogaya Chemical Co., Ltd.).

[0196] Red dyes: VALIFAST RED 1308, 1320, 1355, 1360, 1364, 1388, 2320, 3108, 3304, 3306, 3311, 3312, 3320, OIL RED 330, 5B, OG, RR (manufactured by Orient Chemical Industries, Ltd.), Aizen Spilon Red BEH S-Liquid (manufactured by Hodogaya Chemical Co., Ltd.).

[0197] Yellow dyes: VALIFAST YELLOW 1101, 1108, 1109, 1151, 1171, 3108, 3120, 3150, 3170, 3180, 4120, 4121, OIL YELLOW 107, 129, 136, 3G, GG-S (manufactured by Orient Chemical Industries, Ltd.), Aizen Spilon Yellow RH S-Liquid (manufactured by Hodogaya Chemical Co., Ltd.).

[0198] Blue dyes: VALIFAST BLUE 1063, 1605, 1621, 2606, 2620, 2650, 2670, OIL BLUE 2N, 613, 630, 650M (manufactured by Orient Chemical Industries, Ltd.).

[0199] The content of the light absorber in the composition for forming the glass surface treatment film is not particularly limited, but is, for example, 0.1% by mass to 10% by mass, preferably 1% by mass to 5% by mass, relative to the film constituent components.

[0200] (Glass surface treatment film)

[0201] The glass surface treatment film of the present invention is formed from the composition for forming the glass surface treatment film of the present invention.

[0202] The glass surface treatment film can be formed, for example, by coating the composition for forming the glass surface treatment film on the surface of a glass substrate and drying it.

[0203] As the coating method, there is no particular limitation, and examples thereof include various wet processing methods.

[0204] As a coating method, for example, a drop cast method, a spin coating method, a doctor blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, a printing method (letterpress, gravure, lithography, screen printing, etc.) and the like can be cited.

[0205] There is no particular limitation on the drying temperature, and for example, 30°C to 120°C can be cited.

[0206] There is no particular limitation on the drying time, and for example, 10 seconds to 10 minutes can be cited.

[0207] There is no particular limitation on the film thickness of the glass surface treatment film, but it is preferably 10 nm to 10 μm, more preferably 20 nm to 5 μm, and particularly preferably 50 nm to 1 μm.

[0208] The film thickness of the glass surface treatment film can be measured by, for example, an optical interference method. As a measuring device, for example, F-50 manufactured by Filmetrics Co., Ltd. can be used.

[0209] By forming a glass surface treatment film on the surface of a glass substrate, the surface resistivity of this surface can be reduced. As a result, it becomes easy to hold the glass substrate using an electrostatic adsorption method.

[0210] The surface resistivity of the glass surface treatment film is, for example, preferably 1.0×10 12 Ω / □ or less, and more preferably 5.0×10 11 Ω / □ or less. The surface resistivity of the glass surface treatment film can be 1.0×10 4 Ω / □ or more, can be 1.0×10 6 Ω / □ or more, and can be 1.0×10 8 Ω / □ or more.

[0211] In addition, the surface resistivity (SR) of the glass surface treatment film is preferably such that the ratio (SR / SR G ) of the surface resistivity (SR) of the glass surface treatment film to the surface resistivity (SR G ) of the glass substrate on which the glass surface treatment film is to be disposed becomes 1 / 10 or less, and more preferably becomes 1 / 10 2 or less. There is no particular limitation on the lower limit value of the ratio (SR / SR G ), but the ratio (SR / SR G ) can be 1 / 10 8 or more, can be 1 / 10 6 or more, and can be 1 / 10 4 or more.

[0212] (Laminated body)

[0213] The laminate of the present invention has a glass substrate and the glass surface treatment film of the present invention.

[0214] In the laminate, the glass surface treatment film may be formed on one side of the glass substrate or on both sides. When the glass surface treatment films are formed on both sides of the glass substrate, these glass surface treatment films may have the same composition or different compositions, and may have the same film thickness or different film thicknesses.

[0215] The material of the glass substrate is not particularly limited, and examples thereof include non-alkali glass, silica glass, and the like.

