Coated substrate and process of preparation

Abstract

To provide a coated glass substrate that both counteracts the negative effects of electromagnetic radiation and has improved durability to humidity, and a process for preparation of the coated glass substrate.SOLUTION: A coated glass substrate comprises: a transparent glass substrate coated with a blocking layer comprising a material having Si-O-Si bonds and a blocking component, wherein the blocking component comprises fluorone and / or a fluorone derivative.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a coated glass substrate and a process for producing the coated glass substrate. do. [Background technology]

[0002] The harmful effects of ultraviolet (UV) light can occur, for example, when a substantially clear or transparent bottle is exposed to sunlight or fluorescent light. This is a problem in the brewing industry because exposure to light can cause beer to "spoil." It can decompose sohumulone (an organic molecule present in beer derived from hops) and its photodegradation biosynthesis The product combines with sulfur to produce unpleasant compounds, especially 3-methyl-2-butene-1-thiol (3 Even in very small amounts (parts per trillion), these sulfur-containing compounds produce beta-blockers (MBTs). This can affect the taste and aroma of the drink, an effect also known as skunking.

[0003] This problem is partially addressed by using darker colored bottles, usually green or brown. The brown bottles in particular have been more or less successful at blocking UV rays. However, its use can reduce production volume, energy consumption, etc. by changing between different glass compositions. This can lead to other problems, especially in continuous production processes, such as energy and material loss. Rub.

[0004] The production of glass bottles or jars by modern methods is well known (see, for example, "Glass Making Today, edited by P. J. Doyle; Portcullis Press, ISBN 0 86108 047 5). Typically, the blank shape is first prepared by placing a slug or "gob" of molten glass into the blank mold. The "blank" formed in this way is The "clay" is transferred to a "blow" mold where it is blown into the inside of the mold to create the article. This process is subject to variability, but is consistent with modern production methods. Typically, molded glass containers are produced that emerge from a mold with significant loss of glass from the molding process. It has residual heat.

[0005] US2013 / 0299378A1 discloses a composition comprising a silane, a solvent, a catalyst and water. The paper describes a process in which a solution of the compound is applied to the exterior surface of a glass container at a temperature of 40-60°C. The glass container is then heated to a temperature exceeding 500°C to form a Si-O- The solution may be doped with a UV blocking material. Summary of the Invention [Problem to be solved by the invention]

[0006] However, there are coatings that counteract the adverse effects of electromagnetic radiation and improve moisture resistance. It would be desirable to provide a UV-blocking glass substrate. It is not easy to determine where the coating has been deposited, so it is best to use a more visual approach. It would be advantageous to provide a coating that stands up well and also provides an attractive aesthetic appearance. It would also be desirable to provide a coated glass substrate having [Means for solving the problem]

[0007] According to a first aspect of the present invention, The blocking layer is coated with a material having a Si-O-Si bond and a blocking component. A coated glass substrate comprising a blocking-coated transparent glass substrate, A coated glass substrate is provided, the components of which include fluorones and / or fluorone derivatives. It will be offered.

[0008] The inventors have surprisingly found that the composition of the blocking layer determines the tendency for the blocking layer to peel off. The coating provides improved moisture resistance to glass substrates, as demonstrated by a reduced tendency to Furthermore, the coated glass substrates have an aesthetic appearance that is immediately recognizable to the naked eye. It exhibits a pleasing coloring.

[0009] In the context of the present invention, when a layer is "based on" a particular material or materials, In the case of a layer, it means that the layer mainly consists of the corresponding material or materials, typically It means comprising at least about 50 atomic % (at. %) of a material or materials.

[0010] In the following discussion of the invention, unless stated to the contrary, the parameters are within their allowable ranges. Disclosure of alternative limits or floor values ​​is an indication that one of the values ​​is significantly preferred over the other. between the more preferred and less preferred alternative values, Each intermediate value of the parameter is compared to the less preferred value and to the less preferred value. For each value between the least desirable value and the intermediate value, there is an implicit status that is preferred in itself. This should be interpreted as a statement.

[0011] Throughout this specification, the terms "comprising" or "comprises" means that the specified component(s) are included, but exclude the presence of others. "consisting essentially of" or "essentially The term "consists essentially of" means that the specified components are included, but are not impure. Materials that exist as objects, and exist as a result of the processes used to provide the components Except for unavoidable materials and ingredients added for purposes other than achieving the technical effects of the present invention. It means to exclude other ingredients. Typically, when referring to a composition, it essentially means a set of The composition contains less than 5% by weight of unspecified components, generally less than 3% by weight, more preferably Generally it contains less than 1% by weight.

[0012] The terms "consisting of" and "consists of" are used interchangeably. "includes" means to include the specified ingredient and to exclude other ingredients.

[0013] Where appropriate, depending on the context, we may use the words "comprising" or "comprises". The use of terms such as "consisting essentially of" or "essentially may be interpreted to include the meaning "consists essentially of" Also, the meaning of "consisting of" or "consisting of" may be construed as inclusive.

[0014] References in this specification such as "within the range of x to y" include the interpretation "from x to y" and Thus, it is intended to include the value x and the value y.

[0015] In the context of the present invention, a transparent material or a transparent substrate is a material that can transmit visible light. A material or substrate that transmits visible light across or through said material. The ability to clearly see objects or images located behind a material through said material or substrate It is possible to do so.

[0016] In the context of the present invention, the "thickness" of a layer is the thickness of the layer for any given position on the surface of the layer. A layer having a surface opposite to the surface of the layer from the surface position, the surface being in the direction of the smallest dimension of the layer. It is expressed by the distance through

[0017] In the context of this invention, a "derivative" is a compound that is structurally related to another chemical entity and therefore It is a chemical that can be theoretically derived in the past.

