JP7115054B2 - glass reinforced substrate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a glass-reinforced substrate having, on at least one side thereof, a cured film made of a crosslinked product of a specific glass-reinforced material containing a siloxane resin.

In recent years, various display terminals such as wearable terminals, smartphones, and tablet PCs (personal computers) have a decorative film made of colored ink for printing on the front surface of the display panel such as a liquid crystal display device or an organic EL (electroluminescence) display device. It has a structure in which formed cover glasses are bonded together. In some display terminals, a structure in which a cover glass having a transparent electrode and having a touch sensor function is laminated on glass is also applied. However, in these display terminals, the cover glass is likely to break when the display terminal is dropped due to insufficient strength of the glass itself of the cover glass or a decrease in glass strength due to inorganic films such as transparent electrodes on the glass. I had a problem.

As a technique for improving glass strength, a tempered glass substrate represented by Corning Gorilla Glass is known. This is a technique of treating a glass substrate with a chemical solution or the like to provide compressive stress layers on both sides of the glass, thereby increasing the strength of the glass compared to ordinary glass.

As another technique for improving glass strength, a technique for forming a resin film on a glass substrate is known. For example, a composite comprising a glass substrate having microcracks on its surface and a resin layer disposed on the glass substrate, wherein the resin of the resin layer enters at least part of the interior of the microcracks. (see, for example, Patent Document 1), a glass protective film produced using a composition containing a polyfunctional epoxy (meth)acrylate compound, a polyfunctional thiol compound, and a radical polymerization initiator (see, for example, Patent Document 2) , an inorganic glass, an acrylic polymer formed on at least one main surface of the inorganic glass, a compound having at least two (meth)acryloyl groups, and a resin composition containing a polymerization initiator. A transparent substrate (see, for example, Patent Document 3) provided with a resin layer, a translucent chemically strengthened glass substrate, a first surface of the translucent chemically strengthened glass substrate and a second surface opposite to the first surface A substrate for a protective plate for a display device (see, for example, Patent Document 4), a reinforced glass and a resin layer provided on one surface of the glass A curable composition for forming a cured film between the formed transparent conductive film and a curable composition containing a compound having an organic group and a siloxane bond (see, for example, Patent Document 5). Proposed.

WO2015/194324 Japanese Unexamined Patent Application Publication No. 2016-3160 JP 2016-107441 A JP 2014-228615 A JP 2016-124720 A

Although the strength of the glass can be improved by the technique of forming a resin film on the tempered glass substrate or the glass substrate described in Patent Documents 1 to 5, the reduction in the weight of the display terminal in recent years requires a thinner cover glass. Therefore, higher glass strength is required. In particular, in the case of tempered glass substrates, when a large tempered glass substrate is cut to a size suitable for a smartphone or the like into small pieces, there is a problem that microcracks occur in the glass and the strength of the glass decreases. On the other hand, if the glass strength is improved by increasing the thickness of the resin film, the transmittance decreases, so it is difficult to achieve both the glass strength and the transmittance.

SUMMARY OF THE INVENTION An object of the present invention is to provide a glass-reinforced substrate having high glass strength and high transmittance.

In order to solve the above problems, the present invention mainly has the following configurations.
A glass-reinforced substrate having, on at least one side thereof, a cured film made of a crosslinked product of a glass-reinforced material and having a thickness of 0.5 to 10 μm and a transmittance of 90% or more at a wavelength of 400 nm, wherein the glass-reinforced material contains a siloxane resin and silica particles, or contains a siloxane resin having a radically polymerizable group and a radical photopolymerization initiator.

According to the present invention, it is possible to provide a glass-reinforced substrate having high glass strength and high transmittance.

The present invention will be described in more detail below.

The glass-reinforced substrate of the present invention has, on at least one surface of the tempered glass substrate, a cured film made of a crosslinked product of a glass-reinforced material and having a thickness of 0.5 to 10 μm and a transmittance of 90% or more at a wavelength of 400 nm. The glass reinforcing material contains a siloxane resin and silica particles, or contains a siloxane resin having a radically polymerizable group and a radical photopolymerization initiator. A siloxane resin has high transparency and little coloration due to heating, so that a cured film having a high transmittance can be formed by cross-linking. In addition, since it has silanol groups, the glass reinforcing material is easily embedded in microcracks generated in the tempered glass substrate due to the interaction between the silanol groups with the tempered glass substrate, and the strength of the glass can be improved. Furthermore, by containing silica particles, the silanol condensation reaction between the siloxane resin and the silica particles increases the degree of cross-linking of the cured film, and significantly improves the glass strength. Similarly, when the siloxane resin has a radically polymerizable group and the glass reinforcing material contains a photoradical polymerization initiator, the photoradical polymerization reaction increases the degree of cross-linking of the cured film and greatly improves the glass strength. can be made Furthermore, by setting the film thickness and transmittance of the cured film within the above ranges, both glass strength and transmittance can be achieved at high levels.

The tempered glass substrate in the present invention refers to a tempered glass substrate, and preferably has a compressive stress layer on the glass surface. As described above, conventional tempered glass substrates have a problem that the strength of the glass is reduced due to microcracks when they are cut into small pieces from a large tempered glass substrate. , can solve such problems.

Examples of methods for forming a compressive stress layer include a physical strengthening method that utilizes expansion and contraction of glass by heating and cooling, a chemical strengthening method that exchanges alkali ions in glass with other alkali ions having a larger ionic radius, and the like. Are known. All of these methods are known, and any method can be selected. In the case of a thin tempered glass substrate such as a touch panel cover glass, glass tempered by a chemical strengthening method, so-called chemically tempered glass, is preferable. Among the chemically strengthened glasses, aluminosilicate chemically strengthened glass, soda lime chemically strengthened glass, and the like are more preferable. Co., Ltd.) and the like.

The thickness of the tempered glass substrate is preferably 0.1 to 2.0 mm. By setting the thickness of the tempered glass substrate to 0.1 mm or more, the strength of the glass can be further improved. On the other hand, by setting the thickness of the tempered glass substrate to 2.0 mm or less, it can be easily cut into small pieces. Moreover, the tempered glass substrate can be made lighter.

The glass-reinforced substrate of the present invention has a cured film made of a crosslinked product of a glass-reinforced material. The glass reinforcing material contains a siloxane resin and silica particles (first aspect), or contains a siloxane resin having a radically polymerizable group and a radical photopolymerization initiator (second aspect).

First, the glass-reinforced material of the first aspect will be explained. The glass reinforcing material of the first aspect contains siloxane resin and silica particles, and may further contain other components. As described above, by containing a siloxane resin and silica particles, it is possible to achieve both high glass strength and high transmittance. In addition, the silanol condensation reaction between the siloxane resin and the silica particles promotes cross-linking, and the pencil hardness, Young's modulus and compressive stress of the cured film can be improved. Furthermore, by containing silica particles in the first aspect, it is possible to reduce the difference in refractive index between the tempered glass substrate and the cured film, thereby reducing unevenness caused by variations in the thickness of the cured film.

A siloxane resin refers to a polymer having a repeating unit having a siloxane skeleton, and is preferably a hydrolyzed condensate of an organosilane compound. However, when the siloxane resin has an oxetanyl group, it shall be classified as a "siloxane compound having an oxetanyl group" described later. The weight-average molecular weight (Mw) of the siloxane resin is preferably 2,000 to 7,000 from the viewpoint of improving coating properties. Here, the Mw of the siloxane resin refers to a polystyrene conversion value measured by gel permeation chromatography (GPC).

The siloxane resin in the invention preferably has a radically polymerizable group. By having a radically polymerizable group together with a photoradical polymerization initiator described later, the degree of crosslinking of the cured film is increased by the progress of radical polymerization reaction by radicals generated by light irradiation, and the glass strength can be further improved.

Examples of radically polymerizable groups include vinyl groups, α-methylvinyl groups, allyl groups, styryl groups, and (meth)acryloyl groups. A (meth)acryloyl group is preferred from the viewpoint of increasing the degree of cross-linking of the cured film.

As the siloxane resin having a radically polymerizable group, a hydrolytic condensate of an organosilane compound having a radically polymerizable group is preferred. A hydrolytic condensate of an organosilane compound having a radically polymerizable group and another organosilane compound may also be used. Organosilane compounds having a radically polymerizable group include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinyl methyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styrylmethyldimethoxysilane, p-styryl methyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and the like. You may use 2 or more types of these. Among these, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane are used from the viewpoint of further increasing the degree of crosslinking of the cured film. is preferred.

Other organosilane compounds include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Diethyldimethoxysilane, n-Propyltrimethoxysilane, Isopropyltrimethoxysilane, Diisopropyldimethoxysilane, n-Butyltrimethoxysilane, Isobutyltrimethoxysilane, Isobutyltriethoxysilane, Diisobutyldimethoxysilane , n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-decyltri ethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N -(1,3-dimethylbutylidene)-3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3- Ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, bis(3-(triethoxysilyl)propyl ) disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride and the like. You may use 2 or more types of these.

A siloxane resin can be obtained by hydrolyzing and condensing an organosilane compound. For example, it can be obtained by hydrolyzing an organosilane compound and then subjecting the obtained silanol compound to a condensation reaction in the presence or absence of a solvent.

