Glass-resin composite

Abstract

A glass-resin composite according to one aspect of the present invention comprises: a glass layer that has a first surface and a second surface which is on the opposite side from the first surface; and a resin layer that is provided to the second surface. A laser processing mark that extends from the first surface in a direction orthogonal to the first surface is formed in the glass layer. The distance between the laser processing mark and the first surface is not more than 20% of the thickness of the glass layer. The length of the laser processing mark in the direction orthogonal to the first surface is 5-50% the thickness of the glass layer.

Description

Glass Resin Composite

[0001] The present invention relates to a glass resin composite.

[0002] Glass resin laminates in which a resin layer is laminated on an extremely thin, flexible thin glass (hereinafter also referred to as "glass sheet") are used in image display devices such as liquid crystal display elements and organic EL elements, semiconductor elements, solar cells, etc. The glass sheet used in the glass resin laminate is flexible and can be wound into a roll, so that a roll-to-roll process can be used to unwind the rolled glass sheet, apply processing such as laminating or printing a resin layer, and then rewind it into a roll to produce a glass resin laminate.

[0003] As a method for manufacturing a glass resin laminate using a roll-to-roll process, for example, a method has been disclosed in which a roll-to-roll laminating device is used to laminate a flexible glass layer to other material sheets including a PVA layer and a TAC layer in a polarizer structure to form a laminate roll (see, for example, Patent Document 1).

[0004] U.S. Patent No. 8,525,405

[0005] However, Patent Document 1 does not describe how to prevent cracks from occurring in the flexible glass layer when a laminated roll is cut or otherwise formed into chips, and then the chipped laminated roll is attached to a flexible film substrate wound into a roll and transported using a roll-to-roll process.

[0006] When a chipped glass resin composite is attached to a roll-shaped film substrate via an adhesive or the like, and then transported as a web (web handling) using a roll-to-roll process and wound into a roll, there has been a problem in that cracks may occur in the glass layer.

[0007] An object of one aspect of the present invention is to provide a glass resin composite in which cracks are less likely to occur in the glass layer.

[0008] A glass resin composite according to one aspect of the present invention comprises a glass layer including a first surface and a second surface opposite the first surface, and a resin layer provided on the second surface, wherein a laser processing mark is formed on the glass layer extending from the first surface in a direction perpendicular to the first surface, the distance between the laser processing mark and the first surface is 20% or less of the thickness of the glass layer, and the length of the laser processing mark in the direction perpendicular to the first surface is 5% or more and 50% or less of the thickness of the glass layer.

[0009] One aspect of the present invention can provide a glass resin composite in which cracks are less likely to occur in the glass layer.

[0010] FIG. 1 is a side view showing the configuration of a glass resin composite according to the present embodiment; FIG. 2 is a perspective view showing the configuration of a glass resin composite according to the present embodiment; FIG. 3 is a view (part 1) explaining an example of a method for manufacturing a glass resin composite according to the present embodiment; FIG. 4 is a view (part 2) explaining an example of a method for manufacturing a glass resin composite according to the present embodiment; FIG. 5 is a view (part 1) explaining an evaluation method in examples; and FIG. 6 is a view (part 2) explaining an evaluation method in examples.

[0011] Hereinafter, an embodiment of the present invention will be described in detail. To facilitate understanding of the description, the same components in the drawings will be denoted by the same reference numerals, and duplicated descriptions will be omitted. Also, the scale of each component in the drawings may differ from the actual scale.

[0012] <Glass Resin Composite> A glass resin composite according to an embodiment of the present invention will be described. Fig. 1 is a side view showing the configuration of a glass resin composite according to this embodiment. Fig. 2 is a perspective view showing the configuration of a glass resin composite according to this embodiment.

[0013] As shown in FIGS. 1 and 2 , a glass resin composite 1 according to this embodiment includes a glass layer 10 including a first surface 10a and a second surface 10b opposite the first surface 10a, and a resin layer 20 provided on the second surface 10b. The glass layer 10 is formed with a laser processing mark 11 extending from the first surface 10a in a direction perpendicular to the first surface 10a. The distance L1 between the laser processing mark 11 and the first surface 10a is 20% or less of the thickness L2 of the glass layer 10, and the length L3 of the laser processing mark 11 in the direction perpendicular to the first surface 10a is 5% to 50% of the thickness L2 of the glass layer 10. Here, the distance L1 refers to the shortest distance between the laser processing mark 11 and the first surface 10a, and the thickness L2 of the glass layer 10 refers to the length perpendicular to the first surface 10a. This configuration makes it possible to provide a glass resin composite 1 in which cracks are less likely to occur in the glass layer 10. For example, the glass resin composite 1 is attached to one main surface of a rolled flexible film substrate via an adhesive or the like using a roll-to-roll process, and even when the film is wound into a roll, cracks are unlikely to occur in the glass layer 10.