[0018] In the context of the present invention, a "container" is a container suitable for containing, inter alia, liquids, powders and gels. It is an instrument that

[0019] If a container is completely filled, for example with a liquid, only a portion of its surface will be in contact with said liquid. In the context of this invention, the "inner surface" of a container is the surface that is closest to the container when it is completely filled. This refers to that part of the surface of a container that is in contact with the liquid when the container is completely filled. The remainder of the surface of the container that is not in contact with the liquid when it is in contact with the liquid is referred to as the "exterior surface."

[0020] Preferably, the transparent glass substrate is a glass container. Preferably, the glass container is a bottle. , a vial, a tube, a canister or a jar.

[0021] Preferably, the blocking layer is located on the exterior surface of the container. The blocking layer may coat the entire exterior surface of the container. The blocking layer may coat a portion of the exterior surface of the container. At least 70% of the exterior surface of the container, more preferably at least 80%, even more preferably preferably coats at least 90%, and most preferably at least 95%.

[0022] The glass container preferably includes a closed bottom located at a first end of the glass container. Preferably, the glass container further includes a body extending from the closed base and closed all around. Preferably, the glass container has an open mouth (commonly called a "finish") Preferably, the opening is located at the second end of the glass container. The second end of the vessel is preferably an end of the glass container opposite the first end (i.e. Preferably, the body extends axially from the bottom. do.

[0023] Preferably, the glass container further includes a neck extending from the body and terminating in the opening. Preferably, the neck extends axially from the body. Preferably, the neck is generally conical in shape. be.

[0024] Preferably, the blocking layer does not coat the opening. Reduces the possibility of problems caused by filling the container with material and it coming into contact with the blocking layer Preferably, the blocking layer is at least 0.5 cm from the opening, more preferably at least 0.5 cm from the opening. At least 1 cm from the opening, and even more preferably at least 1.5 cm from the opening. cm, most preferably at least 2 cm from the opening, preferably at More preferably, the opening is at most 4 cm away, and even more preferably, the opening is at most 3.5 cm away. The entire exterior surface of the container is coated except for an area up to 3 cm from the mouth.

[0025] Preferably, the blocking layer is obtained by a sol-gel process. In the present specification, the term "sol-gel process" refers to a process in which at least one silicon coupling blocking agents (e.g., those of the formula Si in which each R group is an organic group that can be the same or different from one or more of the other R groups) It refers to the process in which a medium containing an alkoxide of (OR)4 is hydrolyzed. When hydrolyzed, the silicone coupling agent undergoes a process equivalent to the polymerization of the silicone coupling agent. Hydroxylated species (e.g., compounds of the formula Si) that condense together via the process to form inorganic oxide particles. (OH)4). Typically, these hydrolysis and condensation reactions are carried out first in a sol (a suspension of oxide particles) which gradually becomes concentrated and the particles that form Thus, the general expression The name "sol-gel" is given to this type of process.

[0026] Preferably, the material having Si-O-Si bonds is a crosslinked network of Si-O-Si bonds. Preferably, the material having a Si-O-Si bond is Si-O- The material of the blocking layer is bonded to a transparent glass substrate via a Si bond. The -O-Si bond may be an ionic or covalent bond.

[0027] Preferably, the material having Si-O-Si bonds further comprises one or more organic functional groups. Preferably, the one or more organic functional groups each have 1 to 10 carbon atoms, more preferably Preferably it contains 2 to 8 carbon atoms, even more preferably 3 to 7 carbon atoms. Preferably, the one or more organic functional groups further comprise at least one alkyl moiety. Preferably, the one or more organic functional groups further comprise at least one ether moiety. Preferably, the one or more organic functional groups include at least one glycidoxyalkyl group and and / or derivatives, more preferably at least one glycidoxypropyl group and / or or derivatives.

[0028] The blocking layer may include a material having one or more silicate ester functional groups. The silicate ester functional groups are selected from the group consisting of i) polyols and / or diols and ii) silanols. The silanol can be obtained via a reaction between a silanol and a silanol as defined below. , may be derived from a silane or a silane coupling agent.

[0029] Preferably, the blocking layer further comprises a polyol and / or a diol.

[0030] The polyol may be, for example, a polyoxyalkylene such as polyoxypropylenetriol. Polyether polyols such as nitrile; glycerol, sorbitol, mannitol Maltitol, lactitol, xylitol, isomalt, erythritol, poly Vinyl alcohol; and Bornesitol, Conduritol, Inositol, Ononitol ol, pinitol, pinpollitol, quebrachitol, quinic acid, shikimic acid, valienol , cyclitols such as biscumitol and cyclitol. Preferably, the polyol comprises glycerol.

[0031] The diol is ethylene glycol, diethylene glycol, 1,2-ethanediol, propane-1,2-diol, propane-1,3-diol, 2-methyl-2-propane Pyr-1,3-propanediol, neopentyl glycol, 1,4-butanediol, Bisphenol A, Propylene-1,3-diol, Beta Propylene Glycol, Rezo Rucinol, methanediol, cyclohexanediol and 1,5-pentanediol may include one or more of:

[0032] Preferably, the blocking component has a size of 10 to 500 nm, more preferably 200 to 500 nm. nm, even more preferably 250-500 nm, even more preferably 300-500 nm, even more preferably 350 to 500 nm, and most preferably 380 to 500 nm. A material that can block, and preferably absorb, electromagnetic radiation in a range of wavelengths. These preferred wavelength ranges are within the range where skunking of beer can occur. Therefore, it is eligible.

