WO2021261119A1 - Optical laminate - Google Patents

Optical laminate Download PDF

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Publication number
WO2021261119A1
WO2021261119A1 PCT/JP2021/018805 JP2021018805W WO2021261119A1 WO 2021261119 A1 WO2021261119 A1 WO 2021261119A1 JP 2021018805 W JP2021018805 W JP 2021018805W WO 2021261119 A1 WO2021261119 A1 WO 2021261119A1
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WO
WIPO (PCT)
Prior art keywords
film
adhesive layer
glass plate
thickness
optical laminate
Prior art date
Application number
PCT/JP2021/018805
Other languages
French (fr)
Japanese (ja)
Inventor
孝伸 矢野
貴巳 疋田
岳仁 淵田
洪賛 趙
Original Assignee
日東電工株式会社
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
Priority claimed from JP2020194696A external-priority patent/JP7198256B2/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020227042814A priority Critical patent/KR20230026309A/en
Priority to CN202180045371.XA priority patent/CN115776941A/en
Publication of WO2021261119A1 publication Critical patent/WO2021261119A1/en

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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
    • 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
    • B32B17/10009—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
    • B32B17/10018—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 comprising only one glass sheet
    • 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
    • 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
    • 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
    • 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
    • B32B17/1055—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 resin layer, i.e. interlayer
    • B32B17/10779—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 resin layer, i.e. interlayer containing polyester
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/206—Organic displays, e.g. OLED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • the present invention relates to an optical laminate including a glass plate.
  • An optical laminate including a glass plate, an adhesive layer, and a polyethylene terephthalate film or a triacetyl cellulose film is known (see, for example, Patent Document 1 below). ).
  • the glass plate has excellent optical properties but low impact resistance. Impact resistance is a property of suppressing damage including cracks in the glass plate when the glass plate is impacted.
  • the optical laminate described in the examples of Patent Document 1 has a three-layer laminated structure.
  • optical laminates are required to have a higher level of impact resistance.
  • the thickness of the glass plate is made very thick, the impact resistance is improved.
  • thinner glass is desirable from the viewpoint of thinning and weight reduction.
  • the present invention provides an optical laminate having excellent impact resistance.
  • the inventors of the present application have surprisingly provided a thin glass plate having a thickness of 40 ⁇ m or more and 60 ⁇ m or less in the optical laminate, and also provided a specific tan ⁇ and a specific tensile storage elastic modulus E'.
  • the impact resistance of the optical laminate can be improved by providing the optical laminate with a film having a thickness of 20 ⁇ m or less on the opposite surface to the glass plate of the film. I found it.
  • a glass plate, an adhesive layer, a film, and an adhesive layer are provided in order toward one side in the thickness direction, and the glass plate has a thickness of 40 ⁇ m or more and 60 ⁇ m or less.
  • the average tan ⁇ of the film at a frequency of 10 Hz, a heating rate of 2 ° C./min, and a dynamic viscoelasticity test in a tensile mode from -100 ° C to -50 ° C is 0.06 or more, and the dynamic viscoelasticity.
  • An optical laminate having an average tensile storage elastic modulus E'of the film at ⁇ 100 ° C. to ⁇ 50 ° C. determined by a test is 3 GPa or more and 6 GPa or less, and the pressure-sensitive adhesive layer has a thickness of 20 ⁇ m or less.
  • the optical laminate of the present invention has a glass plate having a thickness of 40 ⁇ m or more and 60 ⁇ m or less, and a film having a specific tan ⁇ and a specific tensile storage elastic modulus E'is provided via an adhesive layer, and has a thickness of 20 ⁇ m or less. Since it has an adhesive layer, it has excellent impact resistance.
  • FIG. 1 is a cross-sectional view of an embodiment of the optical laminate of the present invention.
  • FIG. 2 is a cross-sectional view of an organic electroluminescence display device including the optical laminate shown in FIG.
  • the optical laminate 1 has, for example, a flat plate shape extending in the plane direction.
  • the plane direction is orthogonal to the thickness direction of the optical laminate 1.
  • the optical laminate 1 includes a glass plate 2, an adhesive layer 3, a film 4, and an adhesive layer 12 in this order toward one side in the thickness direction.
  • the glass plate 2 extends in the plane direction.
  • the glass plate 2 forms the other surface in the thickness direction of the optical laminate 1.
  • the total light transmittance of the glass plate 2 is, for example, 80% or more, preferably 85% or more, and for example, 99% or less.
  • a commercially available product can be used, and for example, the G-leaf series (registered trademark, manufactured by Nippon Electric Glass Co., Ltd.) can be used.
  • the thickness of the glass plate 2 is 40 ⁇ m or more and 60 ⁇ m or less. If the thickness of the glass plate 2 is sufficiently thick, the impact resistance is improved. From this point of view, it is considered that the thicker the glass plate 2 is, the more the impact resistance is improved. However, when the thickness of the glass plate 2 is 40 ⁇ m or more and 60 ⁇ m or less, a specific tan ⁇ and a specific tensile storage elastic modulus E'.
  • the optical laminate 1 can be improved in impact resistance by providing the optical laminate 1 with the film 4 having the adhesive layer 3 via the adhesive layer 3 and further providing the pressure-sensitive adhesive layer 12 having a thickness of 20 ⁇ m or less.
  • the thickness of the glass plate 2 is preferably 42 ⁇ m or more, more preferably 45 ⁇ m or more, and further preferably 48 ⁇ m or more.
  • the thickness of the glass plate 2 is, for example, 58 ⁇ m or less, preferably 55 ⁇ m or less, and more preferably 52 ⁇ m or less. Since the glass plate 2 has the above-mentioned thickness, it is called a thin glass plate.
  • the adhesive layer 3 extends in the plane direction.
  • the adhesive layer 3 is arranged on one side of the glass plate 2 in the thickness direction. Specifically, the adhesive layer 3 comes into contact with one side of the glass plate 2 in the thickness direction.
  • the adhesive layer 3 is not a pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) made of a pressure-sensitive adhesive (pressure-sensitive adhesive), but a cured product of a curable adhesive.
  • the adhesive layer 3 is a cured product of a curable adhesive that undergoes a curing reaction by irradiation with active energy rays or heating.
  • the curable adhesive is a curing raw material for the adhesive layer 3, and examples thereof include an active energy curing type and a thermosetting type, preferably an active energy curing type.
  • Specific examples of the curable adhesive include an acrylic adhesive composition, an epoxy adhesive composition, and a silicone adhesive composition. From the viewpoint of obtaining excellent impact resistance, an epoxy adhesive is used. The composition may be mentioned.
  • the epoxy adhesive composition contains an epoxy resin as a main ingredient.
  • the epoxy resin include a bifunctional epoxy resin containing two epoxy groups and a polyfunctional epoxy resin containing three or more epoxy groups. These can be used alone or in combination of two or more. A combination of the bifunctional epoxy resin and the polyfunctional epoxy resin is preferable.
  • the bifunctional epoxy resin examples include aromatic epoxy resins such as bisphenol type epoxy resin, novolak type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, and triphenylmethane type epoxy resin, for example, triepoxypropyl isocyanurate. , Hydant-in epoxy resin and other nitrogen-containing ring epoxy resins, and examples thereof include aliphatic type epoxy resins, glycidyl ether type epoxy resins, and glycidylamine type epoxy resins. As the bifunctional epoxy resin, an aliphatic type epoxy resin is preferable.
  • the aliphatic epoxy resin includes an aliphatic alicyclic epoxy resin.
  • the epoxy equivalent of the bifunctional epoxy resin is, for example, 100 g / eq. As mentioned above, preferably 120 g / eq. The above, and for example, 250 g / eq. Hereinafter, preferably, 150 g / eq. It is as follows.
  • the ratio of the bifunctional epoxy resin in the epoxy resin is, for example, 80% by mass or more, preferably 90% by mass or more, and for example, 99% by mass or less, preferably 97% by mass or less.
  • polyfunctional epoxy resin examples include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylol ethane type epoxy resin, dicyclopentadiene type epoxy resin, and trifunctional aliphatic epoxy resin.
  • polyfunctional epoxy resins having three or more functionalities such as.
  • the polyfunctional epoxy resin is preferably a trifunctional aliphatic epoxy resin.
  • the epoxy equivalent of the polyfunctional epoxy resin is, for example, 130 g / eq. As mentioned above, preferably 150 g / eq. The above, and for example, 220 g / eq. Hereinafter, preferably, 200 g / eq. It is as follows.
  • the proportion of the polyfunctional epoxy resin in the epoxy resin is, for example, 1% by mass or more, preferably 3% by mass or more, and for example, 20% by mass or less, preferably 10% by mass or less.
