WO2020203124A1 - ガラス樹脂積層体の製造方法 - Google Patents

ガラス樹脂積層体の製造方法 Download PDF

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Publication number
WO2020203124A1
WO2020203124A1 PCT/JP2020/010552 JP2020010552W WO2020203124A1 WO 2020203124 A1 WO2020203124 A1 WO 2020203124A1 JP 2020010552 W JP2020010552 W JP 2020010552W WO 2020203124 A1 WO2020203124 A1 WO 2020203124A1
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WO
WIPO (PCT)
Prior art keywords
glass
film
resin
adhesive layer
roll
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/JP2020/010552
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
佐藤　啓介
毅 村重
稲垣　淳一
岸　敦史
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.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
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 Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to KR1020217030480A priority Critical patent/KR102846869B1/ko
Priority to EP24208888.8A priority patent/EP4530066B1/en
Priority to EP20783614.9A priority patent/EP3950291B1/en
Priority to CN202080023694.4A priority patent/CN113613868B/zh
Priority to JP2021511339A priority patent/JPWO2020203124A1/ja
Priority to US17/598,357 priority patent/US12030281B2/en
Publication of WO2020203124A1 publication Critical patent/WO2020203124A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025051111A priority patent/JP2025094229A/ja
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0007—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
    • B32B37/003—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality to avoid air inclusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
    • B32B17/10825—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts
    • B32B17/10862—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using pressing-rolls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
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    • B29C66/7375—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
    • B29C66/73751—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being uncured, i.e. non cross-linked, non vulcanized
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • B29C66/8122—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps characterised by the composition of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/8145—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the constructional aspects of the pressing elements, e.g. of the welding jaws or clamps
    • B29C66/81457—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the constructional aspects of the pressing elements, e.g. of the welding jaws or clamps comprising a block or layer of deformable material, e.g. sponge, foam, rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
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    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to a method for producing a glass resin laminate.
  • liquid crystal cells equipped with a touch sensor function on the screen are being used in a wide range of fields, from mobile phones to information displays.
  • a display panel in which a film or glass having a sensor function is laminated on a polarizing plate, and tempered glass called a front plate is arranged on the outermost layer via an adhesive layer for filling a step on the sensor surface.
  • a liquid crystal panel called an in-cell, in which a touch sensor is incorporated in a glass substrate of a liquid crystal cell, has appeared from the viewpoint of thinning and weight reduction.
  • tempered glass is becoming thinner, but there is a limit to thinning because tempered glass self-destructs due to the compressive stress of the glass when it is 300 ⁇ m or less. Under such circumstances, increasing the hardness of the front plate using resin has been studied, but the reality is that sufficient hardness cannot be obtained.
  • a thin glass film is attracting attention as a front plate of a liquid crystal cell.
  • This glass film is laminated with, for example, a resin film containing a polarizing plate via an adhesive layer.
  • the adhesive layer tends to be thin due to the demand for thinning of the product.
  • the laminating of the glass film and the resin film is performed, for example, while being sandwiched between two rolls arranged vertically adjacent to each other. At this time, if foreign matter adheres to the roll surface on the side in contact with the resin film, the glass film having high rigidity is hardly deformed, and the resin film having low rigidity is mainly deformed.
  • the present invention has been made in view of the above points, and when the glass film and the resin film are laminated via the adhesive layer, the occurrence of bubble defects can be suppressed as compared with the conventional case even when the adhesive layer is thin.
  • An object of the present invention is to provide a method for producing a glass resin laminate.
  • the glass film and the resin film are arranged so as to face the first roll for pressing the resin film and the first roll and press the glass film.
  • a method for producing a glass resin laminate which comprises a step of sandwiching the surface layer of the first roll and bonding the resin film via an adhesive layer, wherein the elasticity of the surface layer of the first roll is P1 and the elasticity of the resin film.
  • the ratio P1 / P2 of the elastic ratio P1 to the elastic ratio P2 satisfies 3 ⁇ 10 -3 ⁇ P1 / P2 ⁇ 1.0.
  • a method for producing a glass resin laminate capable of suppressing the occurrence of bubble defects even when the adhesive layer is thin can be obtained. Can be provided.
  • FIG. 1A and 1B are cross-sectional views illustrating a glass-resin laminated body
  • FIG. 1A is a glass film and a resin film before lamination
  • FIG. 1B is a glass film and a resin film after lamination (that is, glass). Resin laminate) is shown.
