Composition for forming glass surface protective film

Abstract

Provided is a composition for forming a glass surface protective film that contains a coloring agent having a maximum absorption wavelength in a range of 600-800 nm, and a solvent, and that is used for protecting a glass substrate.

Description

Composition for forming a glass surface protective film

[0001] The present invention relates to a composition for forming a glass surface protective film.

[0002] Workpieces such as semiconductor wafers and glass substrates used in display manufacturing are transported to other processing stages after completing their respective processing steps. During this process, a protective film is sometimes applied to the glass surface to protect the glass substrate from scratches and foreign matter.

[0003] On the other hand, when a glass substrate is subjected to various processes, it may be necessary to accurately position the glass substrate at an appropriate position. Therefore, alignment of the glass substrate (moving and adjusting it to a target position) is performed. Regarding the alignment of the glass substrate, for example, a method for detecting the edge position of a transparent substrate held by a substrate holding unit has been proposed, which includes the steps of: holding the substrate on the substrate holding unit so that the edge extends in a direction intersecting a mark provided on the substrate holding unit; capturing images of the mark and the substrate using refraction of light; and detecting the edge position of the substrate based on positional information of a boundary between an image of the mark captured through the substrate and an image of the mark outside the edge of the substrate (see Patent Document 1).

[0004] JP 2009-168507 A

[0005] Infrared rays are sometimes used to detect glass substrates during alignment, but if the glass substrate is transparent to infrared rays, it becomes difficult to detect the glass substrate.

[0006] The present invention has been made in consideration of such circumstances, and aims to provide a composition for forming a glass surface protective film that facilitates detection of glass substrates using infrared rays, a laminate obtained using the composition for forming a glass surface protective film, a method for manufacturing a laminate using the composition for forming a glass surface protective film, and a method for removing a glass surface protective film using the laminate.

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0008] That is, the present invention encompasses the following: [1] A composition for forming a glass surface protective film, which contains a colorant having a maximum absorption wavelength in the range of 600 nm to 800 nm and a solvent, and is used to protect a glass substrate. [2] The composition for forming a glass surface protective film according to [1], further containing a polymer. [3] The composition for forming a glass surface protective film according to [2], wherein the polymer is an alkali-soluble polymer. [4] The composition for forming a glass surface protective film according to [2] or [3], wherein the content of the colorant is 1 mass % to 25 mass % based on the content of the polymer. [5] The composition for forming a glass surface protective film according to any of [1] to [4], wherein the colorant is a dye. [6] The composition for forming a glass surface protective film according to any of [1] to [5], wherein the solvent contains at least one selected from the group consisting of an alcohol, a carboxylic acid having a hydroxy group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether, and water. [7] A glass surface protective film formed from the composition for forming a glass surface protective film according to any one of [1] to [6]. [8] The glass surface protective film according to [7], which has a minimum light transmittance of 50% or less in the wavelength range of 620 nm to 780 nm. [9] A laminate having a glass substrate and the glass surface protective film according to [7] or [8].

[10] A method for manufacturing a laminate, comprising a step of forming a glass surface protective film on the surface of a glass substrate using the composition for forming a glass surface protective film according to any one of [1] to [6].

[11] A method for removing a glass surface protective film, comprising a step of applying a remover of either water or an alkaline aqueous solution to the laminate according to [9], and removing the glass surface protective film from the glass substrate.

[0009] According to the present invention, there are provided a composition for forming a glass surface protective film that facilitates detection of a glass substrate using infrared rays, a laminate obtained using the composition for forming a glass surface protective film, a method for manufacturing a laminate using the composition for forming a glass surface protective film, and a method for removing a glass surface protective film using the laminate.

[0010] (Glass surface protective film-forming composition) The glass surface protective film-forming composition of the present invention contains a colorant and a solvent. The glass surface protective film-forming composition may further contain a polymer. A film formed from the glass surface protective film-forming composition can prevent scratches on the glass substrate and adhesion of foreign matter to the glass substrate.

