JP2017065930A - Method for producing glass sheet with resin coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a glass sheet with a resin coating film, which enables continuous processing and has improved productivity.SOLUTION: In a method for producing a glass sheet 13 with a resin coating film, an electrospray device 20 having a nozzle and a counter electrode, a resin solution sent to the nozzle, and a glass sheet 11 having a thickness of 10-300 μm are prepared. The glass sheet 11 being conveyed is coated with the resin solution using the electrospray device 20, and is dried with dryer 30, thereby forming a resin coating film 12 on the glass sheet 12.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a glass sheet with a resin coating film.

  A display device such as a liquid crystal display, a semiconductor element, and the like are provided with a cover glass to protect the surface. In recent years, with the reduction in size and weight of display devices and semiconductor elements, the glass used for these devices has been made extremely thin.

  When glass is thinned, it becomes easy to break. Therefore, when progressing in thinning, it is necessary to ensure strength that can withstand actual use at the same time. Therefore, it is considered that a resin layer is formed on the surface of the glass substrate to form a composite to ensure impact resistance and durability. As a method for forming a thin film on the surface of a substrate such as glass, various methods such as a spray method, an ink jet method, and a printing method have been proposed (for example, see Patent Documents 1 to 3).

Special table 2013-512190 gazette International Publication 2011/001613 International Publication No. 2013/105534

  However, in the conventional method described above, since the processing is performed in a state where the glass substrate is fixed to a thin film forming apparatus for forming a thin film, the processing must be intermittent, and it is difficult to improve productivity. In addition, there is a possibility that the glass substrate may be damaged by contact with the load applied when the glass substrate is installed in the device or when the glass substrate is taken out of the device, or with a jig in the device, and in some cases This is a factor that decreases the performance.

  This invention is made | formed in view of the above, Comprising: It aims at providing the manufacturing method of the glass sheet with a resin coating film which can be processed continuously and productivity was improved.

  According to one aspect of the present invention, there is provided a method for producing a glass sheet with a resin coating film, an electrospray apparatus having a nozzle and a counter electrode, a resin solution fed to the nozzle, and a thickness of 10 to 300 μm. And the resin solution is applied to the glass sheet being transported using the electrospray apparatus to form a resin coating film on the glass sheet.

  According to the embodiment of the present invention, it is possible to provide a method for producing a glass sheet with a resin coating film that can be continuously processed and has improved productivity.

It is a figure which illustrates schematic structure of the glass sheet manufacturing apparatus in embodiment. It is the schematic which illustrates the structure of the electrospray apparatus in embodiment. It is the schematic which illustrates the structure of the electrospray apparatus in embodiment. It is the schematic which illustrates the structure of the electrospray apparatus in embodiment. It is the schematic which illustrates the structure of the electrospray apparatus in embodiment. It is the schematic which illustrates the structure of the electrospray apparatus in embodiment.

  Hereinafter, embodiments for carrying out the invention will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and redundant description may be omitted.

<Glass sheet manufacturing equipment with resin coating>
FIG. 1 is a diagram illustrating a schematic configuration of a glass sheet manufacturing apparatus 100 with a resin coating film in the embodiment. The glass sheet manufacturing apparatus 100 with a resin coating film forms the resin coating film 12 on the surface of the glass sheet 11, and manufactures the glass sheet 13 with a resin coating film.

  As shown in FIG. 1, the glass sheet manufacturing apparatus 100 includes a supply roll 10, an electrospray apparatus 20, a drying apparatus 30, and a collection roll 40.

  The supply roll 10 is provided so as to be rotatable around a central axis, and a glass sheet 11 is wound around the periphery in a roll shape. The supply roll 10 rotates to feed out the glass sheet 11 and supply the glass sheet 11 to the electrospray apparatus 20.

  The electrospray apparatus 20 includes a nozzle and a counter electrode facing the nozzle, and forms the resin coating film 12 on one or both surfaces of the glass sheet 11 conveyed between the nozzle and the counter electrode by an electrospray method. The configuration of the electrospray device 20 will be described later.