  • the proportion of the epoxy resin in the epoxy adhesive composition is, for example, 60% by mass or more, preferably 75% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less.
  • the epoxy resin a commercially available product can be used, and as the aliphatic alicyclic epoxy resin, seroxide 2021P (manufactured by Daicel Chemical Co., Ltd.) and EHPE3150 (manufactured by Daicel Chemical Co., Ltd.) are used as the trifunctional aliphatic epoxy resin.
  • the epoxy adhesive composition contains a photoacid generator if it is an active energy curable type.
  • the photoacid generator include triarylsulfonium salts and the like.
  • the photoacid generator a commercially available product can be used, and CPI101A (manufactured by San Afro) or the like is used as the triarylsulfonium salt.
  • the proportion of the photoacid generator in the epoxy adhesive composition is, for example, 1% by mass or more, preferably 10% by mass or more, and for example, 30% by mass or less, preferably 20% by mass or less.
  • the epoxy adhesive composition can contain additives such as an oxetane-based resin and a silane coupling agent in an appropriate ratio.
  • oxetane-based resin examples include monofunctional oxetane such as 3-ethyl-3-oxetanemethanol and 2-ethylhexyloxetane, for example, xylylenebis oxetane, 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl). ) Bifunctional oxetane such as methoxy] methyl ⁇ oxetane.
  • oxetane-based resin a commercially available product can be used, and Aron oxetane (manufactured by Toagosei Co., Ltd.) or the like is used.
  • silane coupling agent examples include an epoxy group-containing silane coupling agent such as 3-glycidoxypropyltrimethoxysilane.
  • silane coupling agent a commercially available product can be used, and examples thereof include KBM series (manufactured by Shin-Etsu Silicone Co., Ltd.).
  • the thickness of the adhesive layer 3 is not limited.
  • the thickness of the adhesive layer 3 is, for example, 0.1 ⁇ m or more, and is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less.
  • the total light transmittance of the adhesive layer 3 is, for example, 80% or more, preferably 85% or more, and for example, 99% or less.
  • the tensile storage elastic modulus E'of the adhesive layer 3 at 25 ° C. is, for example, 1 GPa or more, preferably 2 GPa or more, more preferably 3 GPa or more, still more preferably 4 GPa or more, and for example, 100 GPa or less. be.
  • the tensile storage elastic modulus E'of the adhesive layer 3 at 25 ° C. is determined by measuring the dynamic viscoelasticity in a temperature dispersion mode under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min.
  • measured by the nanoindenter method is, for example, 1 GPa or more, preferably 2 GPa or more, more preferably 3 GPa or more, still more preferably 4 GPa or more, and also. For example, it is 100 GPa or less.
  • the measurement conditions of the nanoindenter method are as follows.
  • the film 4 is located on the opposite side of the glass plate 2 with respect to the adhesive layer 3.
  • the film 4 extends in the plane direction.
  • the film 4 is arranged on one side of the adhesive layer 3 in the thickness direction.
  • the film 4 is in contact with one side of the adhesive layer 3 in the thickness direction.
  • the adhesive layer 3 is in contact with one surface of the glass plate 2 in the thickness direction and the other surface of the film 4 in the thickness direction, and the glass plate 2 and the film 4 are bonded (bonded) to each other.
  • ⁇ Average of tan ⁇ of film 4> The average tan ⁇ of the film 4 at -100 ° C to -50 ° C determined by the dynamic viscoelasticity test in the frequency of 10 Hz, the heating rate of 2 ° C / min, the data acquisition interval of 0.5 min, and the tensile mode is 0.06 or more. be. If the average of tan ⁇ of the film 4 from ⁇ 100 ° C. to ⁇ 50 ° C. is less than 0.06, the impact resistance of the optical laminate 1 is lowered.
  • the average of the tan ⁇ of the film 4 at ⁇ 100 ° C. to ⁇ 50 ° C. is an index showing the responsiveness when the object collides with the optical laminate 1 at high speed. If the average of tan ⁇ is high, the impact received by the glass plate 2 can be sufficiently alleviated by the film 4, and the impact resistance of the optical laminate 1 can be improved.
  • the upper limit of the average tan ⁇ of the film 4 from -100 ° C to -50 ° C is not limited.
  • the average of tan ⁇ of the film 4 from ⁇ 100 ° C. to ⁇ 50 ° C. is, for example, 0.50 or less.
  • the dynamic viscoelasticity test will be described in later examples.
  • the average tensile storage elastic modulus E'of the film 4 at -100 ° C to -50 ° C determined by a dynamic viscoelasticity test in a frequency of 10 Hz, a heating rate of 2 ° C / min, a data acquisition interval of 0.5 min, and a tensile mode is It is 3 GPa or more, preferably 4 GP or more, more preferably 5 GP or more, and 6 GPa or less.
  • the average tensile storage elastic modulus E'of the film 4 from ⁇ 100 ° C. to ⁇ 50 ° C. exceeds 6 GPa, the film 4 becomes too hard and the impact resistance of the optical laminate 1 deteriorates.
  • the film 4 is too soft, and as a result, the impact resistance of the optical laminate 1 is sufficiently improved. Can not.
  • Examples of the film 4 include a polyester film.
  • Examples of the polyester film include polyethylene terephthalate film (PET), polybutylene terephthalate (PBT) film, and polyethylene naphthalate (PEN) film.
  • PET polyethylene terephthalate film
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • the thickness of the film 4 is not limited.
  • the thickness of the film 4 is, for example, 10 ⁇ m or more, preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, still more preferably 40 ⁇ m or more, and for example, 150 ⁇ m or less, preferably 100 ⁇ m or less, preferably 75 ⁇ m. It is as follows.
  • the total light transmittance of the film 4 is, for example, 80% or more, preferably 85% or more, and for example, 99% or less.
  • the pressure-sensitive adhesive layer 12 forms one side of the film 4 in the thickness direction.
  • the pressure-sensitive adhesive layer 12 is arranged on one side of the film 4 in the thickness direction. Specifically, the pressure-sensitive adhesive layer 12 comes into contact with one side of the film 4 in the thickness direction.
  • the pressure-sensitive adhesive layer 12 is an adhesive body that is pressure-sensitively adhered without a curing reaction.
  • the material of the pressure-sensitive adhesive layer 12 is not limited.
  • Examples of the material of the pressure-sensitive adhesive layer 12 include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, a polyamide-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a fluorine-based pressure-sensitive adhesive. Examples thereof include adhesives, epoxy adhesives, and polyether adhesives. As the material, an acrylic pressure-sensitive adhesive is preferable. The formulation and physical properties of the pressure-sensitive adhesive layer 12 are described in detail in, for example, Japanese Patent Application Laid-Open No. 2018-28873.
  • the shear storage elastic modulus G'at 25 ° C. of the pressure-sensitive adhesive layer 12 is, for example, 0.01 MPa or more, and for example 0.20 MPa or less.
  • the shear storage elastic modulus G' is determined by a dynamic viscoelasticity test at a frequency of 1 Hz, a heating rate of 5 ° C./min, and a shear (twist) mode.
  • the thickness of the pressure-sensitive adhesive layer 12 is 20 ⁇ m or less. If the thickness of the pressure-sensitive adhesive layer 12 exceeds 20 ⁇ m, the impact resistance of the optical laminate 1 is lowered.
  • the thickness of the pressure-sensitive adhesive layer 12 is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more.
  • the thickness of the optical laminate 1 is, for example, 70 ⁇ m or more, and 250 ⁇ m or less, for example.
  • ⁇ Manufacturing method of optical laminate 1 A method for manufacturing the optical laminate 1 will be described.
  • a curable adhesive is placed (applied) on one side in the thickness direction of the glass plate 2 and / or the other side in the thickness direction of the film 4, and then the glass plate 2 and / or the glass plate 2 and The curable adhesive is sandwiched between the films 4.
  • the curable adhesive is cured.
  • the curable adhesive is an active energy curable type
  • the curable adhesive is irradiated with active energy including ultraviolet rays.
  • the curable adhesive is irradiated with ultraviolet rays from the glass plate 2 side.
  • the curable adhesive is thermosetting, heat the curable adhesive. As a result, the adhesive layer 3 that firmly adheres the glass plate 2 and the film 4 is formed.
  • the pressure-sensitive adhesive layer 12 is arranged on one side of the film 4 in the thickness direction.
  • a varnish containing an adhesive is applied and dried on one side of the film 4 in the thickness direction.
  • the pressure-sensitive adhesive layer 12 formed on the release sheet (not shown) can be transferred to one side of the film 4 in the thickness direction.
  • an optical laminate 1 including a glass plate 2, an adhesive layer 3, a film 4, and an adhesive layer 12 is obtained.