Various conditions for the hydrolysis reaction can be appropriately set in consideration of the reaction scale, the size and shape of the reaction vessel, and the like. For example, it is preferable to add an acid catalyst and water to an organosilane compound in a solvent over 1 to 180 minutes, and then react the mixture at room temperature to 110° C. for 1 to 180 minutes. By carrying out the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 30-105°C.

The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. As the acid catalyst, an acidic aqueous solution containing formic acid, acetic acid and phosphoric acid is preferred. The amount of the acid catalyst to be added is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of all the organosilane compounds used in the hydrolysis reaction. By setting the amount of the acid catalyst within the above range, the hydrolysis reaction can proceed more efficiently.

After the silanol compound is obtained by the hydrolysis reaction of the organosilane compound, the reaction solution is preferably heated at 50° C. or more and the boiling point of the solvent or less for 1 to 100 hours for condensation reaction. Further, reheating or addition of a base catalyst may be performed in order to increase the degree of polymerization of the polysiloxane.

Examples of the solvent used for the hydrolysis reaction of the organosilane compound and the condensation reaction of the silanol compound include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, and 4-methyl-2-pentanol. , 3-methyl-2-butanol, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol; ethylene glycol, Glycols such as propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene ethers such as glycol dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone; amides such as dimethylformamide and dimethylacetamide Group; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, lactic acid acetates such as butyl; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane; Diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether from the viewpoint of further improving the transmittance and crack resistance of the cured film. , propylene glycol monobutyl ether, γ-butyrolactone and the like are preferably used.

When a solvent is produced by the hydrolysis reaction, hydrolysis can be carried out without a solvent. After completion of the reaction, it is also preferable to add a solvent to adjust the concentration to be suitable as a glass reinforcing material. Further, depending on the purpose, after hydrolysis, an appropriate amount of the alcohol produced may be distilled off under heating and/or under reduced pressure, and then a suitable solvent may be added.

The amount of solvent used in the hydrolysis reaction is preferably 80 to 500 parts by weight with respect to 100 parts by weight of all organosilane compounds. By setting the amount of the solvent within the above range, the hydrolysis reaction can proceed more efficiently.

Moreover, the water used for the hydrolysis reaction is preferably ion-exchanged water. The amount of water is preferably 1.0 to 4.0 mol per 1 mol of silane atoms.

From the viewpoint of further improving the transmittance and compressive stress of the cured film, the content of the siloxane resin in the glass-reinforced material of the first aspect is preferably 15% by weight or more, more preferably 25% by weight or more, based on the solid content. On the other hand, from the viewpoint of further improving the glass strength, the content of the siloxane resin is preferably 90% by weight or less, more preferably 80% by weight or less in the solid content.

The average particle size of the silica particles is preferably 1 to 200 nm, more preferably 1 to 70 nm, from the viewpoint of further improving the transmittance of the cured film. Here, the average particle size of silica particles can be determined by a dynamic light scattering method. Specifically, a dispersion liquid having a silica particle concentration of 10 to 30% by weight is irradiated with light having a wavelength of 780 nm by a semiconductor laser, and after measuring the scattered light, frequency analysis is performed by the FFT-heterodyne method. Particle size can be determined.

Silica particles include, for example, sicastar (manufactured by Corefront Co., Ltd.) and "Reolosil" (registered trademark) (manufactured by Tokuyama Corporation). These may be pulverized or dispersed using a dispersing machine such as a bead mill. Silica particle dispersions include, for example, IPA-ST, MIBK-ST, IPA-ST-L, IPA-ST-ZL, PGM-ST, PMA-ST (all manufactured by Nissan Chemical Industries, Ltd.), " Oscar” (registered trademark) 101, “Oscar” 105, “Oscar” 106, “Cataloid” (registered trademark)-S (all manufactured by Nikki Shokubai Kasei Co., Ltd.), “Quatron” (registered trademark) PL-1- IPA, PL-1-TOL, PL-2L-PGME, PL-2L-MEK, PL-2L, GP-2L (all manufactured by Fuso Chemical Industry Co., Ltd.) and the like. You may contain 2 or more types of these.

The content of silica particles in the first aspect of the glass-reinforced material is preferably 10% by weight or more, more preferably 20% by weight or more in the solid content, from the viewpoint of further improving the glass strength and reducing unevenness. On the other hand, from the viewpoint of further improving the transmittance of the cured film and the adhesion to the glass substrate, the content of silica particles is preferably 50% by weight or less, more preferably 40% by weight or less in the solid content.

The glass reinforcing material of the first aspect preferably further contains a photoradical polymerization initiator, which will be described later, and in combination with a siloxane resin having a radically polymerizable group, the degree of cross-linking of the cured film is increased by a photoradical polymerization reaction. can be increased, and the glass strength can be further improved. In this case, the content of the photoradical polymerization initiator in the glass-reinforced material of the first aspect is 0.5% by weight in the solid content from the viewpoint of sufficiently advancing the reaction of the radically polymerizable groups to further improve the glass strength. The above is preferable, and 1% by weight or more is more preferable. On the other hand, the content of the radical photopolymerization initiator is preferably 20% by weight or less, more preferably 10% by weight or less in the solid content, from the viewpoint of further improving the transmittance of the cured film.

The glass-reinforced material of the first aspect may further contain various additives described below.

Next, the glass-reinforced material of the second aspect will be explained. The glass reinforcing material of the second aspect contains a siloxane resin having a radically polymerizable group and a radical photopolymerization initiator, and may further contain other components. As described above, by containing a siloxane resin having a radically polymerizable group and a radical photopolymerization initiator, it is possible to achieve both high levels of glass strength and transmittance.

Examples of the siloxane resin having a radically polymerizable group include those exemplified in the first aspect.

The content of the siloxane resin having a radically polymerizable group in the glass-reinforced material of the second aspect is preferably 15% by weight or more, preferably 25% by weight, based on the solid content, from the viewpoint of further improving the transmittance and compressive stress of the cured film. The above is more preferable. On the other hand, from the viewpoint of further improving the glass strength, the content of the siloxane resin having a radically polymerizable group is preferably 90% by weight or less, more preferably 85% by weight or less in the solid content.

Examples of photoradical polymerization initiators include alkylphenone photoradical polymerization initiators such as α-aminoalkylphenone photoradical polymerization initiators and α-hydroxyalkylphenone photoradical polymerization initiators; acylphosphine oxide photoradicals; Polymerization initiator; oxime ester-based photoradical polymerization initiator; benzophenone-based photoradical polymerization initiator; oxanthone-based photoradical polymerization initiator; imidazole-based photoradical polymerization initiator; benzothiazole-based photoradical polymerization initiator; Radical polymerization initiator; carbazole-based radical photopolymerization initiator; triazine-based photoradical polymerization initiator; benzoic acid ester-based photoradical polymerization initiator; phosphorus-based photoradical polymerization initiator; are mentioned. You may contain 2 or more types of these.

Among these, α-aminoalkylphenone-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, and oxime ester-based photoradical polymerization initiators are used from the viewpoint of further increasing the degree of crosslinking of the cured film and further improving the glass strength. A benzophenone photoradical polymerization initiator having an amino group and a benzoic acid ester photoradical polymerization initiator having an amino group are preferred.

Examples of α-aminoalkylphenone photoradical polymerization initiators include 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methyl benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and the like . Examples of acylphosphine oxide photoradical polymerization initiators include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxy benzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide and the like. Examples of oxime ester photoradical polymerization initiators include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)- 2-(O-benzoyloxime)], 1-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) and the like. Benzophenone photoradical polymerization initiators having an amino group include, for example, 4,4-bis(dimethylamino)benzophenone and 4,4-bis(diethylamino)benzophenone. Benzoic acid ester photoradical polymerization initiators having an amino group include, for example, ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, and ethyl p-diethylaminobenzoate.

The content of the photoradical polymerization initiator in the glass-reinforced material of the second aspect is preferably 0.5% by weight or more in the solid content from the viewpoint of sufficiently advancing the reaction of the radically polymerizable groups to further improve the glass strength. , more preferably 1% by weight or more. On the other hand, the content of the radical photopolymerization initiator is preferably 20% by weight or less, more preferably 10% by weight or less in the solid content, from the viewpoint of further improving the transmittance of the cured film.

The glass reinforcing material of the second aspect preferably further contains a compound having two or more radically polymerizable groups. By containing a compound having two or more radically polymerizable groups, the glass strength can be further improved by a radical polymerization reaction with the radically polymerizable groups contained in the siloxane resin. In addition, the crosslinking of the siloxane resin can be promoted, and the pencil hardness, Young's modulus and compressive stress of the cured film can be improved.

Examples of the radically polymerizable group include those exemplified as the radically polymerizable group possessed by the siloxane resin.

Polyfunctional (meth)acrylates are preferred as compounds having two or more radically polymerizable groups. Polyfunctional (meth)acrylate refers to a compound having two or more (meth)acrylate groups, for example, 2,2-[9H-fluorene-9,9-diylbis(1,4-phenylene)bisoxy]diethanol Di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate , glycerin di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, Compounds having two (meth)acrylate groups such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate; 2-Hydroxyethyl)isocyanuric acid ester, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate , ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate and the like. You may contain 2 or more types of these.