[0014] The distance L4 between the laser processing mark 11 and the second surface 10b can be set to more than 30% of the thickness L2 of the glass layer 10. Here, the distance L4 means the shortest distance between the laser processing mark 11 and the second surface 10b.

[0015] The thickness of the glass resin composite 1 is 800 μm or less, preferably 700 μm or less, more preferably 400 μm or less, and even more preferably 350 μm or less.

[0016] In this specification, the thickness of the glass resin composite 1 refers to the length in a direction perpendicular to the first surface 10a of the glass resin composite 1. The thickness of the glass resin composite 1 may be, for example, the thickness measured at an arbitrary location on the cross section of the glass resin composite 1, or may be the average value of measurements measured at several arbitrary locations. Hereinafter, the definition of thickness is similarly defined for other members.

[0017] [Glass Layer] The glass layer 10 has a quadrilateral shape in a plan view and has four side surfaces 10c connecting the first surface 10a and the second surface 10b. The laser processing marks 11 may be formed on each of the four side surfaces 10c. This configuration can prevent external forces from concentrating on some of the four side surfaces 10c, making it possible to provide a glass resin composite 1 in which cracks are less likely to occur in the glass layer 10. In this specification, a quadrilateral is defined as a quadrilateral formed from four sides, and the shape of the corners is not limited, and includes a quadrilateral with rounded corners, a quadrilateral with right-angle corners cut off at an angle, and the like.

[0018] Specifically, a plurality of laser processing marks 11 may be formed on each of the four side surfaces 10 c, spaced apart from one another, from one end to the other in the longitudinal direction of the side surface 10 c. This configuration can further suppress the concentration of external forces on one of the four side surfaces 10 c, making it possible to provide a glass resin composite 1 in which cracks are even less likely to occur in the glass layer 10.

[0019] The glass layer 10 may have a plate (sheet) shape, and the width and length of the glass layer 10 may be any appropriate size.

[0020] The glass layer 10 is formed using a long glass ribbon. The glass layer 10 is obtained by cutting the long glass ribbon, for example. Note that the term "long" means an elongated shape having a length that is sufficiently longer than its width, and includes, for example, an elongated rectangular shape having a length that is 10 times or more, preferably 20 times or more, as compared to its width.

[0021] The glass layer 10 can be formed using any suitable glass material. The glass material constituting the glass layer 10 is preferably inorganic glass. Examples of inorganic glass, classified by composition, include soda-lime glass, borate glass, aluminosilicate glass, and quartz glass, and, classified by alkali component, include alkali-free glass and low-alkali glass. The alkali metal component (e.g., Na) of the above glass may be a glass having a low alkali content. ２ O.K. ２ , Li ２ The content of O) is preferably 15% by mass or less, and more preferably 10% by mass or less.

[0022] The thickness of the glass layer 10 is preferably 20% to 75% of the thickness of the glass resin composite 1, more preferably 25% to 71%, and even more preferably 28% to 65%. If the thickness of the glass layer 10 relative to the thickness of the glass resin composite 1 is within the above preferred range, it is possible to provide a glass resin composite 1 in which cracks are less likely to occur in the glass layer 10. Furthermore, because the glass layer 10 becomes easier to bend, cracks are less likely to occur in the glass layer 10 even when the glass resin composite 1 is wound into a roll using, for example, a roll-to-roll process.

[0023] The thickness of the glass layer 10 can be designed appropriately depending on the thickness of the glass resin composite 1, and is preferably, for example, 30 μm or more and 300 μm or less. The thickness of the glass layer 10 is more preferably 35 μm or more, and even more preferably 40 μm or more. The thickness of the glass layer 10 is more preferably 250 μm or less, and even more preferably 230 μm or less. When the thickness of the glass layer 10 is within the above preferred range, it is possible to provide a glass resin composite 1 in which cracks are less likely to occur in the glass layer 10. Furthermore, because the glass layer 10 becomes easier to bend, cracks are less likely to occur in the glass layer 10 even when the glass resin composite 1 is wound into a roll using, for example, a roll-to-roll process.