  • the optical laminate 1 may be provided with a release sheet (not shown).
  • the optical laminate 1 includes a glass plate 2, an adhesive layer 3, a film 4, an adhesive layer 12, and a release sheet (not shown).
  • the optical laminate 1 is used for various optical applications, and is provided in, for example, an image display device.
  • the image display device include an organic electroluminescence display device (hereinafter, simply abbreviated as “organic EL display device”).
  • the organic EL display device 10 has a flat plate shape extending in the plane direction. Since the organic EL display device 10 includes the conductive film 13 described below, it functions as a touch panel type input display device.
  • the organic EL display device 10 includes an optical laminate 1, a conductive film 13, a second pressure-sensitive adhesive layer 14, and an image display member 15.
  • the upper side of the paper surface is the user's visual recognition side, which is the front side (corresponding to the other side in the thickness direction of FIG. 1), and the lower side of the paper surface is the back side (one side in the thickness direction of FIG. 1). Equivalent to).
  • the optical laminate 1 includes a glass plate 2, an adhesive layer 3, a film 4, and an adhesive layer 12 in this order toward the back side.
  • the conductive film 13 includes a conductive layer 16 and a base material layer 17 in order toward the back side.
  • the conductive layer 16 has a predetermined pattern. The surface and sides of the conductive layer 16 come into contact with the pressure-sensitive adhesive layer 12.
  • Examples of the material of the conductive layer 16 include metal oxides, conductive fibers (fibers), and metals.
  • the metal oxide include composite oxides. Examples of the composite oxide include indium zinc composite oxide (IZO), indium gallium zinc composite oxide (IGZO), indium gallium composite oxide (IGO), indium tin composite oxide (ITO), and antimonthine composite. Oxide (ATO) can be mentioned.
  • Examples of conductive fibers include metal nanowires and carbon nanotubes. Metals include, for example, gold, platinum, silver, and copper.
  • the conductive layer 16 integrally has a sensor electrode portion 18 located in the central portion in the plane direction and a drawer wiring portion 19 located in the periphery of the sensor electrode portion 18. Details of the conductive layer 16 are described in, for example, JP-A-2017-102443, JP-A-2014-113705, and JP-A-2014-219667.
  • the base material layer 17 is arranged on the back surface of the conductive layer 16 and the back surface of the pressure-sensitive adhesive layer 12.
  • the base material layer 17 extends in the plane direction.
  • the base material layer 17 is, for example, a resin layer.
  • the material of the base material layer 17 include olefin resin, polyester resin, (meth) acrylic resin, polycarbonate resin, polyether sulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, and polystyrene resin. Can be mentioned.
  • the olefin resin include polyethylene, polypropylene, and cycloolefin polymer (COP).
  • the polyester resin include PET, PBT, and PEN.
  • the (meth) acrylic resin include poly (meth) acrylate resins. Details of the base material layer 17 are described in, for example, Japanese Patent Application Laid-Open No. 2018-181722.
  • the second pressure-sensitive adhesive layer 14 is arranged on the back surface of the conductive film 13. Specifically, the second pressure-sensitive adhesive layer 14 is in contact with the back surface of the conductive film 13. The material of the second pressure-sensitive adhesive layer 14 is the same as the material of the pressure-sensitive adhesive layer 12.
  • the image display member 15 forms the back surface of the organic EL display device 10.
  • the image display member 15 is arranged on the back side of the conductive film 13 via the second pressure-sensitive adhesive layer 14.
  • the image display member 15 extends in the plane direction.
  • the image display member 15 is an organic EL element.
  • the image display member 15 includes a display substrate, two electrodes, an organic EL layer sandwiched between the two electrodes, and a sealing layer. The configuration and physical properties of the image display member 15 are described in detail in, for example, Japanese Patent Application Laid-Open No. 2018-28873.
  • the optical laminate 1 has a glass plate 2 having a thickness of 40 ⁇ m or more and 60 ⁇ m or less, an adhesive layer 3, and an average of tan ⁇ from ⁇ 100 ° C. to ⁇ 50 ° C. of 0.06 or more, and ⁇ 100 ° C.
  • a film 4 having an average tensile storage elastic modulus E'at -50 ° C. of 3 GPa or more and 6 GPa or less is provided, and a pressure-sensitive adhesive layer 12 is further provided. Further, the pressure-sensitive adhesive layer 12 has a thickness of 20 ⁇ m or less. Therefore, the optical laminate 1 is excellent in impact resistance.
  • the film 4 is a single layer, but the number of layers of the film 4 is not limited.
  • the film 4 may have a plurality of layers.
  • the optical laminate of the present invention has excellent impact resistance, even a glass plate having a thickness of 40 ⁇ m or more and 60 ⁇ m or less has sufficient impact resistance. Since a glass plate having a thickness of 40 ⁇ m or more and 60 ⁇ m or less is excellent in flexibility, the optical laminate of the present invention can be suitably used for flexible displays such as foldable displays and rollable displays.
  • the optical laminate 1 can further include a functional layer 37.
  • the functional layer 37 is arranged on the other surface of the glass plate 2 in the thickness direction.
  • Examples of the functional layer 37 include a hard coat layer, an anti-scattering layer, an anti-fouling layer, and an anti-reflection layer. These may be a single layer or a plurality of these may be laminated.
  • Example 1 A glass plate 2 (G-leaf) having a thickness of 50 ⁇ m and a film 4 (Diafoil S100, manufactured by Mitsubishi Chemical Corporation) made of a polyethylene terephthalate film having a thickness of 50 ⁇ m were prepared.
  • 70 parts by mass of an aliphatic alicyclic epoxy resin (celloxide 2021P, epoxy equivalent 128 to 133 g / eq., Manufactured by Daicel Chemical Co., Ltd.), a trifunctional aliphatic epoxy resin (EHPE3150, epoxy equivalent 170 to 190 g / eq., Daicel).
  • epoxy adhesive composition was prepared by blending 2 parts by mass and 2 parts by mass of a photoacid generator (CPI101A, triarylsulfonium salt, manufactured by San Afro). This epoxy adhesive composition was sandwiched between the glass plate 2 and the film 4.
  • a photoacid generator CPI101A, triarylsulfonium salt, manufactured by San Afro. This epoxy adhesive composition was sandwiched between the glass plate 2 and the film 4.
  • the curable adhesive was irradiated with ultraviolet rays from the glass plate 2 side.
  • an adhesive layer 3 having a thickness of 1 ⁇ m made of a cured body that firmly adheres the glass plate 2 and the film 4 was formed.
  • the elastic modulus of the adhesive layer 3 at 25 ° C. measured by the nanoindenter method was 4.9 GPa.
  • the pressure-sensitive adhesive layer 12 having a thickness of 15 ⁇ m was placed on one side of the film 4 in the thickness direction by transfer.
  • the pressure-sensitive adhesive layer 12 was prepared as follows.
  • LA lauryl acrylate
  • EHA 2-ethylhexyl acrylate
  • HBA 4-hydroxybutyl acrylate
  • NDP N-vinyl-2-pyrrolidone
  • BASF BASF
  • DCPMA dicyclopentanyl methacrylate
  • MMA methyl methacrylate
  • ⁇ -thioglycerol 100 parts by mass of toluene
  • reaction solution was heated to 130 ° C., and toluene, the chain transfer agent and the unreacted monomer were dried and removed to obtain a solid acrylic oligomer.
  • the weight average molecular weight of the acrylic oligomer was 5100.
  • the glass transition temperature (Tg) was 130 ° C.
  • the pressure-sensitive adhesive composition is applied to the surface of a release sheet made of PET film (Mitsubishi Chemical "Diafoil MRF75”), and then a release sheet made of another PET film (Mitsubishi Chemical "Diafoil MRF75”) is applied. It was attached to the film. Then, the coating film was irradiated with ultraviolet rays to prepare an adhesive layer 12 having a thickness of 15 ⁇ m.
  • the shear storage elastic modulus G'at 25 ° C. of the pressure-sensitive adhesive layer 12 was 0.03 MGPa.
  • the measurement method is as follows.
  • the pressure-sensitive adhesive layer 12 is externally processed into a disk shape, sandwiched between parallel plates, and the pressure-sensitive adhesive layer 12 is measured by dynamic viscoelasticity measurement under the following conditions using "Advanced Shearometric Exhibition System (ARES)” manufactured by Shearetic Scientific.
  • the shear storage elastic modulus G'at 25 ° C. was determined.
  • an optical laminate 1 including a glass plate 2, an adhesive layer 3, a film 4, and an adhesive layer 12 was manufactured.
