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WO2015118983A1 - Procédé de production d'une feuille de verre ayant un film de revêtement de résine - Google Patents

Procédé de production d'une feuille de verre ayant un film de revêtement de résine Download PDF

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Publication number
WO2015118983A1
WO2015118983A1 PCT/JP2015/052029 JP2015052029W WO2015118983A1 WO 2015118983 A1 WO2015118983 A1 WO 2015118983A1 JP 2015052029 W JP2015052029 W JP 2015052029W WO 2015118983 A1 WO2015118983 A1 WO 2015118983A1
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WO
WIPO (PCT)
Prior art keywords
glass sheet
coating film
resin coating
resin
nozzle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/052029
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English (en)
Japanese (ja)
Inventor
小金澤　光司
聡 白鳥
良太 中島
哲哉 小山
信之 芝田
弘賢 山本
和也 新田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2015118983A1 publication Critical patent/WO2015118983A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C03C17/324—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/115—Deposition methods from solutions or suspensions electro-enhanced deposition

Definitions

  • 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 or a semiconductor element is provided with a cover glass to protect the surface.
  • a cover glass to protect the surface.
  • the processing since the processing is performed with the glass substrate fixed to a thin film forming apparatus for forming a thin film, the processing must be intermittent, and it is difficult to improve productivity.
  • 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.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a method for producing a glass sheet with a resin coating film that can be continuously processed and has improved productivity.
  • a method for producing a glass sheet with a resin coating film comprising an electrospray device having a nozzle and a counter electrode, a resin solution fed to the nozzle, and a thickness of 10 to 300 ⁇ m. 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.
  • 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.
  • the glass sheet manufacturing apparatus 100 has a supply roll 10, an electrospray apparatus 20, a drying apparatus 30, and a collection roll 40 as shown in FIG.
  • 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 has a nozzle and a counter electrode facing the nozzle, and forms a resin coating 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.
  • 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 around a central axis, and 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 is wound in a roll shape and collected.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 supply 24 to apply a voltage, and forms an electric field between the tip of the nozzle 21 and the counter electrode 22 connected to the ground.
  • the 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 the 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 applied to the nozzle 21 is not particularly limited, but is preferably 5 to 30 kV, more preferably 5 to 25 kV, and even 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 the uniform wet resin coating film 12 ′ is easily obtained.
  • the distance between the tip of the nozzle 21 and the counter electrode 22 is not particularly limited, but is preferably 10 to 200 mm, more preferably 30 to 200 mm, and still more preferably 50 to 150 mm. 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, the resin solution 23 will become difficult to apply to the surface of the glass sheet 11, and it will become easy to obtain the 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.
  • the liquid feeding speed of the resin solution 23 is not particularly limited, but is preferably 10 to 2000 ⁇ L / min per nozzle, more preferably 50 to 1000 ⁇ L / min, and further preferably 100 to 1000 ⁇ L / min. If the liquid feeding speed is equal to or lower than the above upper limit value, a uniform wet resin coating film 12 ′ can be easily obtained. If the liquid feeding speed is equal to or higher than the lower limit, productivity can be improved, and a sufficient solvent for leveling is present, so that it is easy to ensure the uniformity of the wet resin coating film 12 '.
  • the liquid feeding pressure of the resin solution 23 is not particularly limited, but is preferably 1 kPa to 0.5 MPa, for example, and more preferably 5 kPa to 0.1 MPa. 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.
  • the environmental humidity (relative humidity) in the electrospray apparatus 20 is not particularly limited, but is preferably 20 to 90%, preferably 30 to 90%, and more preferably 60 to 90%. If the humidity is equal to or higher than the above lower limit value, the resin solution 23 is difficult to be applied to the surface of the glass sheet 11 and the 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
  • the conveying speed of the glass sheet 11 is not particularly limited, but is preferably 0.1 to 100 m / min, and more preferably 1 to 50 m / min. In particular, it is preferable that the glass sheet 11 is continuously conveyed because it is easy to increase productivity.
  • 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.
  • 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.
  • 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.
  • 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 in which no gas is used 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 a zigzag alignment. A staggered arrangement is preferred because there is little interference between nozzles.
  • 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.
  • 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.
  • 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.
  • 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 formed 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 along the conveying direction of the glass sheet 11 (more preferably, a curved surface having a center or axis on the opposite side of the nozzle 21 from 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, the position will be stabilized by the rigidity of the glass sheet 11 itself, and it will be easy to obtain the 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).
  • 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.
  • the roughness is, for example, preferably 0.05 to 1 ⁇ m, more preferably 0.1 to 0.6 ⁇ m in terms of arithmetic average roughness (Ra) defined by JIS B0601.
  • the size of the roller electrode 25 is not particularly limited.
  • the diameter is preferably 50 to 1000 mm, and more preferably 200 to 1000 mm.
  • the contact area between the roller electrode 25 and the glass sheet 11 is reduced, and it is more preferable that the metal constituting the roller electrode 25 and the glass sheet 11 are not in direct contact.
  • 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.
  • the surface of the roller electrode 25 is preferably coated with a slippery fluororesin.
  • 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.
  • the flying distance of the glass sheet in the air turn bar 27 is not particularly limited, but is preferably 0.1 to 5 mm, and more preferably 0.5 to 3 mm.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG.5 and FIG.6 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.
  • the material and composition of the glass sheet 11 are not limited.