The content of the compound having two or more radically polymerizable groups in the glass reinforcing material of the second aspect is preferably 5% by weight or more in the solid content from the viewpoint of increasing the degree of crosslinking of the cured film and further improving the glass strength. , more preferably 10% by weight or more. On the other hand, the content of the compound having two or more radically polymerizable groups is preferably 50% by weight or less, more preferably 30% by weight or less in the solid content, from the viewpoint of improving the compressive stress of the cured film.

The glass reinforcing material of the second aspect preferably further contains the silica particles described above. By containing silica particles, both glass strength and transmittance can be achieved at higher levels. In addition, the silanol condensation reaction between the siloxane resin and the silica particles promotes cross-linking, and the pencil hardness, Young's modulus and compressive stress of the cured film can be improved. Further, by containing silica particles, it is possible to reduce the difference in refractive index between the tempered glass substrate and the cured film, thereby reducing unevenness caused by variations in the thickness of the cured film. The content of the silica particles is preferably 10% by weight or more, more preferably 20% by weight or more, based on the solid content, from the viewpoint of further improving the glass strength and reducing unevenness. On the other hand, from the viewpoint of further improving the transmittance of the cured film and the adhesion to the glass substrate, the content of silica particles is preferably 50% by weight or less, more preferably 40% by weight or less in the solid content.

The glass reinforcing materials of the first aspect and the second aspect may contain a siloxane compound having an oxetanyl group. By containing the siloxane compound having an oxetanyl group, the compressive stress of the cured film is alleviated by the ring-opening reaction of the oxetane ring, and the adhesion between the tempered glass substrate and the cured film can be improved.

Examples of the siloxane compound having an oxetanyl group include compounds represented by the following general formula (1).

In general formula (1) above, R ¹ to R ⁴ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a group represented by general formula (2) below. However, at least one of R ¹ to R ⁴ is a group represented by the following general formula (2). w represents an integer of 1-10. From the viewpoint of reactivity, the alkyl group preferably has 1 to 6 carbon atoms, and the cycloalkyl group preferably has 3 to 6 carbon atoms.

In general formula (2) above, R ⁵ to R ⁹ each represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a perfluoroalkyl group having 1 to 4 carbon atoms. p represents an integer of 1 to 6;

The siloxane compound represented by the general formula (1) can be obtained by hydrolyzing an alkoxysilane compound having an oxetanyl group, optionally together with an alkoxysilane compound having no oxetanyl group.

Examples of alkoxysilane compounds having an oxetanyl group include (oxetan-3-yl)methyltrimethoxysilane, (oxetan-3-yl)methyltriethoxysilane, (oxetan-3-yl)methyltri-n-propyloxysilane. , (oxetan-3-yl)methyltri-i-propyloxysilane, (oxetan-3-yl)methyltriacetoxysilane, (oxetan-3-yl)methylmethyldimethoxysilane, (oxetan-3-yl)methylmethyldisilane Ethoxysilane, (oxetan-3-yl)methylmethyldi-n-propyloxysilane, (oxetan-3-yl)methylmethyldi-i-propyloxysilane, (oxetan-3-yl)methylmethyldiacetoxysilane, (oxetane-3 -yl)methylethyldimethoxysilane, (oxetan-3-yl)methylethyldiethoxysilane, (oxetan-3-yl)methylethyldi-n-propyloxysilane, (oxetan-3-yl)methylethyldi-i-propyloxysilane , (oxetan-3-yl)methylethyldiacetoxysilane, (oxetan-3-yl)methylphenyldimethoxysilane, (oxetan-3-yl)methylphenyldiethoxysilane, (oxetan-3-yl)methylphenyldi- n-propyloxysilane, (oxetan-3-yl)methylphenyldi-i-propyloxysilane, (oxetan-3-yl)methylphenyldiacetoxysilane, di(oxetan-3-yl)methyldimethoxysilane, di( Oxetan-3-yl)methyldiethoxysilane, di(oxetan-3-yl)methyldi-n-propyloxysilane, di(oxetan-3-yl)methyldi-i-propyloxysilane, di(oxetan-3-yl) ) methyldiacetoxysilane, di(oxetan-3-yl)methylmethylmethoxysilane, di(oxetan-3-yl)methylmethylethoxysilane, di(oxetan-3-yl)methylmethyl-n-propyloxysilane, di (oxetan-3-yl)methylmethyl-i-propyloxysilane, di(oxetan-3-yl)methylmethylacetoxysilane, di(oxetan-3-yl)methylethylmethoxysilane, di(oxetan-3-yl) methylethylethoxysilane, di(oxetan-3-yl)methylethyl-n-propyloxysilane, di(oxetane-3 -yl)methylethyl-i-propyloxysilane, di(oxetan-3-yl)methylethylacetoxysilane, di(oxetan-3-yl)methylphenylmethoxysilane, di(oxetan-3-yl)methylphenylethoxysilane , di(oxetan-3-yl)methylphenyl-n-propyloxysilane, di(oxetan-3-yl)methylphenyl-i-propyloxysilane, di(oxetan-3-yl)methylphenylacetoxysilane, tri( Oxetan-3-yl)methylmethoxysilane, tri(oxetan-3-yl)methylethoxysilane, tri(oxetan-3-yl)methyl-n-propyloxysilane, tri(oxetan-3-yl)methyl-i- propyloxysilane, tri(oxetan-3-yl)methylacetoxysilane, and the like. You may use 2 or more types of these.

Examples of alkoxysilane compounds having no oxetanyl group include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyl triethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldi Ethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, triphenylsilanol, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane Silane, Triethylethoxysilane, Tripropylmethoxysilane, Tripropylethoxysilane, Trimethylsilylacetate, Trimethylsilylbenzoate, Triethylsilylacetate, Triethylsilylbenzoate, Benzyldimethylmethoxysilane, Benzyldimethylethoxysilane, Diphenylmethoxymethylsilane, Diphenylethoxymethylsilane, acetyltriphenylsilane, ethoxytriphenylsilane, hexamethyldisiloxane, hexaethyldimethyldisiloxane, hexapropyldisiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisiloxane, 1,3-diphenyl -1,1,3,3-tetramethyldisiloxane, 1,3-dimethyl-1,1,3,3-tetraphenyldisiloxane, and the like. You may use 2 or more types of these.

Examples of the siloxane compound having an oxetanyl group include "Aron Oxetane" (registered trademark) OXT-191 (trade name, manufactured by Toagosei Co., Ltd.) (R ¹ to R ⁴ in general formula (1) are (3-ethyl -3-oxetanyl)methyl group, w averages 5), compounds represented by the following general formula (3) or (6), and the like. You may contain 2 or more types of these.

In the general formula (3), R ¹⁰ and R ¹² are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, represents a furyl group or a thienyl group. R ¹¹ represents a group represented by the following general formula (4). d represents an integer of 0 to 3; Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. The fluoroalkyl group having 1 to 6 carbon atoms includes, for example, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group and the like. Examples of the aryl group having 6 to 18 carbon atoms include phenyl group and naphthyl group.

In general formula (4) above, R ¹³ , R ¹⁵ , R ¹⁶ and R ¹⁸ represent an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 18 carbon atoms, and R ¹⁴ and R ¹⁷ each have 1 carbon atom. It represents an alkyl group of ∼4, an aryl group of 6 to 18 carbon atoms, or a group represented by the following general formula (5). u represents an integer from 0 to 200; When u is 2 or more, multiple R ¹⁴ and R ¹⁷ may be the same or different.

In general formula (5) above, R ¹⁹ to R ²³ each represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 18 carbon atoms. Z represents an integer from 0 to 100; When z is 2 or more, multiple R ¹⁹ and R ²³ may be the same or different.

In the general formula (6), R ²⁴ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a furyl group, or represents a thienyl group, and R ²⁵ represents a 3- to 10-valent organic group. Examples thereof include linear, branched or cage-like polysiloxane-containing groups represented by any of the following general formulas (7) to (9). In general formula (6), j represents an integer of 3 to 10 equal to the valence of ^R25 .

As the siloxane compound having a cage-shaped oxetanyl group represented by the general formula (9), for example, silsesquioxane derivatives OX-SQ TX-100, OX-SQ SI-20 (trade name, Toagosei Co., Ltd.) and the like.

Among these, those having a plurality of oxetanyl groups are preferred. By having a plurality of oxetanyl groups, the compression stress relaxation effect of the cured film due to the ring-opening reaction of the oxetane ring is improved, and the adhesion to the glass substrate can be further improved.

The content of the siloxane compound having an oxetanyl group in the glass-reinforced material of the first aspect and the second aspect is 0.1 in the solid content from the viewpoint of further relaxing the compressive stress of the cured film and further improving adhesion. % by weight or more is preferable, and 0.5% by weight or more is more preferable. On the other hand, the content of the siloxane compound having an oxetanyl group is preferably 10% by weight or less, more preferably 6% by weight or less in the solid content, from the viewpoint of improving the compressive stress of the cured film and further improving the glass strength.

The glass reinforcing materials of the first aspect and the second aspect may contain a metal chelate compound represented by the following general formula (10). Since the metal chelate compound acts as a catalyst for the silanol condensation reaction of the siloxane resin, the degree of cross-linking of the cured film increases, and the glass strength can be further improved.