[0011] <Colorant> The colorant has a maximum absorption wavelength in the range of 600 nm to 800 nm. When the colorant has a maximum absorption wavelength in the range of 600 nm to 800 nm, the protective film obtained from the composition for forming a glass surface protective film is easily detectable by infrared light. As a result, a glass substrate having such a protective film on its surface can be easily aligned using infrared light.

[0012] The maximum absorption wavelength in this specification refers to the maximum absorption wavelength in the wavelength range of 400 nm to 850 nm. The maximum absorption wavelength of a colorant can be measured, for example, by preparing a sample by dissolving the colorant in water or an organic solvent so that the concentration of the colorant becomes 20 mg / L, and using a UV-3600 manufactured by Shimadzu Corporation.

[0013] The colorant may be a pigment or a dye, but is preferably a dye from the viewpoint of suitably achieving the effects of the present invention.

[0014] Examples of colorants having a maximum absorption wavelength in the range of 600 nm to 800 nm include the following dyes: Basic Green 1 (Cas RN: 633-03-4) Acid Green 50 (Cas RN: 3087-16-9) Sudan Black B (Cas RN: 4197-25-5) IR-775 Chloride (Cas RN: 199444-11-6) Acid Green 27 (Cas RN: 6408-57-7)

[0015] The content of the colorant is not particularly limited, but is preferably 1% by mass to 25% by mass, and more preferably 1% by mass to 20% by mass, based on the film-constituting components. The film-constituting components refer to the components that constitute the glass surface protective film. In other words, the film-constituting components refer to all components of the composition for forming a glass surface protective film excluding the solvent.

[0016] When the composition for forming a glass surface protective film contains a polymer, the content of the colorant is preferably 1% by mass to 25% by mass, more preferably 1% by mass to 20% by mass, based on the content of the polymer.

[0017] <Polymer> The polymer is used, for example, to impart film-forming properties to the glass surface protective film. The polymer is not particularly limited, but an alkali-soluble polymer is preferred because it provides excellent removability of the glass surface protective film.

[0018] <<Alkali-Soluble Polymer>> The alkali-soluble polymer is a polymer having an alkali-soluble group (e.g., a carboxy group, a sulfonic acid group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, etc.) and may be any polymer that is soluble in an alkaline aqueous solution. Examples of the alkaline aqueous solution include a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution.

[0019] The alkali-soluble polymer may be an addition polymer of a monomer containing a polymerizable unsaturated compound having an alkali-soluble group. The addition polymer may be a homopolymer or a copolymer.

[0020] Examples of polymerizable unsaturated compounds having an alkali-soluble group include polymerizable unsaturated compounds having a carboxy group, polymerizable unsaturated compounds having an alcoholic hydroxyl group, and polymerizable unsaturated compounds having a phenolic hydroxyl group.

[0021] Examples of polymerizable unsaturated compounds having a carboxy group that can be used include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and (meth)acrylic acid derivatives having a carboxy group and an ester bond such as 2-succinoylethyl (meth)acrylate, 2-maleinoylethyl (meth)acrylate, and 2-hexahydrophthaloylethyl (meth)acrylate.

[0022] Examples of the polymerizable unsaturated compound having an alcoholic hydroxyl group include aliphatic (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; and aromatic (meth)acrylates such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl (meth)acrylate, 2-hydroxy-3-(1-naphthoxy)propyl (meth)acrylate, and 2-hydroxy-3-(2-naphthoxy)propyl (meth)acrylate.

[0023] Examples of polymerizable unsaturated compounds having a phenolic hydroxyl group include hydroxystyrene.

[0024] The alkali-soluble polymer is preferably polyhydroxystyrene. The polyhydroxystyrene may be a homopolymer of hydroxystyrene, a copolymer of hydroxystyrene and another monomer, a branched polyhydroxystyrene, or a modified polyhydroxystyrene. Examples of branched polyhydroxystyrene include the branched polyhydroxystyrenes described in WO2009 / 038126. Examples of modified polyhydroxystyrene include the modified polyhydroxystyrene resins described in JP-A-2013-227364.

[0025] The alkali-soluble polymers can be used alone or in combination of two or more.

[0026] The content of the polymer in the composition for forming a glass surface protective 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, based on the film constituent components.