  The drying device 30 heats the glass sheet 11 having the wet resin coating film 12 ′ formed on the surface by the electrospray device 20, removes the solvent from the wet resin coating film 12 ′, and dries to form the resin coating film 12. To do. The glass sheet 11 is conveyed and passes through the electrospray device 20 and the drying device 30 to become a glass sheet 13 with a resin coating film on which a resin coating film 12 is formed. In addition, the drying apparatus 30 should just be able to heat and remove a solvent from the resin coating film 12, and a system, a structure, etc. are not limited.

  The collection roll 40 is provided so as to be rotatable about a central axis, and collects the glass sheet 13 with a resin coating film on which the resin coating film 12 is formed on the surface of the glass sheet 11 in a roll shape and collects the collection roll 40.

  In the glass sheet manufacturing apparatus 100 with a resin coating film demonstrated above, the formation process of the resin coating film 12 is continuously performed to the glass sheet 11 currently conveyed. Therefore, in the manufacturing method of the glass sheet 13 with a resin coating film using the glass sheet manufacturing apparatus 100 with a resin coating film, the processing is continuously performed in this way, so that productivity is improved and impact resistance and durability are improved. The glass sheet 13 with a resin coating film excellent in the above can be obtained.

  Instead of the collection roll 40, a cutting device that cuts the glass sheet 13 with a resin coating film discharged from the drying device 30 into a desired size may be provided. Further, a static eliminator that removes the charge remaining on the surface of the glass sheet 13 may be provided at the subsequent stage of the electrospray device 20. In addition, a charging device for precharging the surface of the glass sheet 13 to a reverse charge in advance may be provided in the front stage of the electrospray device 20. Further, as illustrated in FIG. 1, the glass sheet 13 may be a long sheet supplied from the supply roll 10. The glass sheet 13 is formed in advance in a sheet shape of a predetermined size and electrosprayed one by one. It may be conveyed to the device 20 and the drying device 30. The glass sheet 13 is preferably a long sheet supplied from the supply roll 10 in terms of high productivity.

  In FIG. 1, the glass sheet 11 and the glass sheet 13 with a resin coating film are drawn so as to exist on the same plane before and after the electrospray device 20, but may not necessarily exist on the same plane. Good.

<Electrospray device>
Next, the electrospray apparatus 20 will be described. FIG. 2 is a schematic view illustrating the configuration of the electrospray apparatus 20. The electrospray apparatus 20 includes a nozzle 21, a counter electrode 22, and a power source 24, and forms a wet resin coating film 12 ′ on the surface of the glass sheet 11 being transported between the nozzle 21 and the counter electrode 22.

  The nozzle 21 is connected to the positive electrode or the negative electrode of the power source 24 to be applied with a voltage, and forms an electric field between the tip of the nozzle 21 and the counter electrode 22 connected to the ground.

  A resin solution 23 is fed to the nozzle 21, and the charged resin solution 23 is sprayed from the discharge port at the tip of the nozzle 21 by a voltage applied to the nozzle 21 from the power supply 24. The resin solution 23 sprayed from the discharge port of the nozzle 21 is repelled by Coulomb force and split into droplets having electric charges. The solvent contained in the resin solution 23 is volatilized by the division, and the charge density is increased by the volatilization, whereby the droplets of the resin solution 23 are further repelled and repeat the division. The droplets of the resin solution 23 that has been finely divided by repeated splitting are guided to an electric field formed between the nozzle 21 and the counter electrode 22 and adhere to the surface of the glass sheet 11 to form a resin coating film. To do.

  The applied voltage applied to the nozzle 21, the distance between the tip of the nozzle 21 and the counter electrode 22, the feeding speed of the resin solution 23, the feeding pressure of the resin solution 23, the environmental humidity in the electrospray device 20, etc. 11 is appropriately set according to the thickness of the wet resin coating film 12 ′ (the thickness of the resin coating film 12) formed on the film 11, the conveyance speed of the glass sheet 11, and the like.

  The applied voltage (potential difference between the nozzle 21 and the counter electrode 22) applied to the nozzle 21 is not particularly limited, but is preferably 5 to 30 kV, more preferably 5 to 25 kV, and still more preferably 10 to 20 kV. If the applied voltage is equal to or higher than the above lower limit value, the area where the resin solution 23 is applied to the surface of the glass sheet 11 can be maintained at a required size, and productivity is easily improved. Further, if the applied voltage is equal to or lower than the above upper limit value, the resin solution 23 is difficult to be applied to the surface of the glass sheet 11, and a uniform wet resin coating film 12 ′ is easily obtained.