[0216] The size of the glass substrate is not particularly limited.

[0217] The film thickness of the glass substrate is not particularly limited. For example, it is preferably 100 μm to 5 mm, more preferably 200 μm to 2 mm, and particularly preferably 500 μm to 1 mm.

[0218] The surface of the glass substrate may be flat or may have irregularities.

[0219] The size of the irregularities is not particularly limited.

[0220] The irregularities may be, for example, irregularities formed by various processes.

[0221] Various processes may also be performed on the surface of the glass substrate.

[0222] Examples of the processes include semiconductor formation process, electrode formation process, light-emitting element formation process, and the like.

[0223] (Manufacturing method of the laminate)

[0224] The manufacturing method of the laminate of the present invention includes the following step: forming a glass surface treatment film on the surface of a glass substrate using the composition for forming a glass surface treatment film of the present invention.

[0225] Examples of the method for forming the glass surface treatment film include the formation methods described in the description of the glass surface treatment film of the present invention.

[0226] Examples of the glass substrate include the glass substrate examples illustrated in the description of the laminate of the present invention.

[0227] Examples of the glass surface treatment film include the examples illustrated in the description of the glass surface treatment film of the present invention.

[0228] (Removing method of the glass surface treatment film)

[0229] The method for removing the glass surface treatment film of the present invention includes the following steps: applying a removal liquid to the laminate of the present invention to remove the glass surface treatment film from the glass substrate.

[0230] Examples of the removal liquid include water, alkaline aqueous solutions, organic solvents, etc., but water and alkaline aqueous solutions are preferred.

[0231] Examples of water include ion-exchanged water, pure water, etc. The pH of water is usually 7.0.

[0232] Examples of the alkaline aqueous solution include alkaline aqueous solutions obtained by dissolving at least one of alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc.

[0233] There is no particular limitation on the method of applying the removal liquid to the laminate, and examples include an immersion method, a spraying method, etc.

[0234] There is no particular limitation on the immersion time in the immersion method.

[0235] There is no particular limitation on the usage amount in the spraying method.

[0236] The removal liquid can be at room temperature or about 30°C to 40°C.

[0237] Examples of the holding of the glass substrate using the electrostatic adsorption method include the holding during the processing of the glass substrate, the holding during the movement or transportation of the glass substrate, etc.

[0238] By holding the glass substrate by the electrostatic adsorption method, for example, the glass substrate can be held with good positional accuracy during the processing of the glass substrate, the movement or transportation of the glass substrate.

[0239] For the electrostatic adsorption member used to electrostatically adsorb the glass substrate, for example, an electrode layer for electrostatic adsorption is provided inside a dielectric member made of ceramics or the like. The electrostatic adsorption member has, for example, an adsorption surface for electrostatically adsorbing the glass substrate. The electrostatic adsorption member can be, for example, in a strip shape.

[0240] The movement or transportation of the glass substrate using the electrostatic adsorption method can be, for example, the belt conveyor transportation using a strip-shaped electrostatic adsorption member, or the movement or transportation using a robotic arm with an electrostatic adsorption member installed at the front end of the arm.

[0241] Examples

[0242] Hereinafter, examples are given to illustrate the present invention more specifically, but the present invention is not limited to the following examples. It should be noted that the devices used are as follows.

[0243] [Device]

[0244] (1) Surface resistance measuring instrument: manufactured by Shishido Electrostatics Co., Ltd., MEGARESTA II

[0245] (2) Optical film thickness meter: F-50 manufactured by Filmetrics Co., Ltd.

[0246] (3) Electrostatic chuck: manufactured by Tsukuba Seiko Co., Ltd., hand-held type, Soft Palm

[0247] [1] Preparation of Composition for Forming Glass Surface Treatment Film

[0248] <Modulation Example 1>

[0249] To 1.0 g of polyhydroxystyrene (VP-15000, manufactured by Nippon Soda Co., Ltd.), 0.1 g of a surfactant (n-dodecylbenzenesulfonic acid, manufactured by Kanto Chemical Co., Inc.) and 42.9 g of a solvent (propylene glycol monomethyl ether) were added to obtain a composition for forming a glass surface treatment film.