[0024] The length and width of the glass layer 10 are not particularly limited and can be designed appropriately depending on the size of the glass resin composite 1. The length of the glass layer 10 is, for example, preferably 50 mm or more and 5000 mm or less, and more preferably 100 mm or more and 1500 mm or less. The width of the glass layer 10 is, for example, preferably 50 mm or more and 5000 mm or less, and more preferably 100 mm or more and 1500 mm or less. The length and width of the glass layer 10 may be the same or different.

[0025] The glass layer 10 is preferably transparent. Here, transparency refers to light transmittance that allows visible light (light with a wavelength of 380 nm or more and 780 nm or less) to pass through the interior of the glass layer 10 when irradiated from the outside of the glass layer 10, and the visible light transmittance of the glass layer 10 is preferably 85% or more. The light transmittance is measured using "Plastics - Determination of total luminous transmittance and total luminous reflectance" as defined in JIS K 7375:2008.

[0026] The refractive index of the glass layer 10 at a wavelength of 550 nm may be 1.4 or more and 1.65 or less.

[0027] The density of the glass layer 10 is not particularly limited and is, for example, 2.3 g / cm ３ 3.0g / cm or more ３ The following may be used.

[0028] The manufacturing method of the glass layer 10 is not particularly limited, and a general manufacturing method may be used. The glass layer 10 is manufactured by, for example, melting a mixture containing a main raw material such as silica or alumina, an antifoaming agent such as mirabilite or antimony oxide, and a reducing agent such as carbon at a temperature of 1400°C to 1600°C, forming the mixture into a thin plate, and then cooling it. The glass layer 10 may be chemically polished with a solvent such as hydrofluoric acid, as necessary, to make the glass layer thinner or to improve its smoothness.

[0029] A common method may be used to form the glass layer 10. Examples of methods that can be used to form the glass layer 10 include a slot downdraw method, a fusion method, and a float method. Among these, when the fusion method is used, the surface of the glass layer 10 is not contaminated with tin or the like as in the case of the float method, so polishing is not necessary and it is easy to ensure surface smoothness and thinness. Therefore, from these viewpoints, it is preferable to use the fusion method.

[0030] A commercially available glass sheet may be used as the glass layer 10 as is, or a commercially available glass sheet may be polished to a desired thickness and used. Examples of commercially available glass sheets include "7059," "1737," and "EAGLE2000" manufactured by Corning Incorporated, "AN100" manufactured by Asahi Glass Co., Ltd., "NA-35" manufactured by NH Technoglass Co., Ltd., "OA-10" manufactured by Nippon Electric Glass Co., Ltd., and "D263" or "AF45" manufactured by Schott Corporation.

[0031] [Resin Layer] As shown in FIGS. 1 and 2, the resin layer 20 is a layer made of resin, and may be provided by laminating one or more resin layers.

[0032] The resin layer 20 includes a first surface 20a on which the glass layer 10 is provided and a second surface 20b opposite to the first surface 20a. The second surface 20b is exposed. The resin layer 20 may have a quadrangular shape in a plan view and may have four side surfaces 20c connecting the first surface 20a and the second surface 20b. The four side surfaces 20c may be inclined inward toward the second surface 20b.

[0033] The resin layer included in the resin layer 20 can be made of any appropriate resin depending on the application and the like of the glass resin composite 1. Examples of resins that form the resin layer include polyvinyl alcohol (PVA)-based resins, polyolefin-based resins, cyclic olefin-based resins, polycarbonate-based resins, cellulose-based resins, polyester-based resins, polyamide-based resins, polyimide-based resins, polyether-based resins, polystyrene-based resins, (meth)acrylic-based resins, (meth)acrylic urethane-based resins, polysulfone-based resins, acetate-based resins, epoxy-based resins, silicone-based resins, polyarylate-based resins, polysulfone-based resins, polyetherimide-based resins, epoxy-based resins, urethane-based resins, and silicone-based resins.

[0034] The thickness of the resin layer 20 is not particularly limited, and may be any thickness appropriate depending on the application, type, etc.

[0035] The resin layer 20 can be used as an optical film, a conductive film, a light control film, etc. Examples of optical films include a polarizing plate, a retardation plate, and an isotropic film.

[0036] A case where the resin layer 20 is used as a polarizing plate will be described.

[0037] The polarizing plate has a film-like polarizer.

[0038] The thickness of the polarizer is not particularly limited and may be set arbitrarily depending on the purpose. The thickness of the polarizer may be, for example, 1 μm or more and 80 μm or less.

[0039] The polarizer preferably exhibits absorption dichroism at a wavelength of 380 nm or more and 780 nm or less. The single transmittance of the polarizer is preferably 40.0% or more. The degree of polarization of the polarizer is preferably 99.8% or more.