  Although the distance of the front-end | tip of the nozzle 21 and the counter electrode 22 is not specifically limited, For example, 10-200 mm is preferable, 30-200 mm is more preferable, 50-150 mm is further more preferable. If the distance between the tip of the nozzle 21 and the counter electrode 22 is equal to or greater than the lower limit, the area where the resin solution 23 is applied to the surface of the glass sheet 11 can be maintained at a required size, and productivity is improved. Cheap. Moreover, if it is below the said upper limit, it will become difficult to apply the resin solution 23 on the surface of the glass sheet 11, and it will become easy to obtain uniform wet resin coating film 12 '. In particular, if the distance between the tip of the nozzle 21 and the counter electrode 22 is unnecessarily increased, the solvent is excessively evaporated while the droplets are flying, and the formation of the wet resin coating film 12 ′ tends to be uneven.

  Although the liquid feeding speed of the resin solution 23 is not particularly limited, for example, it is preferably 10 to 2000 μL / min, more preferably 50 to 1000 μL / min, and further preferably 100 to 1000 μL / min per nozzle. If the liquid feeding speed is not more than the above upper limit value, it becomes easy to obtain a uniform wet resin coating film 12 '. Further, when the liquid feeding speed is equal to or higher than the lower limit, productivity can be improved, and since there is a sufficient solvent for leveling, it is easy to ensure the uniformity of the wet resin coating film 12 '.

  Although the liquid feeding pressure of the resin solution 23 is not specifically limited, For example, 1 kPa-0.5 MPa is preferable and 5 kPa-0.1 MPa is more preferable. If the liquid feeding pressure is not more than the above upper limit value, it is easy to maintain the uniformity of the resin coating film. If the liquid feeding speed is equal to or higher than the lower limit, it is easy to increase productivity, and it is easy to ensure the homogeneity of the wet resin coating film 12 'because there is a sufficient solvent for leveling.

  Although the environmental humidity (relative humidity) in the electrospray apparatus 20 is not specifically limited, For example, 20 to 90% is preferable, 30 to 90% is preferable, and 60 to 90% is more preferable. If the humidity is equal to or higher than the lower limit, the resin solution 23 is hardly applied to the surface of the glass sheet 11 with a mottle, and a uniform wet resin coating film 12 ′ is easily obtained. Moreover, if humidity is below the said upper limit, the area where the resin solution 23 is apply | coated to the surface of the glass sheet 11 can be maintained at a required magnitude | size, and productivity is improved.

  Although the conveyance speed of the glass sheet 11 is not specifically limited, For example, 0.1-100 m / min is preferable and 1-50 m / min is more preferable. In particular, it is preferable that the glass sheet 11 is continuously conveyed because it is easy to increase productivity.

  When the electrospray method is used when the resin solution 23 is applied to the glass sheet 11, the nozzle 21 does not contact the glass sheet 11, so that the glass sheet 11 can be prevented from being damaged. In particular, the thin glass sheet 11 being transported may be damaged by a slight impact. Such a risk of breakage tends to increase when defects such as scratches are present on the glass surface. For this reason, it is necessary to suppress the possibility of scratching. In this respect, the electrospray method in which the head of the nozzle 21 does not contact the glass sheet 11 is excellent. That is, continuous application to the thin glass sheet 11 that is easily damaged is possible by employing the electrospray method.

  Further, in the electrospray method, when the glass sheet 11 has a thickness unevenness (non-uniform thickness state), or when the glass sheet 11 vibrates (change in the distance between the nozzle 21 and the glass sheet 11). Even so, there is an advantage that the thickness of the formed wet resin coating film 12 'can be easily kept uniform. Furthermore, the spray method that does not use an electric field has the disadvantage that the coating efficiency is low and the utilization efficiency of the resin is low, and the nonuniformity of the thickness of the wet resin coating film 12 ′ is likely to occur due to slight variations in conditions. There is.

  The electrospray method employed in the present invention is preferably an airless method that does not use gas when the resin solution 23 is discharged from the nozzle 21. The airless method makes it easy to increase the coating efficiency.