[0250] <Modulation Example 2>

[0251] To 1.0 g of polyhydroxystyrene (VP-15000, manufactured by Nippon Soda Co., Ltd.), 0.3 g of a surfactant (n-dodecylbenzenesulfonic acid, manufactured by Kanto Chemical Co., Inc.) and 50.7 g of a solvent (propylene glycol monomethyl ether) were added to obtain a composition for forming a glass surface treatment film.

[0252] <Modulation Example 3>

[0253] To 1.0 g of polyhydroxystyrene (VP-15000, manufactured by Nippon Soda Co., Ltd.), 0.1 g of an anionic polymer (polystyrenesulfonic acid, manufactured by Aldrich) and 42.9 g of a mixed solvent (pure water / propylene glycol monomethyl ether = 3 / 7 (wt / wt)) were added to obtain a composition for forming a glass surface treatment film.

[0254] <Modulation Example 4>

[0255] To 1.0 g of polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.1 g of a surfactant (n-dodecylbenzenesulfonic acid, manufactured by Kanto Chemical Co., Inc.) and 42.9 g of a solvent (propylene glycol monomethyl ether) were added to obtain a composition for forming a glass surface treatment film.

[0256] <Modulation Example 5>

[0257] 1.0 g of polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with 0.3 g of a surfactant (dodecylbenzenesulfonic acid, manufactured by Kanto Chemical Co., Inc.) and 50.7 g of a solvent (propylene glycol monomethyl ether) to obtain a composition for forming a glass surface treatment film.

[0258] <Modulation Example 6>

[0259] 1.0 g of polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with 0.1 g of an anionic polymer (polystyrenesulfonic acid, manufactured by Aldrich) and 42.9 g of a mixed solvent (pure water / propylene glycol monomethyl ether = 3 / 7 (wt / wt)) to obtain a composition for forming a glass surface treatment film.

[0260] <Modulation Example 7>

[0261] 1.0 g of polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with 0.3 g of an anionic polymer (polystyrenesulfonic acid, manufactured by Aldrich) and 50.7 g of a mixed solvent (pure water / propylene glycol monomethyl ether = 3 / 7 (wt / wt)) to obtain a composition for forming a glass surface treatment film.

[0262] <Modulation Example 8>

[0263] 1.0 g of polyhydroxystyrene (VP-15000, manufactured by Nippon Soda Co., Ltd.) was added with 39.0 g of a solvent (propylene glycol monomethyl ether) to obtain a composition for forming a glass surface treatment film.

[0264] <Modulation Example 9>

[0265] 1.0 g of polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with 39.0 g of a solvent (propylene glycol monomethyl ether) to obtain a composition for forming a glass surface treatment film.

[0266] <Modulation Example 10>

[0267] 1.0 g of polyhydroxystyrene (VP-15000, manufactured by Nippon Soda Co., Ltd.) was added with 0.3 g of a surfactant (dinonylnaphthalenedisulfonic acid, manufactured by Kusumoto Chemicals, Ltd.), 41.6 g of a solvent (propylene glycol monomethyl ether) and 0.42 g of a solvent (isobutyl alcohol) to obtain a composition for forming a glass surface treatment film.

[0268] <Modulation Example 11>

[0269] 1.0 g of polyhydroxystyrene (VP-8000, manufactured by Nippon Soda Co., Ltd.) was added with 0.1 g of an anionic polymer (polystyrenesulfonic acid (PS-1H), manufactured by Tosoh Finechem Corporation) and 42.9 g of a mixed solvent (pure water / propylene glycol monomethyl ether = 1 / 9 (wt / wt)) to obtain a composition for forming a glass surface treatment film.

[0270] <Modulation Example 12>

[0271] To 1.0 g of polyhydroxystyrene (VP-8000, manufactured by Nippon Soda Co., Ltd.), 0.3 g of an anionic polymer (polystyrene sulfonic acid (PS-1H), manufactured by Tosoh Finechem Corporation) and 50.7 g of a mixed solvent (pure water / propylene glycol monomethyl ether = 1 / 9 (wt / wt)) were added to obtain a composition for forming a glass surface treatment film.

