Glass resin composite

Abstract

One aspect of the glass-resin composite of the present invention comprises: a glass layer including a first surface and a second surface opposite to the first surface, and a resin layer disposed on the second surface, wherein a laser processing mark is formed on the glass layer extending from the first surface in a direction orthogonal to the first surface, the distance between the laser processing mark and the first surface is 20% or less relative to the thickness of the glass layer, and the length of the laser processing mark in the direction orthogonal to the first surface is a length that is 5% or more and 50% or less relative to the thickness of the glass layer.

Description

Technical Field

[0001] This invention relates to glass-resin composites. Background Technology

[0002] Glass-resin laminates, in image display devices such as liquid crystal display elements and organic EL elements, semiconductor elements, and solar cells, are used where a resin layer is laminated on an extremely thin, flexible glass sheet (hereinafter also referred to as a "glass sheet"). The glass sheet used in the glass-resin laminate is flexible and can be rolled into a roll. Therefore, the glass sheet can be rolled out using a roll-to-roll process, and after processing such as bonding or printing of the resin layer, it can be rolled up again to manufacture the glass-resin laminate.

[0003] As a method for manufacturing glass resin laminates using roll-to-roll processes, for example, a method has been disclosed for forming a laminate roll by laminating a flexible glass layer onto other material sheets, such as a PVA layer and a TAC layer, which include a polarizing mirror structure, using a roll-to-roll lamination apparatus (for example, see Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: US Patent No. 8525405 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] However, Patent Document 1 does not describe the following: when the laminated roll is sliced ​​by cutting or the like, and the sliced ​​laminated roll is pasted onto a flexible film substrate wound into a roll and transported using a roll-to-roll process, the generation of cracks in the flexible glass layer is suppressed.

[0009] The following problems exist: when the sliced ​​glass resin composite is bonded to the roll-shaped film substrate by adhesives, etc., and the roll is transported (roll processing) and rolled into a roll using a roll-to-roll process, cracks sometimes occur in the glass layer.

[0010] One aspect of the present invention is to provide a glass-resin composite that is not prone to cracking in the glass layer.

[0011] Problem Solving Methods

[0012] One aspect of the glass-resin composite of the present invention comprises: a glass layer including a first surface and a second surface opposite to the first surface, and a resin layer disposed on the second surface, wherein a laser processing mark is formed on the glass layer extending from the first surface in a direction orthogonal to the first surface, the distance between the laser processing mark and the first surface is 20% or less relative to the thickness of the glass layer, and the length of the laser processing mark in the direction orthogonal to the first surface is a length that is 5% or more and 50% or less relative to the thickness of the glass layer.

[0013] The effects of the invention

[0014] One aspect of the present invention can provide a glass-resin composite that is less prone to cracking in the glass layer. Attached Figure Description

[0015] Figure 1 This is a side view showing the structure of the glass-resin composite of this embodiment.

[0016] Figure 2 This is a perspective view showing the structure of the glass-resin composite of this embodiment.

[0017] Figure 3 Figure 1 illustrates an example of the manufacturing method of the glass-resin composite according to this embodiment.

[0018] Figure 4 Figure 2 illustrates an example of the manufacturing method of the glass-resin composite according to this embodiment.

[0019] Figure 5A Figure (1) illustrates the evaluation method in the embodiments.

[0020] Figure 5B Figure (2) illustrates the evaluation method in the embodiments.

[0021] Symbol Explanation

[0022] 1 Glass-resin composite

[0023] 10 glass layers

[0024] 11 Laser processing marks

[0025] 20 resin layers

[0026] 10a, 20a Side 1

[0027] Page 2 of 10b and 20b

[0028] 10c, 20c side view Detailed Implementation

[0029] The embodiments of the present invention will now be described in detail. It should be noted that, to facilitate understanding, the same reference numerals are used for the same constituent elements in the accompanying drawings, and repeated descriptions are omitted. Furthermore, the scale of the components in the drawings may sometimes differ from the actual scale.

[0030] <Glass-Resin Composite>

[0031] The glass-resin composite of the present invention will be described. Figure 1 This is a side view showing the structure of the glass-resin composite of this embodiment. Figure 2 This is a perspective view showing the structure of the glass-resin composite of this embodiment.