  A plurality of nozzles 21 may be provided in the width direction orthogonal to the conveyance direction of the glass sheet 11. A plurality of nozzle rows in which a plurality of nozzles 21 are arranged in the width direction may be provided in the conveyance direction of the glass sheet 11. Providing the plurality of nozzles 21 makes it possible to form a resin coating on a larger area of the glass sheet 11 and improve productivity. The arrangement of the plurality of nozzles 21 may be arranged in a lattice pattern or zigzag alignment. A staggered arrangement is preferred because there is little interference between nozzles.

  When a plurality of nozzles 21 are provided, the voltage applied to each nozzle 21 may be uniform or may be adjustable for each nozzle. In order to easily make the thickness of the wet resin coating film 12 'uniform, it is preferable that the applied voltage can be adjusted for each nozzle. The polarity of the applied voltage may be the same for the plurality of nozzles 21 or may be alternating between positive and negative.

  Further, the nozzle 21 may be provided with a guard ring for controlling a region where the resin solution 23 is applied.

  The direction of the nozzle 21 may be provided vertically downward in the direction of gravity, or may be provided obliquely, horizontally, or upward. In particular, in order to suppress defects in the wet resin coating film 12 'due to liquid dripping from the nozzle tip, the nozzle direction is preferably inclined by 10 degrees or more from the vertical direction of the gravitational direction, more preferably by 30 degrees or more. . However, providing horizontally is a case where it is inclined 90 degrees from the vertical direction of gravity.

  The counter electrode 22 is a plate-like member made of, for example, a conductive metal material, and is connected to the ground and provided at a predetermined distance from the tip of the nozzle 21. The counter electrode 22 is preferably connected to a pole different from the pole to which the nozzle 21 of the power supply 24 is connected. A space is preferably provided between the counter electrode 22 and the conveyed glass sheet 11. The counter electrode 22 and the glass sheet 11 are provided so as to reduce the contact area. The most desirable aspect is no contact.

  The counter electrode 22 preferably has a curved surface (more preferably, a curved surface having a center or axis on the side opposite to the nozzle 21 across the glass sheet 11) along the conveyance direction of the glass sheet 11. That is, it is preferable that the resin solution 23 is applied (preferably from the outside of the arc) in a state where the glass sheet 11 is bent along the counter electrode 22. If it is this aspect, a position will be stabilized by the rigidity of glass sheet 11 itself, and it will be easy to obtain wet resin coating film 12 'which has a uniform film thickness. Further, according to this aspect, even if the glass sheet 11 has defects such as latent scratches, the resin solution 23 is likely to cover these defects. Examples of the counter electrode 22 include a roller electrode and an air turn bar (electrode).

  Further, the electrode provided opposite to the nozzle 21 may be a roller electrode 25 provided rotatably as shown in FIG. The roller electrode 25 is controlled to rotate in synchronization with the conveyed glass sheet 11 so as not to damage the glass sheet 11.

  The surface of the roller electrode 25 is preferably roughened from the viewpoint of reducing the contact area with the glass sheet 11. As the roughness, for example, the arithmetic average roughness (Ra) defined by JIS B0601 is preferably 0.05 to 1 μm, and more preferably 0.1 to 0.6 μm.

  Although it does not specifically limit as a magnitude | size of the roller electrode 25, For example, the diameter is 50-1000 mm, and 200-1000 mm is more preferable.

  It is preferable to reduce the contact area between the roller electrode 25 and the glass sheet 11, and it is more preferable that the metal constituting the roller electrode 25 and the glass sheet 11 do not directly contact each other. In order not to make direct contact, there are a method of jetting gas from the surface of the roller electrode 25, a method of providing a liquid film on the surface of the roller electrode 25, a method of coating the surface of the roller electrode 25 with a resin, and the like.

  It is preferable that the surface of the roller electrode 25 is coated with a slippery fluororesin. Preferred examples of the fluororesin include polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA).

  The electrode may be an air turn bar 27 as shown in FIG. The air turn bar 27 is provided at a portion where the conveyance path of the glass sheet 11 is bent, and jets air from the surface to support the glass sheet 11 in a non-contact manner. Since the air turn bar 27 supports the glass sheet 11 in a non-contact manner, the surface of the glass sheet 11 is not damaged.

  Although the flying distance of the glass sheet in the air turn bar 27 is not particularly limited, for example, 0.1 to 5 mm is preferable, and 0.5 to 3 mm is more preferable.