In general formula (10) above, M represents a metal atom, ^R26 represents hydrogen, an alkyl group, an aryl group or an alkenyl group, and ^R27 and ^R28 each independently represents a hydrogen, alkyl group, aryl group or alkenyl group. or represents an alkoxy group. However, the alkyl group, aryl group, alkenyl group or alkoxy group may be substituted with a substituent. e represents the valence of the metal atom M, and f represents an integer from 0 to e. From the viewpoint of reactivity, ef is preferably 0.

From the viewpoint of the transmittance of the cured film, the metal atom M is preferably titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, or calcium, and more preferably zirconium or aluminum.

Examples of R ²⁶ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- octyl group, n-nonyl group, n-decyl group, n-octadecyl group, phenyl group, vinyl group, allyl group, oleyl group and the like.

Examples of R ²⁷ and R ²⁸ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, phenyl group, vinyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-octadecyl group, benzyloxy group and the like.

Zirconium chelate compounds in which the metal atom M is zirconium include, for example, zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra(2, 2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetramethylacetoacetate, zirconium tetraethylacetoacetate, zirconium tetramethylmalonate, zirconium tetraethylmalonate, zirconium tetrabenzoylacetonate, zirconium tetradibenzoyl methanate, zirconium mono n-butoxyacetylacetonate bis(ethylacetoacetate), zirconium mono n-butoxyethylacetoacetate bis(acetylacetonate), zirconium mono n-butoxy tris(acetylacetonate), zirconium mono n-butoxy Tris(acetylacetonate), zirconium di(n-butoxy)bis(ethylacetoacetate), zirconium di(n-butoxy)bis(acetylacetonate), zirconium di(n-butoxy)bis(ethylmalonate), zirconium di(n-butoxy)bis(benzoylacetonate), zirconium di(n-butoxy)bis(dibenzoylmethanate) and the like.

Aluminum chelate compounds in which the metal atom M is aluminum include, for example, aluminum tris isopropoxide, aluminum tris n-propoxide, aluminum tris sec-butoxide, aluminum tris n-butoxide, aluminum trisphenoxide, aluminum tris acetylacetonate, aluminum Tris (2,2,6,6-tetramethyl-3,5-heptanedionate), aluminum trisethylacetoacetate, aluminum trismethylacetoacetate, aluminum trismethylmalonate, aluminum trisethylmalonate, aluminum ethylacetate di (isopropoxide), aluminum acetylacetonate) di(isopropoxide), aluminum methylacetoacetate di(isopropoxide), aluminum octadecylacetoacetate di(isopropylate), aluminum monoacetylacetonate bis(ethylacetoacetate) etc.

Among these, zirconium tetra-normal propoxide, zirconium tetra-normal butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra(2,2,6,6 -tetramethyl-3,5-heptanedionate), zirconium tetramethylmalonate, zirconium tetraethylmalonate, zirconium tetraethylacetoacetate, zirconium di-n-butoxy bis(ethylacetoacetate), zirconium mono-n-butoxy acetylacetonate bis(ethyl acetoacetate), aluminum trisacetylacetonate, aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate), aluminum trisethylacetoacetate, aluminum trismethylacetoacetate, aluminum trismethylmalonate , aluminum trisethylmalonate, aluminum ethylacetate di(isopropoxide), aluminum acetylacetonate) di(isopropoxide), aluminum methylacetoacetate di(isopropoxide), aluminum octadecylacetoacetate di(isopropylate), Aluminum monoacetylacetonate bis(ethylacetoacetate) is preferred.

The content of the metal chelate compound in the glass reinforcing material of the first aspect and the second aspect is 0.1% by weight or more in the solid content from the viewpoint of further improving the degree of crosslinking of the cured film and further improving the glass strength. is preferred, and 0.5% by weight or more is more preferred. On the other hand, the content of the metal chelate compound is preferably 10% by weight or less, more preferably 7% by weight or less in the solid content, from the viewpoint of the stability of the glass reinforcing material over time.

The glass reinforced material of the first aspect and the second aspect may contain an adhesion improver. By containing the adhesion improver, the adhesion between the cured film and the tempered glass substrate can be improved.

Adhesion improvers include, for example, silane coupling agents having functional groups such as vinyl groups, epoxy groups, styryl groups, (meth)acryloxy groups, and amino groups. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, p-thrityltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acrylate roxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3- aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, p-thrityltrimethoxysilane and the like are preferred.

The content of the adhesion improver in the glass reinforcing material of the first aspect and the second aspect is preferably 0.1% by weight or more in the solid content from the viewpoint of further improving the adhesion between the cured film and the tempered glass substrate. , more preferably 0.5% by weight or more. On the other hand, from the viewpoint of the stability of the glass reinforcing material over time, the content of the adhesion improver is preferably 10% by weight or less, more preferably 5% by weight or less in the solid content.

The glass reinforcing materials of the first aspect and the second aspect may contain various cross-linking agents to promote or facilitate cross-linking of the glass reinforcing material. Examples of cross-linking agents include nitrogen-containing organic substances, silicone resin cross-linking agents, isocyanate compounds and their polymers, methylolated melamine derivatives, and methylolated urea derivatives. You may contain 2 or more types of these. Among them, a methylolated melamine derivative and a methylolated urea derivative are preferably used from the viewpoint of crosslinkability and stability of the glass reinforcing material over time.

Curing of the siloxane resin is accelerated by acid, so the glass reinforcing material of the first and second embodiments may contain a curing catalyst such as a thermal acid generator or a photoacid generator. Examples of thermal acid generators include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI-110L, SI -145L, SI-150L, SI-160L, SI-180L (manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate , 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate, 4-methoxycarbonyloxyphenyldimethylsulfonium trifluoromethane sulfonate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium trifluoromethanesulfonate and the like. Examples of photoacid generators include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, NAI-1002, NAI -1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106 , PAI-1001 (manufactured by Midori Chemical Co., Ltd.), SP-077, SP-082 (manufactured by ADEKA Co., Ltd.), TPS-PFBS (manufactured by Toyo Gosei Co., Ltd.), MDT (manufactured by , Heraeus), WPAG-281, WPAG-336, WPAG-339, WPAG-342, WPAG-344, WPAG-350, WPAG-370, WPAG-372, WPAG-449, WPAG-469, WPAG-505, WPAG-506 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

The content of the curing catalyst such as the thermal acid generator and the photoacid generator in the glass reinforcing material of the first aspect and the second aspect is from the viewpoint of further improving the degree of crosslinking of the cured film and further improving the glass strength. , preferably 0.1% by weight or more, more preferably 0.3% by weight or more in the solid content. On the other hand, from the viewpoint of the stability of the glass reinforcing material over time, the content of the curing catalyst such as the thermal acid generator or the photoacid generator is preferably 5% by weight or less, more preferably 3% by weight or less in the solid content.

The glass reinforcing materials of the first aspect and the second aspect may contain a polymerization inhibitor. By containing a polymerization inhibitor, the stability over time of the glass reinforcing material can be improved. Examples of polymerization inhibitors include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di(t-butyl)-p-cresol, phenothiazine and 4-methoxyphenol.

The content of the polymerization inhibitor in the glass-reinforced materials of the first aspect and the second aspect is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, based on the solid content. On the other hand, from the viewpoint of not inhibiting cross-linking of the cured film, the content of the polymerization inhibitor is preferably 5% by weight or less, more preferably 1% by weight or less in the solid content.

The glass reinforcing materials of the first aspect and the second aspect may contain an ultraviolet absorber. By containing the ultraviolet absorber, the light resistance of the cured film of the glass reinforcing material can be improved. Benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are preferably used as the ultraviolet absorber in terms of transparency and non-coloring properties.

Examples of benzotriazole compounds include 2-(2H benzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-t-pentylphenol, 2-(2H benzotriazole -2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2'- hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole and the like.

Benzophenone compounds include, for example, 2-hydroxy-4-methoxybenzophenone.

Examples of triazine compounds include 2-(4,6-diphenyl-1,3,5triazin-2-yl)-5-[(hexyl)oxy]-phenol and the like.

The content of the ultraviolet absorber in the glass reinforcing material of the first aspect and the second aspect is preferably 10% by weight or less from the viewpoint of improving the adhesion to the substrate such as glass that serves as the base of the cured film, 5% by weight or less is more preferable.

The glass reinforcing material of the first aspect and the second aspect may contain a solvent. By containing a solvent, each component can be uniformly dissolved. Examples of solvents include aliphatic hydrocarbons, carboxylic acid esters, ketones, ethers, and alcohols. You may contain 2 or more types of these. A compound having an alcoholic hydroxyl group and a cyclic compound having a carbonyl group are preferable from the viewpoint of uniformly dissolving each component and improving the transparency of the resulting coating film.

Examples of compounds having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4 -methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether , 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, and the like. Among these, diacetone alcohol and 3-methyl-3-methoxy-1-butanol are preferred from the viewpoint of storage stability.

Specific examples of cyclic compounds having a carbonyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone and cycloheptanone. Among these, γ-butyrolactone is particularly preferably used.