[0040] The polarizer is preferably an iodine-based polarizer, which can be made of a polyvinyl alcohol-based resin (PVA-based resin) containing iodine.

[0041] Any appropriate resin can be used as the PVA-based resin. Examples of PVA-based resins include polyvinyl alcohol and ethylene-vinyl alcohol copolymers. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. Ethylene-vinyl alcohol copolymers can be obtained by saponifying ethylene-vinyl acetate copolymers. The saponification degree of the PVA-based resin is usually 85 mol % or more and 100 mol % or less. The saponification degree can be determined in accordance with JIS K6726-1994. By using a PVA-based resin having such a saponification degree, a polarizer with excellent durability can be obtained.

[0042] The average degree of polymerization of the PVA-based resin may be appropriately selected depending on the purpose, and is usually from 1000 to 10000. The average degree of polymerization can be determined in accordance with JIS K 6726:1994.

[0043] The polarizing plate may have a protective film on at least one surface of the polarizer. The protective film may be formed using any appropriate material, and examples of the material for the protective film include polyester resins such as polyethylene terephthalate (PET), cellulose resins such as triacetyl cellulose (TAC), cycloolefin resins such as norbornene resins, olefin resins such as polyethylene and polypropylene, and (meth)acrylic resins.

[0044] The protective film may have ultraviolet absorbing ability. The protective film can exhibit ultraviolet absorbing ability by appropriately containing any ultraviolet absorber. Examples of ultraviolet absorbers include oxybenzophenone-based compounds, benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, nickel complex salt-based compounds, and triazine-based compounds. The content of the ultraviolet absorber may be any amount that can exhibit sufficient ultraviolet absorbing ability, and is, for example, preferably 0.01 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the protective film.

[0045] The protective film can be formed by a general film-forming method, such as melt extrusion, solution casting, calendering, or compression molding.

[0046] The polarizer and the protective film are laminated together via any suitable adhesive layer.

[0047] The thickness of the protective film is not particularly limited and may be, for example, 5 μm or more and 55 μm or less.

[0048] The resin layer 20 may have a transparent conductive layer. Examples of the transparent conductive layer include a metal oxide layer, a metal layer, a layer containing a conductive polymer, a layer containing metal nanowires, and a layer made of a metal mesh.

[0049] [Protective Layer] The glass resin composite 1 may be temporarily provided with a protective layer on the first surface 10a of the glass layer 10. The protective film temporarily protects the surface of the glass layer 10 and prevents contamination of the surface due to adhesion of foreign matter or the like.

[0050] Examples of materials that can be used to form the protective film include polyethylene, polyvinyl chloride, polyethylene terephthalate, polyvinylidene chloride, polypropylene, polyvinyl alcohol, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid copolymer, nylon, cellophane, and silicone resin.

[0051] The thickness of the protective layer is not particularly limited, but may be, for example, 100 μm or less.

[0052] The glass resin composite 1 may optionally include a functional layer such as a transparent electrode, an anti-reflection layer, or an anti-fouling layer on the first surface 10a of the glass layer 10. The thickness of the functional layer is not particularly limited, but may be, for example, 1 μm or less.

[0053] <Method for Manufacturing Glass Resin Composite> FIGS. 3 and 4 are diagrams (part 1) for explaining an example of a method for manufacturing a glass resin composite according to this embodiment.

[0054] (Formation of Laminate) The laminate 1S is formed by laminating the glass layer 10 and the resin layer 20. The laminate 1S is obtained by laminating the resin layer 20, which has been formed into a predetermined shape by press working or the like, and the glass layer 10 via an adhesive layer. Alternatively, the laminate 1S may be formed by continuously laminating the resin layer 20 and the glass layer 10 via the adhesive layer using a roll-to-roll process.

[0055] The length of the glass layer 10 before cutting is, for example, preferably 50 m or more, more preferably 100 m or more, and even more preferably 500 m or more. The upper limit of the length of the glass layer 10 before cutting is not particularly limited and may be, for example, 1000 m.

[0056] When the resin layer 20 includes an adhesive layer as a resin layer, the laminate 1S can be formed by laminating the remaining resin layer of the resin layer 20 onto the glass layer 10 via the adhesive layer, which is one of the resin layers of the resin layer 20.

[0057] In addition, the laminate 1S can be formed by applying a resin solution that forms a resin layer to the second surface 10b of the glass layer 10 or a main surface of one resin layer (adhesive layer) that is different from the glass layer 10 side to form the resin layer 20.