  5 and 6 are schematic views illustrating the configuration of the electrospray apparatus 20 that forms a resin coating film on both surfaces of the glass sheet 11.

  For example, as shown in FIG. 5, the electrospray apparatus 20 is provided with a nozzle 21 connected to a power source 24 and an air turn bar 27 connected to the ground at two places where the conveyance path of the glass sheet 11 is bent. The structure which forms a resin coating film in the different surface of the glass sheet 11 may be sufficient. For example, as shown in FIG. 6, the nozzle 21 and the counter electrode 22 are provided before and after the portion where the conveyance path of the glass sheet 11 is bent, and a resin coating film is formed on a different surface of the glass sheet 11. There may be. With any configuration, the glass sheet 13 with a resin coating film in which the resin coating film is formed on both surfaces of the glass sheet 11 can be formed. Moreover, you may provide a drying apparatus separately after application | coating in each nozzle 21. FIG. In addition, the structure of the electrospray apparatus 20 shown in FIG.5 and FIG.6 is an example, and you may form a resin coating film on both surfaces of the glass sheet 11 by a different structure.

<Glass sheet>
The glass sheet 11 is not limited in material and composition, and for example, soda lime glass, alkali-borosilicate glass, non-alkali-borosilicate glass, non-alkali-aluminosilicate glass, or the like can be used. Among these, alkali-free borosilicate glass and alkali-aluminosilicate glass are preferable in terms of excellent durability, high elastic modulus, and low linear expansion coefficient. In addition, alkali-free borosilicate glass and alkali-aluminosilicate glass (hereinafter referred to as “alkali-free glass”) are preferable because when a semiconductor element is formed on the glass, an element defect due to alkali does not occur. . The alkali-free glass refers to a glass having an alkali metal oxide content of less than 1 mol% (may be 0 mol%) when the glass composition is represented by an oxide.

  The thickness of the glass sheet 11 is 10-300 micrometers. When the thickness is 10 μm or more, sufficient impact resistance can be obtained when the resin coating film 12 is formed, and it is difficult to break. Moreover, if thickness is 300 micrometers or less, the glass sheet 13 with a resin coating film will become easy to obtain a softness | flexibility. As for the thickness of the glass sheet 11, 20-200 micrometers is more preferable, and 30-100 micrometers is especially preferable.

  Further, the thickness of the glass sheet 11 is preferably uniform. Specifically, the thickness deviation is 15% or less in terms of PV (Peak to Valley) value (for example, the deviation with respect to 100 μm in thickness). Is preferably 15 μm or less. When the thickness is uniform, the appearance of the glass sheet 11 is improved.

  The surface of the glass sheet 11 is preferably flat. The flatter the glass sheet 11, the higher the light transmittance, and the surface roughness is arithmetic average roughness (Ra) defined by JIS B0601, preferably 30 nm or less, and more preferably 1 nm or less. Moreover, it is preferable that the surface of the glass sheet 11 is flat because when the electrode such as a transparent conductive film is laminated on the surface, the film resistance becomes uniform and defects are hardly generated.

  The dielectric constant of the glass sheet 11 is preferably 5 to 7 at 10 kHz. Moreover, 70-95 GPa is preferable and the Young's modulus of the glass sheet 11 has more preferable 75-90 GPa.

The linear expansion coefficient of the glass sheet 11 is preferably 3 × 10 ^{−6 to} 5 × 10 ⁻⁶ / ° C. (3 to 5 ppm / ° C.) at 0 to 200 ° C. The glass sheet 11 having these characteristics is suitable as a photoelectric conversion element, a protective plate such as a display member, a substrate of a semiconductor device, and the like.

  The glass sheet 11 may be subjected to a strengthening process. As the strengthening treatment, chemical strengthening is preferable. If it is chemical strengthening, the thin glass sheet 11 can be effectively strengthened. When the glass sheet 11 is subjected to the tempering treatment, an effect is obtained that the glass sheet 11 with a resin coating film is hardly damaged even if it is thin and lightweight.

<Resin coating film>
The resin coating film 12 formed on the glass sheet 11 protects the surface of the glass sheet 11 and prevents the surface from being scratched or broken. Moreover, when the glass sheet 11 is broken, it is prevented that fragments are scattered.