  • the glass resin laminate 1 has a glass film 10 and a resin film 20.
  • the glass film 10 is bonded to the resin film 20 via the adhesive layer 21 of the resin film 20.
  • the glass film 10 is not particularly limited, and an appropriate glass film 10 can be adopted depending on the intended purpose.
  • the glass film 10 includes, for example, soda-lime glass, borosilicate glass, aluminosilicate glass, quartz glass and the like.
  • non-alkali glass and low-alkali glass can be mentioned.
  • the content of the alkali metal component (for example, Na 2 O, K 2 O, Li 2 O) of the glass is preferably 15% by weight or less, and more preferably 10% by weight or less.
  • the thickness of the glass film 10 is preferably 50 ⁇ m to 150 ⁇ m, more preferably 60 ⁇ m to 140 ⁇ m, further preferably 70 ⁇ m to 130 ⁇ m, and particularly preferably 80 ⁇ m to 120 ⁇ m. Within such a range, a glass resin laminate 1 having excellent flexibility, capable of being processed by a roll-to-roll process, and having excellent productivity with less cracking of the glass film can be obtained.
  • the light transmittance of the glass film 10 at a wavelength of 550 nm is preferably 85% or more.
  • the refractive index of the glass film 10 at a wavelength of 550 nm is preferably 1.4 to 1.65.
  • the density of the glass film 10 is preferably 2.3 g / cm 3 to 3.0 g / cm 3 , and more preferably 2.3 g / cm 3 to 2.7 g / cm 3 .
  • a glass film in the above range can provide a glass resin laminate 1 that can contribute to weight reduction of image display.
  • the molding method of the glass film 10 is not particularly limited, and an appropriate one can be adopted according to the purpose.
  • the glass film 10 is a mixture containing a main raw material such as silica and alumina, a defoaming agent such as sardine and antimony oxide, and a reducing agent such as carbon at a temperature of about 1400 ° C to 1600 ° C. It can be produced by melting, forming into a thin plate, and then cooling.
  • Examples of the method for forming the glass film 10 include a slot down draw method, a fusion method, and a float method.
  • the glass film formed into a plate shape by these methods may be chemically polished with a solvent such as hydrofluoric acid, if necessary, in order to thin the plate or improve the smoothness.
  • the resin film 20 includes an adhesive layer 21, a polarizing plate 22, an adhesive layer 28, and a release film 29 in this order.
  • the resin film 20 may further include another layer.
  • the resin film 20 can be provided with a retardation layer between the polarizing plate 22 and the pressure-sensitive adhesive layer 28, but the resin film 20 is not limited thereto.
  • the adhesive layer 21 may be provided on the glass film 10.
  • the resin film 20 includes the polarizing plate 22, the pressure-sensitive adhesive layer 28, and the release film 29 in this order, and if necessary, another layer.
  • the elastic modulus of the resin film 20 is preferably 0.1 GPa to 8.0 GPa, more preferably 0.2 GPa to 7.0 GPa, and further preferably 0.3 GPa to 5.0 GPa.
  • the elastic modulus can be measured under the following conditions using an autograph.
  • the pressure-sensitive adhesive layer refers to a layer that has adhesiveness at room temperature and adheres to an adherend with a light pressure. Therefore, even when the adherend attached to the pressure-sensitive adhesive layer is peeled off, the pressure-sensitive adhesive layer retains a practical adhesive force.
  • the adhesive layer is a layer capable of binding substances by interposing between the substances. Therefore, when the adherend attached to the adhesive layer is peeled off, the adhesive layer does not have a practical adhesive force.
  • the polarizing plate 22 is arranged on the side of the adhesive layer 21 opposite to the side to be adhered to the glass film 10.
  • the polarizing plate 22 has a polarizing element 221 and a first protective film 222, and a second protective film 223.
  • the first protective film 222 is arranged on the adhesive layer 21 side of the polarizer 221 and the second protective film 223 is arranged on the adhesive layer 28 side of the polarizer 221.
  • the release film 29 is arranged on the side opposite to the polarizer 221 of the second protective film 223 via the adhesive layer 28.
  • the adhesive layer 21 is not particularly limited, and an appropriate adhesive can be adopted depending on the intended purpose.
  • the adhesive include polyester-based adhesives, polyurethane-based adhesives, polyvinyl alcohol-based adhesives, and epoxy-based adhesives. Among these, an epoxy adhesive that can obtain particularly good adhesion is preferable.