[0058] Examples of methods for applying the resin solution used to form the resin layer include coating methods such as air doctor coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, electrodeposition coating, dip coating, and die coating; printing methods such as relief printing methods such as flexographic printing; intaglio printing methods such as direct gravure printing and offset gravure printing; lithographic printing methods such as offset printing; and stencil printing methods such as screen printing.

[0059] When one of the resin layers constituting the resin layer 20 is a curable resin layer such as an adhesive layer, the resin solution constituting the resin layer may be cured using any appropriate curing method depending on the type of resin layer. Examples of the curing method include a method of curing the resin solution by ultraviolet irradiation or heat treatment. A pressure-sensitive adhesive (PSA) may also be used as a material constituting the adhesive layer.

[0060] (Cutting of Laminate) Next, the laminate 1S formed by laminating the glass layer 10 and the resin layer 20 is cut to a predetermined size, thereby obtaining a glass resin composite 1.

[0061] As shown in Fig. 3, the laminate 1S has a plurality of product areas A defined therein, which will become glass resin composites 1 when separated. In the example of Fig. 3, the product areas A are arranged vertically and horizontally at a predetermined interval, but this is not limiting. For example, the product areas A may be arranged one-dimensionally.

[0062] The method for cutting the laminate 1S is a method in which the laminate 1S is divided by irradiating it with laser light.

[0063] The laminate 1S may be cut into individual glass layers 10 or resin layers 20 separately.

[0064] A method of dividing the laminate 1S by irradiating with laser light will be described. When using the method of dividing the laminate 1S by irradiating with laser light, the laminate 1S may be divided using a laser light irradiation device that irradiates any appropriate laser light.

[0065] The laminate 1S is placed on a stage of a laser beam irradiation device. The stage is movably disposed relative to the laser beam irradiation device, and the laser light source is fixedly disposed relative to the laser beam irradiation device. The laser beam irradiation device moves the stage to move the position of the laser beam irradiated onto the laminate 1S.

[0066] The laser light is, for example, CO ２ Examples of such lasers include gas lasers such as lasers and excimer lasers; solid-state lasers such as YAG lasers; semiconductor lasers; and ultrashort pulse lasers.

[0067] The laminate 1S may be cut by forming laser processing marks 11 along the planned cutting line in the laminate 1S with a laser beam. The laser processing marks 11 may be provided intermittently along the planned cutting line, or may be provided as a continuous line. The laser processing marks 11 do not penetrate the glass layer 10.

[0068] The outer periphery of each product region A of the laminate 1S is irradiated with laser light from the second surface 20b side of the resin layer 20. For example, the outer periphery of each product region A shown in FIG. 3 is sequentially irradiated with laser light in a grid pattern. As shown in FIG. 4, the laser light may be irradiated until, for example, through holes 20x penetrating the resin layer 20 are formed and the second surface 10b of the glass layer 10 is exposed. In the example shown in FIG. 4, through holes 20x are formed, but laser processing marks that do not penetrate the resin layer 20 may also be formed.

[0069] Next, the outer periphery of each product region A of the laminate 1S is irradiated with laser light L from the first surface 10a side of the glass layer 10. For example, the outer periphery of each product region A shown in Figures 3 and 4 is irradiated with laser light L intermittently in a dot pattern at predetermined intervals along a grid. At this time, by adjusting the height of the stage (the height in a direction perpendicular to the first surface 10a), the distance L1 between the laser processing marks 11 and the first surface 10a can be set to 20% or less of the thickness L2 of the glass layer 10, and the length L3 of the laser processing marks 11 in the direction perpendicular to the first surface 10a can be set to 5% to 50% of the thickness of the glass layer 10.

[0070] It is preferable to use different laser beams for irradiating the first surface 10a of the glass layer 10 and the first surface 20a of the resin layer 20. In the step of irradiating the first surface 10a of the glass layer 10 with a laser, laser processing marks 11 are formed in the glass layer 10, and in the step of irradiating the first surface 20a of the resin layer 20 with a laser, through holes 20x or non-penetrating laser processing marks are formed in the resin layer 20, thereby making it easier to cut the laminate 1S.

[0071] An ultrashort pulse laser is preferably used as the laser light irradiated onto the first surface 10a of the glass layer 10. The wavelength of the ultrashort pulse laser emitted from the ultrashort pulse laser device is preferably 500 nm or more and 2500 nm or less. The pulse width of the ultrashort pulse laser is preferably 100 picoseconds or less, and more preferably 50 picoseconds or less. The oscillation mode of the ultrashort pulse laser may be single pulse oscillation or burst mode multi-pulse oscillation.