[0272] <Modulation Example 13>

[0273] To 1.0 g of polyhydroxystyrene (VP-8000, manufactured by Nippon Soda Co., Ltd.), 0.2 g of an anionic polymer (polystyrene sulfonic acid (PS-1H), manufactured by Tosoh Finechem Corporation) and 6.8 g of a mixed solvent (pure water / propylene glycol monomethyl ether = 3 / 7 (wt / wt)) were added to obtain a composition for forming a glass surface treatment film.

[0274] <Examples 1 to 8, Comparative Examples 1 and 2>

[0275] [2] Measurement of surface resistivity of the film

[0276] The compositions for forming a glass surface treatment film obtained in Modulation Examples 1 to 13 were spin-coated on a 4-inch glass wafer (manufactured by Corning, Eagle XG) to a final film thickness of 100 nm, heated at 90 °C for 1 minute, and a glass surface treatment film was formed on the glass wafer. Using a surface resistance measuring instrument (measurement voltage: 500 V), the probe was brought into contact with the glass surface treatment film side of the glass wafer on which the glass surface treatment film was formed, and the surface resistivity 60 seconds after contact was measured. The results are shown in Table 1.

[0277] [3] Evaluation of electrostatic adsorption properties

[0278] The compositions for forming a glass surface treatment film obtained in Modulation Examples 1 to 13 were spin-coated on a 4-inch glass wafer (manufactured by Corning, Eagle XG) to a final film thickness of 100 nm, heated at 90 °C for 1 minute, and a glass surface treatment film was formed on the glass wafer. Using a hand-held electrostatic chuck (manufactured by Tsukuba Seiko Co., Ltd., Soft Palm, applied voltage: 0.3 kV), the electrostatic chuck was brought into contact with the glass surface treatment film side of the glass wafer on which the glass surface treatment film was formed, and after lifting the glass wafer vertically, the glass wafer was vertically tilted to evaluate the electrostatic adsorption properties. The case of adsorption was recorded as "〇", and the case of non-adsorption was recorded as "×". The results are shown in Table 1.

[0279] [4] Confirmation of solubility of the film in an alkaline aqueous solution

[0280] The glass surface treatment film-forming compositions obtained in Formulation Examples 1 to 3, 8, and 10 to 13 were spin-coated on 4-inch silicon wafers to a final film thickness of 100 nm, heated at 90 °C for 1 minute, and a glass surface treatment film was formed on the silicon wafers. Then, the obtained laminate was cut into squares with sides of 3 cm to produce test substrates.

[0281] The film thickness (film thickness before immersion) of the produced test substrates was measured. Further, each film together with the substrate was immersed in NMD-3 (composition: 2.38 mass% aqueous solution of tetramethylammonium hydroxide, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 1 minute, dried with an air gun, and then the film thickness of each film (film thickness after immersion) was measured again.

[0282] The residual film ratio (%) by immersion was calculated using the following formula.

[0283] Residual film ratio (%) = [Film thickness after immersion (nm) / Film thickness before immersion (nm)] × 100

[0284] The results were recorded in Table 2.

[0285] [5] Confirmation of solubility of the film in pure water

[0286] The glass surface treatment film-forming compositions obtained in Formulation Examples 4 to 7 and 9 were spin-coated on 4-inch silicon wafers to a final film thickness of 100 nm, heated at 90 °C for 1 minute, and a glass surface treatment film was formed on the silicon wafers. Then, the obtained laminate was cut into squares with sides of 3 cm to produce test substrates.

[0287] The film thickness (film thickness before immersion) of the produced test substrates was measured. Further, each film together with the substrate was immersed in pure water for 1 minute, dried with an air gun, and then the film thickness of each film (film thickness after immersion) was measured again.

[0288] The residual film ratio (%) by immersion was calculated using the following formula.

[0289] Residual film ratio (%) = [Film thickness after immersion (nm) / Film thickness before immersion (nm)] × 100

[0290] The results were recorded in Table 3.