[0027] <Solvent> The solvent is not particularly limited and may be water or an organic solvent. Examples of the organic solvent include alcohols, carboxylic acids having a hydroxy group, linear or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic acid esters (monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers).

[0028] Examples of the alcohol include monoalcohol solvents and polyhydric alcohol solvents. Examples of the monoalcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, and n-octanol. Examples of polyhydric alcohol solvents include ethanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, etc. Examples of polyhydric alcohol solvents include ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, etc.

[0029] Examples of carboxylic acids having a hydroxy group include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, and methyl 2-hydroxy-3-methylbutyrate.

[0030] Examples of linear or cyclic alkyl ketones include methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0031] An example of the cyclic lactone is γ-butyrolactone.

[0032] Examples of alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether. Examples of alkylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether.

[0033] Examples of alkylene glycol monoalkyl ether carboxylic acid esters include monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers. Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene glycol monoalkyl ether acetates. Examples of alkylene glycol monoalkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate. Examples of the alkoxycarboxylic acid ester of alkylene glycol monoalkyl ether include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.

[0034] Specific examples of other solvents include toluene, xylene, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, and ethyl hydroxyacetate. Examples of suitable solvents include methyl 3-methoxy-2-methylpropionate, methyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 4-methyl-2-pentanol.

[0035] Among these solvents, alkylene glycol monoalkyl ethers, monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and water are preferred.

[0036] These solvents may be used alone or in combination of two or more thereof. Furthermore, these solvents may be used alone as an organic solvent, in combination of two or more organic solvents, or in combination of an organic solvent and water.

[0037] The mass proportion of the organic solvent in the solvent is not particularly limited, but is preferably 50 mass % to 100 mass %.

[0038] The content of the solvent in the composition for forming a glass surface protective film 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.

[0039] <Crosslinking Agent> The composition for forming a glass surface protective film may contain a crosslinking agent in order to enhance the solvent resistance of the glass surface protective film to be formed. Note that the crosslinking agent is a substance different from the polymer.

[0040] The crosslinking agent is not particularly limited, and examples of the crosslinking agent include compounds having two or more of the following structures: (In the structure, R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.) The bond is bonded to, for example, a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0041] R １０１ is preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.

[0042] As the crosslinking agent, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, or a compound having a phenolic hydroxy group is preferred. These may be used alone or in combination of two or more.

[0043] The melamine compound is not particularly limited as long as it has a group capable of reacting with a hydroxy group, and examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which one to six methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which one to six methylol groups of hexamethylol melamine are acyloxymethylated, or a mixture thereof.

[0044] The guanamine compound is not particularly limited as long as it has a group capable of reacting with a hydroxy group, and examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof.

[0045] The glycoluril compound is not particularly limited as long as it has a group capable of reacting with a hydroxy group, and examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof, and a compound in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or a mixture thereof.

[0046] The glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E). (In formula (1E), four R １ each independently represents a methyl group or an ethyl group, R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0047] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0048] The glycoluril derivative represented by formula (1E) can be 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).

[0049] (In formula (2E), R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0050] (In formula (3d), R １ represents a methyl group or an ethyl group.)

[0051] Examples of glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0052] The urea compound is not particularly limited as long as it has a group capable of reacting with a hydroxy group, and examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which one to four methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, and tetramethoxyethyl urea.

[0053] Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (111) or (112). (In formula (111) and formula (112), Q ２ represents a single bond or a divalent organic group. ８ , R ９ , R １１ and R １２ R represents a hydrogen atom or a methyl group. ７ and R １０ n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. ９ is 1≦n ９ an integer ≦3, n １０ is 2≦n １０ n is an integer ≦5 １１ is 0≦n １１ an integer ≦3, n １２is 0≦n １２ an integer ≦3, 3≦(n ９ +n １０ +n １１ +n １２ ) represents an integer ≦6. １３ is 1≦n １３ an integer ≦3, n １４ is 1≦n １４ n is an integer ≦4 １５ is 0≦n １５ an integer ≦3, n １６ is 0≦n １６ an integer ≦3, 2≦(n １３ +n １４ +n １５ +n １６ ) represents an integer of ≦5. m2 represents an integer of 2 to 10. ２ In the above, the m2-valent organic group includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.