  • Comparative Example 1 The optical laminate 1 was manufactured in the same manner as in Example 1. However, the thickness of the pressure-sensitive adhesive layer 12 was changed to 25 ⁇ m.
  • Comparative Example 2 The optical laminate 1 was manufactured in the same manner as in Example 1. However, the thickness of the glass plate 2 was changed to 70 ⁇ m.
  • Comparative Example 3 The optical laminate 1 was manufactured in the same manner as in Example 1. However, as the film 4, a triacetyl cellulose film (KC4UYW, manufactured by Konica Minolta) having a thickness of 40 ⁇ m was used.
  • a triacetyl cellulose film (KC4UYW, manufactured by Konica Minolta) having a thickness of 40 ⁇ m was used.
  • Comparative Example 4 The optical laminate 1 was manufactured in the same manner as in Example 1. However, as the film 4, a triacetyl cellulose film (KC8UAW, manufactured by Konica Minolta) having a thickness of 80 ⁇ m was used.
  • KC8UAW triacetyl cellulose film
  • Each of the average tensile storage elastic moduli E'of the film 4 from -100 ° C to -50 ° C was calculated by dividing the sum of all the above acquired data from -100 ° C to -50 ° C by the number of data. ..
  • Each of the averages of tan ⁇ of film 4 from ⁇ 100 ° C. to ⁇ 50 ° C. was calculated by dividing the sum of all the above-mentioned acquired data from ⁇ 100 ° C. to ⁇ 50 ° C. by the number of data.
  • ⁇ Pen drop crack test> The following pen drop cracking test was carried out for the optical laminate 1 of each Example and Comparative Example. As shown by the virtual line in FIG. 1, first, the optical laminate 1 was placed on the surface of the resin film 34 so that the glass plate 2 faces upward. Specifically, the pressure-sensitive adhesive layer 12 was attached to the surface of the resin film 34.
  • the resin film 34 is a prescale (a monosheet type for prescale MS medium pressure manufactured by Fujifilm, thickness 95 ⁇ m). The resin film 34 is arranged on the surface of a horizontal table (not shown). Next, a pen drop cracking test is carried out in which a 7 g pen 29 (Pentel ballpoint pen BK407 black, ball diameter 0.7 mm) is dropped from a height of 5 cm from the glass plate 2.
  • the height of 5 cm described above is the distance between one side of the glass plate 2 in the thickness direction and the tip portion 32 of the pen 29.
  • the tip portion 32 faces downward and is sharp.
  • the height H1 of the pen drop cracking test becomes 5 cm. If the glass plate 2 does not crack, the height is gradually increased by 1 cm. As a result, the height H1 when the glass plate 2 is cracked is obtained.
  • ⁇ Comparison of each example and comparative example> ⁇ Evaluation of the thickness of the adhesive layer 12> The thickness of the pressure-sensitive adhesive layer 12 is evaluated.
  • Example 1 and Comparative Example 1 are compared.
  • the thickness of the pressure-sensitive adhesive layer 12 of Example 1 is 15 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer 12 of Comparative Example 1 is 25 ⁇ m.
  • the height H1 20 cm of the pen drop cracking test of Example 1 is higher than the height H1 10 cm of the pen drop cracking test of Comparative Example 1. Therefore, it can be seen that the impact resistance of the optical laminate 1 is improved by reducing the thickness of the pressure-sensitive adhesive layer 12 to 20 ⁇ m or less.
  • Example 1 and Comparative Example 2 are compared.
  • the thickness of the glass plate 2 of Example 1 is 50 ⁇ m.
  • the thickness of the glass plate 2 of Comparative Example 2 is 70 ⁇ m.
  • the height H1 20 cm of the pen drop cracking test of Example 1 is higher than the height H17 cm of the pen drop cracking test of Comparative Example 2. Therefore, it can be seen that the impact resistance of the optical laminate 1 is improved by reducing the thickness of the glass plate 2 to 60 cm or less.
  • Example 1, Comparative Example 3 and Comparative Example 4 are compared.
  • the average of tan ⁇ of the film 4 of Example 1 is 0.062.
  • the average of tan ⁇ of each film 4 of Comparative Example 3 and Comparative Example 4 is 0.047 ⁇ m.
  • the height H1 20 cm of the pen drop cracking test of Example 1 is higher than the height H17 cm and 10 cm of the pen drop cracking test of Comparative Example 3 and Comparative Example 4, respectively. Therefore, it can be seen that the impact resistance of the optical laminate 1 is improved by setting the average of tan ⁇ of the film 4 to 0.06 or more.
  • the optical laminate is provided in the image display device.

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Abstract

This optical laminate 1 comprises a glass plate 2, an adhesive layer 3, a film 4, and a pressure-sensitive adhesive layer 12 in the stated order toward one side in the thickness direction. The glass plate 2 has a thickness of 40-60 μm (inclusive). The average tanδ of the film 4 at a temperature from -100°C to -50°C is 0.06 or higher, said average being derived through a dynamic viscoelasticity test in a tension mode and at a frequency of 10 Hz and a warming rate of 2°C/min. The average tensile elastic modulus E' of the film at a temperature from -100°C to -50°C is 3-6 GPa (inclusive), said average being derived through the dynamic viscoelasticity test. The pressure-sensitive adhesive layer 12 has a thickness of 20 μm or less.

Description

光学積層体Optical laminate
　本発明は、ガラス板を備える光学積層体に関する。 The present invention relates to an optical laminate including a glass plate.
　ガラス板と、接着剤層と、ポリエチレンテレフタレートフィルムまたはトリアセチルセルロースフィルムとを備える光学積層体が知られている（例えば、下記特許文献１参照。
）。ガラス板は、光学特性に優れる一方、耐衝撃性が低い。耐衝撃性は、ガラス板が衝撃を受けたときに、ガラス板にクラックを含む損傷を抑制する性質である。特許文献１の実施例に記載の光学積層体は、３層積層構造を有する。 An optical laminate including a glass plate, an adhesive layer, and a polyethylene terephthalate film or a triacetyl cellulose film is known (see, for example, Patent Document 1 below).
). The glass plate has excellent optical properties but low impact resistance. Impact resistance is a property of suppressing damage including cracks in the glass plate when the glass plate is impacted. The optical laminate described in the examples of Patent Document 1 has a three-layer laminated structure.
特開２０１９－２５８９９号公報Japanese Unexamined Patent Publication No. 2019-25899
　近年、光学積層体には、より高いレベルの耐衝撃性が求められる。例えばガラス板の厚みを非常に厚くすれば、耐衝撃性は向上する。しかし薄型化、軽量化の観点で、より薄いガラスが望ましい。 In recent years, optical laminates are required to have a higher level of impact resistance. For example, if the thickness of the glass plate is made very thick, the impact resistance is improved. However, thinner glass is desirable from the viewpoint of thinning and weight reduction.
　本発明は、耐衝撃性に優れる光学積層体を提供する。 The present invention provides an optical laminate having excellent impact resistance.
　そこで、本願発明者らは、鋭意検討した結果、驚くべきことに、厚みが４０μm以上、６０μｍ以下の薄いガラス板を光学積層体に備え、また、特定のｔａｎδおよび特定の引張貯蔵弾性率Ｅ’を有するフィルムを接着剤層を介して光学積層体に備え、さらに厚みが２０μｍ以下の粘着剤層をフィルムのガラス板とは反対面に備えることによって、光学積層体の耐衝撃性を向上できることを見出した。 Therefore, as a result of diligent studies, the inventors of the present application have surprisingly provided a thin glass plate having a thickness of 40 μm or more and 60 μm or less in the optical laminate, and also provided a specific tan δ and a specific tensile storage elastic modulus E'. The impact resistance of the optical laminate can be improved by providing the optical laminate with a film having a thickness of 20 μm or less on the opposite surface to the glass plate of the film. I found it.
　本発明（１）は、ガラス板と、接着剤層と、フィルムと、粘着剤層とを厚み方向一方側に向かって順に備え、前記ガラス板は、４０μｍ以上、６０μｍ以下の厚みを有し、周波数１０Ｈｚ、昇温速度２℃／ｍｉｎ、引張モードの動的粘弾性試験により求められる－１００℃から－５０℃における前記フィルムのｔａｎδの平均が、０．０６以上であり、前記動的粘弾性試験により求められる－１００℃から－５０℃における前記フィルムの引張貯蔵弾性率Ｅ’の平均が、３ＧＰａ以上、６ＧＰａ以下であり、前記粘着剤層は、２０μｍ以下の厚みを有する、光学積層体を含む。 In the present invention (1), a glass plate, an adhesive layer, a film, and an adhesive layer are provided in order toward one side in the thickness direction, and the glass plate has a thickness of 40 μm or more and 60 μm or less. The average tan δ of the film at a frequency of 10 Hz, a heating rate of 2 ° C./min, and a dynamic viscoelasticity test in a tensile mode from -100 ° C to -50 ° C is 0.06 or more, and the dynamic viscoelasticity. An optical laminate having an average tensile storage elastic modulus E'of the film at −100 ° C. to −50 ° C. determined by a test is 3 GPa or more and 6 GPa or less, and the pressure-sensitive adhesive layer has a thickness of 20 μm or less. include.
