WO2019044779A1 - Procédé de production d'un substrat en verre fixé à un film, substrat en verre fixé à un film et procédé de retrait de film - Google Patents

Procédé de production d'un substrat en verre fixé à un film, substrat en verre fixé à un film et procédé de retrait de film Download PDF

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WO2019044779A1
WO2019044779A1 PCT/JP2018/031610 JP2018031610W WO2019044779A1 WO 2019044779 A1 WO2019044779 A1 WO 2019044779A1 JP 2018031610 W JP2018031610 W JP 2018031610W WO 2019044779 A1 WO2019044779 A1 WO 2019044779A1
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Prior art keywords
film
glass substrate
curvature
coated glass
thickness
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PCT/JP2018/031610
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English (en)
Japanese (ja)
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聡司 大神
俊司 和智
尚洋 眞下
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Ａｇｃ株式会社
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Priority to CN201880053665.5A priority Critical patent/CN110997590B/zh
Publication of WO2019044779A1 publication Critical patent/WO2019044779A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions

Definitions

  • the present invention relates to a method of manufacturing a film-coated glass substrate, a film-coated glass substrate, and a method of removing a film.
  • a cover glass is provided on the image display panel to protect the surface of the image display panel.
  • an image display panel such as a liquid crystal panel or an organic EL panel, such as a tablet PC or a smartphone
  • a cover glass is provided on the image display panel to protect the surface of the image display panel.
  • a film-coated glass substrate having a film formed on the surface of the glass substrate is used in order to suppress reflection and enhance scratch resistance.
  • a film-coated glass substrate When a film-coated glass substrate is used as a cover glass, when the film being formed on the glass substrate shrinks or expands relative to the glass substrate in the surface direction of the film, a film stress is generated in the surface direction of the film, The attached glass substrate was easy to warp. If this warpage is large, even when the film-coated glass substrate is bonded to the surface of the image display panel, the film-coated glass substrate may be peeled off, and the yield of manufacturing the portable electronic device is reduced. Therefore, the main surface of the film-coated glass substrate was as flat as possible.
  • Patent Document 1 As a method of suppressing the warp of the film-coated glass substrate, for example, a method of manufacturing a thin film-reinforced glass substrate for forming a thin film on a warped glass substrate so as to suppress the warp of the glass substrate has been proposed (for example, Patent Document 1).
  • a method for manufacturing a thin film-attached tempered glass substrate when a compressive stress layer is formed on the main surface of the glass substrate to produce a tempered glass substrate, the substrate becomes convex or concave in the direction perpendicular to the outer surface of the tempered glass substrate To form a warp. Then, a thin film is formed on the compressive stress layer formed on at least one of the main surfaces of the tempered glass substrate to reduce the warpage of the tempered glass substrate.
  • the warpage of the thin film-attached tempered glass substrate is too small. Therefore, there is a possibility that the appearance quality of the tempered glass substrate with a thin film may be degraded, for example, the main surface of the glass substrate with a thin film may be easily scratched in the process flow after the production of the glass substrate with a thin film.
  • the present invention has been made in view of the above problems, and its main object is to provide a method of manufacturing a film-coated glass substrate which reduces warpage to such an extent that the quality of the appearance is not affected.
  • a method of manufacturing a film-coated glass substrate comprising a glass substrate and a film formed on the main surface of the glass substrate, Film thickness (t f ) and film stress ( ⁇ f ) are formed on a glass substrate with thickness (t g ), Young's modulus (E g ), Poisson's ratio ( ⁇ g ), and curvature ( ⁇ g ) Film forming process, Following formula (1):
  • a method of manufacturing a film-coated glass substrate which reduces warpage to such an extent that the quality on the appearance is not affected.
  • the upper side in the vertical direction may be referred to as the upper side
  • the lower side in the vertical direction may be referred to as the lower side.
  • a three-dimensional orthogonal coordinate system in three axial directions (X-axis direction, Y-axis direction, Z-axis direction) is used, the width direction of the glass substrate is the X direction, the depth direction is the Y direction, and the thickness direction In the Z direction.
  • the direction from the glass substrate toward the film is the + Z axis direction, and the opposite direction is the ⁇ Z axis direction.
  • “-” Indicating a numerical range means that numerical values described before and after that are included as the lower limit value and the upper limit value.
  • FIG. 1 is a flowchart showing a method of manufacturing a film-coated glass substrate according to an embodiment.
  • the method of manufacturing a film-coated glass substrate according to one embodiment includes a step of preparing a glass substrate (step S11) of preparing a glass substrate having a predetermined curvature by warping the main surface of the glass substrate. And a film forming step (step S12) of forming (forming) an antireflective film (AR film) on the main surface of the glass substrate having a predetermined curvature.