[0072] The laser light irradiated onto the first surface 20a of the resin layer 20 is, for example, CO ２ Examples of visible light pulse lasers and ultraviolet light pulse lasers include lasers with an oscillating wavelength of 532 nm, 355 nm, 349 nm, or 266 nm (Nd:YAG, Nd:YLF, or YVO ４a laser that is a high-order harmonic of a solid-state laser light source using a medium, an excimer laser that emits laser light with a wavelength of 351 nm, 248 nm, 222 nm, 193 nm or 157 nm, an F laser that emits laser light with a wavelength of 157 nm, ２ Examples of suitable laser beams include lasers. Furthermore, the laser beam may be a pulsed laser having a wavelength outside the ultraviolet range and a pulse width on the order of femtoseconds or picoseconds. The laser beam irradiated onto the resin layer 20 may be pulsed or continuous wave. The spatial intensity distribution of the laser beam may be a Gaussian distribution or a flat-top distribution.

[0073] The spot diameter at the irradiation position of the laser light on the glass layer 10 and the resin layer 20 may be set appropriately, and may be, for example, 300 μm or less.

[0074] The stage movement speed during irradiation of the laser beam onto the laminate 1S may be set arbitrarily as appropriate. The stage movement speed corresponds to the relative movement speed of the laser beam with respect to the laminate 1S, and by changing the stage movement speed, different energies can be applied to the laminate 1S.

[0075] When different laser beams are irradiated onto the first surface 10a of the glass layer 10 and the first surface 20a of the resin layer 20, the stage movement speed may be different when irradiating the glass layer 10 with laser beam and when irradiating the resin layer 20 with laser beam.

[0076] When an ultrashort pulse laser is irradiated onto the first surface 10a of the glass layer 10 as laser light, the stage movement speed can be adjusted to make it easier to cut the laminate 1S while suppressing damage such as cracks to the glass layer 10.

[0077] The first surface 20a of the resin layer 20 is exposed to CO ２ When irradiating the laser, the stage movement speed is adjusted to prevent the resin layer 20 from being damaged by CO ２ The degree of thermal degradation can be adjusted by using a laser. ２When thermally deteriorated by a laser, the flexibility of the resin layer 20 decreases, and the Young's modulus tends to decrease. ２ The faster the stage moving speed during laser irradiation, the more CO ２ Since thermal degradation caused by the laser is suppressed, the resin layer 20 maintains its flexibility and the decrease in the Young's modulus of the resin layer 20 is suppressed. ２ The slower the stage moving speed during laser irradiation, the more CO ２ Since thermal degradation due to the laser is likely to occur, the flexibility of the resin layer 20 decreases, and the Young's modulus of the resin layer 20 decreases.

[0078] When different laser beams are irradiated onto the first surface 10a of the glass layer 10 and the first surface 20a of the resin layer 20, by cutting the glass layer 10 using an ultrashort pulse laser, damage such as cracks in the glass layer 10 can be suppressed, and the laminate 1S can be easily cut. ２ By using a laser or the like, it is possible to suppress thermal deterioration of the resin layer 20. Therefore, when CO ２ After the laser irradiation, the glass layer 10 is irradiated with ultrashort pulse laser light as the laser light, whereby the laminate 1S can be cut while more effectively preventing thermal deterioration of the resin layer 20.

[0079] When the laser processing marks 11 are provided intermittently, the pitch of the laser processing marks 11 is preferably 10 μm or less, and more preferably 5 μm or less. Within this range, the laminate 1S can be divided well.

[0080] After irradiation with the laser light, the laminate 1S may be divided by, for example, applying an external force to fold the laminate 1S, heating the area near the laser processing marks 11 with infrared light, applying vibrations with an ultrasonic roller, or adsorbing a portion of the laminate 1S to a suction cup and lifting it up.

[0081] As described above, by cutting the laminate 1S, a plurality of glass resin composites 1 are obtained. The obtained plurality of glass resin composites 1 can be attached at predetermined intervals to one main surface of a film substrate via an adhesive or the like by a roll-to-roll process, and then wound into a roll.

[0082] The glass resin composite 1 can be effectively used in image display devices such as liquid crystal display devices and organic EL devices, semiconductor devices, solar cells, and the like.

[0083] In this embodiment, the glass resin composite 1 may have a resin layer 20 on the first surface 10a of the glass layer 10, or may have a resin layer 20 on both the first surface 10a and the second surface 10b of the glass layer 10.