　本発明の光学積層体は、ガラス板の厚みが４０μｍ以上６０μｍ以下であり、特定のｔａｎδおよび特定の引張貯蔵弾性率Ｅ’を有するフィルムを接着剤層を介して備え、さらに２０μｍ以下の厚みを有する粘着剤層を備えるので、耐衝撃性に優れる。 The optical laminate of the present invention has a glass plate having a thickness of 40 μm or more and 60 μm or less, and a film having a specific tan δ and a specific tensile storage elastic modulus E'is provided via an adhesive layer, and has a thickness of 20 μm or less. Since it has an adhesive layer, it has excellent impact resistance.
図１は、本発明の光学積層体の一実施形態の断面図である。FIG. 1 is a cross-sectional view of an embodiment of the optical laminate of the present invention. 図２は、図１に示す光学積層体を備える有機エレクトロルミネセンス表示装置の断面図である。FIG. 2 is a cross-sectional view of an organic electroluminescence display device including the optical laminate shown in FIG.
　＜光学積層体１＞
　本発明の光学積層体の一実施形態を、図１を参照して説明する。 <Optical laminate 1>
An embodiment of the optical laminate of the present invention will be described with reference to FIG.
　この光学積層体１は、例えば、面方向に延びる平板形状を有する。面方向は、光学積層体１の厚み方向に直交する。光学積層体１は、ガラス板２と、接着剤層３と、フィルム４と、粘着剤層１２とを厚み方向一方側に向かって順に備える。 The optical laminate 1 has, for example, a flat plate shape extending in the plane direction. The plane direction is orthogonal to the thickness direction of the optical laminate 1. The optical laminate 1 includes a glass plate 2, an adhesive layer 3, a film 4, and an adhesive layer 12 in this order toward one side in the thickness direction.
　＜ガラス板２＞
　ガラス板２は、面方向に延びる。ガラス板２は、光学積層体１における厚み方向他方面を形成する。ガラス板２の全光線透過率は、例えば、８０％以上、好ましくは、８５％以上であり、また、例えば、９９％以下である。ガラス板２は、市販品を用いることができ、例えば、Ｇ－ｌｅａｆシリーズ（登録商標、日本電気硝子社製）を用いることができる。 <Glass plate 2>
The glass plate 2 extends in the plane direction. The glass plate 2 forms the other surface in the thickness direction of the optical laminate 1. The total light transmittance of the glass plate 2 is, for example, 80% or more, preferably 85% or more, and for example, 99% or less. As the glass plate 2, a commercially available product can be used, and for example, the G-leaf series (registered trademark, manufactured by Nippon Electric Glass Co., Ltd.) can be used.
　＜ガラス板２の厚み＞
　ガラス板２の厚みは、４０μｍ以上、６０μｍ以下である。ガラス板２の厚みが十分に厚ければ耐衝撃性が向上する。この観点から、ガラス板２の厚みがより厚いほど、耐衝撃性もより向上すると考えられるが、ガラス板２の厚みが４０μｍ以上、６０μｍ以下において、特定のｔａｎδおよび特定の引張貯蔵弾性率Ｅ’を有するフィルム４を接着剤層３を介して光学積層体１に備え、さらに２０μｍ以下の粘着剤層１２を備えることによって、光学積層体１は、耐衝撃性を向上することができる。 <Thickness of glass plate 2>
The thickness of the glass plate 2 is 40 μm or more and 60 μm or less. If the thickness of the glass plate 2 is sufficiently thick, the impact resistance is improved. From this point of view, it is considered that the thicker the glass plate 2 is, the more the impact resistance is improved. However, when the thickness of the glass plate 2 is 40 μm or more and 60 μm or less, a specific tan δ and a specific tensile storage elastic modulus E'. The optical laminate 1 can be improved in impact resistance by providing the optical laminate 1 with the film 4 having the adhesive layer 3 via the adhesive layer 3 and further providing the pressure-sensitive adhesive layer 12 having a thickness of 20 μm or less.
　ガラス板２の厚みは、好ましくは、４２μｍ以上、より好ましくは、４５μｍ以上、さらに好ましくは、４８μｍ以上である。ガラス板２の厚みは、例えば、５８μｍ以下、好ましくは、５５μｍ以下、より好ましくは、５２μｍ以下である。なお、ガラス板２は、上記した厚みを有するので、薄ガラス板と称呼される。 The thickness of the glass plate 2 is preferably 42 μm or more, more preferably 45 μm or more, and further preferably 48 μm or more. The thickness of the glass plate 2 is, for example, 58 μm or less, preferably 55 μm or less, and more preferably 52 μm or less. Since the glass plate 2 has the above-mentioned thickness, it is called a thin glass plate.
　＜接着剤層３＞
　接着剤層３は、面方向に延びる。接着剤層３は、ガラス板２の厚み方向一方面に配置されている。具体的には、接着剤層３は、ガラス板２の厚み方向一方面に接触する。接着剤層３は、粘着剤（感圧接着剤）からなる粘着剤層（感圧接着剤層）ではなく、硬化型接着剤の硬化体である。詳しくは、接着剤層３は、活性エネルギー線の照射または加熱よって硬化反応する硬化型接着剤の硬化体である。 <Adhesive layer 3>
The adhesive layer 3 extends in the plane direction. The adhesive layer 3 is arranged on one side of the glass plate 2 in the thickness direction. Specifically, the adhesive layer 3 comes into contact with one side of the glass plate 2 in the thickness direction. The adhesive layer 3 is not a pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) made of a pressure-sensitive adhesive (pressure-sensitive adhesive), but a cured product of a curable adhesive. Specifically, the adhesive layer 3 is a cured product of a curable adhesive that undergoes a curing reaction by irradiation with active energy rays or heating.
　硬化型接着剤は、接着剤層３の硬化原料であって、活性エネルギー硬化型、および、熱硬化型が挙げられ、好ましくは、活性エネルギー硬化型が挙げられる。具体的には、硬化型接着剤としては、例えば、アクリル接着剤組成物、エポキシ接着剤組成物、および、シリコーン接着剤組成物が挙げられ、優れた耐衝撃性を得る観点から、エポキシ接着剤組成物が挙げられる。 The curable adhesive is a curing raw material for the adhesive layer 3, and examples thereof include an active energy curing type and a thermosetting type, preferably an active energy curing type. Specific examples of the curable adhesive include an acrylic adhesive composition, an epoxy adhesive composition, and a silicone adhesive composition. From the viewpoint of obtaining excellent impact resistance, an epoxy adhesive is used. The composition may be mentioned.
　エポキシ接着剤組成物は、エポキシ樹脂を主剤として含む。エポキシ樹脂としては、例えば、２つのエポキシ基を含有する２官能エポキシ樹脂、３つ以上エポキシ基を含有する多官能エポキシ樹脂などが挙げられる。これらは、単独使用または２種以上併用できる。好ましくは、２官能エポキシ樹脂と多官能エポキシ樹脂との併用が挙げられる。 The epoxy adhesive composition contains an epoxy resin as a main ingredient. Examples of the epoxy resin include a bifunctional epoxy resin containing two epoxy groups and a polyfunctional epoxy resin containing three or more epoxy groups. These can be used alone or in combination of two or more. A combination of the bifunctional epoxy resin and the polyfunctional epoxy resin is preferable.