Aliphatic hydrocarbons include, for example, xylene, ethylbenzene, solvent naphtha, and the like.

Examples of carboxylic acid esters include benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-3-methyl-butyl acetate, and diethyl oxalate. , ethyl acetoacetate, cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentyl propionate, propylene glycol monomethyl ether propionate, propylene glycol Monoethyl ether acetate, ethyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate and the like.

Ketones include, for example, cyclopentanone, cyclohexanone, and the like.

Examples of ethers include aliphatic ethers such as propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether and dipropylene glycol monomethyl ether.

From the viewpoint of moderately adjusting the volatility and drying characteristics when applying the glass reinforcing materials of the first aspect and the second aspect to the glass substrate and improving the coating properties, the boiling point under atmospheric pressure is 150 ° C. or higher and 250 ° C. C. or less and a solvent with a boiling point of less than 150.degree. C. under atmospheric pressure. The boiling point of the solvent having a boiling point of 150° C. or higher and 250° C. or lower under atmospheric pressure is more preferably 150° C. or higher and 200° C. or lower.

Solvents having a boiling point of 150° C. or higher and 250° C. or lower under atmospheric pressure include, for example, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol mono-t-butyl ether, 3 -Methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, benzyl acetate, ethyl benzoate, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-3-methyl -butyl acetate, diethyl oxalate, ethyl acetoacetate, cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, isopentyl propionate, propylene glycol monomethyl ether propionate, γ -butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone and the like. Among these, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), 3-methyl-3-methoxy-1-butanol, 3-methoxy-3-methyl-butyl acetate, 3-methoxy-butyl acetate , γ-butyrolactone are particularly preferably used.

Solvents having a boiling point of less than 150° C. under atmospheric pressure include, for example, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, butanol, isobutanol, n-propyl alcohol, ethyl acetate and the like. Among these, propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are particularly preferably used.

The glass reinforcing material of the first aspect and the second aspect may contain a surfactant. By containing a surfactant, it is possible to improve flowability during application. Examples of surfactants include fluorine-based surfactants; silicone-based surfactants; fluorine-containing thermally decomposable surfactants; polyether-modified siloxane-based surfactants; polyalkylene oxide-based surfactants; Acrylate-based surfactants; anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; lauryldimethylamine oxide and laurylcarboxymethyl amphoteric surfactants such as hydroxyethylimidazolium betaine; and nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate. You may contain 2 or more types of these.

Among these, fluorine-based surfactants, silicone-based surfactants, and fluorine-containing thermally decomposable interfaces are used from the viewpoint of suppressing poor coating properties such as repellency and reducing surface tension to suppress unevenness during drying of the coating film. The active agent is preferably a polyether-modified siloxane-based surfactant, more preferably a fluorine-containing thermally decomposable surfactant.

Commercially available fluorosurfactants include, for example, "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (manufactured by DIC Corporation). ), NBX-15, FTX-218 (manufactured by Neos Co., Ltd.) and the like. Examples of commercially available silicone-based surfactants include "BYK" (registered trademark)-333, BYK-301, BYK-331, BYK-345, and BYK-307 (manufactured by BYK-Chemie Japan Co., Ltd.). be done. Commercially available fluorine-containing thermally decomposable surfactants include, for example, “Megafac” (registered trademark) DS-21 (manufactured by DIC Corporation). Commercially available polyether-modified siloxane-based surfactants include, for example, “BYK” (registered trademark)-345, BYK-346, BYK-347, BYK-348, BYK-349 (manufactured by BYK-Chemie Japan Co., Ltd.). (manufactured by Nissin Kagaku Kogyo Co., Ltd.), and "Silface" (registered trademark) SAG002, SAG005, SAG0503A and SAG008 (manufactured by Nissin Chemical Industry Co., Ltd.).

Next, a method for producing a glass-reinforced material will be described. As a method for producing a glass reinforcing material, a siloxane resin and, if necessary, a predetermined amount of other raw materials such as silica particles, a photoradical polymerization initiator, a compound having two or more radical polymerizability, a solvent, etc. are mixed and stirred. method is common.

The glass-reinforced substrate of the present invention has a cured film made of a crosslinked product of the glass-reinforced material described above. The cured film functions as a glass reinforcing film and can improve glass strength. Here, the “crosslinked product” in the present invention refers to a product in which the siloxane resin in the glass reinforcing material is crosslinked by a condensation reaction (thermal crosslinking) of silanol groups or a radical addition reaction (photocrosslinking) of radically polymerizable groups. . By IR analysis of the cured film, it is possible to determine whether or not the cured film is crosslinked from the presence or absence of peaks of silanol groups and double bonds.

The film thickness of the cured film is 0.5 to 10 μm. If the film thickness is less than 0.5 μm, the effect of improving the strength of the glass becomes insufficient and the strength of the glass decreases. From the viewpoint of further improving the glass strength, the film thickness is preferably 1 μm or more. On the other hand, if the film thickness is more than 10 μm, the transmittance is lowered. In addition, the film stress of the cured film increases, and the adhesion to the tempered glass substrate decreases. From the viewpoint of further improving the transmittance and adhesion to the tempered glass substrate, the film thickness is preferably 5 μm or less.

The transmittance of the cured film at a wavelength of 400 nm is 90% or more. When the glass-reinforced substrate of the present invention is used for a display terminal, it preferably has high transmittance in the visible light wavelength region (400 to 700 nm). In the present invention, as the transmittance in the visible light wavelength region, attention is paid to the transmittance at a short wavelength of 400 nm. If the transmittance is less than 90%, the luminance of the display portion of the display terminal is lowered, and the cured film becomes more yellowish, resulting in lower color reproducibility of the displayed content. By setting the transmittance of the cured film to 90% or more, color reproducibility can be improved when the glass-reinforced substrate of the present invention is used for a display terminal such as a smart phone. From the viewpoint of further improving the color reproducibility of the display terminal, the transmittance is preferably 94% or more. The transmittance of the cured film at a wavelength of 400 nm can be measured using an ultraviolet-visible spectrophotometer. In addition, as a method for setting the transmittance of the cured film at a wavelength of 400 nm to the above range, for example, using the glass reinforcing material having the preferable composition described above, and setting the film thickness of the cured film to the above range. .

The pencil hardness of the cured film is preferably 2H or more. By setting the pencil hardness to 2H or more, cracks are less likely to occur on the surface of the cured film, and the strength of the glass can be further improved. More preferably, the pencil hardness is 3H or higher. The pencil hardness of the cured film can be measured by tracing the cured film with a pencil having a predetermined hardness under a load of 750 g at an angle of 45 degrees and observing the presence or absence of scratches. As a method for adjusting the pencil hardness to the range described above, for example, use of the glass reinforcing material having the preferred composition described above may be used.

Young's modulus of the cured film is preferably 7.0 GPa or more. By setting the Young's modulus of the cured film to 7.0 GPa or more, the cured film can suppress deformation of the tempered glass even when an impact is applied to the glass-reinforced substrate, thereby further improving the strength of the glass. Young's modulus is more preferably 9.0 GPa or more. The Young's modulus of the cured film can be measured using an ultra-microhardness tester. As a method for adjusting the Young's modulus to the range described above, for example, use of the glass reinforcing material having the preferred composition described above may be used.

The compressive stress of the cured film is preferably 15-35 MPa. By setting the compressive stress of the cured film to 15 MPa or more, the deformation of the strengthened glass substrate is reduced because the compressive stress of the strengthened glass substrate is alleviated by the compressive stress of the cured film even when the glass strengthened substrate receives an impact. However, cracking of the glass can be suppressed, and the strength of the glass can be further improved. More preferably, the compressive stress is 25 MPa or more. On the other hand, by setting the compressive stress to 35 MPa or less, the adhesion between the tempered glass substrate and the cured film can be improved, and the strength of the glass can be further improved. The compressive stress of the cured film can be measured using a thin film stress measuring device. In addition, as a method for adjusting the compressive stress to the range described above, for example, the use of the glass reinforcing material having the preferable composition described above may be used.

Next, a method for manufacturing a glass-reinforced substrate of the present invention will be described. The glass-reinforced substrate of the present invention can be obtained, for example, by forming a cured film made of a crosslinked product of the above-described glass-reinforced material on a tempered glass substrate. It is preferable to form a cured film by applying a glass reinforcing material onto a tempered glass substrate, drying the dried film, irradiating and developing the dried film, if necessary, and then heat-treating the dried film. Each step will be described in more detail below.

First, a glass reinforcing material is applied onto a tempered glass substrate to obtain a coating film. Examples of coating methods include spin coating using a spinner, spray coating, inkjet coating, die coating, and roll coating. The film thickness of the coating film varies depending on the coating method and the like, but can be appropriately selected so that the film thickness of the cured film is 0.5 to 10 μm.

The obtained coating film is dried to obtain a dry film. Examples of the drying method include heat drying, air drying, reduced pressure drying, and infrared irradiation. Examples of heat drying devices include ovens and hot plates. The drying temperature is preferably 50 to 150° C., and the drying time is preferably 1 minute to 1 hour.