  • the adhesive layer 21 When the adhesive layer 21 is a thermosetting adhesive, it can exhibit peeling resistance by heating and curing (solidifying). Further, when the adhesive layer 21 is a photocurable adhesive such as an ultraviolet curable type, the peeling resistance can be exhibited by irradiating light such as ultraviolet rays to cure the adhesive layer 21. Further, when the adhesive layer 21 is a moisture-curable adhesive, it can be cured by reacting with moisture in the air or the like, so that it can be cured even if it is left to stand, and peeling resistance can be exhibited.
  • the adhesive layer 21 for example, a commercially available adhesive may be used, or various curable resins may be dissolved or dispersed in a solvent to prepare an adhesive solution (or dispersion).
  • the thickness of the adhesive layer 21 is preferably 8 ⁇ m or less, more preferably 0.1 ⁇ m to 8 ⁇ m, further preferably 0.1 ⁇ m to 5 ⁇ m, and particularly preferably 0.1 ⁇ m to 2 ⁇ m. Within such a range, a glass resin laminate 1 having excellent flexibility and puncture resistance can be obtained. Further, the thinner the adhesive layer 21, the thinner the glass resin laminate 1, so that it is possible to meet the demand for thinner products.
  • the elastic modulus of the adhesive layer 21 is preferably 0.5 GPa to 15 GPa, more preferably 0.8 GPa to 10 GPa, and further preferably 1 GPa to 5 GPa. Within such a range, a glass resin laminate 1 having excellent flexibility and puncture resistance can be obtained.
  • the adhesive layer 21 is uncured, and as shown in FIG. 1B, the glass film 10 is cured after being laminated on the resin film 20 to form the glass film 10.
  • a glass resin laminate 1 in which the resin film 20 is bonded is obtained.
  • the method for producing the glass-resin laminate 1 in which the glass film 10 and the resin film 20 are bonded to each other via the adhesive layer 21 will be described later.
  • the thickness of the polarizing plate 22 is preferably 5 ⁇ m to 300 ⁇ m, more preferably 10 ⁇ m to 250 ⁇ m, further preferably 25 ⁇ m to 200 ⁇ m, and particularly preferably 25 ⁇ m to 100 ⁇ m.
  • the elastic modulus of the polarizing plate 22 is preferably 1 GPa or more, more preferably 1 GPa to 10 GPa, further preferably 2 GPa to 7 GPa, and particularly preferably 2 GPa to 5 GPa. Within such a range, the glass resin laminate 1 having excellent puncture resistance can be obtained.
  • the shape of the polarizing plate 22 is not particularly limited, and an appropriate shape can be adopted depending on the purpose. As an example, a square shape having a long side and a short side can be mentioned.
  • the polarizing plate 22 has a rectangular shape, it is preferable that the absorption axis direction of the polarizing element 221 included in the polarizing plate 22 and the long side or the short side of the polarizing plate 22 are substantially parallel.
  • substantially parallel is a concept including not only the case where it is strictly parallel but also the case where the angle formed by both lines is ⁇ 10 ° (preferably ⁇ 5 °).
  • the thickness of the polarizer 221 is not particularly limited, and an appropriate thickness can be adopted depending on the intended purpose.
  • the thickness of the polarizer 221 is typically about 1 ⁇ m to 80 ⁇ m.
  • a thin polarizer may be used as the polarizer 221.
  • the thickness of the polarizer 221 is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, still more preferably 10 ⁇ m or less, and particularly preferably. It is 6 ⁇ m or less.
  • the polarizer 221 preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
  • the simple substance transmittance of the polarizer is preferably 40.0% or more, more preferably 41.0% or more, still more preferably 42.0% or more, and particularly preferably 43.0% or more.
  • the degree of polarization of the polarizer 221 is preferably 99.8% or more, more preferably 99.9% or more, and further preferably 99.95% or more.
  • the polarizer 221 is preferably an iodine-based polarizer. More specifically, the polarizer can be composed of a polyvinyl alcohol-based resin (hereinafter, referred to as "PVA-based resin") film containing iodine.
  • PVA-based resin polyvinyl alcohol-based resin
  • the PVA-based resin that forms the PVA-based resin film is not particularly limited, and an appropriate resin can be used depending on the intended purpose. Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymers.
  • Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
  • the ethylene-vinyl alcohol copolymer is obtained by saponifying the ethylene-vinyl acetate copolymer.