　２官能エポキシ樹脂としては、例えば、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオレン型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂などの芳香族系エポキシ樹脂、例えば、トリエポキシプロピルイソシアヌレート、ヒダントインエポキシ樹脂などの含窒素環エポキシ樹脂、さらには、脂肪族型エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂が挙げられる。２官能エポキシ樹脂として、好ましくは、脂肪族型エポキシ樹脂が挙げられる。脂肪族型エポキシ樹脂は、脂肪族脂環式エポキシ樹脂を含む。２官能エポキシ樹脂のエポキシ当量は、例えば、１００ｇ／ｅｑ．以上、好ましくは、１２０ｇ／ｅｑ．以上であり、また、例えば、２５０ｇ／ｅｑ．以下、好ましくは、１５０ｇ／ｅｑ．以下である。エポキシ樹脂における２官能エポキシ樹脂の割合は、例えば、８０質量％以上、好ましくは、９０質量％以上であり、また、例えば、９９質量％以下、好ましくは、９７質量％以下である。 Examples of the bifunctional epoxy resin include aromatic epoxy resins such as bisphenol type epoxy resin, novolak type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, and triphenylmethane type epoxy resin, for example, triepoxypropyl isocyanurate. , Hydant-in epoxy resin and other nitrogen-containing ring epoxy resins, and examples thereof include aliphatic type epoxy resins, glycidyl ether type epoxy resins, and glycidylamine type epoxy resins. As the bifunctional epoxy resin, an aliphatic type epoxy resin is preferable. The aliphatic epoxy resin includes an aliphatic alicyclic epoxy resin. The epoxy equivalent of the bifunctional epoxy resin is, for example, 100 g / eq. As mentioned above, preferably 120 g / eq. The above, and for example, 250 g / eq. Hereinafter, preferably, 150 g / eq. It is as follows. The ratio of the bifunctional epoxy resin in the epoxy resin is, for example, 80% by mass or more, preferably 90% by mass or more, and for example, 99% by mass or less, preferably 97% by mass or less.
　多官能エポキシ樹脂としては、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、３官能脂肪族エポキシ樹脂などの３官能以上の多官能エポキシ樹脂が挙げられる。多官能エポキシ樹脂として、好ましくは、３官能脂肪族エポキシ樹脂が挙げられる。多官能エポキシ樹脂のエポキシ当量は、例えば、１３０ｇ／ｅｑ．以上、好ましくは、１５０ｇ／ｅｑ．以上であり、また、例えば、２２０ｇ／ｅｑ．以下、好ましくは、２００ｇ／ｅｑ．以下である。エポキシ樹脂における多官能エポキシ樹脂の割合は、例えば、１質量％以上、好ましくは、３質量％以上であり、また、例えば、２０質量％以下、好ましくは、１０質量％以下である。 Examples of the polyfunctional epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylol ethane type epoxy resin, dicyclopentadiene type epoxy resin, and trifunctional aliphatic epoxy resin. Examples thereof include polyfunctional epoxy resins having three or more functionalities such as. The polyfunctional epoxy resin is preferably a trifunctional aliphatic epoxy resin. The epoxy equivalent of the polyfunctional epoxy resin is, for example, 130 g / eq. As mentioned above, preferably 150 g / eq. The above, and for example, 220 g / eq. Hereinafter, preferably, 200 g / eq. It is as follows. The proportion of the polyfunctional epoxy resin in the epoxy resin is, for example, 1% by mass or more, preferably 3% by mass or more, and for example, 20% by mass or less, preferably 10% by mass or less.
　エポキシ接着剤組成物におけるエポキシ樹脂の割合は、例えば、６０質量％以上、好ましくは、７５質量％以上であり、また、例えば、９０質量％以下、好ましくは、８０質量％以下である。 The proportion of the epoxy resin in the epoxy adhesive composition is, for example, 60% by mass or more, preferably 75% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less.
　エポキシ樹脂は、市販品を用いることができ、脂肪族脂環式エポキシ樹脂として、セロキサイド２０２１Ｐ（ダイセル化学社製）、３官能脂肪族エポキシ樹脂として、ＥＨＰＥ３１５０（ダイセル化学社製）などが用いられる。 As the epoxy resin, a commercially available product can be used, and as the aliphatic alicyclic epoxy resin, seroxide 2021P (manufactured by Daicel Chemical Co., Ltd.) and EHPE3150 (manufactured by Daicel Chemical Co., Ltd.) are used as the trifunctional aliphatic epoxy resin.
　また、エポキシ接着剤組成物は、活性エネルギー硬化型であれば、光酸発生剤を含む。光酸発生剤としては、例えば、トリアリールスルホニウム塩などが挙げられる。光酸発生剤は、市販品を用いることができ、トリアリールスルホニウム塩として、ＣＰＩ１０１Ａ（サンアフロ社製）などが用いられる。エポキシ接着剤組成物における光酸発生剤の割合は、例えば、１質量％以上、好ましくは、１０質量％以上であり、また、例えば、３０質量％以下、好ましくは、２０質量％以下である。 Further, the epoxy adhesive composition contains a photoacid generator if it is an active energy curable type. Examples of the photoacid generator include triarylsulfonium salts and the like. As the photoacid generator, a commercially available product can be used, and CPI101A (manufactured by San Afro) or the like is used as the triarylsulfonium salt. The proportion of the photoacid generator in the epoxy adhesive composition is, for example, 1% by mass or more, preferably 10% by mass or more, and for example, 30% by mass or less, preferably 20% by mass or less.
　さらに、エポキシ接着剤組成物は、例えば、オキセタン系樹脂、シランカップリング剤などの添加剤を適宜の割合で含むことができる。 Further, the epoxy adhesive composition can contain additives such as an oxetane-based resin and a silane coupling agent in an appropriate ratio.
　オキセタン系樹脂としては、例えば、３－エチル－３－オキセタンメタノール、２―エチルヘキシルオキセタンなどの単官能オキセタン、例えば、キシリレンビスオキセタン、３―エチル―３｛［（３―エチルオキセタン―３―イル）メトキシ］メチル｝オキセタンなどの２官能オキセタンが挙げられる。オキセタン系樹脂は、市販品を用いることができ、アロンオキセタン（東亞合成社製）などが用いられる。 Examples of the oxetane-based resin include monofunctional oxetane such as 3-ethyl-3-oxetanemethanol and 2-ethylhexyloxetane, for example, xylylenebis oxetane, 3-ethyl-3 {[(3-ethyloxetane-3-yl). ) Bifunctional oxetane such as methoxy] methyl} oxetane. As the oxetane-based resin, a commercially available product can be used, and Aron oxetane (manufactured by Toagosei Co., Ltd.) or the like is used.
　シランカップリング剤として、例えば、３－グリシドキシプロピルトリメトキシシランなどのエポキシ基含有シランカップリング剤などが挙げられる。シランカップリング剤は、市販品を用いることができ、ＫＢＭシリーズ（信越シリコーン社製）などが挙げられる。 Examples of the silane coupling agent include an epoxy group-containing silane coupling agent such as 3-glycidoxypropyltrimethoxysilane. As the silane coupling agent, a commercially available product can be used, and examples thereof include KBM series (manufactured by Shin-Etsu Silicone Co., Ltd.).
　接着剤層３の厚みは、限定されない。接着剤層３の厚みは、例えば、０．１μｍ以上であり、また、例えば、１０μｍ以下、好ましくは、５μｍ以下、より好ましくは、３μｍ以下である。 The thickness of the adhesive layer 3 is not limited. The thickness of the adhesive layer 3 is, for example, 0.1 μm or more, and is, for example, 10 μm or less, preferably 5 μm or less, and more preferably 3 μm or less.
　接着剤層３の全光線透過率は、例えば、８０％以上、好ましくは、８５％以上であり、また、例えば、９９％以下である。 The total light transmittance of the adhesive layer 3 is, for example, 80% or more, preferably 85% or more, and for example, 99% or less.
　２５℃における接着剤層３の引張貯蔵弾性率Ｅ’は、例えば、１ＧＰａ以上、好ましくは、２ＧＰａ以上、より好ましくは、３ＧＰａ以上、さらに好ましくは、４ＧＰａ以上であり、また、例えば、１００ＧＰａ以下である。２５℃における接着剤層３の引張貯蔵弾性率Ｅ’は、周波数１Ｈｚ、昇温速度５℃／分の条件の温度分散モードで動的粘弾性を測定することにより求められる。また、ナノインデンター法で測定される２５℃における接着剤層３の弾性率は、例えば、１ＧＰａ以上、好ましくは、２ＧＰａ以上、より好ましくは、３ＧＰａ以上、さらに好ましくは、４ＧＰａ以上であり、また、例えば、１００ＧＰａ以下である。ナノインデンター法の測定条件は、下記の通りである。 The tensile storage elastic modulus E'of the adhesive layer 3 at 25 ° C. is, for example, 1 GPa or more, preferably 2 GPa or more, more preferably 3 GPa or more, still more preferably 4 GPa or more, and for example, 100 GPa or less. be. The tensile storage elastic modulus E'of the adhesive layer 3 at 25 ° C. is determined by measuring the dynamic viscoelasticity in a temperature dispersion mode under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min. The elastic modulus of the adhesive layer 3 at 25 ° C. measured by the nanoindenter method is, for example, 1 GPa or more, preferably 2 GPa or more, more preferably 3 GPa or more, still more preferably 4 GPa or more, and also. For example, it is 100 GPa or less. The measurement conditions of the nanoindenter method are as follows.