[0032] like Figure 1 and Figure 2 As shown, the glass-resin composite 1 of this embodiment has a glass layer 10 and a resin layer 20. The glass layer 10 includes a first surface 10a and a second surface 10b opposite to the first surface 10a, and the resin layer 20 is disposed on the second surface 10b. Furthermore, a laser processing mark 11 is formed on the glass layer 10, extending from the first surface 10a in a direction orthogonal to the first surface 10a. The distance L1 between the laser processing mark 11 and the first surface 10a is 20% or less relative to the thickness L2 of the glass layer 10, and the length L3 of the laser processing mark 11 in the direction orthogonal to the first surface 10a is 5% or more and 50% or less relative to 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 in the direction perpendicular to the first surface 10a. With this configuration, a glass-resin composite 1 that is less prone to cracking in the glass layer 10 can be provided. For example, even when the glass-resin composite 1 is bonded to one main surface of a flexible film substrate wound into a roll using an adhesive or similar process and then wound into a roll, cracks are not easily generated in the glass layer 10.

[0033] The distance L4 between the laser processing mark 11 and the second surface 10b can be set to be greater than 30% relative to the thickness L2 of the glass layer 10. Here, distance L4 refers to the shortest distance between the laser processing mark 11 and the second surface 10b.

[0034] 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.

[0035] It should be noted that, in this specification, the thickness of the glass-resin composite 1 refers to the length of the glass-resin composite 1 in the direction perpendicular to the first surface 10a. For example, the thickness of the glass-resin composite 1 can be measured at any point in a cross-section of the glass-resin composite 1, or it can be measured at multiple points at any point and set as the average of these measurements. Hereinafter, the definition of thickness will be defined in the same manner for other components.

[0036] [Glass layer]

[0037] The glass layer 10, viewed from above, has a quadrilateral shape and four side surfaces 10c connecting the first surface 10a and the second surface 10b. Laser processing marks 11 can be formed on each of the four side surfaces 10c. This configuration helps to suppress the concentration of external forces on a portion of the four side surfaces 10c, providing a glass-resin composite 1 that is less prone to cracking in the glass layer 10. It should be noted that, in this specification, a quadrilateral is simply a quadrilateral formed by four sides, and the shape of the corners is not limited, including rounded quadrilaterals, quadrilaterals formed by obliquely cutting off right angles, etc.

[0038] Specifically, multiple laser processing marks 11 can be formed at intervals from one end to the other along the length of each of the four sides 10c. This configuration can further suppress the concentration of external forces on a portion of the four sides 10c, and can provide a glass-resin composite 1 that is less prone to cracking in the glass layer 10.

[0039] The glass layer 10 can have a plate-like (sheet-like) shape, and the width and length of the glass layer 10 can be set to any size.

[0040] The glass layer 10 is formed using a strip of glass. The glass layer 10 can be obtained by cutting the strip of glass. It should be noted that "strip" refers to a long, thin shape that is long enough relative to its width, for example, including a long, thin rectangular shape whose length is more than 10 times, preferably more than 20 times, relative to its width.

[0041] The glass layer 10 can be formed using any suitable glass material. The glass material constituting the glass layer 10 is preferably an inorganic glass. Examples of inorganic glasses, based on composition, include soda-lime glass, borosilicate glass, aluminosilicate glass, and quartz glass; examples based on alkali content include alkali-free glass and low-alkali glass. The content of the alkali metal component (e.g., Na₂O, K₂, Li₂O) in the aforementioned glass is preferably 15% by mass or less, more preferably 10% by mass or less.

[0042] The thickness of the glass layer 10 relative to the thickness of the glass-resin composite 1 is preferably 20% or more and 75% or less, more preferably 25% or more and 71% or less, and even more preferably 28% or more and 65% or less. When the thickness of the glass layer 10 relative to the glass-resin composite 1 is within the above-mentioned preferred range, a glass-resin composite 1 that is less prone to cracking in the glass layer 10 can be provided. In addition, since the glass layer 10 is easily bent, the glass-resin composite 1 is less prone to cracking in the glass layer 10 even when it is rolled into a roll, for example, using a roll-to-roll process.

[0043] The thickness of the glass layer 10 can be appropriately designed according to the thickness of the glass-resin composite 1, and is preferably 30 μm or more and 300 μm or less. More preferably, the thickness of the glass layer 10 is 35 μm or more, and even more preferably 40 μm or more. More preferably, the thickness of the glass layer 10 is 250 μm or less, and even more preferably 230 μm or less. When the thickness of the glass layer 10 is within the above-mentioned preferred range, a glass-resin composite 1 that is less prone to cracking in the glass layer 10 can be provided. Furthermore, since the glass layer 10 is easily bent, the glass-resin composite 1 is less prone to cracking in the glass layer 10 even when, for example, it is wound into a roll using a roll-to-roll process.

