WO2015056772A1 - Substrat en verre ayant un film protecteur - Google Patents

Substrat en verre ayant un film protecteur Download PDF

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Publication number
WO2015056772A1
WO2015056772A1 PCT/JP2014/077656 JP2014077656W WO2015056772A1 WO 2015056772 A1 WO2015056772 A1 WO 2015056772A1 JP 2014077656 W JP2014077656 W JP 2014077656W WO 2015056772 A1 WO2015056772 A1 WO 2015056772A1
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group
glass substrate
formula
protective film
alkoxysilane
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PCT/JP2014/077656
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English (en)
Japanese (ja)
Inventor
政太郎 大田
賢一 元山
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日産化学工業株式会社
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Priority to JP2015542678A priority Critical patent/JP6578946B2/ja
Publication of WO2015056772A1 publication Critical patent/WO2015056772A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133302—Rigid substrates, e.g. inorganic substrates

Definitions

  • the present invention relates to a glass substrate having a protective film formed using a protective film forming agent containing polysiloxane.
  • the present invention relates to a glass substrate used for a liquid crystal display element.
  • cover glasses for display protection are often used.
  • Such display devices are required to be lightweight and thin. Therefore, it is also required to reduce the thickness of the cover glass used for display protection.
  • the thickness of the cover glass is reduced, the strength decreases, and there is a problem that the cover glass itself breaks due to falling during use and the like, and the original function of protecting the display device cannot be performed. It was.
  • the air cooling strengthening method physical strengthening method
  • alkali metal ions typically Li ions and Na ions
  • alkali ions typically K ions
  • the air-cooling tempering method requires a high-temperature treatment and has a problem in manufacturing efficiency.
  • the chemical strengthening method has problems in terms of strength reduction due to ion migration accompanying temperature rise and production cost.
  • An object of the present invention is to provide a glass substrate on which a protective film capable of increasing the strength of the glass with a thickness that does not affect the transmittance is formed.
  • the gist of the present invention is as follows. 1.
  • R 1 is a hydrocarbon group having 1 to 12 carbon atoms substituted with a ureido group
  • R 2 is an alkyl group having 1 to 5 carbon atoms
  • p is 1 or 2 Represents an integer
  • formula (2) (R 3 ) n Si (OR 4 ) 4-n (2)
  • R 3 is a hydrogen atom, or a hetero atom, a halogen atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group, or an acryloxy group.
  • a hydrocarbon group having 8 to 8, R 4 is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3)
  • the alkoxysilane represented by the formula (1) is contained in an amount of 0.5 to 60 mol%
  • the alkoxysilane represented by the formula (2) is contained in an amount of 40 to 99.5 mol%.
  • the alkoxysilane represented by the formula (1) is at least one selected from the group consisting of ⁇ -ureidopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane and ⁇ -ureidopropyltripropoxysilane. 4.
  • An electronic device having the glass substrate according to any one of 1 to 5 above.
  • the protective film forming agent used for the glass substrate of the present invention has sufficient hardness and fracture strength at a curing condition lower than 300 ° C. and a thickness of nanometer order, the production efficiency is good, and the optical characteristics of the electronic device It is possible to provide a glass substrate having sufficient strength without affecting the above.
  • the liquid crystal aligning film which suppressed repellency and a pinhole can be formed on the formed electrode protective film. Therefore, even a substrate having low heat resistance such as a plastic substrate is useful for manufacturing a liquid crystal display element having excellent display characteristics.
  • the protective film forming agent used for the glass substrate of the present invention is characterized in that it contains polysiloxane having a ureido group. Therefore, a protective film having a sufficient hardness, particularly an electrode protective film, can be formed by curing at a temperature lower than 300 ° C.
  • the present invention is described in detail below.
  • the protective film formation agent used for the glass substrate of this invention contains the polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by following formula (1).
  • R 1 is a hydrocarbon group having 1 to 12 carbon atoms substituted with a ureido group. More specifically, any hydrogen atom of a hydrocarbon group having 1 to 12 carbon atoms is converted to a ureido group. It means a group substituted with a group. A hydrocarbon group having 1 to 7 carbon atoms substituted with a ureido group is preferred.
  • R 2 is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
  • p represents an integer of 1 or 2.
  • alkoxysilane represented by the formula (1) when p is 1, it is an alkoxysilane represented by the formula (1-1).
  • R 1 Si (OR 2 ) 3 (1-1) When p is 2, it is an alkoxysilane represented by the formula (1-2).
  • (R 2 O) 3 Si—R 1 —Si (OR 2 ) 3 (1-2) Specific examples of the alkoxysilane represented by the formula (1-1) are shown below, but are not limited thereto.
  • ⁇ -ureidopropyltriethoxysilane or ⁇ -ureidopropyltrimethoxysilane is particularly preferable because it is easily available as a commercial product.
  • alkoxysilane represented by the formula (1-2) will be given, but the invention is not limited to these.
  • bis [3- (triethoxysilyl) propyl] urea is particularly preferable because it is easily available as a commercial product.
  • the alkoxysilane represented by the formula (1) is preferably 0.5 mol% or more in all alkoxysilanes used for obtaining the protective film forming agent, from the viewpoint of good printability of the liquid crystal alignment film. . More preferably, it is 1.0 mol% or more. More preferably, it is 2.0 mol% or more. Moreover, it is preferable from the point of sufficient hardening of the protective film formed that the alkoxysilane represented by Formula (1) is 60 mol% or less in all the alkoxysilanes. More preferably, it is 50 mol% or less. More preferably, it is 40 mol% or less.
  • the protective film formation agent used for the glass substrate of this invention polycondenses the alkoxysilane containing at least 1 sort (s) of the alkoxysilane represented by following formula (2) with the alkoxysilane represented by Formula (1).
  • R 3 is a hydrogen atom, or a hetero atom, a halogen atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group, or an acryloxy group.