　装置：Ｔｒｉｂｏｉｎｄｅｎｔｅｒ（Ｈｙｓｉｔｒｏｎ　Ｉｎｃ．製）
　サンプルサイズ：１０×１０ｍｍ
　圧子：Ｃｏｎｃｉａｌ（球形圧子：曲率半径１０μｍ）、
　測定方法：単一押し込み測定
　測定温度：２５℃
　圧子の押込深さ：１００ｎｍ
　温度：２５℃
　解析：荷重－変位曲線に基づくＯｌｉｖｅｒ　Ｐｈａｒｒ解析 Equipment: Triboinder (manufactured by Hybrid Inc.)
Sample size: 10 x 10 mm
Indenter: Concial (spherical indenter: radius of curvature 10 μm),
Measurement method: Single push measurement Measurement temperature: 25 ° C
Indenter indentation depth: 100 nm
Temperature: 25 ° C
Analysis: Oliver Pharr analysis based on load-displacement curve
　＜フィルム４＞
　フィルム４は、接着剤層３に対するガラス板２の反対側に位置する。フィルム４は、面方向に延びる。フィルム４は、接着剤層３の厚み方向一方面に配置している。なお、フィルム４は、接着剤層３の厚み方向一方面に接触している。これによって、接着剤層３は、ガラス板２の厚み方向一方面、および、フィルム４の厚み方向他方面に接触し、ガラス板２とフィルム４とを接着（接合）している。 <Film 4>
The film 4 is located on the opposite side of the glass plate 2 with respect to the adhesive layer 3. The film 4 extends in the plane direction. The film 4 is arranged on one side of the adhesive layer 3 in the thickness direction. The film 4 is in contact with one side of the adhesive layer 3 in the thickness direction. As a result, the adhesive layer 3 is in contact with one surface of the glass plate 2 in the thickness direction and the other surface of the film 4 in the thickness direction, and the glass plate 2 and the film 4 are bonded (bonded) to each other.
＜フィルム４のｔａｎδの平均＞
　周波数１０Ｈｚ、昇温速度２℃／ｍｉｎ、データ取得間隔０．５ｍｉｎ、引張モードの動的粘弾性試験により求められる－１００℃から－５０℃におけるフィルム４のｔａｎδの平均は、０．０６以上である。－１００℃から－５０℃におけるフィルム４のｔａｎδの平均が０．０６未満であれば、光学積層体１の耐衝撃性が低下する。－１００℃から－５０℃におけるフィルム４のｔａｎδの平均は、物体が光学積層体１に高速で衝突したときの応答性を示す指標である。ｔａｎδの平均が高ければ、ガラス板２が受けた衝撃をフィルム４が十分に緩和でき、光学積層体１の耐衝撃性を向上できる。 <Average of tan δ of film 4>
The average tan δ of the film 4 at -100 ° C to -50 ° C determined by the dynamic viscoelasticity test in the frequency of 10 Hz, the heating rate of 2 ° C / min, the data acquisition interval of 0.5 min, and the tensile mode is 0.06 or more. be. If the average of tan δ of the film 4 from −100 ° C. to −50 ° C. is less than 0.06, the impact resistance of the optical laminate 1 is lowered. The average of the tan δ of the film 4 at −100 ° C. to −50 ° C. is an index showing the responsiveness when the object collides with the optical laminate 1 at high speed. If the average of tan δ is high, the impact received by the glass plate 2 can be sufficiently alleviated by the film 4, and the impact resistance of the optical laminate 1 can be improved.
　－１００℃から－５０℃におけるフィルム４のｔａｎδの平均の上限は、限定されない。－１００℃から－５０℃におけるフィルム４のｔａｎδの平均は、例えば、０．５０以下である。動的粘弾性試験は、後の実施例で記載する。 The upper limit of the average tan δ of the film 4 from -100 ° C to -50 ° C is not limited. The average of tan δ of the film 4 from −100 ° C. to −50 ° C. is, for example, 0.50 or less. The dynamic viscoelasticity test will be described in later examples.
＜フィルム４の引張貯蔵弾性率Ｅ’の平均＞
　周波数１０Ｈｚ、昇温速度２℃／ｍｉｎ、データ取得間隔０．５ｍｉｎ、引張モードの動的粘弾性試験により求められる－１００℃から－５０℃におけるフィルム４の引張貯蔵弾性率Ｅ’の平均は、３ＧＰａ以上、好ましくは、４ＧＰ以上、より好ましくは、５ＧＰ以上であり、また、６ＧＰａ以下である。－１００℃から－５０℃におけるフィルム４の引張貯蔵弾性率Ｅ’の平均が６ＧＰａを越えると、フィルム４が硬くなりすぎ、光学積層体１の耐衝撃性が低下する。一方、－１００℃から－５０℃におけるフィルム４の引張貯蔵弾性率Ｅ’の平均が３ＧＰ未満であれば、フィルム４が柔らかすぎるため、その結果、光学積層体１の耐衝撃性を十分に向上できない。 <Average tensile storage elastic modulus E'of film 4>
The average tensile storage elastic modulus E'of the film 4 at -100 ° C to -50 ° C determined by a dynamic viscoelasticity test in a frequency of 10 Hz, a heating rate of 2 ° C / min, a data acquisition interval of 0.5 min, and a tensile mode is It is 3 GPa or more, preferably 4 GP or more, more preferably 5 GP or more, and 6 GPa or less. When the average tensile storage elastic modulus E'of the film 4 from −100 ° C. to −50 ° C. exceeds 6 GPa, the film 4 becomes too hard and the impact resistance of the optical laminate 1 deteriorates. On the other hand, if the average tensile storage elastic modulus E'of the film 4 from -100 ° C to -50 ° C is less than 3GP, the film 4 is too soft, and as a result, the impact resistance of the optical laminate 1 is sufficiently improved. Can not.
　フィルム４としては、例えば、ポリエステルフィルムが挙げられる。ポリエステルフィルムとしては、例えば、ポリエチレンテレフタレートフィルム（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）フィルム、および、ポリエチレンナフタレート（ＰＥＮ）フィルムが挙げられる。フィルム４として、光学積層体１の耐衝撃性を向上させる観点から、好ましくは、ＰＥＴフィルムが挙げられる。 Examples of the film 4 include a polyester film. Examples of the polyester film include polyethylene terephthalate film (PET), polybutylene terephthalate (PBT) film, and polyethylene naphthalate (PEN) film. As the film 4, a PET film is preferable from the viewpoint of improving the impact resistance of the optical laminate 1.
　フィルム４の厚みは、限定されない。フィルム４の厚みは、例えば、１０μｍ以上、好ましくは、２０μｍ以上、より好ましくは、３０μｍ以上、さらに好ましくは、４０μｍ以上であり、また、例えば、１５０μｍ以下、好ましくは、１００μｍ以下、好ましくは、７５μｍ以下である。 The thickness of the film 4 is not limited. The thickness of the film 4 is, for example, 10 μm or more, preferably 20 μm or more, more preferably 30 μm or more, still more preferably 40 μm or more, and for example, 150 μm or less, preferably 100 μm or less, preferably 75 μm. It is as follows.
　フィルム４の全光線透過率は、例えば、８０％以上、好ましくは、８５％以上であり、また、例えば、９９％以下である。 The total light transmittance of the film 4 is, for example, 80% or more, preferably 85% or more, and for example, 99% or less.
＜粘着剤層１２＞
　粘着剤層１２は、フィルム４の厚み方向一方面を形成する。粘着剤層１２は、フィルム４の厚み方向一方面に配置される。具体的には、粘着剤層１２は、フィルム４の厚み方向一方面に接触する。粘着剤層１２は、硬化反応を伴わず、感圧接着する接着体である。 <Adhesive layer 12>
The pressure-sensitive adhesive layer 12 forms one side of the film 4 in the thickness direction. The pressure-sensitive adhesive layer 12 is arranged on one side of the film 4 in the thickness direction. Specifically, the pressure-sensitive adhesive layer 12 comes into contact with one side of the film 4 in the thickness direction. The pressure-sensitive adhesive layer 12 is an adhesive body that is pressure-sensitively adhered without a curing reaction.
　粘着剤層１２の材料は、限定されない。粘着剤層１２の材料としては、例えば、アクリル系粘着剤、ゴム系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、フッ素系粘着剤、エポキシ系粘着剤、および、ポリエーテル系粘着剤が挙げられる。材料としては、好ましくは、アクリル系粘着剤が挙げられる。粘着剤層１２の処方および物性は、例えば、特開２０１８－２８５７３号公報に詳述される。 The material of the pressure-sensitive adhesive layer 12 is not limited. Examples of the material of the pressure-sensitive adhesive layer 12 include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, a polyamide-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a fluorine-based pressure-sensitive adhesive. Examples thereof include adhesives, epoxy adhesives, and polyether adhesives. As the material, an acrylic pressure-sensitive adhesive is preferable. The formulation and physical properties of the pressure-sensitive adhesive layer 12 are described in detail in, for example, Japanese Patent Application Laid-Open No. 2018-28873.