  In the electrospray apparatus 20, the resin solution 23 sprayed from the nozzle 21 to the glass sheet 11 includes, for example, any of fluororesin, polyimide resin, polyester resin, and polycarbonate resin, and the resin coating film 12 including any of these. Is formed on the glass sheet 11.

  The resin solution 23 is not limited as long as it contains any of the resins described above and can be sprayed from the nozzle 21 to the glass sheet 11. For the resin solution 23, the resin may be dissolved in a solvent, or the resin may be synthesized in a solvent and used. In addition, the resin solution 23 may contain components other than the resin and the solvent. For example, when a fluororesin is used, the resin solution 23 is formed when a coating film is formed, such as silanes such as alkoxysilane and alkylsilicate oligomer. A compound capable of reacting may be included.

  The solid content of the resin solution 23 is preferably 0.1 to 70% by mass, and more preferably 1 to 15% by mass. However, solid content means the ratio by which the solid content obtained by drying a solution is contained in the whole solution. For example, 1 g of the solution can be put in an aluminum cup and dried in an oven at 100 ° C. for 10 minutes for measurement. The solvent used for the resin solution 23 may be any solvent that can dissolve the resin, and the boiling point is preferably 50 to 300 ° C, more preferably 100 to 250 ° C.

  The thickness of the resin coating film 12 is preferably 0.1 to 1000 μm, more preferably 0.1 to 500 μm, and particularly preferably 1 to 20 μm. The thickness of the resin coating 12 is preferably 0.001 to 10 with respect to the thickness of the glass sheet 11 when the thickness of the glass sheet 11 is 1, and 0.01 to 5 More preferably, 0.1 to 1 is particularly preferable.

(Fluorine resin)
By including the fluororesin described below, the resin coating film 12 forms a glass sheet 13 with a resin coating film that is excellent in durability, weather resistance, water repellency, antifouling properties, transparency, and the like.

  The fluororesin in the present invention refers to a fluororesin selected from the group consisting of a cured product of a solvent-soluble curable fluororesin, a solvent-soluble fluororesin, and a mixture thereof. The “solvent-soluble curable fluororesin solution” and the “solvent-soluble fluororesin solution” may be collectively referred to as “fluororesin solution”. Here, the solvent solubility is not limited to a case where a solution in a strict sense can be obtained, but includes a state where a stably dispersed state can be maintained. Moreover, the state in which some turbidity is seen in a solution state may be sufficient. Furthermore, it is preferable that the fluororesin solution is filtered. In particular, it is preferable to use a filter paper having a nominal opening of 5 μm or less because a smooth resin coating film 12 can be obtained by removing foreign substances.

  The fluorine content of the fluororesin is preferably 5% by mass or more, and more preferably 10% by mass or more. A high fluorine content is preferable in that the water absorption rate and relative dielectric constant of the resin are lowered, and the reliability and durability when an element is formed are increased. The upper limit of the fluorine content is preferably 76% by mass or less and more preferably 70% by mass or less because it is easy to make a solution. Here, the fluorine content is the proportion of the molecular weight occupied by fluorine atoms, and is usually calculated based on the chemical formula of the monomer. When a plurality of polymers are mixed and used, the fluorine content is calculated from the mixing ratio (mass ratio) thereof.

  Specific examples of the fluororesin (polymer) include a fluorinated olefin polymer and a fluorinated diene compound cyclized polymer. Fluorinated olefins include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, fluoroalkyl (meth) acrylate, fluoroalkyl vinyl ether, perfluoro (alkyldioxole), etc. Is mentioned. Examples of the fluorine-containing diene compound that can be cyclopolymerized include perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether).

  These polymers may be homopolymers of the aforementioned monomers (such as fluorine-containing olefins) or may be copolymers. In the case of a copolymer, it may be a copolymer of the above fluorine-containing olefin and the like and a monomer not containing a fluorine atom. Examples of the monomer not containing a fluorine atom include olefins, vinyl ethers such as alkyl vinyl ether, vinyl esters such as alkyl vinyl ester, and (meth) acrylates such as alkyl (meth) acrylate. Moreover, the monomer which does not contain a fluorine atom may be a compound having a reactive group such as a hydroxyl group. “(Meth) acrylate” is a combination of acrylate and methacrylate.