[0044] The length and width of the glass layer 10 are not particularly limited and can be appropriately designed according to the size of the glass-resin composite 1. The length of the glass layer 10 is preferably 50 mm or more and 5000 mm or less, more preferably 100 mm or more and 1500 mm or less. The width of the glass layer 10 is preferably 50 mm or more and 5000 mm or less, more preferably 100 mm or more and 1500 mm or less. The length and width of the glass layer 10 can be the same or different.

[0045] The glass layer 10 is preferably transparent. It should be noted that transparency means that visible light (light with a wavelength of 380 nm or more and 780 nm or less) can pass through the interior of the glass layer 10 when irradiated from the outside. The visible light transmittance of the glass layer 10 is preferably 85% or more. The light transmittance is measured using the method specified in JIS K 7375:2008, "Plastics - Method for determining total light transmittance and total light reflectance".

[0046] The refractive index of glass layer 10 at a wavelength of 550 nm only needs to be above 1.4 and below 1.65.

[0047] The density of glass layer 10 is not particularly limited; for example, it can be set to 2.3 g / cm³. 3 Above and 3.0 g / cm 3 the following.

[0048] The manufacturing method of glass layer 10 is not particularly limited, and conventional manufacturing methods can be used. For example, glass layer 10 can be manufactured by melting a mixture containing main raw materials such as silica and alumina, defoamers such as sodium sulfate and antimony oxide, and reducing agents such as carbon at a temperature of 1400°C to 1600°C, forming it into a thin sheet, and then cooling it. To achieve thinner sheets and improve smoothness, glass layer 10 can be chemically ground using solvents such as hydrofluoric acid as needed.

[0049] The glass layer 10 can be formed using conventional methods. For example, slot-down draw, melting, and float glass methods can be used. Among these, the melting method avoids surface contamination by tin or other materials, unlike the float glass method, thus eliminating the need for grinding and easily ensuring surface smoothness and thinness. Therefore, from these perspectives, the melting method is preferred.

[0050] Glass layer 10 can be a commercially available product, or a commercially available glass sheet can be ground to the desired thickness. Examples of commercially available glass sheets include Corning's "7059", "1737" or "EAGLE2000", Asahi Glass Co., Ltd.'s "AN100", NH Techno Glass Co., Ltd.'s "NA-35", Nippon Electric Glass Co., Ltd.'s "OA-10", and Schott's "D263" or "AF45".

[0051] [Resin Layer]

[0052] like Figure 1 and Figure 2 As shown, resin layer 20 is a layer formed of resin, and may also be stacked and have more than one resin layer.

[0053] The resin layer 20 includes a first surface 20a on which the glass layer 10 is disposed and a second surface 20b opposite to the first surface 20a. The second surface 20b is exposed. The resin layer 20 may have a quadrilateral shape when viewed from above and has four side surfaces 20c connecting the first surface 20a and the second surface 20b. The four side surfaces 20c may also be inclined inward toward the second surface 20b.

[0054] The resin layer included in the resin layer 20 can be formed from any suitable resin, depending on the intended use of the glass-resin composite 1. Examples of resins forming the resin layer include: polyvinyl alcohol (PVA) resins, polyolefin resins, cyclic olefin resins, polycarbonate resins, cellulose resins, polyester resins, polyamide resins, polyimide resins, polyether resins, polystyrene resins, (meth)acrylic resins, (meth)acrylate resins, polysulfone resins, acetate resins, epoxy resins, silicone resins, polyarylate resins, polysulfone resins, polyetherimide resins, epoxy resins, polyurethane resins, and silicone resins.

[0055] The thickness of the resin layer 20 is not particularly limited and can be set to any thickness depending on the application, type, etc.

[0056] The resin layer 20 can be used as an optical film, a conductive film, a dimming film, etc. Examples of optical films include polarizers, phase retardation plates, and isotropic films.

[0057] The case where resin layer 20 is used as a polarizer will be explained.

[0058] Polarizers have a film-like polarizing lens.