  • 2 to 8 are explanatory views showing a part of the process of the method of manufacturing a film-coated glass substrate according to one embodiment.
  • step S11 first, as shown in FIGS. 2 and 3, a glass substrate 11 having a pair of opposing main surfaces 11a and 11b is prepared.
  • the main surfaces 11a and 11b of the glass substrate 11 are formed in a rectangular shape in plan view.
  • the rectangle includes a rectangle and a square, as well as a shape in which the corner of the rectangle and the square is chamfered.
  • Examples of the material of the glass substrate 11 include soda lime silica glass, borosilicate glass, and aluminosilicate glass.
  • the glass substrate 11 is obtained by melting a glass raw material and forming the molten glass into a plate shape.
  • the forming method may be a general method, and for example, a float method, a fusion method, a downdraw method, a redraw method, or a press forming method may be used. Among them, as a method of manufacturing the glass substrate 11, it is preferable to use a float method suitable for mass production.
  • the thickness (thickness) t g of the glass substrate 11 is designed according to the application of the film-coated glass substrate 10 (see FIGS. 7 and 8) which is a finished product.
  • the thickness t g of the glass substrate 11 is, for example, preferably 0.1 mm to 1.0 mm, more preferably 0.2 mm to 0.5 mm, and 0.2 mm to 0.35 mm. More preferable.
  • the plate thickness t g of the glass substrate 11 is 0.1 mm or more, generation of a crack in the glass substrate 11 can be suppressed.
  • the thickness t g of the glass substrate 11 is 1.0 mm or less, the weight of the glass substrate 11 can be reduced.
  • the thickness t g of the glass substrate 11 refers to the length in the direction perpendicular to the major surfaces 11 a and 11 b of the glass substrate 11.
  • the plate thickness t g of the glass substrate 11 is, for example, the thickness when an arbitrary place is measured in the cross section of the glass substrate 11. In the cross section of the glass substrate 11, when several places are measured at arbitrary places, it is good also as an average value of the thickness of these measurement points.
  • the Young's modulus E g of the glass substrate 11 is preferably 65 MPa to 120 MPa. When the Young's modulus E g falls within the above range, the crack resistance and the strength of the glass substrate 11 can be sufficiently maintained.
  • the Young's modulus E g is more preferably 75 MPa to 120 MPa, still more preferably 85 MPa to 100 MPa. Young's modulus E g can be measured by a known measurement method such as a pendulum method, a resonance method, or an ultrasonic pulse method.
  • the Poisson's ratio g g of the glass substrate 11 is preferably 0.16 to 0.4. If Poisson's ratio [nu g is within the above range, although the glass substrate 11 is generally a glass material, it can be applied. Poisson's ratio g g is the ratio of the strain generated along the stress direction of the glass substrate 11 and the strain generated in the direction orthogonal to the stress direction of the glass substrate 11 when tensile stress is applied to the glass substrate 11 Means Poisson's ratio [nu g, for example, can be used JIS-K7165 (2008), or was measured in accordance like JIS-K7164 (2005) values.
  • the glass substrate 11 may be chemically strengthened.
  • chemical strengthening for example, an ion having a small ion radius such as Li ion or Na ion contained in the surface of the glass substrate 11 is replaced with an ion having a relatively large ion radius such as K ion. Do.
  • a compressive stress layer is formed at a predetermined depth from the surface of the glass substrate 11.
  • the major surfaces 11a and 11b of the prepared glass substrate 11 are warped to form the glass substrate 11 as the major surfaces 11a and 11b of the glass substrate 11, as shown in FIGS.
  • the shape is concavely curved in the + Z axis direction.
  • a glass substrate 11 having a predetermined curvature g g is obtained.
  • the curvature means the degree of bending of the substrate and is the reciprocal of the radius of curvature.
  • the radius of curvature refers to the radius R of an imaginary circle in contact with the substrate, as shown in FIG.
  • the curvature kappa g of the glass substrate 11 refers to the major surface 11a, 11b of curvature of the glass substrate 11 before the AR film is formed by later-described film formation step (step S12). Details of a method of selecting the curvature g g of the glass substrate 11 will be described later.
  • the curvature kappa g of the glass substrate 11, the major surface 11a of the glass substrate 11, 11b is in the film forming direction (this embodiment of the AR film to be deposited in a film formation step (step S12), the When it is concavely curved with respect to + Z axis direction), it is represented by a positive value.