  • the degree of saponification of the PVA-based resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, and more preferably 99.0 mol% to 99.93 mol%. Is.
  • the degree of saponification is determined according to JIS K 6726-1994. By using a PVA-based resin having such a degree of saponification, a polarizer having excellent durability can be obtained. If the degree of saponification is too high, gelation may occur.
  • the average degree of polymerization of the PVA-based resin is not particularly limited and can be appropriately selected according to the purpose.
  • the average degree of polymerization of the PVA-based resin is, for example, 1000 to 10000, preferably 1200 to 5000, and more preferably 1500 to 4500.
  • the average degree of polymerization is determined according to JIS K 6726-1994.
  • Examples of the method for producing the polarizer 221 include a method (I) of stretching and dyeing a single PVA-based resin film, and a method of stretching and dyeing a laminate (i) having a resin base material and a polyvinyl alcohol-based resin layer (i). II) and the like. Since the method (I) is a well-known and commonly used method in the art, detailed description thereof will be omitted.
  • a laminate (i) having a resin base material and a polyvinyl alcohol-based resin layer formed on one side of the resin base material is stretched and dyed, and polarized light is applied onto the resin base material.
  • the laminate (i) can be formed by applying and drying a coating liquid containing a polyvinyl alcohol-based resin on a resin base material. Further, the laminate (i) may be formed by transferring the polyvinyl alcohol-based resin layer onto the resin base material. Details of the production method (II) are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580, and this publication can be incorporated herein by reference.
  • the first protective film 222 and the second protective film 223 are not particularly limited, and an appropriate resin film can be adopted depending on the intended purpose.
  • the material for forming the first protective film 222 and the second protective film 223 include polyester resins such as polyethylene terephthalate (PET), cellulose resins such as triacetyl cellulose (TAC), and cyclos such as norbornene resins.
  • polyester resins such as polyethylene terephthalate (PET), cellulose resins such as triacetyl cellulose (TAC), and cyclos such as norbornene resins.
  • polyester resins such as polyethylene terephthalate (PET), cellulose resins such as triacetyl cellulose (TAC), and cyclos such as norbornene resins.
  • TAC triacetyl cellulose
  • cyclos such as norbornene resins.
  • olefin resins olefin resins
  • olefin resins such as polyethylene and
  • the (meth) acrylic resin for example, a (meth) acrylic resin having a glutarimide structure is used.
  • examples of the (meth) acrylic resin having a glutarimide structure include JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328329, and JP-A. 2006-328334, 2006-337491, 2006-337492, 2006-337493, 2006-337569, 2007-009182, 2009- It is described in JP-A-161744 and JP-A-2010-284840. These statements may be incorporated herein by reference.
  • the first protective film 222, the second protective film 223, and the polarizer 221 can be laminated via any suitable adhesive layer.
  • the resin base material used in the production of the polarizer 221 is peeled off before or after laminating the first protective film 222 and the second protective film 223 and the polarizer 221.
  • the thickness of the first protective film 222 and the second protective film 223 is preferably 4 ⁇ m to 250 ⁇ m, more preferably 5 ⁇ m to 150 ⁇ m, further preferably 10 ⁇ m to 100 ⁇ m, and particularly preferably 10 ⁇ m to 50 ⁇ m. is there.
  • the elastic modulus of the first protective film 222 and the second protective film 223 is 1 GPa or more, preferably 1 GPa to 10 GPa, more preferably 1.8 GPa to 7 GPa, and further preferably 2 GPa to 5 GPa. .. Within such a range, the glass resin laminate 1 having excellent puncture resistance can be obtained.
  • the pressure-sensitive adhesive layer 28 can be formed from any suitable pressure-sensitive adhesive.
  • a pressure-sensitive adhesive for example, a pressure-sensitive adhesive based on a polymer such as an acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based polymer, or a rubber-based polymer is used.
  • Acrylic adhesives are preferably used. This is because the acrylic pressure-sensitive adhesive is excellent in optical transparency, exhibits appropriate wettability, cohesiveness, and adhesiveness, and can be excellent in weather resistance, heat resistance, and the like.
  • an acrylic pressure-sensitive adhesive made of an acrylic polymer having 4 to 12 carbon atoms is preferable.
  • the thickness of the pressure-sensitive adhesive layer 28 is preferably 1 ⁇ m to 100 ⁇ m, more preferably 3 ⁇ m to 80 ⁇ m, and further preferably 3 ⁇ m to 50 ⁇ m. Within such a range, when the glass resin laminate 1 is attached to an optical element such as a liquid crystal cell to produce an optical laminate, the optical laminate having excellent flexibility and puncture resistance can be obtained. can get.