[0059] There are no particular restrictions on the thickness of the polarizer; it can be set arbitrarily according to the purpose. For example, the thickness of the polarizer can be set to be greater than 1 μm and less than 80 μm.

[0060] The polarizer preferably exhibits absorption dichroism at any wavelength above 380 nm and below 780 nm. The single-cell transmittance of the polarizer is preferably 40.0% or higher. The degree of polarization of the polarizer is preferably 99.8% or higher.

[0061] The polarizer is preferably an iodine-based polarizer. Iodine-based polarizers can be formed from polyvinyl alcohol resins (PVA-type resins) containing iodine.

[0062] Any resin can be used as a PVA-type resin. Examples of PVA-type 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 degree of saponification of PVA-type resins is typically 85 mol% or more and 100 mol% or less. The degree of saponification can be determined according to JIS K 6726-1994. By using PVA-type resins with such a degree of saponification, polarizers with excellent durability can be obtained.

[0063] The average degree of polymerization of PVA resins can be arbitrarily selected according to the purpose, typically between 1000 and 10000. It should be noted that the average degree of polymerization can be determined according to JIS K 6726:1994.

[0064] A polarizer may have a protective film on at least one side of the polarizer. The protective film may be formed from any suitable material, and examples of materials for forming the protective film include: polyester resins such as polyethylene terephthalate (PET), cellulose resins such as cellulose triacetate (TAC), cyclic olefin resins such as norbornene resins, olefin resins such as polyethylene and polypropylene, and (meth)acrylic resins.

[0065] The protective film can possess ultraviolet (UV) absorption capabilities. These capabilities can be achieved by appropriately including any UV absorber. Examples of UV absorbers include: benzophenone compounds, benzotriazole compounds, salicylates, benzophenone, cyanoacrylates, nickel complexes, triazine compounds, etc. The proportion of the UV absorber is sufficient to achieve adequate UV absorption; for example, it is preferably 0.01 parts by weight or more and 30 parts by weight or less relative to 100 parts by weight of the protective film.

[0066] Protective films can be formed using conventional film-forming methods. Examples of such methods include melt extrusion, solution casting (solution casting), calendering, and compression molding.

[0067] The polarizer and the protective film are laminated together with any suitable adhesive layer.

[0068] There is no particular limitation on the thickness of the protective film; for example, it can be set to be above 5μm and below 55μm.

[0069] The resin layer 20 may have a transparent conductive layer. Examples of transparent conductive layers include: metal oxide layers, metal layers, layers containing conductive polymers, layers containing metal nanowires, and layers formed of metal meshes.

[0070] [Protective Layer]

[0071] The glass-resin composite 1 may temporarily have 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 inhibits foreign matter from adhering to the surface and causing contamination.

[0072] Materials that constitute the protective film include, for example, 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.

[0073] There is no particular limitation on the thickness of the protective layer; for example, it can be set to less than 100 μm.

[0074] The glass-resin composite 1 may appropriately and arbitrarily provide functional layers such as transparent electrodes, anti-reflective layers, and anti-fouling layers on the first surface 10a of the glass layer 10. The thickness of the functional layers is not particularly limited, for example, it can be set to less than 1 μm.

[0075] <Manufacturing Method of Glass-Resin Composites>

[0076] Figure 3 and Figure 4 Figure 1 illustrates an example of the manufacturing method of the glass-resin composite according to this embodiment.

[0077] (Formation of layered structures)

[0078] A laminate 1S is formed by stacking a glass layer 10 and a resin layer 20. The laminate 1S can be obtained by stacking a resin layer 20 and a glass layer 10, which have been formed into a given shape by means of pressure processing or the like, via an adhesive layer. Alternatively, the resin layer 20 and the glass layer 10 can be continuously stacked via an adhesive layer using a roll-to-roll process.

[0079] The length of the glass layer 10 before cutting is preferably 50m or more, more preferably 100m or more, and even more preferably 500m or more. It should be noted that there is no particular limit to the upper limit of the length of the glass layer 10 before cutting, for example, it can be 1000m.

[0080] 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.

[0081] Alternatively, a resin layer 20 can be formed by applying a resin solution to the second surface 10b of the glass layer 10 or a main surface of a resin layer (adhesive layer) that is different from the side of the glass layer 10, thereby forming a laminate 1S.