  • Absolute value of the curvature kappa g of the glass substrate 11 is preferably 0.03 (1 / m) ⁇ 0.3 (1 / m). If the absolute value of the curvature gg of the glass substrate 11 is 0.3 (1 / m) or less, the AR film can be formed uniformly. If the absolute value of the curvature gg of the glass substrate 11 is 0.03 (1 / m) or more, the convex surface of the glass substrate 11 can be determined visually, so the workability in the film forming process described later is improved.
  • the absolute value of the curvature g g of the glass substrate 11 is more preferably 0.06 (1 / m) or more, still more preferably 0.07 (1 / m) or more, and 0.10 (1 / m).
  • the absolute value of the curvature g g of the glass substrate 11 is more preferably 0.2 (1 / m) or less, and is preferably 0.15 (1 / m) or less, from the viewpoint of forming the AR film more uniformly. And more preferably 0.14 (1 / m) or less.
  • a known deformation method of the glass substrate can be used.
  • a method of deforming the glass substrate for example, a method of heating, softening, and deforming the glass substrate 11, a method of chemically strengthening at least one of the main surfaces 11a and 11b of the glass substrate 11, and the like can be used.
  • a method of heating, softening, and deforming the glass substrate 11 for example, there is a method of press-molding with a forming mold or the like while heating the glass substrate 11.
  • the way in which stress is applied to the main surfaces 11a and 11b of the glass substrate 11 not chemically strengthened is made different.
  • the method of heating, softening, and deforming the glass substrate 11 is preferable in terms of easy operation.
  • the AR film 12 is formed on the main surface 11a of the glass substrate 11.
  • membrane which concerns on one Embodiment is obtained.
  • the main surface of the film-coated glass substrate 10 is curved in a convex shape in the direction in which the AR film 12 is formed (in the present embodiment, the + Z-axis direction).
  • the film-coated glass substrate 10 obtained in the film forming step (step S12) is transported by a transport device (not shown). At this time, when the film-coated glass substrate 10 is transported by the transport device in a state in which the main surface of the film-coated glass substrate 10 is curved in a convex shape (in the present embodiment, + Z axis direction) downward. Since the central portion of the main surface of the film-coated glass substrate 10 is in contact with the transport component such as the transport roller or the flat transport plate in the transport device, the central portion of the main surface of the film-coated glass substrate 10 is easily scratched.
  • the transport component such as the transport roller or the flat transport plate in the transport device
  • the film-coated glass substrate 10 is conveyed with its main surface curved in a convex shape (in the present embodiment, the + Z-axis direction) upward.
  • the film-coated glass substrate 10 is transported while maintaining its main surface curved in a convex shape in the + Z-axis direction and warped. Therefore, the outer peripheral portion of the main surface of the film-coated glass substrate 10 is in contact with the transport component such as the roller in the transfer device, and the central portion of the main surface of the film-coated glass substrate 10 can be prevented from contacting. Therefore, the film-coated glass substrate 10 can be transferred by the transfer device while preventing a scratch or the like from being generated at the center of the main surface of the film-coated glass substrate 10 by the contact with the transfer component.
  • the AR film 12 is a film having a function of reducing the reflectance of the surface of the glass substrate 11 and increasing the transmittance.
  • the AR film 12 is a low refractive index layer formed of a material having a refractive index lower than that of the glass substrate 11, and a high refractive index layer formed of a material having a refractive index higher than that of the low refractive index layer on the low refractive index layer. And are alternately laminated.
  • the AR film 12 is made of, for example, AlN, AlON, Al 2 O 3 , SiO 2 , Si 3 N 4 , SiON, ZrO 2 , Ta 2 O 5 , SnO 2 , In 2 O 3 , ZnO, TiO 2 or Nb 2 O It can be formed by dividing and laminating one or more types of low refractive index layers and one or more types of high refractive index layers using one or more types of 5 and the like.
  • the film formation method of the AR film 12 can be appropriately selected according to the type of the AR film 12 and the like.
  • the AR film 12 may be formed by, for example, a vapor phase method such as sputtering, reactive magnetron sputtering, chemical vapor deposition, electron beam evaporation, ion assisted deposition, atomic layer deposition (ALD), etc.
  • a wet method such as a sol-gel method or a spin coating method can be used.
  • the sputtering method is preferable in that a film with high hardness can be obtained under the condition of low film formation temperature. When the temperature of the glass substrate 11 exceeds 200 ° C.
  • the sputtering method for example, it is preferable to use a radical assisted sputtering (RAS) method (see, for example, US Pat. No. 6,103,320) or a metamode method (see, for example, Japanese Patent No. 5783613).