[0033] Preferably, the fluorone derivative is calcein, carboxyfluorescein diacetate. Tosuccinimidyl ester, carboxyfluorescein succinimidyl ester, 6 -Carboxyfluorescein, dichlorofluorescein, eosin, eosin B, eosin Y, Erythrosine, Fluo-3, Fluo-4, Fluorescein, Fluorescein Amida Fluorescein isothiocyanate, Indian yellow, merbromin, 3- Carboxy-6,8-difluoro-7-hydroxycoumarin (Pacific Blue), Rhodamine, rhodamine B, rhodamine 6G, rhodamine 123, carboxy Tetramethylrhodamine (TAMRA), Tetramethylrhodamine (TMR) and its Isothiocyanate derivative (TRITC), sulforhodamine 101 (and its sulfo derivatives) (Texas Red is formed by the addition of tetrahydrofuran to the rhodamine red dye), NHS-rhodamine and and one or more of semi-naphthalenediamine fluoride.

[0034] Preferably, the fluorone and / or fluorone derivative is rhodamine and / or includes rhodamine derivatives.

[0035] Preferably, the blocking layer contains at least 2% by weight of the blocking component, more preferably More preferably at least 4% by weight, even more preferably at least 5% by weight, and most preferably at least at least 5.5% by weight, preferably at most 6% by weight, more preferably at most 15% by weight, Even more preferably, it contains at most 10% by weight, and most preferably at most 8% by weight. The preferred range of is for blocking electromagnetic radiation while avoiding elution due to excess blocking component. This provides the advantage of improving locking. Preferably, the blocking component is dispersed and / or entrapped within the blocking layer.

[0036] The blocking layer preferably has a thickness of at least 1 micrometer, more preferably less than 1 micrometer. at least 10 micrometers, and even more preferably at least 100 micrometers; Most preferably at least 400 micrometers, preferably at most 1000 micrometers meters, more preferably at most 700 micrometers, even more preferably at most A physical thickness of 600 micrometers, most preferably up to 500 micrometers may have the following structure:

[0037] Preferably, the coated glass substrate is made of a material having a Si-O-Si bond and a block copolymer. A coating composition comprising a transparent glass substrate coated with a blocking layer comprising a blocking component. a glass substrate, the blocking component comprises a fluorone and / or a fluorone derivative; The transparent glass substrate is a glass container, the blocking layer coats at least 80% of an exterior surface of the glass container; The material having Si-O-Si bonds has a crosslinked network of Si-O-Si bonds. The material includes The blocking component blocks electromagnetic radiation in the wavelength range of 350 to 500 nm. and The fluorone and / or fluorone derivative is rhodamine and / or rhodamine derivative. Includes amine derivatives.

[0038] According to a second aspect of the present invention, there is provided a coated glass substrate according to the first aspect of the present invention. A fabrication process is provided, The process comprises: a) preparing a solution by mixing at least the silane, the blocking component, water and an acid; or preparing a mixture, wherein the blocking component is fluorone and / or or a fluorone derivative; b) applying said solution or mixture to a surface of a transparent glass substrate; and c) curing the applied solution or mixture.

[0039] Surprisingly, this process can be used to produce films at higher temperatures than previously possible. It is possible to provide a coating on a glass substrate that can block electromagnetic radiation. This makes it possible to coat the glass substrate without cooling it. This allows the coating of freshly manufactured glass substrates, e.g. glass containers. In this process, the glass substrate must be cooled before coating; otherwise , the blocking layer becomes hazy and does not adhere well to the substrate.

[0040] Preferably, steps a), b) and c) are performed in order.

[0041] Preferably, in step a), the mixing occurs by stirring. , for at least 10 minutes, more preferably for at least 20 minutes, and even more preferably for at least The mixture is stirred for at least 30 minutes, and most preferably for at least 40 minutes. In step a), the solution or mixture is aged (i.e., the solution is left to stand). Preferably, in step a) after mixing, the solution or mixture is subjected to at least 2 hours, more preferably at least 7 hours, even more preferably at least 10 hours, Preferably, the solution or mixture is aged for at least 12 hours. Advantageously, this promotes the formation of Si-O-Si bonds. Preferably, mixing and / or Aging is performed at 1°C to 30°C, more preferably 3°C to 20°C, and even more preferably 4°C. It is carried out at a temperature of ~10°C.

[0042] Preferably, in step b), the solution or mixture is applied to the surface of a transparent glass substrate. When the transparent glass substrate is heated, the temperature is preferably less than 150° C., more preferably less than 100° C. More preferably, the temperature is below 70°C, and most preferably below 50°C.

[0043] Preferably, in step c), the applied solution or mixture is at least 20 minutes, more preferably at least 40 minutes, even more preferably at least 50 minutes, Most preferably for at least 55 minutes, preferably for up to 24 hours, more preferably for up to Curing is continued for 10 hours, even more preferably for up to 3 hours, and most preferably for up to 1.5 hours. These preferred times allow for better formation of the required Si-O-Si bonds. and improve durability.

[0044] Preferably, in step c), the applied solution or mixture is heated to a temperature above 20° C. , more preferably above 100°C, even more preferably above 160°C, and most preferably or a temperature of more than 190°C, preferably less than 400°C, more preferably less than 300°C; Even more preferably it is cured at a temperature below 240°C, most preferably below 210°C. These favorable curing temperatures allow for better formation of the required Si-O-Si bonds. and improve durability.