[0084] Hereinafter, the embodiment will be described in more detail with reference to examples and comparative examples, but the embodiment is not limited to these examples and comparative examples.

[0085] <Preparation of Glass Resin Composite> (Preparation of Laminate) A resin layer R1 or R2 was laminated on one main surface of a 300 mm square glass sheet (manufactured by Nippon Electric Glass Co., Ltd., "OA-10", thickness: 100 μm) to form the layer structure shown in Table 1. In the resin layers R1 and R2, the adhesive layer was formed using an epoxy resin (manufactured by Daicel Chemical Industries, Ltd., "Celloxide (registered trademark) 2021P"). In the resin layers R1 and R2, "A4360" manufactured by Toyobo Co., Ltd. was used as the PET, PVA synthesized by saponifying polyvinyl acetate was used as the PVA, and an acrylic adhesive solution prepared as follows was used as the PSA.

[0086] A four-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser was charged with 90.7 parts by mass of butyl acrylate, 3 parts by mass of acrylic acid, 0.3 parts by mass of 2-hydroxybutyl acrylate, and 0.1 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator, along with 100 g of ethyl acetate, to prepare a mixture. Nitrogen gas was introduced to replace the atmosphere with nitrogen while gently stirring the mixture, and the liquid temperature in the flask was maintained at around 55°C while the polymerization reaction was carried out for 8 hours, to prepare an acrylic polymer solution. An acrylic pressure-sensitive adhesive solution was prepared by blending 0.2 parts by mass of an isocyanate crosslinking agent ("Coronate (registered trademark) L" manufactured by Nippon Polyurethane Industry Co., Ltd., an adduct of trimethylolpropane and tolylene diisocyanate), 0.3 parts by mass of benzoyl peroxide ("Niper (registered trademark) BMT" manufactured by Nippon Oil & Fats Corporation), and 0.2 parts by mass of γ-glycidoxypropylmethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts by mass of the solids content of the obtained acrylic polymer solution.

[0087]

[0088] Ultraviolet light (wavelength: 365 nm, intensity: 1000 mJ / cm) was emitted from a high-pressure mercury lamp. ２ The adhesive was cured by irradiating it with the above-mentioned radiation. In this way, laminates of Examples 1 to 6 and Comparative Examples 1 to 4 having the layer structures shown in Table 1 were produced.

[0089] (Removal of Resin Layer) The laminate was placed on a stage with the resin layer side facing up. ２ Using a laser device (250 kHz, output 10 W), CO ２ CO emitted from a laser light source ２ The laser was irradiated onto each resin layer. ２ The laser was focused to a spot diameter of 100 μm using a focusing lens. The stage movement speed was set to 350 mm / s, and the CO ２ The relative movement speed (processing speed) of the laser was set so that the in-plane dimensions of the laminate were 150 mm x 150 mm. ２ Each resin layer was irradiated with a laser to remove each resin layer, and each laminate was cut in half.

[0090] In addition, CO ２ By increasing the stage movement speed during laser irradiation, CO ２ Since thermal degradation caused by the laser is suppressed, the decrease in Young's modulus of the glass sheet and the resin layer is suppressed. ２ If the stage movement speed during laser irradiation is slowed down, the CO ２ Laser heat degradation is more likely to occur.

[0091] (Formation of laser processing marks) Next, the glass sheet side was placed on the stage with the upper surface facing up, and an ultrashort pulse laser device (oscillation wavelength 1064 nm, ultrashort pulse laser pulse width 10 psec, pulse repetition frequency 125 kHz, pulse energy 80 uJ) was used to irradiate the ultrashort pulse laser emitted from the ultrashort pulse laser light source through an optical system onto the surface opposite the resin film side of the glass sheet. The stage movement speed was set to 125 mm / s, and the relative movement speed (processing speed) of the ultrashort pulse laser with respect to the laminate was set, and the ultrashort pulse laser was scanned along the periphery of the adhesive layer and the resin layer to form laser processing marks with a pitch of 1 μm. At this time, by adjusting the height of the stage, a laser processing mark having a distance L1 between the laser processing mark and the first surface of the glass layer, a distance L4 between the laser processing mark and the second surface of the glass layer, and a length L3 was formed, as shown in Table 1.

[0092] The laminate was then bent and cut into a plurality of pieces (four pieces) to prepare glass resin composite test pieces (composite chips) of Examples 1 to 6 and Comparative Examples 1 to 4.

[0093] <Evaluation> The occurrence of cracks in the glass sheet of the glass resin composite test piece of each example and comparative example was evaluated. Figures 5A and 5B are diagrams illustrating the evaluation method in the examples.