  • the release film 29 can be formed of, for example, a resin such as polyethylene terephthalate (PET), polyethylene (PE), or polypropylene (PP).
  • the thickness of the release film 29 is preferably 5 ⁇ m to 125 ⁇ m, more preferably 20 ⁇ m to 75 ⁇ m, and further preferably 30 ⁇ m to 50 ⁇ m.
  • the release film 29 is peeled off at the interface with the pressure-sensitive adhesive layer 28 before the glass-resin laminate 1 is attached to an optical element such as a liquid crystal cell.
  • FIG. 2 is a diagram illustrating a process of laminating a glass film on a resin film.
  • the resin film 20 is suspended on the rolls 110, 120, and 130 and conveyed in the direction of the arrow.
  • the resin film 20 is conveyed by, for example, a roll-to-roll method.
  • the roll 140 is arranged at a position facing the roll 110 in the vertical direction.
  • FIG. 2 shows three rolls for transporting the resin film 20, but this is an example, and the number of rolls can be appropriately determined as needed.
  • the glass film 10 is conveyed in the direction of the arrow and is laminated on the resin film 20 between the roll 110 and the roll 140. At this time, the roll 140 presses the glass film 10, and the roll 110 presses the resin film 20.
  • the glass film 10 is laminated on the resin film 20.
  • the adhesive layer 21 is uncured.
  • the adhesive layer 21 is cured in a curing step (not shown) arranged downstream of the rolls 110 and 140 in the transport direction (arrow direction) to complete the glass resin laminate 1.
  • the thickness of the adhesive layer 21 is almost the same before and after curing.
  • FIG. 3 is a diagram for explaining a conventional problem when laminating a glass film on a resin film.
  • a roll 110X is used instead of the roll 110 shown in FIG.
  • the roll 110X is made of iron. That is, in the roll 110X, the portion corresponding to the surface layer of the roll 110 is formed of iron.
  • foreign matter F may adhere to the roll 110X.
  • the roll 110X side of the resin film 20 comes into contact with the foreign matter F, but at this time, the highly rigid iron roll 110X and the glass film 10 are hardly deformed.
  • the resin film 20 having low rigidity is mainly deformed. Therefore, unevenness corresponding to the shape of the foreign matter F may occur on the side of the resin film 20 in contact with the glass film 10, and air may enter the concave portion to cause a bubble defect B.
  • Bubble defect B is large enough to be visually recognized by humans. Therefore, when the glass resin laminate 1 is used in a product such as a display device, only a certain number or less is allowed, and it is preferable that the result is zero. Therefore, in order to solve such a conventional problem, in the present embodiment, measures are taken to suppress the occurrence of the bubble defect B. This will be described with reference to FIGS. 4 and 5.
  • FIG. 4 is a diagram for explaining a method of suppressing the occurrence of bubble defects, and shows an enlarged view of the vicinity of rolls 110 and 140 in FIG.
  • the surface layer of the roll 110 is formed of a material having a lower elastic modulus than iron. ..
  • the surface layer refers to a region from the surface of the roll 110 to the inside by about 1 mm in the center direction.
  • the material having a lower elastic modulus than iron is not particularly limited, but for example, resins such as polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and rubbers such as silicone rubber, urethane rubber, and nitrile rubber. Can be mentioned. Among these, silicone rubber having excellent flexibility is particularly preferable.
  • FIG. 5 is an enlarged view of part A in FIG. In FIG. 5, the surface layers of the resin film 20 and the roll 110 are deformed due to the presence of the foreign matter F.
  • the length of the foreign matter F in the direction perpendicular to the surface of the resin film 20 before compression is t, and the foreign matter F after compression is taken into consideration when the glass film 10 is laminated on the resin film 20.
  • the length on the resin film 20 side is ⁇ lp and the length on the roll 110 side is ⁇ lr.
  • the elastic modulus of the resin film 20 is Ep and the elastic modulus of the surface layer of the roll 110 is Er
  • the following equation (1) is derived from the relationship between the strain on both sides of the foreign matter F and the elastic modulus.
  • the length t of the target foreign matter F before compression is about 20 to 100 ⁇ m. This is because if a foreign substance F having a size of this size is present, a visible bubble defect B is likely to occur.
  • t 100 ⁇ m.