  • RAS radical assisted sputtering
  • the film thickness (thickness) t f of the AR film 12 is designed in accordance with the application of the film-coated glass substrate 10 as a finished product.
  • the film thickness t f of the AR film 12 is preferably, for example, 0.3 ⁇ m to 5.0 ⁇ m.
  • the film thickness t f of the AR film 12 is too thick, the transmittance decreases and the optical characteristics deteriorate.
  • the film thickness t f of the AR film 12 is thin, the film becomes weak to a flaw. Therefore, if the film thickness t f of the AR film 12 is 0.4 ⁇ m to 4.0 ⁇ m, well-balanced performance can be exhibited.
  • the thickness t f of the AR film 12 is more preferably 0.6 ⁇ m to 3.5 ⁇ m.
  • the film thickness t f of the AR film 12 refers to the length in the direction perpendicular to the main surface of the AR film 12.
  • the film thickness t f of the AR film 12 is, for example, the thickness when an arbitrary location is measured in the cross section of the AR film 12 as in the thickness t g of the glass substrate 11. When measuring several places at any place, it is the average value of the thickness of these measurement points.
  • the AR film 12 shrinks or expands in the surface direction of the AR film 12 with respect to the glass substrate 11, whereby the surface direction of the AR film 12 Film stress occurs. Due to this film stress, the main surfaces 11a and 11b of the glass substrate 11 are curved in a convex or concave shape in the + Z-axis direction, and a curved film-coated glass substrate 10 is obtained.
  • the film stress means the internal stress of the AR film 12.
  • the film stress of the AR film 12 may be a stress in a compression direction (compression stress) or a stress in a tension direction (tensile stress).
  • the film stress ⁇ f is a tensile stress, it is represented by a positive value, and in the case of a compressive stress, it is represented by a negative value (a minus (-) sign).
  • the AR film 12 has a compressive stress, and causes the major surfaces 11 a and 11 b of the glass substrate 11 to be warped in a convex shape in the + Z axis direction.
  • the absolute value of the film stress sigma f of AR film 12 is, for example, is preferably 10 MPa ⁇ 800 MPa.
  • the film stress sigma f of AR film 12 When the film stress sigma f of AR film 12 is large, which will be described later, the absolute value of the film thickness t f and the film stress sigma value obtained by multiplying the f t f ⁇ f (hereinafter,
  • the film stress ⁇ f can be calculated from the value obtained by measuring the amount of deformation of the film-coated glass substrate 10 per predetermined length.
  • the film stress ⁇ f is, for example, a surface profile on a line passing through the center in the X-axis direction of the film-coated glass substrate 10 using a known device such as a thin film stress measuring device manufactured by KLA-TENCOR (eg, Measure the curvature radius at 50 points).
  • the film stress ⁇ f of the AR film 12 can be calculated from the determined radius of curvature by using the Stoney equation of the following equation (i) described later.
  • the film stress ⁇ f may also be calculated by measuring the radius of curvature of the film-coated glass substrate 10 before and after processing the glass substrate 11 to be thinner by 10% or more of the plate thickness and performing analysis by the finite element method. it can.
  • the film thickness t f and the film stress ⁇ f of the AR film 12 obtained under the same conditions as the film forming step (step S12) are measured in the preparation step of the glass substrate (step S11). Check if equation (1) holds.
  • t f is the thickness of the AR film
  • ⁇ f is the film stress of the AR film
  • g g is the Poisson's ratio of the glass substrate
  • E g is the glass The Young's modulus of the substrate
  • t g is the thickness of the glass substrate
  • the AR film 12 for measuring the film thickness t f and the film stress ⁇ f is preferably formed on a glass substrate, but a substrate made of a material other than glass may be used.
  • ⁇ f is the film stress of the AR film
  • E g is the Young's modulus of the glass substrate
  • t g is the thickness of the glass substrate
  • ⁇ g is the glass The Poisson's ratio of the substrate
  • t f is the thickness of the AR film
  • R after is the radius of curvature of the glass substrate with a film
  • R before is the radius of curvature of the glass substrate before the deposition of the AR film. is there.
  • 1 / R before in the above-mentioned formula (i) is zero.
  • 1 / R after is represented by (6t f ⁇ f (1 ⁇ v g ) / (E g t g 2 ) ⁇ 10 6 ), which is the same as the left side of the above equation (1).
  • the predicted curvature change ⁇ f of the film-coated glass substrate is obtained from the above equation (1), but the AR film 12 is formed on the ideal plane using the glass substrate having an ideal plane with zero flatness.
  • the curvature of the film-coated glass substrate obtained may be measured.