[0045] Silanes have the following formula (1): SiX4 formula (1) [wherein X is a hydrolyzable functional group or a halogen atom] .

[0046] The hydrolyzable functional group can be, for example, an alkoxy group, an acetoxy group, and an alkenyloxy group. Examples of the alkoxy group include those having 1 to 6 carbon atoms, preferably Preferably, the alkoxy group has 1 to 4 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, and A preferred hydrolyzable functional group is an alkoxy group. The halogen atom is, for example, chlorine or bromine, preferably chlorine. The silane is a tetraalkoxysilane, such as tetraethoxysilane (TEOS). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.

[0047] Preferably, the molar percentage of silane in the solution or mixture prepared in step a) ( mol % is at least 1 mol %, more preferably at least 2 mol %, even more preferably or at least 3 mol %, most preferably at least 4 mol %, preferably at most 15 mol %, more preferably at most 10 mol %, even more preferably at most 8 mol %, and most preferably at most Preferably, the maximum is 6.5 mol %. Mole % of silane is: (the number of moles of silane in the solution or mixture prepared in step a) / total number of moles in the solution or mixture prepared in step a) × 100%: .

[0048] Preferably, the weight percentage (wt%) of the silane in the solution or mixture prepared in step a) ( wt%) is at least 5 wt%, more preferably at least 10 wt%, even more preferably or at least 15% by weight, most preferably at least 20% by weight, preferably at most 45% by weight, more preferably at most 40% by weight, even more preferably at most 35% by weight , most preferably at most 30% by weight. The solution or mixture prepared in step a) The weight percent of silane in is the mass of silane in the solution or mixture prepared in (step a). / total mass of the solution or mixture prepared in step a) × 100%.

[0049] Preferably, the components mixed in step a) are of formula (2): R 1 m R 2 n Six 4-m-n Formula (2) [In the formula, R 1 is an organic group having a reactive functional group, R 2 is an organic compound having no reactive functional group X is a hydrolyzable functional group or a halogen atom; m is an integer of 1 to 3; n is an integer of 0 to 2. and m+n is an integer of 1 to 3. include.

[0050] The reactive functional group is, for example, a vinyl group, an acryloyl group, a methacryloyl group, an isocyanate group, or the like. Late group, ureido group, mercapto group, sulfide group, isocyanate group, epoxy group, and an amino group. The epoxy group is at least one selected from a glycidyl group, particularly The amino group may be a primary amino group, a secondary amino group, or a part of an oxyglycidyl group. The preferred reactive functional groups are epoxide groups, aryl groups, and tertiary amino groups. The organic group having a reactive functional group is preferably an oxy group or an amino group, and more preferably an epoxy group. is, for example, an organic group (e.g., a vinyl group) that itself acts as a reactive functional group. or, for example, a fatty acid in which at least one hydrogen atom has been replaced with a reactive functional group. Examples of the aliphatic hydrocarbon group include those having 1 to 10 carbon atoms. and branched alkyl groups having 3 to 10 carbon atoms. An example of a hydrogen group is a phenyl group.

[0051] The organic group having no reactive functional group is, for example, an aliphatic or aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include linear alkyl groups having 1 to 10 carbon atoms and alkyl groups having 3 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group. can be.

[0052] The hydrolyzable functional group or halogen atom, which is an example of X in formula (2), is as follows with respect to formula (1): This is the same as the example mentioned above.

[0053] The integer m is preferably 1 or 2, the integer n is preferably 0 or 1, The number m+n is preferably 1 or 2.

[0054] Examples of silane coupling agents include vinyltriethoxysilane and p-styryltrimethylsilane. 3-Glycidoxypropyltrimethoxysilane (GPTMS), 3-Gly Silane, 3-methacryloxypropyltrimethoxysilane Lan, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilane (propyl) isocyanurate, 3-ureidopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane butyropropyltrimethoxysilane and derivatives.

[0055] Preferably, the silane coupling agent of the solution or mixture prepared in step a) is The mole percent (mol %) is at least 0.5 mole %, more preferably at least 1 mole %. %, even more preferably at least 1.5 mol %, and most preferably at least 1.8 mol %. %, preferably at most 10 mol %, more preferably at most 5 mol %, even more preferably Preferably at most 3 mol %, most preferably at most 2 mol %. The mole percent of the silane coupling agent in the solution or mixture is determined by the mole percent of the solution or mixture prepared in (step a). Moles of silane coupling agent in the solution or mixture prepared in step a) is defined as: (total moles of mixture) × 100%.

[0056] Preferably, the polymerization of the silane coupling agent of the solution or mixture prepared in step a) is carried out. The weight percent (wt%) is at least 2% by weight, more preferably at least 5% by weight, and even more preferably at least 5% by weight. More preferably, the amount is at least 8% by weight, and most preferably at least 10% by weight. More preferably at most 25% by weight, more preferably at most 20% by weight, even more preferably at most 15% by weight, most preferably up to 12% by weight. The weight percent of the silane coupling agent in the solution or mixture prepared in (step a) is: is the mass of silane coupling agent in the mixture / the solution or mixture prepared in step a) It is defined as: (total mass of) × 100%.

[0057] Preferably, the solution or mixture prepared in step a) comprises a polyol and / or further comprises a diol.

[0058] Examples of polyols and / or diols and blocking components are those of the first aspect of the present invention. This is the same as the example described above regarding the type.