[0291] <Comparative Example 3>

[0292] [6] Measurement of surface resistivity of the film

[0293] Using a surface resistance meter (measurement voltage: 500 V), the probe was brought into contact with the surface of a 4-inch glass wafer (manufactured by Corning, Eagle XG), and the surface resistivity 60 seconds after contact was measured. The results are shown in Table 1.

[0294] [7] Evaluation of electrostatic adsorption

[0295] Using a hand-held electrostatic chuck (manufactured by Tsukuba Seiko, Soft Palm, applied voltage: 0.3 kV), the electrostatic chuck was brought into contact with a 4-inch glass wafer (manufactured by Corning, Eagle XG). After lifting the glass wafer in the vertical direction, the glass wafer was vertically tilted to evaluate the electrostatic adsorption. The adsorbed case was recorded as "〇", and the non-adsorbed case was recorded as "×". The results are shown in Table 1.

[0296] [Table 1]

[0297] Composition Surface Resistivity (Ω / □) Electrostatic Adsorbability Example 1 Modulation Example 1 <![CDATA[1.6×10 11 > 〇 Example 2 Modulation Example 2 <![CDATA[1.7×10 10 > 〇 Example 3 Modulation Example 3 <![CDATA[2.9×10 11 > 〇 Example 4 Modulation Example 4 <![CDATA[3.0×10 10 > 〇 Example 5 Modulation Example 5 <![CDATA[8.5×10 9 > 〇 Example 6 Modulation Example 6 <![CDATA[9.5×10 9 > ○ Example 7 Modulation Example 7 <![CDATA[9.1×10 8 > 〇 Example 8 Modulation Example 10 <![CDATA[5.3×10 9 > ○ Example 9 Modulation Example 11 <![CDATA[7.4×10 10 > 〇 Example 10 Modulation Example 12 <![CDATA[3.2×10 8 > 〇 Example 11 Modulation Example 13 <![CDATA[3.8×10 7 > 〇 Comparative Example 1 Modulation Example 8 <![CDATA[>9.9×10 12 > × Comparative Example 2 Modulation Example 9 <![CDATA[>9.9×10 12 > × Comparative Example 3 None <![CDATA[>9.9×10 12 > ×

[0298] [Table 2]

[0299]

[0300] [Table 3]

[0301]

Claims

1. A composition for forming a glass surface treatment film, which contains a conductive substance and a solvent, The composition for forming a glass surface treatment film is used to hold a glass substrate by electrostatic adsorption.

2. The composition for forming a glass surface treatment film according to claim 1, which further contains a polymer.

3. The composition for forming a glass surface treatment film according to claim 2, wherein the polymer is a water-soluble polymer or an alkali-soluble polymer.

4. The composition for forming a glass surface treatment film according to claim 1, wherein the conductive substance is at least one selected from surfactants and ionic liquids.

5. The composition for forming a glass surface treatment film according to claim 1, wherein the conductive substance is a conductive polymer.

6. The composition for forming a glass surface treatment film according to claim 1, wherein the conductive substance is at least one selected from conductive fillers of carbon-based, metal-based, metal oxide-based, metal-coated, and metal oxide-coated systems.

7. The composition for forming a glass surface treatment film according to claim 1, wherein the solvent contains at least one selected from alkylene glycol monoalkyl ethers, monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and water.

8. The composition for forming a glass surface treatment film according to claim 1, which further contains a crosslinking agent.

9. A glass surface treatment film, which is formed from the composition for forming a glass surface treatment film according to any one of claims 1 to 8.

10. A laminate, which has a glass substrate and the glass surface treatment film according to claim 9.

11. A method for manufacturing a laminate, which includes the following step: forming a glass surface treatment film on the surface of a glass substrate by using the composition for forming a glass surface treatment film according to any one of claims 1 to 8.

12. A method for removing a glass surface treatment film, which includes the following step: applying any one of a water and an alkaline aqueous solution as a removal liquid to the laminate according to claim 10 to remove the glass surface treatment film from the glass substrate.

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