It is preferable to irradiate the obtained dry film with actinic rays such as ultraviolet rays, visible rays, electron beams and X-rays to obtain an exposed film. Actinic rays may be irradiated through a mask having a desired pattern, or the entire surface of the dry film may be irradiated with actinic rays. When the glass reinforcing material contains a photoradical polymerization initiator, the cross-linking of the dry film can be promoted by irradiating with actinic rays. It is preferable to irradiate the glass-reinforced material of the present invention with i-line (365 nm), h-line (405 nm) and g-line (436 nm) of a mercury lamp.

Further, when the glass reinforcing material contains a radical polymerization initiator, the unexposed area is removed by developing with an alkaline developer or the like after irradiating actinic rays through a mask having a desired pattern, Negative patterns can also be obtained. Examples of alkaline compounds used in the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; ethylamine, n-propylamine, and the like. secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), choline quaternary ammonium salts such as; alcohol amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol and diethylaminoethanol; 1,5-diazabicyclo[4,3,0]-5-nonane, organic alkalis such as cyclic amines such as morpholine, and the like.

The concentration of the alkaline compound in the alkaline developer is preferably 0.02 to 1% by weight. In order to improve the pattern shape after development, a surfactant such as a nonionic surfactant may be added in an amount of 0.1 to 5% by weight. Furthermore, when the developer is an alkaline aqueous solution, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone, etc. may be added to the developer.

The developing method includes, for example, an immersion method, a spray method, a puddle method, and the like. The obtained pattern may be rinsed with pure water or the like.

By subjecting the obtained dry film, exposed film or pattern to heat treatment (post-baking), cross-linking of the siloxane resin proceeds and a cured film can be obtained. The heat treatment may be performed in air, in a nitrogen atmosphere, or in a vacuum. The heating temperature is preferably 150-300° C., and the heating time is preferably 0.25-5 hours. The heating temperature may be changed continuously or stepwise.

INDUSTRIAL APPLICABILITY The glass-reinforced substrate of the present invention can be suitably used for display devices such as smartphones and tablet PCs, vehicle-mounted displays, and cover glasses applied to the front surfaces of instrument panels.

EXAMPLES The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples. Examples 3, 9, 10 and 12 shall be read as Reference Examples 1, 2, 3 and 4, respectively.

<Evaluation method>
"Transmittance"
Glass tempering was carried out in the same manner as in each example and comparative example, except that the glass reinforcing material obtained in each example and comparative example was applied to a 5 cm square Tempax glass substrate instead of the aluminosilicate chemically strengthened glass substrate. A cured film comprising a crosslinked product of the material was produced. The obtained cured film on the Tempax glass substrate was measured for transmittance at a measurement wavelength of 400 nm using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation).

"village"
The tempered glass substrates obtained in each example and comparative example were visually observed under a fluorescent lamp and under a Na lamp, respectively, and the presence or absence of unevenness was evaluated according to the following criteria. From the viewpoint of industrial use, A and B were accepted.
A: Observation under a fluorescent lamp and Na lamp shows no unevenness.
B: No unevenness is observed in observation under a fluorescent lamp, but unevenness is observed in observation of the coating film under a Na lamp.
C: Unevenness is observed in observation under a fluorescent lamp.

"Pencil hardness"
Glass tempering was carried out in the same manner as in each example and comparative example, except that the glass reinforcing material obtained in each example and comparative example was applied to a 5 cm square Tempax glass substrate instead of the aluminosilicate chemically strengthened glass substrate. A cured film comprising a crosslinked product of the material was produced. The resulting cured film on the Tempax glass substrate was traced with a pencil having a predetermined hardness using a pencil hardness tester at a load of 750 g and an angle of 45 degrees, and the presence or absence of scratches was observed to determine the pencil hardness. was measured.

"Young's modulus"
Glass tempering was carried out in the same manner as in each example and comparative example, except that the glass reinforcing material obtained in each example and comparative example was applied to a 5 cm square Tempax glass substrate instead of the aluminosilicate chemically strengthened glass substrate. A cured film comprising a crosslinked product of the material was produced. For the resulting cured film on the Tempax glass substrate, using an ultra-micro hardness tester (manufactured by Fisher Instruments Co., Ltd.), in accordance with ISO-14577-1, unloading rate 0.5 mN, room temperature Young's modulus at 23°C was measured.

"compressive stress"
The glass-reinforced material obtained in each example and comparative example was applied to a 4-inch silicon wafer substrate instead of the aluminosilicate chemically strengthened glass substrate. A cured film made of the crosslinked product was produced. The cured film on the obtained silicone wafer was measured for film stress at room temperature of 23° C. using a thin film stress measuring device (manufactured by Toho Technology Co., Ltd.).

"Glass Strength"
A rigid ball weighing 225 g was dropped from a predetermined height on the opposite side of the cured film (on the side of the tempered glass substrate) of the glass-reinforced substrates obtained in each of the examples and comparative examples, and the presence or absence of cracks in the tempered glass was observed. . When no cracking was observed, the same evaluation was performed by increasing the drop height of the rigid ball, and the minimum height at which the tempered glass substrate cracked was measured. It can be said that the higher the height, the better the glass strength.

[Siloxane resin synthesis example 1]
47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, and 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic anhydride are placed in a 500 mL three-necked flask. ), 82.04 g (0.35 mol) of 3-acryloxypropyltrimethoxysilane, and 182.88 g of diacetone alcohol (hereinafter referred to as “DAA”) were charged, and immersed in an oil bath at 40 ° C. while stirring, adding 55% of water. An aqueous phosphoric acid solution prepared by dissolving 0.391 g of phosphoric acid (0.2 parts by mass based on the charged monomer) in 0.8 g was added with a dropping funnel over 10 minutes. After stirring at 40° C. for 1 hour, the temperature of the oil bath was set to 70° C., stirring was continued for 1 hour, and the temperature of the oil bath was increased to 115° C. over 30 minutes. After 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 2 hours (internal temperature: 100 to 110° C.). A total of 120 g of methanol and water, which are by-products, were distilled during the reaction. DAA was added to the obtained siloxane resin DAA solution so that the polymer concentration was 40% by mass to obtain a siloxane resin (PS-1) solution. The weight average molecular weight (hereinafter referred to as "Mw") of the obtained siloxane resin (PS-1) was measured by GPC and found to be 5,000 (converted to polystyrene).

[Synthesis example 2 of siloxane resin]
47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, and 99.36 g (0.40 mol) of 3-methacryloxypropyltrimethoxysilane are placed in a 500 mL three-necked flask. , 11.82 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane and 188.22 g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were charged and immersed in an oil bath at 40 ° C. while stirring. A phosphoric acid aqueous solution prepared by dissolving 0.397 g of phosphoric acid (0.2 parts by mass based on the charged monomer) in 54.0 g of water was added with a dropping funnel over 10 minutes. After stirring at 40° C. for 1 hour, the temperature of the oil bath was set to 70° C., stirring was continued for 1 hour, and the temperature of the oil bath was increased to 115° C. over 30 minutes. After 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 2 hours (internal temperature: 100 to 110° C.). A total of 120 g of methanol and water, which are by-products, were distilled during the reaction. DAA was added to the obtained DAA solution of the siloxane resin so that the polymer concentration was 40% by mass to obtain a siloxane resin (PS-2) solution. The Mw of the obtained siloxane resin (PS-2) was measured by GPC and found to be 3,000 (converted to polystyrene).

[Siloxane resin synthesis example 3]
54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, and 24 g (0.50 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane were placed in a 500 mL three-necked flask. 64 g (0.10 mol) and 163.35 g of DAA were charged, and while being immersed in an oil bath at 40 ° C. and stirred, 0.535 g of phosphoric acid (0.3 parts by mass based on the charged monomer) was dissolved in 54.0 g of water. An aqueous solution of phosphoric acid was added with a dropping funnel over 10 minutes. After stirring at 40° C. for 1 hour, the temperature of the oil bath was set to 70° C., stirring was continued for 1 hour, and the temperature of the oil bath was increased to 115° C. over 30 minutes. After 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 2 hours (internal temperature: 100 to 110° C.). A total of 120 g of methanol and water, which are by-products, were distilled during the reaction. DAA was added to the obtained DAA solution of the siloxane resin so that the polymer concentration was 40% by mass to obtain a siloxane resin (PS-3) solution. The Mw of the obtained siloxane resin (PS-3) was measured by GPC and found to be 5,000 (converted to polystyrene).

[Example 1]
1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) under yellow light (trade name “Irgacure” (registered trademark) OXE01, manufactured by BASF) 0 .64 g, 0.43 g of zirconium tetraacetylacetonate (trade name “Orgatics” (registered trademark) ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.), DAA (boiling point = 168 ° C.) 2.63 g, PGMEA (boiling point = 146°C) and 38.50g of 3-methyl-3-methoxy-1-butanol (boiling point = 174°C, hereinafter referred to as “MMB”) are dissolved in a mixed solvent to give an oxetanyl group-containing siloxane compound “Aron Oxetane "(registered trademark) OXT-191" 0.21 g, 3-aminopropyltrimethoxysilane (trade name "KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd.) 0.43 g, dipentaerythritol hexaacrylate and dipentaerythritol 4.26 g of a mixture with pentaacrylate (trade name ““KAYARAD” (registered trademark) DPHA” manufactured by Nippon Kayaku Co., Ltd.), 30% by weight dispersion of silica particles in PGMEA (average particle size = 20 to 30 nm, trade name “ PMA-ST" manufactured by Nissan Chemical Industries, Ltd.) 28.37 g, siloxane resin (PS-1) solution 21.28 g, fluorine-containing thermally decomposable surfactant (trade name "DS-21" manufactured by DIC Corporation) 0.20 g of a 5% by weight PGMEA solution (equivalent to a concentration of 100 ppm), and 0.20 g of a 5% by weight solution of PGMEA (concentration: equivalent to 100 ppm) was added and stirred. Filtration was then carried out with a 1.00 μm filter to prepare a glass-reinforced material C-1 with a solid concentration of 23% by weight.