  • the AR probe of the film-coated glass substrate is scanned with a contact type probe along the curved direction of the film-coated glass substrate.
  • the radius of curvature of the film-coated glass substrate is determined. From the obtained radius of curvature, the predicted curvature change ⁇ f of the film-coated glass substrate can be determined.
  • the main surface 11b of the film-coated glass substrate may be scanned with a laser beam.
  • the predicted curvature of the glass substrate deformed by the stress generated by the above equation (i) is larger than 0.025 (1 / m) by 0.10 (1 / m) Of the glass substrate 11 before the AR film 12 is deposited so as to be smaller than 0.025 (1 / m) and preferably smaller than 0.08 (1 / m).
  • the main surfaces 11a and 11b are warped.
  • the curvature g g of the glass substrate 11 is warped so as to satisfy the following formula (2).
  • t f is the thickness of the AR film
  • ⁇ f is the film stress of the AR film
  • g g is the Poisson's ratio of the glass substrate
  • E g is the glass The Young's modulus of the substrate
  • t g is the thickness of the glass substrate
  • ⁇ g is the curvature of the glass substrate.
  • the predicted curvature ( ⁇ f + ⁇ g ) of the film-coated glass substrate 10 is the same as the predicted curvature change ⁇ f of the film-coated glass substrate, the main surface of the film-coated glass substrate is the deposition direction of the AR film 12 (this embodiment) In the case of concave curvature with respect to + Z axis direction), it is represented by a positive value.
  • the predicted curvature ( ⁇ f + ⁇ g ) of the film-coated glass substrate 10 has a negative value (minus ( ⁇ ) when it is convexly curved in the film forming direction of the AR film 12 (in the present embodiment, + Z axis direction). Sign of-).
  • the film-coated glass substrate 10 has a predicted curvature ( ⁇ f + ⁇ g ) within a range larger than 0.025 (1 / m) and smaller than 0.10 (1 / m).
  • the film-coated glass substrate 10 is transported by the transport device (not shown) with the main surface of the film-coated glass substrate 10 curved in a convex shape (in the present embodiment, the + Z-axis direction). Be done. If the predicted curvature ( ⁇ f + ⁇ g ) of the film-coated glass substrate 10 is 0.025 (1 / m) or less, the predicted curvature ( ⁇ f + ⁇ g ) of the film-coated glass substrate 10 is too small.
  • the warp of the film-coated glass substrate 10 can not be maintained by the weight of the glass substrate 10. In this case, the warpage of the film-coated glass substrate 10 is crushed and deformed almost flat. Therefore, in the process flow after the production of the film-coated glass substrate 10, almost the whole of the main surface of the film-coated glass substrate 10 comes in contact with transport components such as transport rollers and flat transport plates in a transport device (not shown). As a result, almost the entire main surface of the film-coated glass substrate 10 may be easily scratched, which may degrade the appearance quality of the thin film-reinforced glass substrate.
  • the predicted curvature ( ⁇ f + ⁇ g ) of the film-coated glass substrate 10 is 0.10 (1 / m) or more, the predicted curvature ( ⁇ f + ⁇ g ) of the film-coated glass substrate 10 is too large. Therefore, even if the film-coated glass substrate 10 is attached to an image display panel such as a portable electronic device, the film-coated glass substrate 10 may be peeled off from the image display panel. In addition, since the warp of the substrate obtained by bonding the film-coated glass substrate 10 to the image display panel is increased, the screen may be distorted and light may leak from the backlight of the portable electronic device. Therefore, the portable electronic device may be a defective product, and the yield of manufacturing the portable electronic device may be lowered.
  • the film-coated glass substrate 10 obtained by selecting the curvature g g of the main surface 11 a of the glass substrate 11 using the method of manufacturing the film-coated glass substrate 10 according to an embodiment is the predicted curvature of the film-coated glass substrate 10
  • the warpage can be reduced to such an extent that the appearance quality is not affected. Therefore, the central portion of the main surface of the film-coated glass substrate 10 can be prevented from being scratched by the process flow after the production of the film-coated glass substrate 10, and the yield of manufacturing the portable electronic device can be increased. it can.
  • the film-coated glass substrate 10 can be suitably used as a cover glass used for a portable electronic device such as a tablet PC or a smartphone, which is required to be thin and lightweight.
  • the glass substrate 11 can be reused by removing the AR film 12 from the glass substrate 11 on which the AR film 12 is formed even after the AR film 12 is formed.
  • the curvature of the glass substrate 11 is returned to the curvature kappa g before AR film 12 is formed.