[0059] Preferably, the polyol and / or the polyol of the solution or mixture prepared in step a) The mole percent (mol%) of the diol is at least 2 mol%, more preferably at least At least 4 mol %, even more preferably at least 5 mol %, and most preferably at least 6 mol %. %, preferably at most 20 mol %, more preferably at most 15 mol %, and even more preferably or at most 10 mol %, most preferably at most 7 mol %. The mole percent of polyol and / or diol in the resulting solution or mixture is determined by (step a ) the moles / stearate of polyol and / or diol in the solution or mixture prepared It is defined as: (total number of moles of the solution or mixture prepared in step a) × 100%.

[0060] Preferably, the polyol and / or the polyol of the solution or mixture prepared in step a) The weight percent (wt%) of the diol is at least 5 wt%, more preferably at least 10% by weight, even more preferably at least 13% by weight, and most preferably at least 1 4% by weight, preferably up to 30% by weight, more preferably up to 25% by weight, and even more preferably Preferably, at most 20% by weight, most preferably at most 16% by weight. The weight percent of polyol and / or diol in the prepared solution or mixture is: (stearyl alcohol, ethyl alcohol, ethyl ether, ethyl ether) The mass of polyol and / or diol in the solution or mixture prepared in step a) It is defined as: (total mass of the solution or mixture prepared in step a) × 100%.

[0061] Preferably, the molar ratio of the blocking components of the solution or mixture prepared in step a) is The percent (mol%) is at least 0.1 mol%, more preferably at least 0.2 mol %, even more preferably at least 0.3 mol %, and most preferably at least 0.4 mol %. %, preferably at most 2 mol %, more preferably at most 1 mol %, even more preferably is at most 0.7 mol %, most preferably at most 0.5 mol %. The mole percentage of the blocking component in the resulting solution or mixture is moles of blocking component in solution or mixture / solution or mixture prepared in step a) It is defined as: (total number of moles of mixture) × 100%.

[0062] Preferably, the weight percent of the blocking component of the solution or mixture prepared in step a) is The weight percent (wt%) is at least 1 weight percent, more preferably at least 1.5 weight percent, and even more preferably at least 1.5 weight percent. More preferably, the amount is at least 2% by weight, and most preferably, at least 2.5% by weight. or at most 10% by weight, more preferably at most 5% by weight, even more preferably at most 4% by weight, most preferably at most 3% by weight. The weight percent of the blocking component in the mixture is: (mass of blocking component in / total mass of solution or mixture prepared in step a) × Defined as: 100%.

[0063] Preferably, the molar percentage of water in the solution or mixture prepared in step a) is %) is at least 50 mol %, more preferably at least 60 mol %, even more preferably or at least 70 mol %, most preferably at least 73 mol %, preferably at most 90 mol%, more preferably at most 80 mol%, even more preferably at most 77 mol% , most preferably up to 75 mol %. The solution or mixture prepared in step a) The mole % of water in the solution or mixture prepared in (step a) is the number of moles of water in the solution or mixture prepared in (step a) / (step b). It is defined as: (total number of moles of the solution or mixture prepared in step a) × 100%.

[0064] Preferably, the weight percent (wt%) of water in the solution or mixture prepared in step a) is ) is at least 15% by weight, more preferably at least 20% by weight, even more preferably At least 25% by weight, most preferably at least 30% by weight, preferably at most 5 0% by weight, more preferably at most 45% by weight, even more preferably at most 40% by weight, Most preferably, it is at most 35% by weight in the solution or mixture prepared in step a). The weight percent of water is: mass of water in the solution or mixture prepared in (step a) / (step It is defined as: a) total mass of the solution or mixture prepared in a) × 100%.

[0065] Preferably, the acid comprises one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid. , the acid includes nitric acid.

[0066] Preferably, the molar percentage of acid in the solution or mixture prepared in step a) is %) is at least 0.1 mol %, more preferably at least 0.2 mol %, and even more preferably Preferably at least 0.25 mol %, most preferably at least 0.3 mol %, More preferably at most 2 mol %, more preferably at most 1 mol %, even more preferably at most 0. 6 mol %, most preferably at most 0.4 mol %. The mole percent of the acid in the solution or mixture is the mole percent of the acid in the solution or mixture prepared in (step a). is defined as: (number of moles / total number of moles of the solution or mixture prepared in step a) × 100% do.

[0067] Preferably, the weight percent (wt%) of the acid in the solution or mixture prepared in step a) is ) is at least 0.1% by weight, more preferably at least 0.3% by weight, even more preferably Preferably at least 0.4% by weight, most preferably at least 0.45% by weight, preferably is at most 5% by weight, more preferably at most 1% by weight, even more preferably at most 0.6 % by weight, most preferably at most 0.55% by weight. The weight percent of the acid in the solution or mixture is determined by: the quality of the acid in the solution or mixture prepared in (step a). It is defined as: amount of the solution or mixture prepared in step a) × 100%.

[0068] Preferably, the components mixed in step a) are methanol, ethanol, n-propanediol, Alcohol, i-propanol, butanol, diethylene glycol, acetone, methyl ethyl Ketone, triethylene glycol, vinylpyrrolidone, toluene, phenol, benzene The mixture may further contain an additional solvent, such as one or more of diethyl alcohol, dioxane, and derivatives. Preferably, the additional solvent is an alcohol, more preferably ethanol.