On a 0.7 μm thick aluminosilicate chemically strengthened glass substrate (CORNING GORILLA GLASS 3 (“Gorilla Glass 3”) manufactured by Corning), the resulting glass reinforcing material C-1 was coated with a spin coater (MS manufactured by Mikasa Co., Ltd.). -A150), and then pre-baked for 2 minutes using a hot plate at 90° C. to obtain a pre-baked film. After that, it is exposed at 500 mJ/cm2 using an exposure machine "XG-5000" manufactured by Dainippon Screen Co., Ltd., and cured for 30 minutes using a hot air oven at 180 ° C., resulting in a crosslinked product of glass reinforcing material C-1. A cured film A-1 having a thickness of 2 μm was obtained. Table 2 shows the results of evaluation by the method described above.

[Example 2]
A cured film A-2 having a film thickness of 5 μm was prepared in the same manner as in Example 1, except that the film thickness of the cured film was changed to 5 μm by adjusting the rotation speed of spin coating. Table 2 shows the results of evaluation by the method described above.

[Example 3]
A cured film A-3 having a film thickness of 8 μm was prepared in the same manner as in Example 1, except that the film thickness of the cured film was changed to 8 μm by adjusting the rotation speed of spin coating. Table 2 shows the results of evaluation by the method described above.

[Example 4]
A cured film A-4 having a film thickness of 1 μm was produced in the same manner as in Example 1, except that the film thickness of the cured film was changed to 1 μm by adjusting the rotation speed of spin coating. Table 2 shows the results of evaluation by the method described above.

[Example 5]
A cured film A-5 having a film thickness of 0.5 μm was prepared in the same manner as in Example 1, except that the film thickness of the cured film was changed to 0.5 μm by adjusting the rotation speed of spin coating. Table 2 shows the results of evaluation by the method described above.

[Example 6]
Under a yellow light, 1.52 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name “Omnirad” (registered trademark) 819, manufactured by IGM), zirconium tetraacetylacetonate (trade name ““ Orgatics "(registered trademark) ZC-150" manufactured by Matsumoto Fine Chemical Co., Ltd.) 1.30 g is dissolved in a mixed solvent of 23.96 g DAA, 1.53 g PGMEA, and 14.80 g MMB, and a siloxane compound having an oxetanyl group "" Aron Oxetane "(registered trademark) OXT-191" 0.98 g, 3-aminopropyltrimethoxysilane (trade name "KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd.) 0.43 g, tris(2-hydroxyethyl) isocyanuric acid acrylic acid ester (trade name “Aronix” (registered trademark) M-315, manufactured by Toagosei Co., Ltd.) 4.35 g, PGMEA 30% by weight dispersion of silica particles (average particle size = 20 to 30 nm, trade name “ PMA-ST" manufactured by Nissan Chemical Industries, Ltd.) 28.99 g, siloxane resin (PS-1) solution 21.74 g, fluorine-containing thermally decomposable surfactant (trade name "DS-21" manufactured by DIC Corporation) 0.20 g of a 5% by weight PGMEA solution (equivalent to a concentration of 100 ppm), and 0.20 g of a 5% by weight solution of PGMEA (concentration: equivalent to 100 ppm) was added and stirred. Filtration was then carried out with a 1.00 μm filter to prepare a glass-reinforced material C-2 with a solid concentration of 26% by weight.

Using the obtained glass reinforcing material C-2, in the same manner as in Example 1, a cured film A-6 having a thickness of 2 μm and comprising a crosslinked product of the glass reinforcing material C-2 was produced. Table 2 shows the results of evaluation by the method described above.

[Example 7]
Under a yellow light, 0.36 g of trifluoromethanesulfonate (trade name "MDT" manufactured by Heraeus) was added to 4.00 g of DAA, 8.80 g of PGMEA, and 3-methoxy-3-methyl-1-butyl acetate (boiling point = 188°C). ) 22.20 g of a mixed solvent, 0.54 g of a silane-modified isocyanurate compound (trade name “KBM-9659” manufactured by Shin-Etsu Chemical Co., Ltd.), a 30% by weight dispersion of silica particles in PGMEA (average particle size = 20 to 30 nm, trade name “PMA-ST” manufactured by Nissan Chemical Industries, Ltd.) 23.89 g, siloxane resin (PS-3) solution 39.82 g, fluorine-containing thermally decomposable surfactant (trade name “DS- 21" 0.20 g of a 5% by weight solution of PGMEA (equivalent to a concentration of 100 ppm) of DIC Corporation), PGMEA5 of a silicone-modified acrylic surfactant (trade name "BYK" (registered trademark)-3550, manufactured by BYK-Chemie) 0.20 g of a weight percent solution (corresponding to a concentration of 100 ppm) was added and stirred. Filtration was then carried out with a 1.00 μm filter to prepare a glass reinforcing material C-3 with a solid concentration of 26% by weight.

Using the obtained glass reinforcing material C-3, in the same manner as in Example 1 except that the curing temperature was changed to 230 ° C., a cured film A- having a thickness of 2 μm made of a crosslinked product of the glass reinforcing material C-3 was obtained. 7 was made. Table 2 shows the results of evaluation by the method described above.

[Example 8]
A cured film A-8 having a film thickness of 5 μm was prepared in the same manner as in Example 7, except that the film thickness of the cured film was changed to 5 μm by adjusting the rotation speed of spin coating. Table 2 shows the results of evaluation by the method described above.

[Example 9]
1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) under yellow light (trade name “Irgacure” (registered trademark) OXE01, manufactured by BASF) 0 .43 g, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name “Omnirad” (registered trademark) 819, manufactured by IGM) 1.07 g, 4-t-butylcatechol 0.02 g, PGMEA 30 .81 g of propylene glycol monomethyl ether (boiling point = 120°C, hereinafter "PGME") was dissolved in a mixed solvent of 23.10 g, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name "KAYARAD" ( DPHA (registered trademark) manufactured by Nippon Kayaku Co., Ltd.) 6.43 g, siloxane resin (PS-2) solution 37.53 g, a mixture of polyether-modified polydimethylsiloxane and polyether (trade name “BYK” (registered trademark) )-333” manufactured by BYK-Chemie) was added with 0.60 g of a 5% by weight PGMEA solution (equivalent to a concentration of 300 ppm) and stirred. Then, filtration was performed with a 1.00 μm filter to prepare glass reinforcing material C-4 with a solid concentration of 23% by weight.

Using the obtained glass reinforcing material C-4, in the same manner as in Example 1 except that the curing temperature was changed to 130 ° C., a cured film A- having a thickness of 2 μm made of a crosslinked product of the glass reinforcing material C-4 was obtained. 9 was made. Table 2 shows the results of evaluation by the method described above.

[Example 10]
Under a yellow light, 1.52 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name “Omnirad” (registered trademark) 819, manufactured by IGM), zirconium tetraacetylacetonate (trade name ““ Orgatics "(registered trademark) ZC-150" manufactured by Matsumoto Fine Chemical Co., Ltd.) 1.30 g is dissolved in a mixed solvent of 14.17 g DAA, 21.82 g PGMEA, and 14.80 g MMB, and a siloxane compound having an oxetanyl group "" Aron Oxetane "(registered trademark) OXT-191" 0.98 g, 3-aminopropyltrimethoxysilane (trade name "KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd.) 0.43 g, tris(2-hydroxyethyl) isocyanuric acid acrylic acid ester (trade name “Aronix” (registered trademark) M-315, Toagosei Co., Ltd.) 6.52 g, siloxane resin (PS-1) solution 38.05 g, fluorine-containing thermally decomposable surfactant (trade name “DS-21” manufactured by DIC Corporation), 0.20 g of a 5% by weight solution of PGMEA (equivalent to a concentration of 100 ppm), a silicone-modified acrylic surfactant (trade name “BYK” (registered trademark)-3550) 0.20 g (equivalent to a concentration of 100 ppm) of a 5% by weight PGMEA solution (manufactured by BYK-Chemie) was added and stirred. Then, filtration was performed with a 1.00 μm filter to prepare glass reinforcing material C-5 with a solid concentration of 26% by weight.

Using the obtained glass reinforcing material C-5, in the same manner as in Example 1, a cured film A-10 having a film thickness of 2 μm composed of a crosslinked product of the glass reinforcing material C-5 was produced. Table 2 shows the results of evaluation by the method described above.