  • Methods of removing the AR film 12 from the film-coated glass substrate 10 include a method of etching using plasma gas, a method of polishing using colloidal silica, and a method of etching using an acidic or alkaline aqueous solution. . Among them, etching is preferably performed using a plasma gas.
  • a source gas such as fluorocarbon gas or halogen gas is introduced into a reaction chamber, and the source gas is excited to be plasma to generate fluorine radicals or chlorine radicals. It is a method of etching and removing deposits.
  • a conventionally known etching apparatus can be used for the method of etching using plasma gas.
  • source gas at the time of etching for example, CF 4 , CHF 4 , C 2 F 6 , C 3 F 8 , C 4 F 8 , C 5 F 8 , C 4 F 6 , CCl 2 F 2 , CBrF 3 etc.
  • a halogen-based gas such as a fluorocarbon-based gas, CCl 4 , BCl 3 , PCl 3 , SF 6 or Cl 2 can be used. In addition, these gases can also be mixed and used.
  • the AR film 12 When the AR film 12 is removed from the film-coated glass substrate 10, the AR film 12 may not be completely removed from the glass substrate 11, and at least a portion of the AR film 12 may be removed.
  • the shape of the glass substrate 11 is rectangular in plan view, but the shape of the glass substrate 11 in plan view is not particularly limited, and may be circular or the like.
  • the main surfaces of the glass substrate 11 and the AR film 12 of the film-coated glass substrate 10 are curved in a convex shape in the + Z-axis direction, but the present invention is not limited thereto.
  • the main surfaces of the glass substrate 11 and the AR film 12 may be concavely curved in the + Z axis direction.
  • the film-coated glass substrate 10 is transported by the transport device with the ⁇ Z axis direction facing upward.
  • the present invention is not limited thereto.
  • Other films other than the AR film 12 such as a scratch prevention film May be.
  • the scratch preventing film is, for example, aluminum oxide, silicon oxide, silicon nitride, silicon carbide, aluminum nitride, zirconium oxide, hafnium oxide, tin oxide Or diamond like carbon (DLC) or the like.
  • the scratch prevention film may be a single layer film or a multilayer film in which a plurality of layers made of the above materials are stacked.
  • Examples 1 to 7 are Examples, and Examples 8 to 11 are Comparative Examples.
  • a square glass substrate 1 having a plate thickness of 400 ⁇ m (0.4 mm) and a side length of 100 mm was prepared in plan view.
  • the glass substrate 1 was pressed while being heated to be warped, and the curvature g g of the glass substrate was set to 0.071 (1 / m). Curvature kappa g of the glass substrate, the curvature of the glass substrate 1 before forming the AR film to be described later.
  • the value of the curvature kappa g of the glass substrate, (in this example, + Z-axis direction) direction of the AR film is deposited when being concavely curved relative to represent a positive value, the AR film is deposited When it is convexly curved in the direction (in this example, the + Z-axis direction in this example), it is represented by a negative value (sign of minus (-)).
  • the values of the predicted curvature change ⁇ ⁇ ⁇ ⁇ f of the film-coated glass substrate and the predicted curvature ( ⁇ f +) g ) of the film-coated glass substrate are similarly expressed.
  • a silicon oxide film (SiO 2 film) and a nitride film are formed on the glass substrate 1 by the RAS method using a load lock sputtering apparatus (RAS-1100 BII, manufactured by Syncron Co., Ltd.) on the main surface of the glass substrate 1
  • a silicon film (Si 3 N 4 film) was alternately deposited to form an AR film having a thickness t f of about 0.43 ⁇ m.
  • SiO 2 films and Si 3 N 4 films are alternately stacked from the glass substrate 1 side, and the final layer is a SiO 2 film, which is nine layers.
  • the film forming conditions for the SiO 2 film and the Si 3 N 4 film are as follows.
  • Target p-Si target sputtering gas: Ar gas (flow rate: 60 sccm) Input power: 7.5kW Reactive gas: O 2 (flow rate: 110 sccm) RF power: 3 kW Substrate temperature: room temperature deposition rate: 0.3 nm / min (Deposition condition of Si 3 N 4 film)
  • Substrate temperature room temperature deposition rate: 0.2 nm / min
  • the film stress of the AR film was measured using a thin film stress meter manufactured by KLA-TENCOR.
  • the scanning point was 50, and the type of laser light was selected as automatic, and the surface shape on the line passing through the centers of the glass substrate before film formation and the glass substrate after film formation was measured.
  • the film stress ⁇ f was calculated from the obtained radius of curvature using the Stoney equation of the above equation (i).
  • the surface hardness was measured using PICODENTOR HM500 manufactured by Fisher Instruments.