  • the surface layer of the roll 110 is compared with the elastic modulus of polyethylene terephthalate (PET), silicone rubber, or the like. It is preferable to form it with a low-grade material. As a result, even when the foreign matter F adheres to the surface of the roll 110, the deformation of the resin film 20 can be suppressed, and the occurrence of the bubble defect B can be suppressed.
  • PET polyethylene terephthalate
  • the elastic modulus of the surface layer of the roll 110 is low, the contribution of deformation by the foreign matter F to the resin film 20 is small, so that the occurrence of bubble defect B can be suppressed. Further, if the deformation of the resin film 20 due to the foreign matter F is small, the degree to which the adhesive layer 21 contributes to alleviation of the deformation is small, so that a thinner adhesive layer 21 can be used.
  • the elastic modulus of the surface layer of the roll 110 when the elastic modulus of the surface layer of the roll 110 is P1 and the elastic modulus of the resin film 20 is P2, the elasticity with respect to the elastic modulus P2. It can be said that the material of the surface layer of the roll 110 may be selected so that the ratio P1 / P2 of the ratio P1 satisfies 3 ⁇ 10 -3 ⁇ P1 / P2 ⁇ 1.0. However, in the roll 110, a portion other than the surface layer may be formed from the same material as the surface layer.
  • the above requirements are more effective as the adhesive layer for bonding the glass film and the resin film is thinner, and the effect is remarkable, for example, when the thickness of the adhesive layer is 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the thickness of the adhesive layer is 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the adhesive layer 10 ⁇ m or more because thickening the adhesive layer causes a problem that the transportability of the resin film is lowered and a problem that the curing time of the adhesive layer is long.
  • the material of the surface layer of the roll 140 does not affect the above examination because the highly rigid glass film 10 is hardly deformed. .. Therefore, the material of the surface layer of the roll 140 may be iron, resin, rubber, or any other material.
  • Example 1 In Example 1, a resin film having an elastic modulus of 5 GPa provided with an adhesive layer having a thickness of 2 ⁇ m was prepared, and a glass film was laminated on the resin film between the vertically opposed rolls. Then, the adhesive layer was cured to prepare a glass resin laminate A. Polyethylene terephthalate (PET) having an elastic modulus of 5 GPa was used for the surface layer of the roll in contact with the resin film.
  • PET Polyethylene terephthalate
  • Example 2 the glass resin laminate B was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was 5 ⁇ m.
  • Example 3 the glass resin laminate C was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was 10 ⁇ m.
  • Comparative Example 1 In Comparative Example 1, a resin film having an elastic modulus of 5 GPa provided with an adhesive layer having a thickness of 2 ⁇ m was prepared, and a glass film was laminated on the resin film between the vertically opposed rolls. Then, the adhesive layer was cured to prepare a glass resin laminate D. Iron having an elastic modulus of 73 GPa was used for the surface layer of the roll in contact with the resin film.
  • Comparative Example 2 In Comparative Example 2, a glass resin laminate E was produced in the same manner as in Comparative Example 1 except that the thickness of the adhesive layer was 5 ⁇ m.
  • Comparative Example 3 the glass resin laminate F was produced in the same manner as in Comparative Example 1 except that the thickness of the adhesive layer was 10 ⁇ m.
  • the number of bubble defects is large regardless of whether the thickness of the adhesive layer is 2 ⁇ m, 5 ⁇ m, or 10 ⁇ m. It was acceptable. In particular, when the thickness of the adhesive layer is 5 ⁇ m or more, the number of bubble defects is 0, which is a very suitable result.
  • PET polyethylene terephthalate
  • the elastic modulus of the surface layer of the roll in contact with the resin film is P1 and the elastic modulus of the resin film is P2 in the manufacturing process of the glass resin laminate
  • the elastic modulus The material of the surface layer of the roll in contact with the resin film is selected so that the ratio P1 / P2 of the elastic modulus P1 to the modulus P2 satisfies 3 ⁇ 10 -3 ⁇ P1 / P2 ⁇ 1.0, and bubble defects occur. It was proved that it can suppress.
  • a resin film having a polarizing plate has been described as an example.
  • the above requirements are effective in a method for producing a glass resin laminate having a step of bonding a glass film and a resin film via an adhesive layer using two opposing rolls, and have a polarizing plate. It is not limited to the resin film.
  • Examples other than the resin film having a polarizing plate include, for example, a PET film and a PEN film.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Quality & Reliability (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
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