[0069] Preferably, the molar percentage of the additional solvent in the solution or mixture prepared in step a) (mol %) is at least 5 mol %, more preferably at least 8 mol %, and even more preferably Preferably at least 10 mol %, most preferably at least 12 mol %, preferably at most At most 25 mol %, more preferably at most 20 mol %, even more preferably at most 15 mol %. % by mole, most preferably up to 13 mol %. The mole % of additional solvent in the solution or mixture prepared in (step a) is the mole % of additional solvent in the solution or mixture prepared in (step a). (moles of solvent / total moles of solution or mixture prepared in step a) × 100%: It is defined as:

[0070] Preferably, the weight percentage of additional solvent in the solution or mixture prepared in step a) The weight percent is at least 5 weight percent, more preferably at least 9 weight percent, and even more preferably Preferably at least 12% by weight, most preferably at least 13% by weight, preferably at most 30% by weight, more preferably at most 22% by weight, even more preferably at most 17% by weight %, most preferably up to 15% by weight. The weight percent of additional solvent in the solution or mixture prepared in (step a) is: Defined as: mass of solvent / total mass of solution or mixture prepared in step a) × 100% will be done.

[0071] Preferably, the ingredients mixed in step a) further comprise a surfactant such as a polysiloxane. Preferably, the polysiloxane is an organically modified polysiloxane, more preferably In particular, polyether-modified polysiloxanes and polymethylalkylsiloxanes. Contains one or more of the following:

[0072] Preferably, the weight percentage of surfactant in the solution or mixture prepared in step a) The weight percent is at least 0.1 weight percent, more preferably at least 0.5 weight percent, and More preferably, it is at least 0.6% by weight, most preferably at least 0.7% by weight, Preferably, at most 5% by weight, more preferably at most 3% by weight, even more preferably at most 2% by weight, most preferably at most 1% by weight. The weight percent of the surfactant in the mixture is: (mass of surfactant / total mass of the solution or mixture prepared in step a) × 100%: is defined.

[0073] In step b) the solution or mixture is preferably applied by spraying, flow coating. By roller coating or slot die, most preferably by spraying. The spray is applied to the surface of a bright glass substrate. Preferably, the spray is performed using at least two nozzles. Preferably, the nozzles are directed toward opposite sides of the transparent glass substrate. do.

[0074] Preferably, in step a) after mixing, the solution or mixture is stirred for at least 2 hours. Aged (i.e. the solution or mixture is allowed to stand); In step b), the solution or mixture is applied to the surface of a transparent glass substrate. the transparent glass substrate is at a temperature exceeding 60°C; The silane is a tetraalkoxysilane; The components mixed in step a) are represented by the following formula (2): R 1 m R 2 n Six 4-m-n Formula (2) [In the formula, R 1 is an organic group having a reactive functional group, R 2 does not have a reactive functional group X is a hydrolyzable functional group or a halogen atom, and m is an integer of 1 to 3. where n is an integer from 0 to 2, and m+n is an integer from 1 to 3. further comprising a coupling agent; and The fluorone and / or fluorone derivative is rhodamine and / or rhodamine derivative. Includes derivatives.

[0075] More preferably, for the embodiment of the preceding paragraph, the solution or mixture prepared in step a) The mixture contains at least 4 mol %, preferably at least 6 mol %, of a polyol and / or has a mole percent (mol %) of a diol, preferably glycerol.

[0076] Preferably, for the embodiment of the previous two paragraphs, the ingredients mixed in step a) are It further comprises an additional solvent, more preferably an alcohol.

[0077] According to a third aspect of the present invention, a blocking layer is coated on a transparent glass substrate. The use of fluorones and / or fluorone derivatives as V-blocking components. and the blocking layer further comprises a material having a Si-O-Si bond. and / or the use of fluorone derivatives.

[0078] According to a fourth aspect of the present invention, a blocking layer for coating a transparent glass substrate is provided. Use of fluorones and / or fluorone derivatives to improve wettability, comprising: The blocking layer further comprises a material having a Si-O-Si bond. and / or use of fluorone derivatives.

[0079] Any of the features described above in relation to the first and second aspects of the invention may also be used in other Any of the inventions described herein may be utilized with any of the above aspects without departing from the spirit and scope of the present invention. Furthermore, it may be combined with any feature of any other invention described herein. The optional features applicable to one aspect of the invention may be used in any combination and in any number. It will be understood that they may be used in conjunction with any of the other aspects of the invention. may be used in any combination and in any number. This includes any dependent claim from a claim which is used as a dependent claim for another claim in the present application, Not limited to these.

[0080] The reader's attention is drawn to the fact that the present application is related to the present application and that the present application is filed contemporaneously or prior thereto. and to all papers and documents open to public inspection together with such documents. The contents of all articles and documents are incorporated herein by reference.

[0081] All claims disclosed in this specification (including the accompanying claims, abstract and drawings) are hereby incorporated by reference. The features and / or all steps of any disclosed method or process are Excluding combinations in which at least some of the features and / or steps are mutually exclusive. can be combined in any combination.

[0082] Each feature disclosed in this specification (including the accompanying claims, abstract and drawings) is Unless otherwise stated, substitute alternative features that serve the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, each disclosed feature is intended to be understood as a generic set of equivalents. or just one example of a similar feature. [Brief description of the drawings]

[0083] The present invention will now be further described by the following specific embodiments, which are not intended to be limiting. FIGURE 1 is a block diagram of a method for manufacturing a semiconductor device according to the present invention; [Figure 1] 1 is a graph of transmittance versus wavelength for an uncoated, colorless bottle, a coated bottle outside the scope of the present invention, and two coated bottles according to the present invention having different coating thicknesses. EXAMPLES

[0084] Uvinul™ 3050 was obtained from Sigma-Aldrich™ Rhodamine 6G was obtained from Sigma-Aldrich™. BYK™ )-345 was obtained from BYK™. GPTMS was obtained from Sigma-Aldric TEOS was obtained from Sigma-Aldrich.