  • R 4 is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n represents an integer of 0 to 3, preferably 0 to 2.
  • R 3 of the alkoxysilane represented by the formula (2) is substituted with a hydrogen atom, a hetero atom, a halogen atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group. Or a hydrocarbon group having 1 to 8 carbon atoms.
  • R 4 has the same meaning as R 2 described above, and the preferred range is also the same.
  • Examples of R 3 include organic groups having 1 to 8 carbon atoms, such as aliphatic hydrocarbons (such as alkyl groups having 1 to 8 carbon atoms); or aliphatic rings, aromatic rings or heterocyclic rings.
  • Such ring structures (cycloalkyl groups having 3 to 8 carbon atoms, benzene, etc.), which may contain unsaturated bonds; heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc. , May have a branched structure.
  • R 3 may be substituted with a halogen atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group, an acryloxy group, or the like.
  • alkoxysilane represented by the formula (2) are given below, but are not limited thereto.
  • alkoxysilane of the formula (2) specific examples of the alkoxysilane when R 3 is a hydrogen atom include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane and the like.
  • alkoxysilane of formula (2) examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and methyltripropoxy.
  • Silane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthio) ethyl Triethoxysilane 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, allyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane,
  • the protective film forming agent used for the glass substrate of the present invention may be one or a plurality of such specific organic groups as long as the effects of the present invention such as adhesion to the substrate, film hardness, and transmittance are not impaired. You may have seed.
  • the alkoxysilane in which n is 0 is tetraalkoxysilane.
  • Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it easily condenses with the alkoxysilane represented by the formula (1).
  • tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
  • the alkoxysilane represented by the formula (2) is preferably 40 to 99.5 mol% in all alkoxysilanes. More preferably, it is 50 to 99.5 mol%. More preferably, it is 60 to 99.5 mol%.
  • the protective film forming agent is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and at least one compound selected from the alkoxysilane represented by the formula (2). Preferably there is.
  • the protective film forming agent used for the glass substrate of the present invention uses one or more kinds of such alkoxysilanes in combination as long as the effects of the present invention, such as film hardness, transmittance, and breaking strength, are not impaired. May be.
  • the method for obtaining the polysiloxane used in the present invention is not particularly limited.
  • the polysiloxane can be obtained by condensing the alkoxysilane having the above-described alkoxysilane of the formula (1) as an essential component in an organic solvent.
  • polysiloxane is obtained as a solution obtained by polycondensation of such alkoxysilanes and uniformly dissolved in an organic solvent.
  • Examples of the polycondensation method include a method of hydrolyzing and condensing the alkoxysilane in a solvent such as alcohol or glycol.
  • the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 moles of water of all alkoxide groups in the alkoxysilane, but it is usually preferable to add an excess amount of water over 0.5 moles.
  • the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
  • acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine Catalysts such as metal salts such as hydrochloric acid, sulfuric acid and nitric acid are used.
  • alkalis such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine
  • Catalysts such as metal salts such as hydrochloric acid, sulfuric acid and nitric acid are used.
  • it is also common to further promote the hydrolysis / condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, heating / stirring at 50 ° C. for 24 hours, heating / stirring under reflux for 1 hour, and the like can be mentioned.
  • a method of polycondensation by heating a mixture of an alkoxysilane, a solvent, and an organic acid such as formic acid, oxalic acid, maleic acid, fumaric acid and the like can be mentioned.
  • a method of polycondensation by heating a mixture of alkoxysilane, solvent and oxalic acid can be mentioned.
  • succinic acid to alcohol in advance to make an alcohol solution of succinic acid
  • alkoxysilane is mixed while the solution is heated.
  • the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. A method of heating for several tens of minutes to several tens of hours under reflux is preferred so that the liquid does not evaporate or volatilize.
  • a mixture of alkoxysilanes may be mixed in advance, or a plurality of types of alkoxysilanes may be mixed sequentially.
  • the solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even when alkoxysilane does not melt
  • Such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1 , 5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol, and other glycols: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether Ethylene glycol monobutyl ether
  • a plurality of the above polymerization solvents may be mixed and used.
  • the polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO 2 (hereinafter referred to as SiO 2 conversion concentration). ) Is generally 20% by mass or less. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.
  • the polysiloxane polymerization solution obtained by the above method may be used as a protective film forming agent as it is, or if necessary, the solution obtained by the above method may be concentrated or a solvent may be added.
  • the protective film forming agent may be diluted with another solvent or substituted with another solvent.
  • the solvent to be used (hereinafter also referred to as additive solvent) may be the same as the polymerization solvent, or may be another solvent.
  • the additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one kind or plural kinds can be arbitrarily selected and used.
  • Such an additive solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and ethyl lactate in addition to the solvents mentioned as examples of the polymerization solvent. It is done.
  • These solvents can adjust the viscosity of the protective film forming agent, and can improve the coating property when the protective film forming agent is applied on the glass substrate by spin coating, flexographic printing, ink jetting, slit coating, or the like.
  • the inorganic fine particles fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in a colloidal solution state are particularly preferable.
  • This colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution.