[Example 11]
Under a yellow light, 1.52 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name “Omnirad” (registered trademark) 819, manufactured by IGM), zirconium tetraacetylacetonate (trade name ““ Orgatics "(registered trademark) ZC-150" manufactured by Matsumoto Fine Chemical Co., Ltd.) 1.30 g is dissolved in a mixed solvent of 17.43 g DAA, 1.53 g PGMEA, and 14.80 g MMB, and a siloxane compound having an oxetanyl group "" Aron Oxetane "(registered trademark) OXT-191" 0.98 g, 3-aminopropyltrimethoxysilane (trade name "KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd.) 0.43 g, PGMEA 30% by weight dispersion of silica particles ( Average particle size = 20 to 30 nm, trade name "PMA-ST" manufactured by Nissan Chemical Industries, Ltd.) 28.99 g, siloxane resin (PS-1) solution 32.61 g, fluorine-containing thermally decomposable surfactant (trade name "DS-21" DIC Corporation) 0.20 g of 5% by weight PGMEA solution (equivalent to a concentration of 100 ppm), silicone-modified acrylic surfactant (trade name "BYK" (registered trademark)-3550, manufactured by BYK Chemie) ) was added with 0.20 g of a 5% by weight PGMEA solution (corresponding to a concentration of 100 ppm) and stirred. Filtration was then carried out with a 1.00 μm filter to prepare a glass-reinforced material C-6 with a solid concentration of 26% by weight.

Using the obtained glass reinforcing material C-6, in the same manner as in Example 1, a cured film A-11 having a film thickness of 2 μm composed of a crosslinked product of the glass reinforcing material C-6 was produced. Table 2 shows the results of evaluation by the method described above.

[Example 12]
Under a yellow light, 1.52 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name “Omnirad” (registered trademark) 819, manufactured by IGM), zirconium tetraacetylacetonate (trade name ““ Orgatics "ZC-150" Matsumoto Fine Chemical Co., Ltd. (1.30 g) was dissolved in a mixed solvent of 4.39 g of DAA, 21.82 g of PGMEA and 14.80 g of MMB. Trademark) OXT-191” 0.98 g, 3-aminopropyltrimethoxysilane (trade name “KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.43 g, siloxane resin (PS-1) solution 54.35 g, containing 0.20 g of a 5% by weight solution of PGMEA (corresponding to a concentration of 100 ppm) of a fluorine thermally decomposable surfactant (trade name “DS-21” manufactured by DIC Corporation), a silicone-modified acrylic surfactant (trade name “BYK” 0.20 g (equivalent to a concentration of 100 ppm) of a 5% by weight PGMEA solution of (registered trademark)-3550 (manufactured by BYK-Chemie) was added and stirred. Filtration was then carried out with a 1.00 μm filter to prepare a glass-reinforced material C-7 having a solid content concentration of 26% by weight.

Using the obtained glass reinforcing material C-7, in the same manner as in Example 1, a cured film A-12 having a thickness of 2 μm and comprising a crosslinked product of the glass reinforcing material C-7 was produced. Table 2 shows the results of evaluation by the method described above.

[Example 13]
Under a yellow light, 1.39 g of zirconium tetraacetylacetonate (trade name “Orgatics” (registered trademark) ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.) was added to 20.06 g of DAA, 0.27 g of PGMEA, and 14.80 g of MMB. Dissolved in a mixed solvent, 1.04 g of a siloxane compound having an oxetanyl group ""Aron oxetane" (registered trademark) OXT-191", 3-aminopropyltrimethoxysilane (trade name "KBM-903" Shin-Etsu Chemical Co., Ltd. 0.46 g, PGMEA 30% by weight dispersion of silica particles (average particle size = 20 to 30 nm, trade name “PMA-ST” manufactured by Nissan Chemical Industries, Ltd.) 30.79 g, siloxane resin (PS-3) solution 30.79 g, 0.20 g of a 5% by weight solution of PGMEA (equivalent to a concentration of 100 ppm) of a fluorine-containing thermally decomposable surfactant (trade name "DS-21" manufactured by DIC Corporation), a silicone-modified acrylic surfactant (product 0.20 g (equivalent to a concentration of 100 ppm) of a 5% by weight PGMEA solution (“BYK” (registered trademark)-3550, manufactured by BYK-Chemie) was added and stirred. Then, filtration was performed with a 1.00 μm filter to prepare a glass-reinforced material C-8 having a solid content concentration of 26% by weight.

Using the obtained glass reinforcing material C-8, in the same manner as in Example 1, a cured film A-13 having a thickness of 2 μm and comprising a crosslinked product of the glass reinforcing material C-8 was produced. Table 2 shows the results of evaluation by the method described above.

[Comparative Example 1]
Under a yellow light, 1.39 g of zirconium tetraacetylacetonate (trade name “Orgatics” (registered trademark) ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.) was added to 8.77 g of DAA, 21.82 g of PGMEA, and 14.80 g of MMB. Dissolved in a mixed solvent, 1.04 g of a siloxane compound having an oxetanyl group ""Aron oxetane" (registered trademark) OXT-191", 3-aminopropyltrimethoxysilane (trade name "KBM-903" Shin-Etsu Chemical Co., Ltd. 0.46 g of siloxane resin (PS-3) solution, 0.20 g of PGMEA 5% by weight solution of fluorine-containing thermally decomposable surfactant (trade name “DS-21” manufactured by DIC Corporation) (concentration 100 ppm) and 0.20 g (equivalent to a concentration of 100 ppm) of a 5% by weight PGMEA solution of a silicone-modified acrylic surfactant (trade name “BYK” (registered trademark)-3550 manufactured by BYK-Chemie) were added and stirred. Filtration was then carried out with a 1.00 μm filter to prepare a glass-reinforced material C-9 with a solid content concentration of 26% by weight.

Using the obtained glass reinforcing material C-9, in the same manner as in Example 1, a cured film A-14 having a thickness of 2 μm and comprising a crosslinked product of the glass reinforcing material C-9 was produced. Table 2 shows the results of evaluation by the method described above.

[Comparative Example 2]
Under a yellow light, 0.45 g of zirconium tetraacetylacetonate (trade name “Orgatics” (registered trademark) ZC-150, manufactured by Matsumoto Fine Chemicals Co., Ltd.) was added to 4.72 g of DAA, 22.53 g of PGMEA, and 15.40 g of MMB. It was dissolved in a mixed solvent, and 56.30 g of a siloxane resin (PS-3) solution and 0.3% of a PGMEA 5% by weight solution of a fluorosurfactant (trade name ““Megafac” (registered trademark) F477” manufactured by DIC Corporation) were added. 60 g (corresponding to a concentration of 300 ppm) was added and stirred. Then, filtration was performed with a 1.00 μm filter to prepare glass reinforcing material C-10 having a solid content concentration of 23% by weight.

Using the obtained glass reinforcing material C-10, the same procedure as in Example 1 was performed except that the curing temperature was changed to 240 ° C. without exposure, and the thickness of the crosslinked product of the glass reinforcing material C-10 was 2 μm. A cured film A-15 was produced. Table 2 shows the results of evaluation by the method described above.

[Comparative Example 3]
A cured film A-16 having a thickness of 12 μm was prepared in the same manner as in Example 1, except that the film thickness of the cured film was changed to 12 μm by adjusting the rotation speed of spin coating. Table 2 shows the results of evaluation by the method described above.

[Comparative Example 4]
A cured film A-17 having a thickness of 0.3 μm was prepared in the same manner as in Example 1, except that the film thickness of the cured film was changed to 0.3 μm by adjusting the rotation speed of spin coating. Table 2 shows the results of evaluation by the method described above.

[Comparative Example 5]
Table 2 shows the results of evaluation by the above-described method without coating a chemically strengthened glass substrate (Gorilla Glass 3 manufactured by Corning Inc.) with a film thickness of 0.7 μm without applying a glass reinforcing material.

Table 1 shows the compositions of the glass reinforcing materials C-1 to C-10 (excluding the solvent), and Table 2 shows the evaluation results of Examples 1 to 13 and Comparative Examples 1 to 5.

It can be seen that the glass-reinforced substrates produced in Examples have high glass strength and high transmittance.

Since the glass-reinforced substrate of the present invention has high glass strength and high transmittance, it can be used as a cover glass for display devices such as smartphones.

Claims (6)

Glass reinforcement having, on at least one side of a tempered glass substrate, a cured film made of a crosslinked product of a glass reinforcing material containing siloxane resin and silica particles, having a thickness of 0.5 to 5 μm and a transmittance of 90% or more at a wavelength of 400 nm. substrate. On at least one side of a tempered glass substrate, a siloxane resin having a radically polymerizable group, a photoradical polymerization initiator, and a crosslinked product of a glass reinforcing material containing silica particles , with a film thickness of 0.5 to 5 μm, and transmission at a wavelength of 400 nm. A glass-reinforced substrate having a cured film with a rate of 90% or more. 3. The glass-reinforced substrate according to claim 2, wherein the glass-reinforced material further contains a compound having two or more radically polymerizable groups. 4. The glass-reinforced substrate according to claim 1 , wherein the cured film has a pencil hardness of 2H or more. The glass-reinforced substrate according to any one of claims 1 to 4 , wherein the cured film has a Young's modulus of 7.0 GPa or more. The glass-reinforced substrate according to any one of claims 1 to 5 , wherein the cured film has a compressive stress of 15 to 35 MPa.