[0054] Examples of the compound represented by formula (111) or formula (112) include the following compounds. The above compound is available as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of the product is TMOM-BP, a product name of Asahi Organic Chemicals Co., Ltd.

[0055] Among these, glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which one to four methylol groups are methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which one to four methylol groups are acyloxymethylated or mixtures thereof, with tetramethoxymethyl glycoluril being preferred.

[0056] The molecular weight of the crosslinking agent is not particularly limited, but is preferably 1,000 or less.

[0057] The content of the crosslinking agent in the composition for forming a glass surface protective film is not particularly limited, but is, for example, 1% by mass to 50% by mass, and preferably 5% by mass to 40% by mass, based on the film constituent components.

[0058] <Acid Generator> The acid generator contained as an optional component in the composition for forming a glass surface protective film may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0059] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0060] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0061] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0062] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0063] The acid generators may be used singly or in combination of two or more.

[0064] When an acid generator is used, the content of the acid generator relative to the crosslinking agent is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass.

[0065] The composition for forming a glass surface protective film may or may not contain a conductive substance, such as a surfactant, an ionic liquid, or a conductive polymer.

[0066] (Glass surface protective film) The glass surface protective film of the present invention is formed from the composition for forming a glass surface protective film of the present invention. The glass surface protective film can be formed, for example, by applying the composition for forming a glass surface protective film to the surface of a glass substrate and drying it.

[0067] The coating method is not particularly limited and may be, for example, various wet process methods, such as drop casting, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet printing, and printing methods (relief printing, intaglio printing, lithography, screen printing, etc.).

[0068] The drying temperature is not particularly limited and may be, for example, 30° C. to 120° C. The drying time is not particularly limited and may be, for example, 10 seconds to 10 minutes.

[0069] The thickness of the glass surface protective film is not particularly limited, but is preferably 10 nm to 10 μm, more preferably 20 nm to 5 μm, and particularly preferably 50 nm to 1 μm. The thickness of the glass surface protective film can be measured, for example, using optical interferometry. As a measuring device, for example, F-50 manufactured by Filmetrics Inc. can be used.

[0070] The glass surface protective film preferably has a minimum light transmittance of 50% or less within the wavelength range of 620 nm to 780 nm. This facilitates detection of the glass substrate using infrared light (e.g., wavelengths of 620 nm to 780 nm). The lower limit of the minimum light transmittance within the wavelength range of 620 nm to 780 nm is not particularly limited, but for example, the minimum value may be 0% or greater or 1% or greater. The light transmittance within the wavelength range of 620 nm to 780 nm can be determined, for example, by fixing a quartz substrate on which a glass surface protective film has been formed and an uncoated quartz substrate as a reference to a stage within an apparatus and measuring the transmittance of the glass surface protective film formed on the quartz substrate in 1 nm increments over the wavelength range of 190 to 800 nm. The transmittance can be measured, for example, using a spectrophotometer (transmittance meter, UV3600Plus, manufactured by Shimadzu Corporation).

[0071] (Laminate) The laminate of the present invention has a glass substrate and the glass surface protective film of the present invention. In the laminate, the glass surface protective film may be formed on one side or both sides of the glass substrate. When glass surface protective films are formed on both sides of the glass substrate, the glass surface protective films may have the same composition or different compositions and may have the same film thickness or different film thicknesses.

[0072] The material of the glass substrate is not particularly limited, and examples thereof include alkali-free glass, silica glass, etc. The size of the glass substrate is not particularly limited, and the thickness of the glass substrate is not particularly limited, and is, for example, preferably 100 μm to 5 mm, more preferably 200 μm to 2 mm, and particularly preferably 500 μm to 1 mm.

[0073] The surface of the glass substrate may be flat or may have irregularities. The size of the irregularities is not particularly limited. The irregularities may be formed by, for example, various processes.