  • the inorganic fine particles preferably have an average particle size of 0.001 to 0.1 ⁇ m, more preferably 0.001 to 0.1 ⁇ m. When the average particle diameter of the inorganic fine particles exceeds 0.2 ⁇ m, the transparency of the cured film formed using the prepared coating liquid may be lowered.
  • Examples of the dispersion medium for inorganic fine particles include water and organic solvents.
  • the colloidal solution is preferably adjusted to have a pH or pKa of 1 to 10 from the viewpoint of the stability of the protective film forming agent. More preferably, it is 2-7.
  • organic solvent used for the dispersion medium of the colloidal solution examples include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and ⁇ -butyrolactone; Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion
  • metalloxane oligomer and metalloxane polymer single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used.
  • the metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, nitrate, hydrochloride, or carboxylate by a conventional method such as hydrolysis.
  • metalloxane oligomers and metalloxane polymers include siloxane oligomers or siloxane polymers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat.
  • siloxane oligomers or siloxane polymers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat.
  • titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Kanto Chemical. You may use these individually or in mixture of 2 or more types.
  • a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.
  • the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with or after polysiloxane, and is not particularly limited.
  • a desired protective film can be obtained by applying the protective film-forming agent of the present invention to a glass substrate and thermosetting it.
  • a known or well-known method can be adopted as a method for applying the protective film forming agent.
  • a dip method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, an air knife coating method, a flexographic printing method, an ink jet method, a slit coating method and the like can be employed.
  • a favorable coating film can be formed by the flexographic printing method, the slit coating method, the ink jet method, the spray coating method, and the gravure coating method.
  • the base material used includes: glass; glass with a transparent electrode such as ATO, FTO (fluorine-doped tin oxide), ITO, IZO; and base material such as tempered glass.
  • a transparent electrode such as ATO, FTO (fluorine-doped tin oxide), ITO, IZO
  • base material such as tempered glass.
  • the tempered glass include glass tempered by an air-cooling tempering method, chemically tempered glass, and aluminosilicate glass.
  • the protective film forming agent is generally filtered using a filter or the like before coating.
  • the coating film formed on the substrate is dried at a temperature of room temperature to 120 ° C. and then thermally cured at a temperature of 100 to 3000 ° C., preferably 150 to 300 ° C. At this time, the time required for drying may be 30 seconds or more, but 10 minutes or less is sufficient.
  • thermosetting can be selected as appropriate, but may be 5 minutes or longer.
  • a low curing temperature it is easy to obtain a protective film having sufficient hardness by increasing the curing time.
  • the protective film formation agent used for the glass substrate of this invention can obtain the cured film which has sufficient hardness even if it is the curing temperature over 180 degreeC.
  • the thickness of the protective film is preferably in the range of 30 nm to 300 nm, more preferably 30 nm to 200 nm, and even more preferably 50 nm to 110 nm.
  • thermosetting It is also effective to irradiate energy rays (ultraviolet rays or the like) using a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp or the like prior to thermosetting.
  • energy rays ultraviolet rays or the like
  • the curing temperature can be further lowered, or the hardness of the coating can be increased.
  • the irradiation amount of the energy beam can be appropriately selected as necessary, but usually several hundred to several thousand mJ / cm 2 is appropriate.
  • the protective film forming agent of the present invention can form a protective film having the above-described characteristics, it is very useful for increasing the breaking strength of a glass substrate provided with the protective film and improving the visual characteristics of an electronic device. .
  • TEOS tetraethoxysilane UPS: 3-ureidopropyltriethoxysilane MeOH: methanol
  • PGME propylene glycol monomethyl ether
  • HG hexylene glycol
  • BCS ethylene glycol monobutyl ether
  • PB propylene glycol monobutyl ether
  • tempered glass A tempered glass made by Musashino Fine Glass Co., Ltd. with a chamfered substrate with a compressive stress layer depth of 15-18 ⁇ m, substrate width of 60mm, and substrate thickness of 0.55mm, and exposure and chemical etching.
  • Example 1 The polysiloxane solution (A) (50 g) synthesized in Synthesis Example 1 was diluted with PGME (30 g), HG (10 g), BCS (5 g), and PB (5 g) to obtain a coating liquid for film formation (A1).
  • This coating liquid for forming a film (A1) was applied onto soda lime glass (glass thickness 0.7 mm) with a spin coater to form a coating film. Thereafter, it was dried on a hot plate at 80 ° C. for 3 minutes and then cured in a clean oven at 150 ° C. for 30 minutes to obtain a 100 nm film. Pencil hardness measurement and transmittance measurement were performed on this glass substrate. The results are shown in Table 1.
  • Example 1 As shown in Table 1, in Example 1, the pencil hardness was 8H and the average transmittance was 93.2%.
  • Comparative Example 1 has a pencil hardness of 2H and an average transmittance of 93.0%, and Comparative Example 2 has an average transmittance of 91.4% and the transmittance and pencil hardness are not compatible.
  • ⁇ AFM measurement> A range of 10 ⁇ m ⁇ 10 ⁇ m was observed on the glass substrates obtained in Example 1 and Comparative Example 1 using 3800N of SII Nano Technology Co., Ltd., and cantilever SI-DF40 (with back surface AL). The results are shown in FIGS. 1 and 2, respectively. As shown in FIG. 2, microcracks were observed in the glass substrate of Comparative Example 1. On the other hand, as shown in FIG. 1, no microcracks were observed on the glass substrate of Example 1 having a protective film formed using the coating liquid A1.
  • Example 2 The coating liquid for forming a film (A1) was applied onto tempered glass with a spin coater to form a coating film. Thereafter, it was dried on a hot plate at 80 ° C. for 3 minutes and then cured in a clean oven at 300 ° C. for 30 minutes to obtain a 100 nm film. A four-point bending test was performed on this glass substrate. The results are shown in Table 2.
  • the glass substrate of the present invention can increase the breaking strength by forming an inorganic coating. Since this inorganic coating has a high hardness, it is possible to suppress the occurrence of microcracks again and increase the transmittance.