  Solvent-soluble fluororesins include vinylidene fluoride homopolymers or copolymers, cyclic fluorine-containing monomers such as perfluoro (alkyldioxole) (carbons in which the carbon atoms of the polymerizable unsaturated groups constitute the ring) (Monomers that are atoms) homopolymers or copolymers, homopolymers or copolymers of fluorinated diene compounds that can be cyclopolymerized, copolymers of tetrafluoroethylene and vinyl alcohol, fluoroalkyl (meta And a copolymer of acrylate and (meth) acrylates containing no fluorine atom. The homopolymer or copolymer of the cyclic fluorine-containing monomer and the homopolymer or copolymer of the fluorine-containing diene compound capable of cyclopolymerization are polymers having a ring structure in the main chain (mainly A polymer in which a part of the carbon atoms of the chain is a carbon atom constituting a ring).

  Solvent-soluble fluororesins include homopolymers of vinylidene fluoride, copolymers of perfluoro (dimethyldioxole) and tetrafluoroethylene, cyclized polymers of perfluoro (butenyl vinyl ether), and tetrafluoroethylene and vinyl. A copolymer with alcohol is preferable, and a homopolymer of vinylidene fluoride and a cyclized polymer of perfluoro (butenyl vinyl ether) are particularly preferable. The homopolymer of vinylidene fluoride is a polymer that can be crosslinked by heat treatment, but in the present invention, it is a solvent-soluble fluororesin (not a curable fluororesin).

  Examples of the solvent-soluble curable fluororesin include copolymers of chlorotrifluoroethylene or tetrafluoroethylene and alkyl vinyl ethers having a curable functional group such as a hydroxyl group, and fluorine-containing arylene ethers having a polymerizable functional group such as a vinyl group. A polymer etc. are mentioned. Alternatively, the copolymer of tetrafluoroethylene and vinyl alcohol can be reacted with an alkyl silicate oligomer to obtain a curable fluororesin.

  The curable fluororesin having a reactive group can be made into a cured product using a compound having a functional group that reacts with the reactive group as a curing agent or a crosslinking agent. For example, a curable fluororesin having a hydroxyl group can be made into a cured product with a curing agent having an isocyanate group. In addition, a fluororesin having a polymerizable functional group such as a vinyl group can be cured with a radical generator or the like.

  Examples of the solvent-soluble curable fluororesin include a hydroxyl group-containing fluororesin composed of a copolymer of chlorotrifluoroethylene and a hydroxyl group-containing vinyl ether, or a copolymer of tetrafluoroethylene and vinyl alcohol with an alkyl silicate oligomer. And a fluorinated arylene ether polymer having a vinyl group, particularly preferably a fluorinated arylene ether polymer having a vinyl group.

  As a glass transition temperature of a fluororesin, 200 degrees C or less is preferable and 150 degrees C or less is more preferable. When the glass transition temperature is low, stress hardly remains in the resin coating film 12, and the warp of the glass sheet 13 with the resin coating film is suppressed, and flatness is maintained. The transmittance of the fluororesin is preferably 80% or more and more preferably 90% or more in the wavelength range of 400 to 700 nm.

(Polyimide resin)
By including the polyimide resin described below, the resin coating film 12 forms a glass sheet 13 with a resin coating film that is excellent in durability, weather resistance, heat resistance, mechanical strength characteristics, and the like.

  The polyimide resin in the present invention is preferably a polyimide resin obtained by applying a polyamic acid dissolved in a solvent and drying and curing the resin after application. The polyamic acid solution is preferably filtered. In particular, it is preferable to use a filter paper having a nominal opening of 5 μm or less because a smooth resin coating film 12 can be obtained by removing foreign substances.

  Examples of the polyimide resin include aromatic polyimide resins and aliphatic polyimide resins. An aromatic polyimide resin is preferred because of its excellent heat resistance.

(Polyester resin)
By including the polyester resin described below, the resin coating film 12 forms a glass sheet 13 with a resin coating film that is excellent in durability, electrical characteristics, mechanical strength characteristics, and the like.

  Examples of the polyester resin solution in the present invention include a polyester resin dissolved in a solvent. The polyester resin solution is preferably filtered. In particular, it is preferable to use a filter paper having a nominal opening of 5 μm or less because a smooth resin coating film 12 can be obtained by removing foreign substances.