[0074] The surface of the glass substrate may be subjected to various processes, such as semiconductor formation, electrode formation, and light-emitting element formation.

[0075] (Method for producing laminate) The method for producing a laminate of the present invention includes a step of forming a glass surface protective film on the surface of a glass substrate using the composition for forming a glass surface protective film of the present invention. Examples of the method for forming the glass surface protective film include the formation methods described in the description of the glass surface protective film of the present invention.

[0076] Examples of the glass substrate include the glass substrates exemplified in the description of the laminate of the present invention. Examples of the glass surface protective film include the glass surface protective film exemplified in the description of the glass surface protective film of the present invention.

[0077] (Method for Removing a Glass Surface Protective Film) The method for removing a glass surface protective film of the present invention includes the step of applying a remover to the laminate of the present invention to remove the glass surface protective film from the glass substrate.

[0078] Examples of the removal liquid include water, an alkaline aqueous solution, and an organic solvent, with water and an alkaline aqueous solution being preferred.

[0079] Examples of water include ion-exchanged water and pure water. The pH of the water is usually 7.0. Examples of alkaline aqueous solutions include alkaline aqueous solutions in which at least one alkaline compound 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, or 1,5-diazabicyclo-[4.3.0]-5-nonene is dissolved.

[0080] The method for applying the remover to the laminate is not particularly limited, and examples thereof include an immersion method and a spray method. The immersion time in the immersion method is not particularly limited. The amount of the remover used in the spray method is not particularly limited. The remover may be at room temperature or about 30°C to 40°C.

[0081] The glass substrate may be, for example, a glass substrate held using an electrostatic adsorption system. Examples of holding a glass substrate using an electrostatic adsorption system include holding the glass substrate when processing the glass substrate and holding the glass substrate when moving or transporting the glass substrate. By holding the glass substrate using an electrostatic adsorption system, for example, the glass substrate can be held with high positional accuracy when processing the glass substrate or when moving or transporting the glass substrate. In an electrostatic adsorption member for electrostatically adsorbing a glass substrate, for example, an electrode layer for electrostatic adsorption is provided inside a dielectric member made of ceramic or the like. The electrostatic adsorption member has, for example, an adsorption surface to which the glass substrate is electrostatically adsorbed. The electrostatic adsorption member may be, for example, belt-shaped. The movement or transport of the glass substrate using an electrostatic adsorption system may be, for example, belt conveyor transport using a belt-shaped electrostatic adsorption member, or movement or transport using a robot arm with an electrostatic adsorption member attached to the tip of the arm.

[0082] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used is as follows.

[0083] <Apparatus> (1) Optical film thickness meter: F-50 manufactured by Filmetrics, Inc. (2) Transmittance meter: UV3600Plus manufactured by Shimadzu Corporation (3) Contact angle meter: DM-702 manufactured by Kyowa Interface Science Co., Ltd.

[0084] <Examples and Comparative Examples> The following resins, dyes, and solvents were mixed in the proportions shown in Table 1, and the mixture was filtered through a 0.2 μm fluororesin or olefin resin filter to prepare compositions for forming glass surface protective films.

[0085]

[0086] The following resins were used: VP-8000: Polyhydroxystyrene (product name: VP-8000, manufactured by Nippon Soda Co., Ltd.)

[0087] The dyes used were as follows: Basic Green 1 (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength: 630 nm) Acid Green 50 (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength: 635 nm) Sudan Black B (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength: 610 nm) IR-775 Chloride (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength: 775 nm) Acid Green 27 (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength: 645 nm) IR-813 p-Toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength: 813 nm) Mordant Black 17 (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength: 520 nm)

[0088] The following solvents were used: PGME: propylene glycol monomethyl ether; pure water

[0089] <Water Resistance Test of Films> The compositions for forming glass surface protective films obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated onto 4-inch silicon wafers and heated at 120°C for 1 minute to form surface protective films with thicknesses of approximately 100 to 1,500 nm on the substrates, thereby preparing evaluation substrates. The film thickness on the evaluation substrates was then measured (film thickness before immersion). 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 was measured again (film thickness after immersion). The remaining film rate (%) after immersion was calculated using the following formula: remaining film rate (%) = [film thickness after immersion (nm) / film thickness before immersion (nm)] × 100 The results are shown in Table 2. A remaining film rate of 95% or more was rated "good," and a remaining film rate of less than 95% was rated "poor."