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Abstract

La présente invention porte sur un substrat en verre sur lequel est formé un film protecteur permettant d'accroître la résistance du verre à une épaisseur qui n'a pas d'incidence sur la transmittance, en d'autres termes sur un substrat en verre ayant un film protecteur formé à l'aide d'un agent de formation de film protecteur contenant un polysiloxane obtenu au moyen de la polycondensation d'un alcoxysilane et contenant au moins un alcoxysilane représenté par la formule (1) et la formule (2).
PCT/JP2014/077656 2013-10-18 2014-10-17 Substrat en verre ayant un film protecteur WO2015056772A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017022638A1 (fr) * 2015-07-31 2017-02-09 日産化学工業株式会社 Substrat de verre approprié en tant que verre de protection, etc., d'un dispositif d'affichage mobile
CN116472319A (zh) * 2020-09-21 2023-07-21 株式会社世可 用于超薄型强度增强涂布剂的化合物及包含该化合物的强度增强涂布剂

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Publication number Priority date Publication date Assignee Title
WO2017022638A1 (fr) * 2015-07-31 2017-02-09 日産化学工業株式会社 Substrat de verre approprié en tant que verre de protection, etc., d'un dispositif d'affichage mobile
CN108139506A (zh) * 2015-07-31 2018-06-08 日产化学工业株式会社 适合于移动显示设备的玻璃盖片等的玻璃基板
JPWO2017022638A1 (ja) * 2015-07-31 2018-07-12 日産化学工業株式会社 モバイルディスプレイ機器のカバーガラス等に好適なガラス基板
CN108139506B (zh) * 2015-07-31 2019-11-15 日产化学工业株式会社 适合于移动显示设备的玻璃盖片等的玻璃基板
CN116472319A (zh) * 2020-09-21 2023-07-21 株式会社世可 用于超薄型强度增强涂布剂的化合物及包含该化合物的强度增强涂布剂

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