[0082] Examples of coating methods for the resin solution used in the formation of the resin layer include: air knife coating, doctor blade coating, doctor blade coating, reverse coating, transfer roller coating, gravure roller coating, kiss coating, cast coating, spraying, slotted hole coating, calendering coating, electrodeposition coating, dip coating, mold coating, etc.; flexographic printing, etc.; gravure printing, such as direct gravure printing, offset gravure printing, etc.; offset printing, such as lithographic printing, etc.; screen printing, etc.

[0083] When one of the resin layers constituting resin layer 20 is a curable resin layer such as an adhesive layer, any curing method can be appropriately used to cure the resin solution constituting the resin layer, depending on the type of resin layer. Examples of curing methods include curing the resin solution by ultraviolet irradiation or heat treatment. Pressure-sensitive adhesives (PSA) can also be used as the material constituting the adhesive layer.

[0084] (Cut off a layered structure)

[0085] Next, the laminate 1S formed by stacking glass layer 10 and resin layer 20 is cut to a given size to obtain glass-resin composite 1.

[0086] like Figure 3 As shown, the laminate 1S is divided into multiple product regions A that can be monolithically processed into a glass-resin composite 1. Figure 3 In the example, product area A is configured horizontally and vertically at given intervals, but it is not limited to this. For example, product area A can also be configured in one dimension.

[0087] The method for cutting the laminate 1S is to divide the laminate 1S by irradiating it with a laser.

[0088] The cutting of the laminate 1S can be performed separately for the glass layer 10 or the resin layer 20.

[0089] A method for dividing the laminate 1S by irradiation with a laser will be described. When using the method of dividing the laminate 1S by irradiation with a laser, any laser irradiation device that irradiates the laser can be used to divide the laminate 1S.

[0090] The laminate 1S is disposed on the stage of the laser irradiation device. The stage is configured to be movable relative to the laser irradiation device, while the laser source is fixedly disposed. The laser irradiation device moves the position of the laser irradiating the laminate 1S by moving the stage.

[0091] Examples of lasers include gas lasers such as CO2 lasers and excimer lasers; solid-state lasers such as YAG lasers; semiconductor lasers; and ultrashort pulse lasers.

[0092] The laminate 1S can be cut by using a laser to create laser processing marks 11 along a predetermined cutting line. The laser processing marks 11 can be set intermittently along the predetermined cutting line or in the form of a continuous line. The laser processing marks 11 do not penetrate the glass layer 10.

[0093] A laser is irradiated from the second surface 20b side of the resin layer 20 towards the outer periphery of each product region A of the laminate 1S. For example, for Figure 3 The outer periphery of each product area A shown is sequentially irradiated with laser light in a grid pattern. For example... Figure 4 As shown, the laser can, for example, irradiate until the second surface 10b of the glass layer 10 is exposed, forming a through-hole 20x that penetrates the resin layer 20. Figure 4 In the example shown, although through-hole 20x is formed, laser processing marks that do not penetrate the resin layer 20 can also be formed.

[0094] Next, laser L is irradiated from the first surface 10a side of glass layer 10 onto the outer periphery of each product region A of the laminate 1S. For example, laser L is irradiated intermittently in a dotted pattern along the lattice at given intervals. Figure 3 and Figure 4 Laser L is applied to the outer periphery of each product area A shown. At this time, by adjusting the height of the stage (the height in the direction orthogonal to the first surface 10a), the distance L1 between the laser processing mark 11 and the first surface 10a can be made less than 20% of the thickness L2 of the glass layer 10, and the length L3 of the laser processing mark 11 in the direction orthogonal to the first surface 10a can be more than 5% and less than 50% of the thickness of the glass layer 10.

[0095] It is preferable to use different lasers for irradiating the first surface 10a of the glass layer 10 and the first surface 20a of the resin layer 20. In the process 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. In the process 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 enabling the laminate 1S to be easily cut.

[0096] As the laser irradiating the first surface 10a of the glass layer 10, an ultrashort pulse laser is preferably used. The wavelength of the ultrashort pulse laser oscillating 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, more preferably 50 picoseconds or less. The oscillation mode of the ultrashort pulse laser can be single-pulse oscillation or burst mode multi-pulse oscillation.