  • soda lime glass, alkali-borosilicate glass, non-alkali-borosilicate glass, non-alkali-aluminosilicate glass, or the like can be used.
  • alkali-free borosilicate glass and alkali-aluminosilicate glass are preferable in terms of excellent durability, high elastic modulus, and low linear expansion coefficient.
  • 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 to 300 ⁇ m. When the thickness is 10 ⁇ m 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
  • the thickness of the glass sheet 11 is more preferably 20 to 200 ⁇ m, particularly preferably 30 to 100 ⁇ m.
  • 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 the thickness of 100 ⁇ m). Is preferably 15 ⁇ m or less. When the thickness is uniform, the appearance of the glass sheet 11 is improved.
  • PV Peak to Valley
  • 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.
  • Ra arithmetic average roughness
  • 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.
  • the Young's modulus of the glass sheet 11 is preferably 70 to 95 GPa, more preferably 75 to 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 tempering process.
  • a tempering process As the strengthening treatment, chemical strengthening is preferable. If it is chemical strengthening, the thin glass sheet 11 can be effectively strengthened.
  • the tempering treatment an effect is obtained that the glass sheet 11 with a resin coating film is not easily damaged even if the glass sheet 11 is thin and lightweight.
  • 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.
  • 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.
  • the resin may be dissolved in a solvent, or the resin may be synthesized in a solvent and used.
  • the resin solution 23 may contain components other than the resin and the solvent.
  • a fluororesin when 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 preferably 1 to 15% by mass.
  • solid content means the ratio by which the solid content obtained by drying a solution is contained in the whole solution.
  • 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 in the resin solution 23 is not particularly limited as long as it 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 ⁇ m, more preferably 0.1 to 500 ⁇ m, and particularly preferably 1 to 20 ⁇ m. Further, the thickness of the resin coating film 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 is 0.01 to 5 More preferably, 0.1 to 1 is particularly preferable.
  • 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 means 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”.
  • 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.
  • the fluororesin solution is filtered. In particular, it is preferable to use a filter paper having a nominal opening of 5 ⁇ m 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.
  • 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.
  • fluororesin 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.
  • fluorine-containing diene compound that can be cyclopolymerized include perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether).
  • polymers may be homopolymers of the aforementioned monomers (such as fluorine-containing olefins) or copolymers.
  • a copolymer it may be a copolymer of the above fluorine-containing olefin and the like and a monomer not containing a fluorine atom.
  • 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.
  • 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.
  • 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 copoly
  • 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).
  • solvent-soluble curable fluororesin examples 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.
  • 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.
  • a curable fluororesin having a hydroxyl group can be made into a cured product with a curing agent having an isocyanate group.
  • a fluororesin having a polymerizable functional group such as a vinyl group can be cured with a radical generator or the like.
  • solvent-soluble curable fluororesin examples 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.
  • the glass transition temperature of the fluororesin is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower. 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.
  • 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.
  • polyimide resin examples include aromatic polyimide resins and aliphatic polyimide resins.
  • aromatic polyimide resin is preferred because of its excellent heat resistance.
  • 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.
  • the polyester resin solution in the present invention includes a polyester resin dissolved in a solvent.
  • the polyester resin solution is preferably filtered.
  • polyester resin examples include aromatic polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); and aliphatic polyester resins such as polycaprolactone and polylactic acid.
  • aromatic polyester resin is preferred because of its excellent heat resistance.
  • 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.
  • the glass sheet 13 with a resin coating film having the resin coating film 12 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, preferably 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.
  • the thickness of the glass sheet 13 with a resin coating film is preferably uniform because the appearance is good.
  • the standard deviation of the thickness is preferably 50% or less, and more preferably 35% or less.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention a pour but de proposer un procédé de production d'une feuille de verre ayant un film de revêtement de résine, qui permet un traitement continu et a une productivité améliorée. À cet effet, l'invention concerne un procédé de production d'une feuille de verre ayant un film de revêtement de résine, dans lequel : un dispositif d'électropulvérisation comprenant une buse et une contre-électrode, une solution de résine qui est envoyée vers la buse et une feuille de verre ayant une épaisseur de 10 à 300 µm sont préparés ; et la feuille de verre étant transportée est revêtue par la solution de résine par utilisation du dispositif d'électropulvérisation, formant ainsi un film de revêtement de résine sur la feuille de verre.
PCT/JP2015/052029 2014-02-06 2015-01-26 Procédé de production d'une feuille de verre ayant un film de revêtement de résine Ceased WO2015118983A1 (fr)

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JP2014-021680 2014-02-06
JP2014021680A JP2017065930A (ja) 2014-02-06 2014-02-06 樹脂塗膜付ガラスシートの製造方法

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WO2018066527A1 (fr) * 2016-10-05 2018-04-12 旭硝子株式会社 Composition contenant un polymère fluoré et procédé de production d'un substrat sur lequel est déposé un film de polymère fluoré
KR20190067160A (ko) 2016-10-05 2019-06-14 에이지씨 가부시키가이샤 함불소 중합체 함유 조성물 및 함불소 중합체막이 형성된 기재의 제조 방법
DE112017005051T5 (de) 2016-10-05 2019-06-19 AGC Inc. Zusammensetzung, die ein fluoriertes Polymer enthält, und Verfahren zur Herstellung eines Substrats, das mit einem fluorierten Polymerfilm versehen ist
JPWO2018066527A1 (ja) * 2016-10-05 2019-08-29 Ａｇｃ株式会社 含フッ素重合体含有組成物および含フッ素重合体膜付き基材の製造方法
US11084946B2 (en) 2016-10-05 2021-08-10 AGC Inc. Composition containing fluorinated polymer and method for producing fluorinated polymer film-provided substrate

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