[0094] First, as shown in FIG. 5A, the glass resin composite test piece (glass resin composite 1) was bent into a U-shape with the glass sheet (glass layer 10) facing inward, and the bent state was maintained for 10 seconds with a distance L5 of 50 mm between both ends. Next, as shown in FIG. 5B, the glass resin composite test piece was bent into a U-shape with the glass sheet facing outward, and the distance between both ends (breakage distance) L6 when a crack occurred in the glass sheet was measured. Here, distance L5 refers to the distance between both ends of the outer surface of the resin layer 20, and distance L6 refers to the distance between both ends of the outer surface of the glass layer 10. As evaluation criteria, if the breakage distance L6 = 100 mm or less, it was deemed usable, and if the breakage distance L6 = less than 100 mm, it was deemed unusable. For each of the 10 glass resin composite test pieces, if all were usable, it was rated A, and if even one was unusable, it was rated B. Evaluation results A was deemed pass, and B was deemed fail.

[0095]

[0096] As shown in Table 2, no cracks occurred in any of the ten glass resin composite test pieces (composite chips) of Examples 1 to 6. Cracks were observed in all ten or seven of the glass resin composite test pieces of Comparative Examples 1 to 4. From the above, it was confirmed that cracks are less likely to occur in the glass layer in glass resin composites in which the distance L1 is 20% or less of the thickness of the glass layer and the length L3 of the laser processing mark is 5% or more and 50% or less of the thickness of the glass layer.

[0097] Although the embodiments have been described above, they are presented as examples and the present invention is not limited to the above embodiments. The above embodiments can be implemented in various other forms, and various combinations, omissions, substitutions, modifications, etc. can be made without departing from the spirit of the invention. These embodiments and their modifications are included within the scope and spirit of the invention, and are also included in the inventions and their equivalents as set forth in the claims.

[0098] Examples of embodiments of the present invention are as follows. <Aspect 1> A glass resin composite including a glass layer including a first surface and a second surface opposite the first surface; and a resin layer provided on the second surface, wherein a laser processing mark is formed on the glass layer extending from the first surface in a direction perpendicular to the first surface, the distance between the laser processing mark and the first surface is 20% or less of the thickness of the glass layer, and the length of the laser processing mark in the direction perpendicular to the first surface is 5% to 50% of the thickness of the glass layer. <Aspect 2> The glass resin composite according to Aspect 1, wherein the glass layer has a quadrangular shape in a plan view and four side surfaces connecting the first surface and the second surface, and the laser processing mark is formed on each of the four side surfaces. <Aspect 3> The glass resin composite according to Aspect 2, wherein the laser processing mark is formed on each of the four side surfaces from one end to the other end in the longitudinal direction of the side surfaces. Aspect 4: The glass resin composite according to any one of Aspects 1 to 3, wherein the thickness of the glass layer is 20% or more and 75% or less of the thickness of the glass resin composite. Aspect 5: The glass resin composite according to any one of Aspects 1 to 4, wherein the thickness of the glass layer is 30 μm or more and 300 μm or less.

[0099] This international application claims priority to Japanese Patent Application No. 2024-022698, filed on February 19, 2024, the entire contents of which are incorporated herein by reference.

[0100] REFERENCE SIGNS LIST 1 glass resin composite 10 glass layer 11 laser processing marks 20 resin layer 10a, 20a first surface 10b, 20b second surface 10c, 20c side surface

Claims

1. A glass resin composite comprising: a glass layer including a first surface and a second surface opposite the first surface; and a resin layer provided on the second surface, wherein a laser processing mark is formed on the glass layer extending from the first surface in a direction perpendicular to the first surface, the distance between the laser processing mark and the first surface is 20% or less of the thickness of the glass layer, and the length of the laser processing mark in the direction perpendicular to the first surface is 5% or more and 50% or less of the thickness of the glass layer.

2. The glass resin composite according to claim 1, wherein the glass layer has a quadrangular shape in a plan view and has four side surfaces connecting the first surface and the second surface, and the laser processing marks are formed on each of the four side surfaces.

3. A glass resin composite according to claim 2, wherein a plurality of the laser processing marks are formed on each of the four side surfaces, spaced apart from one another, from one end to the other in the longitudinal direction of the side surface.

4. A glass resin composite according to claim 1, wherein the thickness of the glass layer is 20% or more and 75% or less of the thickness of the glass resin composite.

5. The glass resin composite according to claim 1, wherein the thickness of the glass layer is 30 μm or more and 300 μm or less.

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