  • the indenter using a Vickers indenter, gradually change the maximum load arrival time to 10 seconds, the creep time to 5 seconds, and the indentation load from 0.05 mN to 500 mN, and perform measurement five times under each condition. It was taken as the measurement result of the measured value which obtained the average value. At this time, the load was adjusted so that the maximum indentation depth was between 10 nm and 100 nm, and the maximum value of the Martens hardness with the maximum indentation depth of 10 nm to 100 nm was taken as the measurement value. The higher the Martens hardness, the harder the surface of the AR film, and thus the higher the scratch resistance of the AR film.
  • the predicted curvature change ( ⁇ f + ⁇ g ) of the film-coated glass substrate was determined by combining the predicted curvature change ⁇ f of the film-coated glass substrate and the curvature g g of the glass substrate 1 before forming the AR film.
  • the transportability was evaluated based on whether the film-coated glass substrate was easily scratched by contact with the table when the film-coated glass substrate was placed on a SUS table having a curvature of 0.01 (1 / m).
  • a scratch generated on one main surface of the film-coated glass substrate I asked for the number.
  • the film-coated glass substrate is repeatedly placed and lifted 100 times, and then the other main surface of the film-coated glass substrate The number of wounds that occurred was determined.
  • ⁇ E * is less than 1 is judged as very good (in FIG. 1, indicated by a double circle), and the case where ⁇ E * is in the range of 1 or more and less than 10 is good (in FIG. I judged.
  • (Stickability) Bonding property shows the durability at the time of bonding a film-coated glass substrate to a liquid crystal substrate.
  • a durability test was performed. The endurance test was conducted by sequentially placing the liquid crystal substrate having the film-coated glass substrate attached thereto under three different conditions. First, the liquid crystal substrate to which the film-coated glass substrate was attached was placed in an atmosphere of 65 ° C. and 90% humidity for 500 hours. Next, the liquid crystal substrate to which the film-coated glass substrate was attached was placed in an atmosphere at 80 ° C. for 500 hours. Finally, the liquid crystal substrate having the film-coated glass substrate attached thereto was placed in an atmosphere of ⁇ 30 ° C.
  • Example 2 Example 1 was repeated except that the curvature ⁇ g of the glass substrate 1 was changed to 0.139 (1 / m).
  • Example 3 In Example 1, the thickness t g of the glass substrate 1 is 210 ⁇ m, the curvature g g of the glass substrate 1 is 0.10 (1 / m), the film stress ⁇ f of the AR film is ⁇ 211 MPa, and the predicted curvature of the film-coated glass substrate Example except that the change ⁇ f f is changed to -0.132 (1 / m) and the flow rate of the film forming gas (Ar gas) used in forming the SiO 2 layer and the Si 3 N 4 layer is changed to 360 sccm It went in the same way as 1. The Martens hardness of the obtained AR film was about 4.3 GPa.
  • Example 4 Example 1 was repeated except that the curvature ⁇ g of the glass substrate 1 was changed to 0.030 (1 / m).
  • Example 5 In Example 1, the curvature g g of the glass substrate 1 is 0.300 (1 / m), the thickness t f of the AR film is 1.1 ⁇ m, and the predicted curvature change ⁇ f of the film-coated glass substrate is ⁇ 0.256 (1 It carried out like Example 1 except having changed into / m).
  • Example 5 was carried out in the same manner as Example 5, except that the curvature g g of the glass substrate 1 was changed to 0.330 (1 / m).
  • Example 7 In Example 3, the thickness t g of the glass substrate 1 is 400 ⁇ m, the curvature g g of the glass substrate 1 is 0.130 (1 / m), and the predicted curvature change ⁇ f of the film-coated glass substrate is ⁇ 0.036 (1/1). The same procedure as in Example 3 was performed except that m) was changed.
  • Example 1 was carried out in the same manner as Example 1 except that the curvature g g of the glass substrate 1 was changed to 0.005 (1 / m).
  • Example 9 In Example 1, the thickness t g of the glass substrate 1 is 210 ⁇ m, the curvature g g is ⁇ 0.014 (1 / m), the film stress ⁇ f of the AR film is ⁇ 211 MPa, and the predicted curvature change ⁇ f of the film-coated glass substrate As in Example 1 except that the flow rate of the film forming gas (Ar gas) used in forming the SiO 2 layer and the Si 3 N 4 layer was changed to 360 sccm by changing I went to. The Martens hardness of the obtained AR film was about 4.3 GPa.
  • the film forming gas Ar gas
  • Example 10 Example 1 was repeated except that the curvature ⁇ g of the glass substrate 1 was changed to 0.100 (1 / m).