[0097] Examples of lasers that irradiate the first surface 20a of the resin layer 20 include CO2 lasers, CO lasers, visible light pulsed lasers, and ultraviolet pulsed lasers. Examples of visible light pulsed lasers and ultraviolet pulsed lasers include lasers with oscillating wavelengths of 532 nm, 355 nm, 349 nm, or 266 nm (high harmonics of solid-state laser sources using Nd:YAG, Nd:YLF, or YVO4 as the medium), excimer lasers with oscillating wavelengths of 351 nm, 248 nm, 222 nm, 193 nm, or 157 nm, and F2 lasers with oscillating wavelengths of 157 nm. Alternatively, pulsed lasers with oscillating wavelengths outside the ultraviolet region and pulse widths on the order of femtoseconds or picoseconds can be used. The oscillation mode of the laser irradiating the resin layer 20 can be pulsed oscillation or continuous oscillation. The spatial intensity distribution of the laser can be Gaussian or flat-topped.

[0098] The diameter of the laser spot at the irradiation position of the glass layer 10 and the resin layer 20 can be appropriately set, for example, it can be set to less than 300μm.

[0099] The stage moving speed when irradiating the laminate 1S with laser can be set arbitrarily. The stage moving speed corresponds to the relative moving speed of the laser with respect to the laminate 1S. By changing the stage moving speed, different energies can be imparted to the laminate 1S.

[0100] When different lasers are irradiated onto the first surface 10a of the glass layer 10 and the first surface 20a of the resin layer 20, the stage can move at different speeds when the laser is irradiated onto the glass layer 10 and the laser is irradiated onto the resin layer 20.

[0101] When the first surface 10a of the glass layer 10 is irradiated with an ultrashort pulse laser, the laminate 1S can be easily cut off while suppressing damage such as cracks to the glass layer 10 by adjusting the moving speed of the stage.

[0102] When the first surface 20a of the resin layer 20 is irradiated with a CO2 laser, the degree of thermal degradation of the resin layer 20 due to the CO2 laser can be adjusted by changing the stage movement speed. When the resin layer 20 undergoes thermal degradation due to the CO2 laser, it tends to exhibit decreased flexibility and a decrease in Young's modulus. A higher stage movement speed during CO2 laser irradiation suppresses thermal degradation of the resin layer 20 caused by the CO2 laser, thus maintaining the flexibility of the resin layer 20 and suppressing the decrease in Young's modulus. Conversely, a lower stage movement speed during CO2 laser irradiation makes thermal degradation of the resin layer 20 more likely to occur, resulting in decreased flexibility and a decrease in Young's modulus.

[0103] By irradiating the first surface 10a of the glass layer 10 and the first surface 20a of the resin layer 20 with different lasers, the glass layer 10 can be cut using an ultrashort pulse laser, thereby suppressing damage such as cracks to the glass layer 10 and easily cutting the laminate 1S. For the resin layer 20, thermal degradation of the resin layer 20 can be suppressed by using a CO2 laser or the like. Therefore, by irradiating the resin layer 20 with a CO2 laser and then irradiating the glass layer 10 with an ultrashort pulse laser, the laminate 1S can be cut more effectively while preventing thermal degradation of the resin layer 20.

[0104] When laser processing marks 11 are intermittently set, the spacing of the laser processing marks 11 is preferably 10 μm or less, more preferably 5 μm or less. Within this range, the laminate 1S can be well segmented.

[0105] After laser irradiation, the laminate 1S can be divided using methods such as applying external force to bend the laminate 1S convexly, heating the area near the laser processing mark 11 with infrared light, applying vibration by an ultrasonic roller, or adsorbing a portion of the laminate 1S onto a suction cup and lifting it.

[0106] As described above, multiple glass resin composites 1 can be obtained by cutting the laminate 1S. The resulting multiple glass resin composites 1 can be, for example, adhered to a main surface of a film substrate at a given interval via an adhesive or the like using a roll-to-roll process and then rolled into a roll.

[0107] Glass-resin composite 1 can be effectively used in image display devices such as liquid crystal display elements and organic EL elements, semiconductor elements, solar cells, etc.

[0108] It should be noted that, 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 it may have a resin layer 20 on both the first surface 10a and the second surface 10b of the glass layer 10.

[0109] Example

[0110] The following examples and comparative examples illustrate the implementation in more detail, but the implementation is not limited to these examples and comparative examples.