[0085] [Comparative Example 1] A solution / mixture was prepared by mixing the ingredients shown in Table 1 below for 35 minutes. [Table 1] [Table 1. Mass of each component used in the solution / mixture prepared in Comparative Example 1]

[0086] After stirring, the solution / mixture was aged at 5° C. for 12 hours. The solution / mixture was spray coated onto a clear, colorless flint bottle at a temperature of 20°C. The spray coating uses two nozzles: a PTFE tube and a syringe driver. The applied solution / mixture was then cured at 200° C. for 2 hours.

[0087] The light transmission characteristics of the shoulders of the resulting coated bottles were evaluated using a PerkinElmer™ Testing was performed using a Lambda 900 spectrometer, and the results are shown in Figure 1 and discussed below.

[0088] [Example 1] Solutions / mixtures were prepared using the ingredients shown in Table 2 below and the same approach as in Comparative Example 1. did. [Table 2] [Table 2. Mass of each component used in the solution / mixture prepared in Example 1]

[0089] After stirring, the solution / mixture was aged at 5° C. for 12 hours. Using the same approach as in Comparative Example 1, a transparent, colorless flint bottle at a temperature of 120° C. The solution / mixture was then spray-coated at 200° C. Allowed to cure for 2 hours.

[0090] The same solutions / mixtures were prepared using the ingredients shown in Table 2 in the same manner as in the previous paragraph. Another flint bottle was coated with the same paint, but with a thicker coating. Except for the fact that a deposit of ting has occurred.

[0091] Both of the coated bottles of Example 1 exhibited a noticeable pink color and showed a thick coating. The color of the thin coating was a deeper pink than that of the thin coating.

[0092] The light transmission properties of the resulting coated bottles were tested as in Comparative Example 1. An uncoated, clear, colorless flint bottle was also tested in the same manner. The results are shown in Figure 1. This is explained below.

[0093] [Results: UV blocking ability] Figure 1 shows an uncoated, transparent, colorless flint bottle (no coating, (with label), and the coated bottle prepared in Comparative Example 1 (Uvinul® 305 0), and the thin-coated and thick-coated bottles prepared in Example 1 and Rhodamine 6G-thin coating and Rhodamine 6G-thick coating, respectively 1 shows a graph of transmittance versus wavelength.

[0094] As noted, both the bottles of Comparative Example 1 and Example 1 were coated. In comparison with the untreated colorless bottle, the UV blocking ability was demonstrated. The bottles emit light in the 380-500 nm wavelength range, which is of particular interest to beer skunking. The UV blocking ability was better than that of the bottle of Comparative Example 1. The decrease in transmission from thin to thick coatings is consistent with the decrease in UV blocking as well as color intensity. This paper explains how you can fine-tune the performance of your application.

[0095] [Results: Moisture resistance] Two clear (flint) bottles were coated: one according to Comparative Example 1 and one according to Comparative Example 2. One is from Example 1. From the body of each bottle, a section measuring approximately 4 cm x 3 cm was A sample was cut to the same thickness as the bottle.

[0096] These samples were evaluated by humidity testing to investigate their resistance to harsh environments. The machine used was a Thermotron™ 7800 environmental chamber. Conditions were 95% humidity and 50°C. Samples were checked after 24 and 48 hours. did.

[0097] 24 hours later Comparative Example 1 sample - delamination of coating occurred. Patchy coating on sample remains. Example 1 sample - coating had no visually apparent defects and no signs of delamination None.

[0098] After 48 hours Comparative Example 1 Sample - Further delamination of coating and coating coverage declined further. Example 1 sample - coating had no visually apparent defects and no signs of delamination None.

[0099] These results clearly demonstrate the improved moisture resistance of the coated glass substrate of the present invention. do.

[0100] The invention is not limited to the details of the foregoing embodiments. The invention is not limited to the details of the foregoing embodiments. Any novel or optional features disclosed in the claims, abstract and drawings any novel combination or steps of any method or process disclosed, It extends to any novel entity or any novel combination.

Claims

1. The blocking layer is coated with a material having a Si-O-Si bond and a blocking component. A coated glass substrate comprising a transparent glass substrate coated with a The blocking component comprises fluorone and / or a fluorone derivative. Glass substrate.

2. The transparent glass substrate is a glass container, and the blocking layer is a glass container. The coated glass substrate of claim 1 located on an exterior surface of a vessel.

3. The material having Si—O—Si bonds has a crosslinked network of Si—O—Si bonds. Preferably, the material having the Si—O—Si bond is one or more organic The coated glass substrate of claim 1 or 2, further comprising a functional group.

4. The blocking layer further comprises a polyol and / or a diol.

4. The coated glass substrate according to any one of claims 3 to 3.

5. The fluorone derivatives are calcein, carboxyfluorescein diacetate succinate, Carboxyfluorescein succinimidyl ester, 6-carbofluorescein succinimidyl ester, Dichlorofluorescein, Eosin, Eosin B, Eosin Y, E Lithrosine, Fluo-3, Fluo-4, Fluorescein, Fluorescein amidite, Fluorescein isothiocyanate, Indian Yellow, Merbromin, 3-Carboxy C-6,8-difluoro-7-hydroxycoumarin (Pacific Blue), Phloxine , rhodamine, rhodamine B, rhodamine 6G, rhodamine 123, carboxytetramethyl Tetramethylrhodamine (TAMRA), tetramethylrhodamine (TMR) and their isothiocyanates Cyanate derivatives (TRITC), sulforhodamine 101 (and its sulfonyl chlorine derivatives) Rhodamine Red, NHS-Rhodamine and Semina The coating of any one of claims 1 to 4, comprising one or more of the following: Glass substrate.