[0090]

[0091] <Film Solubility Test> The compositions for forming a glass surface protective film obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated onto 4-inch silicon wafers and heated at 120°C for 1 minute to form a surface protective film with a thickness of approximately 100 to 1,500 nm on the substrate, thereby preparing evaluation substrates. The film thickness on the evaluation substrate was then measured (film thickness before immersion). Each film, together with the substrate, was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and pure water for 1 minute, dried with an air gun, and then the film thickness of each film was measured again (film thickness after immersion). The remaining film ratio (%) after immersion was calculated using the following formula: remaining film ratio (%) = [film thickness after immersion (nm) / film thickness before immersion (nm)] × 100. The results are shown in Table 3. A remaining film ratio of 5% or less was rated "good," and a remaining film ratio of more than 5% was rated "poor."

[0092]

[0093] <Anti-fouling Test> The compositions for forming a glass surface protective film obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated onto a 4-inch silicon wafer and heated at 120°C for 1 minute to form a surface protective film with a thickness of approximately 100 to 1500 nm on the substrate, thereby preparing a substrate for evaluation. Then, an uncoated silicon wafer surface was placed on the evaluation substrate so that it was in contact with the surface protective film, and the substrate was left to stand at room temperature for 1 hour. Thereafter, the contact angle of the uncoated silicon wafer surface was measured using pure water, and the results are shown in Table 4. A contact angle of 10° or less confirmed low contamination due to film components.

[0094]

[0095] <Transmittance Measurement> The compositions for forming a glass surface protective film obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated onto a 4 cm square quartz substrate and heated at 120°C for 1 minute to form a surface protective film with a thickness of approximately 100 to 1500 nm on the substrate. The quartz substrate on which the surface protective film had been formed and an uncoated quartz substrate as a reference were fixed to a stage within the apparatus, and the transmittance of the surface protective film formed on the quartz substrate was measured in 1 nm increments in the wavelength range of 190 to 800 nm. The results of the lowest transmittance in the wavelength range of 620 to 780 nm are listed in Table 5. It was confirmed that Examples 1 to 8 had lower transmittance in the wavelength range of 620 to 780 nm than Comparative Examples 1 to 3.

[0096]

Claims

1. A composition for forming a glass surface protective film, which contains a colorant having a maximum absorption wavelength in the range of 600 nm to 800 nm and a solvent, and is used to protect glass substrates.

2. The composition for forming a glass surface protective film according to claim 1, further comprising a polymer.

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

4. The composition for forming a glass surface protective film according to claim 2, wherein the content of the colorant is 1% by mass to 25% by mass relative to the content of the polymer.

5. The composition for forming a glass surface protective film according to claim 1, wherein the colorant is a dye.

6. A composition for forming a glass surface protective film according to claim 1, wherein the solvent contains at least one selected from the group consisting of alcohols, carboxylic acids having a hydroxy group, linear or cyclic alkyl ketones, cyclic lactones, alkylene glycol monoalkyl ethers, monocarboxylic acid esters of alkylene glycol monoalkyl ethers, alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers, and water.

7. A glass surface protective film formed from the composition for forming a glass surface protective film according to any one of claims 1 to 6.

8. The glass surface protective film according to claim 7, wherein the minimum transmittance of light in the wavelength range of 620 nm to 780 nm is 50% or less.

9. A laminate comprising a glass substrate and the glass surface protective film according to claim 7.

10. A method for producing a laminate, comprising a step of forming a glass surface protective film on the surface of a glass substrate using a composition for forming a glass surface protective film according to any one of claims 1 to 6.

11. A method for removing a glass surface protective film, comprising the step of applying a remover, which is either water or an alkaline aqueous solution, to the laminate described in claim 9, thereby removing the glass surface protective film from the glass substrate.

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