[0111] <Fabrication of Glass-Resin Composites>

[0112] (Creating a layered body)

[0113] On one main surface of a 300 mm square glass sheet (manufactured by Nippon Electric Glass Co., Ltd., "OA-10", thickness: 100 μm), resin layer R1 or resin layer R2 is laminated on the main surface in a manner as shown in Table 1. In resin layers R1 and R2, the adhesive layer is formed using an epoxy resin (manufactured by CELLOXIDE Chemical Co., Ltd., "CELLOXIDE (registered trademark) 2021P"). In resin layers R1 and R2, the PET used is "A4360" manufactured by Toyobo Co., Ltd., the PVA used is PVA synthesized by saponifying polyvinyl acetate, and the PSA uses an acrylic adhesive solution prepared as described below.

[0114] A mixture was prepared by adding 90.7 parts by weight of butyl acrylate, 3 parts by weight of acrylic acid, 0.3 parts by weight of 2-hydroxybutyl acrylate, 0.1 parts by weight of 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile) as a polymerization initiator, and 100 g of ethyl acetate to a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and cooler. While slowly stirring the mixture, nitrogen was introduced for nitrogen purging. The liquid temperature in the flask was maintained at approximately 55°C for 8 hours to prepare an acrylic polymer solution. An acrylic adhesive solution was prepared by combining 0.2 parts by mass of an isocyanate crosslinking agent ("CORONATE L", an adduct of trimethylolpropane toluene diisocyanate, manufactured by Nippon Polyurethanes Co., Ltd., a registered trademark) with 100 parts by mass of the solid component of the obtained acrylic polymer solution, 0.3 parts by mass of benzoyl peroxide ("NYPER BMT", manufactured by Nippon Oils & Fats Co., Ltd., a registered trademark) and 0.2 parts by mass of γ-epoxypropoxypropylmethoxysilane ("KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd., a registered trademark) with 0.2 parts by mass of γ-epoxypropoxypropylmethoxysilane.

[0115]

[0116] By irradiating the adhesive with ultraviolet light (wavelength: 365nm, intensity: 1000mJ / cm²) using a high-pressure mercury lamp. 2 (Above), thereby curing the adhesive. Thus, laminates having the layer structures shown in Table 1 for Examples 1-6 and Comparative Examples 1-4 were produced.

[0117] (Resin layer removal)

[0118] The resin layer side of the laminate was placed on a stage with the resin layer side as the upper surface. A CO2 laser device (250kHz, 10W output) was used to irradiate each resin layer with CO2 laser light oscillated from a CO2 laser source. A condenser lens was used to focus the CO2 laser light into a spot diameter of 100μm. The stage moving speed was set to 350mm / s, and the relative moving speed (processing speed) of the CO2 laser relative to the laminate was set so that the in-plane dimensions of the laminate were 150mm×150mm. The CO2 laser irradiated each resin layer, removing each resin layer and halving each laminate.

[0119] It should be noted that by increasing the stage movement speed during CO2 laser irradiation, the thermal degradation of the glass slide and resin layer caused by the CO2 laser can be suppressed, thus inhibiting the decrease in the Young's modulus of the glass slide and resin layer. On the other hand, if the stage movement speed during CO2 laser irradiation is slowed down, thermal degradation of the glass slide and resin layer caused by the CO2 laser is more likely to occur.

[0120] (Formation of laser processing marks)

[0121] Next, the glass slide side was placed on a stage as the upper surface. Using an ultrashort pulse laser device (oscillation wavelength 1064 nm, pulse width 10 psec, pulse repetition frequency 125 kHz, pulse energy 80 μJ), ultrashort pulse laser light oscillated from the ultrashort pulse laser source was irradiated onto the surface of the glass slide opposite to the resin film side via an optical system. The stage moving speed was set to 125 mm / s, and the relative moving speed (processing speed) of the ultrashort pulse laser relative to the laminate was set. The ultrashort pulse laser was scanned along the outer periphery of the adhesive layer and resin layer, forming laser processing marks with a spacing of 1 μm. At this point, by adjusting the height of the stage, the distance L1 between the laser processing mark and the first surface of the glass layer, the distance L4 between the laser processing mark and the second surface of the glass layer, and the laser processing mark with a length L3, as shown in Table 1, were formed.

[0122] Then, by bending the laminate, the laminate was divided into multiple (4) pieces, thereby producing glass-resin composite test pieces (composite slices) of Examples 1-6 and Comparative Examples 1-4.

[0123] <Evaluation>

[0124] The degree of crack formation in the glass sheets of the glass-resin composite test pieces of each embodiment and comparative example was evaluated. Figure 5A and Figure 5B This is a diagram illustrating the evaluation method in the embodiments.