6. The fluorone and / or fluorone derivative is rhodamine and / or rhodamine derivative. The coated glass substrate according to any one of claims 1 to 5, comprising an amine derivative.

7. The blocking layer is coated with a material having a Si-O-Si bond and a blocking component. The coated glass substrate comprises a transparent glass substrate coated with the blocking component comprises a fluorone and / or a fluorone derivative; The transparent glass substrate is a glass container, the blocking layer coats at least 80% of an exterior surface of the glass container; The material having Si—O—Si bonds has a crosslinked network of Si—O—Si bonds. The material includes The blocking component blocks electromagnetic radiation in the wavelength range of 350 to 500 nm. It is a material that can The fluorone and / or fluorone derivative is rhodamine and / or rhodamine derivative. The coated glass substrate according to any one of claims 1 to 6, comprising an amine derivative.

8. A process for producing a coated glass substrate according to any one of claims 1 to 7, 、 a) preparing a solution by mixing at least the silane, the blocking component, water and an acid; or preparing a mixture, wherein the blocking component is fluorone and / or or a fluorone derivative; b) applying said solution or mixture to a surface of a transparent glass substrate; and c) curing the applied solution or mixture.

9. In step a) after mixing, the solution or mixture is preferably stirred for at least 2 hours. Preferably at least 7 hours, even more preferably at least 10 hours, most preferably 9. The process of claim 8, wherein the mixture is aged for at least 12 hours.

10. In step b), the solution or mixture is applied to the surface of the transparent glass substrate. When the transparent glass substrate is heated to a temperature of less than 150° C., preferably less than 100° C., more preferably 10. The method according to claim 8 or 9, preferably at a temperature of less than 70° C., most preferably at a temperature of less than 50° C. process.

11. In step c), the applied solution or mixture is allowed to stand for at least 20 minutes. Preferably, the reaction is continued for at least 40 minutes, more preferably for at least 50 minutes, and most preferably for at least At most 55 minutes, preferably at most 24 hours, more preferably at most 10 hours, even more preferably at most 10 hours. More preferably, the composition is cured for a maximum of 3 hours, and most preferably for a maximum of 1.5 hours.

10. The process according to any one of claims 1 to 9.

12. In step c), the applied solution or mixture is preferably at a temperature above 20° C. More preferably, the temperature is more than 100°C, more preferably more than 160°C, and most preferably more than 190°C. Preferably, the temperature is less than 400° C., more preferably less than 300° C., and even more preferably Any of claims 8 to 11 is cured at a temperature below 240°C, most preferably below 210°C. The process described in any one of the preceding claims.

13. The silane has the following formula (1): SiX 4 Formula (1) [wherein X is a hydrolyzable functional group or a halogen atom] 3. The process according to any one of claims 2 to 3.

14. The silane is a tetraalkoxysilane such as tetraethoxysilane (TEOS). The process according to any one of claims 8 to 13,

15. The components mixed in step a) are represented by the following formula (2): R 1 m R 2 n SiX 4-m-n Formula (2) [In the formula, R １ represents an organic group having a reactive functional group, R ２ is an organic compound having no reactive functional group X is a hydrolyzable functional group or a halogen atom; m is an integer of 1 to 3; and n is an integer of 0 to 2. and m+n is an integer of 1 to 3. The process according to any one of claims 8 to 14, comprising

16. The silane coupling agent is vinyltriethoxysilane, p-styryltrimethoxysilane Silane, 3-glycidoxypropyltrimethoxysilane (GPTMS), 3-glycidoxy 3-propylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, N- Phenyl-3-aminopropyltrimethoxysilane, Tris-(trimethoxysilylpro propyl) isocyanurate, 3-ureidopropyltrimethoxysilane, 3-mercaptopropyl 16. The process of claim 15, comprising one or more of propyltrimethoxysilane and derivatives. Process.

17. The polyol and / or diol of the solution or mixture prepared in step a). is at least 2 mol %, preferably at least 4 mol %, More preferably at least 5 mol %, most preferably at least 6 mol %, and preferably at most At most 20 mol %, more preferably at most 15 mol %, even more preferably at most 10 mol %. % by mole, most preferably up to 7 mol %. vinegar.

18. In step a) after mixing, the solution or mixture is aged for at least 2 hours. It was In step b), the solution or mixture is applied to the surface of the transparent glass substrate. When the transparent glass substrate is applied, the transparent glass substrate is at a temperature of less than 50° C. the silane is a tetraalkoxysilane; The components mixed in step a) are represented by the following formula (2): R 1 m R 2 n SiX 4-m-n Formula (2) [In the formula, R １ is an organic group having a reactive functional group, R ２ does not have a reactive functional group X is a hydrolyzable functional group or a halogen atom, and m is an integer of 1 to 3. where n is an integer of 0 to 2, and m+n is an integer of 1 to 3. Further comprising a coupling agent, The fluorone and / or fluorone derivative is rhodamine and / or rhodamine derivative. The process according to any one of claims 8 to 17, comprising a amine derivative.

19. As a UV blocking component in a blocking layer coating a transparent glass substrate, The use of fluorones and / or fluorone derivatives, wherein the blocking layer is Fluorone and / or fluorone derivatives further comprising materials having i-O-Si bonds Use of the body.

20. A full-fledged anti-humidity coating for the blocking layer of transparent glass substrates. Use of orone and / or fluorone derivatives, wherein the blocking layer is Si- Fluorone and / or fluorone derivatives further comprising materials having O-Si bonds. use.

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