  • Example 7 was carried out in the same manner as Example 7 except that the curvature g g of the glass substrate 1 was changed to 0.112 (1 / m).
  • Example 8 and Example 9 since the absolute value of the predicted curvature ( ⁇ f + ⁇ g ) of the film-coated glass substrate was large, the force with which the film-coated glass substrate tends to peel off from the liquid crystal substrate becomes large. The attached glass substrate was peeled off from the liquid crystal substrate. In Examples 10 and 11, the absolute value of the predicted curvature ( ⁇ f + ⁇ g ) of the film-coated glass substrate was less than 0.025 (1 / m).
  • Example 10 and Example 11 since the absolute value of the predicted curvature ( ⁇ f + ⁇ g ) of the film-coated glass substrate was too small, when the film-coated glass substrate was placed on the table and repeatedly lifted, any of the film-coated glass substrates Also on the main surface, two or more scratches occurred due to the film-coated glass substrate coming into contact with the table. Therefore, in Example 10 and Example 11, the center part of the main surface was damaged no matter which of the main surfaces of the film-coated glass substrate was transported downward.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Surface Treatment Of Glass (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)

Abstract

Le procédé de production d'un substrat en verre fixé à un film selon la présente invention est un procédé de production d'un substrat en verre fixé à un film composé d'un substrat en verre et d'un film formé sur une surface principale du substrat en verre, le procédé comprenant une étape de formation de film consistant à former un film ayant une épaisseur de film ((tf) et une contrainte de film (σf) sur un substrat en verre ayant une épaisseur (tg), un module de Young (Eg), un coefficient de Poisson (νg) et une courbure (κg), la courbure du substrat en verre s'inscrivant dans la plage satisfaisant la formule (2) à condition que la plage représentée par la formule (1) soit satisfaite.
PCT/JP2018/031610 2017-09-01 2018-08-27 Procédé de production d'un substrat en verre fixé à un film, substrat en verre fixé à un film et procédé de retrait de film WO2019044779A1 (fr)

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Citations (6)

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JP2002267803A (ja) * 2001-03-12 2002-09-18 Olympus Optical Co Ltd 反射防止膜及び光学部品
JP2006176854A (ja) * 2004-12-24 2006-07-06 Olympus Corp 光学多層膜の形成方法及び光学素子
JP2007156321A (ja) * 2005-12-08 2007-06-21 Seiko Epson Corp 光学多層膜フィルタの製造方法
JP2007193132A (ja) * 2006-01-19 2007-08-02 Seiko Epson Corp 光学部品の製造方法
JP2010058989A (ja) * 2008-09-01 2010-03-18 Nippon Electric Glass Co Ltd 薄膜付きガラス基板の製造方法
WO2016115311A1 (fr) * 2015-01-14 2016-07-21 Corning Incorporated Substrat en verre et dispositif d'affichage comprenant celui-ci

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JP2002363733A (ja) * 2001-06-04 2002-12-18 Nippon Sheet Glass Co Ltd 被膜の形成方法
JP4071458B2 (ja) * 2001-06-05 2008-04-02 釜屋電機株式会社 抵抗器の製造法
JP2007047531A (ja) * 2005-08-11 2007-02-22 Seiko Epson Corp 光学多層膜フィルタ及び光学多層膜フィルタの製造方法
JP5332085B2 (ja) * 2006-06-28 2013-11-06 日本電気硝子株式会社 フラットパネルディスプレイ用のガラス基板の製造方法
US8993104B2 (en) * 2013-03-12 2015-03-31 Guardian Industries Corp. Method of making a coated article and/or glazing for automobiles and/or the like
JP2017030997A (ja) * 2015-07-30 2017-02-09 日本電気硝子株式会社 薄膜付き強化ガラス基板の製造方法及び薄膜付き強化ガラス基板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002267803A (ja) * 2001-03-12 2002-09-18 Olympus Optical Co Ltd 反射防止膜及び光学部品
JP2006176854A (ja) * 2004-12-24 2006-07-06 Olympus Corp 光学多層膜の形成方法及び光学素子
JP2007156321A (ja) * 2005-12-08 2007-06-21 Seiko Epson Corp 光学多層膜フィルタの製造方法
JP2007193132A (ja) * 2006-01-19 2007-08-02 Seiko Epson Corp 光学部品の製造方法
JP2010058989A (ja) * 2008-09-01 2010-03-18 Nippon Electric Glass Co Ltd 薄膜付きガラス基板の製造方法
WO2016115311A1 (fr) * 2015-01-14 2016-07-21 Corning Incorporated Substrat en verre et dispositif d'affichage comprenant celui-ci

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