[0125] First, such as Figure 5AAs shown, the glass-resin composite test piece (glass-resin composite 1) was bent into a U-shape with the glass sheet (glass layer 10) as the inside, and held in this bent state for 10 seconds with the distance between the two ends L5 = 50 mm. Then, as... Figure 5B As shown, the glass-resin composite test piece was bent into a U-shape with the glass sheet facing outwards, and the distance between the two ends (fracture distance) L6 when a crack occurred in the glass sheet was measured. Here, distance L5 refers to the distance between the two ends of the outer surface of the resin layer 20, and distance L6 refers to the distance between the two ends of the outer surface of the glass layer 10. As an evaluation criterion, a fracture distance L6 of less than 100 mm is evaluated as practically usable, and a fracture distance L6 of less than 100 mm is evaluated as impractical. For each set of 10 glass-resin composite test pieces, if all are practically usable, the evaluation is A; even if one piece is impractical, the evaluation is B. Evaluation result A is considered acceptable, and B is considered unacceptable.

[0126]

[0127] As shown in Table 2, none of the 10 glass-resin composite test pieces (composite slices) from Examples 1-6 showed any crack formation. In Comparative Examples 1-4, crack formation was observed in either all 10 or 7 of the test pieces. Based on these results, it was confirmed that glass-resin composites with a distance L1 less than 20% of the glass layer thickness and a laser processing mark length L3 between 5% and 50% of the glass layer thickness are less prone to crack formation in the glass layer.

[0128] The embodiments have been described above, but these embodiments are provided as examples and the present invention is not limited to them. The embodiments described above can be implemented in various other ways, and various combinations, omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, and are included in the scope of the invention as described in the claims and its equivalents.

[0129] It should be noted that the embodiments of the present invention are described below, for example.

[0130] <Method 1>

[0131] A glass-resin composite material having:

[0132] A glass layer including a first surface and a second surface opposite to the first surface, and

[0133] The resin layer disposed on the second surface mentioned above,

[0134] Laser processing marks are formed on the aforementioned glass layer, extending from the first surface in a direction orthogonal to the first surface.

[0135] The distance between the aforementioned laser processing marks and the first surface is less than 20% relative to the thickness of the glass layer.

[0136] The length of the laser processing mark in the direction orthogonal to the first surface is a length that is 5% to 50% of the thickness of the glass layer.

[0137] <Method 2>

[0138] The glass-resin composite according to method 1, wherein...

[0139] The aforementioned glass layer has a quadrilateral shape when viewed from above, and has four sides connecting the first surface and the second surface.

[0140] The laser processing marks mentioned above were formed on the four sides.

[0141] <Method 3>

[0142] The glass-resin composite according to method 2, wherein...

[0143] The laser processing marks are formed on each of the four sides from one end to the other along the length of the side.

[0144] <Method 4>

[0145] The glass-resin composite according to any one of methods 1 to 3, wherein...

[0146] The thickness of the glass layer is 20% or more and 75% or less relative to the thickness of the glass resin composite.

[0147] <Method 5>

[0148] The glass-resin composite according to any one of methods 1 to 4, wherein...

[0149] The thickness of the aforementioned glass layer is 30 μm or more and 300 μm or less.

[0150] This international application claims priority based on Japanese Patent Application No. 2024-022698, filed on February 19, 2024, the entire contents of which are incorporated herein by reference.

Claims

1. A glass-resin composite material, comprising: A glass layer comprising a first surface and a second surface opposite to the first surface, and The resin layer disposed on the second surface, Laser processing marks are formed on the glass layer, extending from the first surface in a direction orthogonal to the first surface. The distance between the laser processing mark and the first surface is less than 20% relative to the thickness of the glass layer. The length of the laser processing mark in the direction orthogonal to the first surface is a length that is more than 5% and less than 50% of the thickness of the glass layer.

2. The glass-resin composite according to claim 1, wherein, The glass layer has a quadrilateral shape when viewed from above, and has four sides connecting the first surface and the second surface. The laser processing marks are formed on the four sides respectively.

3. The glass-resin composite according to claim 2, wherein, Multiple laser processing marks are formed on each of the four sides at intervals from one end to the other along the length of the side.

4. The glass-resin composite according to claim 1, wherein, The thickness of the glass layer is more than 20% and less than 75% 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 greater than 30 μm and less than 300 μm.

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