  Examples of the polyester resin include aromatic polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); and aliphatic polyester resins such as polycaprolactone and polylactic acid. An aromatic polyester resin is preferred because of its excellent heat resistance.

(Polycarbonate resin)
By including the polycarbonate resin described below, the resin coating film 12 forms a glass sheet 13 with a resin coating film having excellent durability, electrical characteristics, mechanical strength characteristics, and the like.

  Examples of the polycarbonate resin solution in the present invention include those obtained by dissolving a polycarbonate resin in a solvent. The polycarbonate resin solution is preferably filtered. In particular, it is preferable to use a filter paper having a nominal opening of 5 μm or less because a smooth resin coating film 12 can be obtained by removing foreign substances.

<Glass sheet with resin coating>
The glass sheet 13 with a resin coating film in which the resin coating film 12 is formed on one or both surfaces of the glass sheet 11 preferably has a light transmittance of 80% or more at a wavelength of 400 to 700 nm, and 90% or more. Is more preferable and it is especially preferable that it is 93% or more. It is preferable that the glass sheet 13 with a resin coating film is transparent in the said wavelength range, ie, the range of visible light. Since the glass sheet 13 with a resin coating film has transparency, it can be used, for example, as a protective plate disposed on the front surface of the display device. Further, for example, when used as a base material for a light emitting element, a power generation element, etc., the light emission efficiency and the power generation efficiency are not lowered.

  Moreover, since the external appearance becomes favorable, it is preferable that the thickness of the glass sheet 13 with a resin coating film is uniform. Specifically, the standard deviation of the thickness is preferably 50% or less, and more preferably 35% or less.

  As explained above, according to the method for producing a glass sheet with a resin coating film according to the present embodiment, it is possible to produce the glass sheet 13 with a resin coating film having excellent impact resistance, durability, and the like. Since a resin coating film can be continuously formed on the surface of the glass sheet 11, the productivity is improved. Moreover, a resin coating film can be formed on the glass sheet 11 in a non-contact manner, and productivity does not decrease due to damage or the like of the glass sheet 11.

  As mentioned above, although the manufacturing method of the glass sheet with a resin coating film concerning embodiment was demonstrated, this invention is not limited to the said embodiment, A various deformation | transformation and improvement are possible within the scope of the present invention.

DESCRIPTION OF SYMBOLS 10 Supply roll 11 Glass sheet 12 Resin coating film 13 Glass sheet 20 with resin coating 20 Electrospray apparatus 21 Nozzle 22 Counter electrode 23 Resin solution 25 Roller electrode 27 Air turn bar 20 Drying apparatus 40 Recovery roll 100 Glass sheet manufacturing apparatus with a resin coating film

Claims (9)

A method for producing a glass sheet with a resin coating,
Preparing an electrospray apparatus having a nozzle and a counter electrode, a resin solution fed to the nozzle, and a glass sheet having a thickness of 10 to 300 μm;
Using the electrospray device, the resin solution is applied to the glass sheet being conveyed, and a resin coating film is formed on the glass sheet.
The manufacturing method of the glass sheet with a resin coating film.   The manufacturing method of the glass sheet with a resin coating film of Claim 1 which cut | disconnects the said glass sheet in which the said resin coating film was formed.   The manufacturing method of the glass sheet with a resin coating film of Claim 1 which winds up the said glass sheet in which the said resin coating film was formed.   The said resin coating film is a manufacturing method of the glass sheet with a resin coating film as described in any one of Claim 1 to 3 containing a fluororesin.   The said resin coating film is a manufacturing method of the glass sheet with a resin coating film as described in any one of Claim 1 to 3 containing a polyimide resin.   The glass sheet with a resin coating film according to any one of claims 1 to 5, wherein the resin solution is applied to the glass sheet being transported between the nozzle and the counter electrode of the electrospray device. Production method.   The method for producing a glass sheet with a resin coating film according to any one of claims 1 to 6, wherein a space is provided between the counter electrode and the glass sheet being conveyed.   The said counter electrode is a manufacturing method of the glass sheet with a resin coating film as described in any one of Claim 1 to 6 which is a roller electrode rotated synchronizing with the said glass sheet currently conveyed.   The manufacturing method of the glass sheet with a resin coating film as described in any one of Claim 1 to 8 which neutralizes the said glass sheet in which the said resin coating film was formed.

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