　粘着剤層１２の２５℃におけるせん断貯蔵弾性率Ｇ’は、例えば、０．０１MＰａ以上であり、また、例えば、０．２０ＭＰａ以下である。せん断貯蔵弾性率Ｇ’は、周波数１Ｈｚ、昇温速度５℃／ｍｉｎ、せん断（ひねり）モードの動的粘弾性試験により求められる。 The shear storage elastic modulus G'at 25 ° C. of the pressure-sensitive adhesive layer 12 is, for example, 0.01 MPa or more, and for example 0.20 MPa or less. The shear storage elastic modulus G'is determined by a dynamic viscoelasticity test at a frequency of 1 Hz, a heating rate of 5 ° C./min, and a shear (twist) mode.
　粘着剤層１２の厚みは、２０μｍ以下である。粘着剤層１２の厚みが２０μｍを越えれば、光学積層体１の耐衝撃性が低下する。粘着剤層１２の厚みは、例えば、５μｍ以上、好ましくは、１０μｍ以上である。 The thickness of the pressure-sensitive adhesive layer 12 is 20 μm or less. If the thickness of the pressure-sensitive adhesive layer 12 exceeds 20 μm, the impact resistance of the optical laminate 1 is lowered. The thickness of the pressure-sensitive adhesive layer 12 is, for example, 5 μm or more, preferably 10 μm or more.
　光学積層体１の厚みは、例えば、７０μｍ以上であり、また、例えば、２５０μｍ以下以下である。 The thickness of the optical laminate 1 is, for example, 70 μm or more, and 250 μm or less, for example.
　＜光学積層体１の製造方法＞
　光学積層体１の製造方法を説明する。光学積層体１の製造方法では、例えば、まず、ガラス板２の厚み方向一方面および／またはフィルム４の厚み方向他方面に、硬化型接着剤を配置（塗布）し続いて、ガラス板２およびフィルム４で、硬化型接着剤を挟み込む。 <Manufacturing method of optical laminate 1>
A method for manufacturing the optical laminate 1 will be described. In the method for manufacturing the optical laminate 1, for example, first, a curable adhesive is placed (applied) on one side in the thickness direction of the glass plate 2 and / or the other side in the thickness direction of the film 4, and then the glass plate 2 and / or the glass plate 2 and The curable adhesive is sandwiched between the films 4.
　その後、硬化型接着剤を硬化させる。硬化型接着剤が活性エネルギー硬化型であれば、紫外線を含む活性エネルギーを硬化型接着剤に照射する。具体的には、紫外線を、ガラス板２側から硬化型接着剤に照射する。硬化型接着剤が熱硬化型であれば、硬化型接着剤を加熱する。これにより、ガラス板２およびフィルム４を強固に接着する接着剤層３を形成する。 After that, the curable adhesive is cured. If the curable adhesive is an active energy curable type, the curable adhesive is irradiated with active energy including ultraviolet rays. Specifically, the curable adhesive is irradiated with ultraviolet rays from the glass plate 2 side. If the curable adhesive is thermosetting, heat the curable adhesive. As a result, the adhesive layer 3 that firmly adheres the glass plate 2 and the film 4 is formed.
　その後、フィルム４の厚み方向一方面に粘着剤層１２を配置する。例えば、粘着剤を含むワニスをフィルム４の厚み方向一方面に塗布および乾燥する。または、図示しない剥離シートに形成した粘着剤層１２をフィルム４の厚み方向一方面に転写することもできる。
　これによって、ガラス板２と、接着剤層３と、フィルム４と、粘着剤層１２とを備える光学積層体１を得る。なお、図示しない剥離シートを光学積層体１に備えてもよい。その場合には、光学積層体１は、ガラス板２と、接着剤層３と、フィルム４と、粘着剤層１２と、図示しない剥離シートとを備える。 After that, the pressure-sensitive adhesive layer 12 is arranged on one side of the film 4 in the thickness direction. For example, a varnish containing an adhesive is applied and dried on one side of the film 4 in the thickness direction. Alternatively, the pressure-sensitive adhesive layer 12 formed on the release sheet (not shown) can be transferred to one side of the film 4 in the thickness direction.
As a result, an optical laminate 1 including a glass plate 2, an adhesive layer 3, a film 4, and an adhesive layer 12 is obtained. The optical laminate 1 may be provided with a release sheet (not shown). In that case, the optical laminate 1 includes a glass plate 2, an adhesive layer 3, a film 4, an adhesive layer 12, and a release sheet (not shown).
　＜光学積層体１の用途＞
　光学積層体１は、各種光学用途に用いられ、例えば、画像表示装置に備えられる。画像表示装置としては、例えば、有機エレクトロルミネセンス表示装置（以下、単に「有機ＥＬ表示装置」と略称する。）が挙げられる。 <Use of optical laminate 1>
The optical laminate 1 is used for various optical applications, and is provided in, for example, an image display device. Examples of the image display device include an organic electroluminescence display device (hereinafter, simply abbreviated as “organic EL display device”).
　次に、光学積層体１を備える有機ＥＬ表示装置１０を、図２を参照して説明する。 Next, the organic EL display device 10 including the optical laminate 1 will be described with reference to FIG.
＜有機ＥＬ表示装置１０＞
　有機ＥＬ表示装置１０は、面方向に延びる平板形状を有する。有機ＥＬ表示装置１０は、次に説明する導電性フィルム１３を備えることから、タッチパネル型入力表示装置として機能する。有機ＥＬ表示装置１０は、光学積層体１と、導電性フィルム１３と、第２粘着剤層１４と、画像表示部材１５とを備える。なお、この有機ＥＬ表示装置１０では、紙面上側が、ユーザーの視認側であって、表側（図１の厚み方向他方側に相当）であり、紙面下側が、裏側（図１の厚み方向一方側に相当）である。 <Organic EL display device 10>
The organic EL display device 10 has a flat plate shape extending in the plane direction. Since the organic EL display device 10 includes the conductive film 13 described below, it functions as a touch panel type input display device. The organic EL display device 10 includes an optical laminate 1, a conductive film 13, a second pressure-sensitive adhesive layer 14, and an image display member 15. In the organic EL display device 10, the upper side of the paper surface is the user's visual recognition side, which is the front side (corresponding to the other side in the thickness direction of FIG. 1), and the lower side of the paper surface is the back side (one side in the thickness direction of FIG. 1). Equivalent to).
＜光学積層体１＞
　光学積層体１は、ガラス板２と、接着剤層３と、フィルム４と、粘着剤層１２とを裏側に向かって順に備える。 <Optical laminate 1>
The optical laminate 1 includes a glass plate 2, an adhesive layer 3, a film 4, and an adhesive layer 12 in this order toward the back side.
＜導電性フィルム１３＞
　導電性フィルム１３は、導電層１６と、基材層１７とを裏側に向かって順に備える。 <Conductive film 13>
The conductive film 13 includes a conductive layer 16 and a base material layer 17 in order toward the back side.
＜導電層１６＞
　導電層１６は、所定パターンを有する。導電層１６の表面および側面は、粘着剤層１２に接触する。導電層１６の材料としては、例えば、金属酸化物、導電性繊維（繊維）、および、金属が挙げられる。金属酸化物としては、複合酸化物が挙げられる。複合酸化物としては、例えば、インジウム亜鉛複合酸化物（ＩＺＯ）、インジウムガリウム亜鉛複合酸化物（ＩＧＺＯ）、インジウムガリウム複合酸化物（ＩＧＯ）、インジウムスズ複合酸化物（ＩＴＯ）、および、アンチモンスズ複合酸化物（ＡＴＯ）が挙げられる。導電性繊維としては、例えば、金属ナノワイヤ、および、カーボンナノチューブが挙げられる。金属としては、例えば、金、白金、銀、および、銅が挙げられる。導電層１６は、面方向中央部に位置するセンサ電極部１８と、センサ電極部１８に周辺に位置する引出し配線部１９とを一体的に有する。導電層１６の詳細は、例えば、特開２０１７－１０２４４３号公報、特開２０１４－１１３７０５号公報、および、特開２０１４－２１９６６７号公報に記載される。 <Conductive layer 16>
The conductive layer 16 has a predetermined pattern. The surface and sides of the conductive layer 16 come into contact with the pressure-sensitive adhesive layer 12. Examples of the material of the conductive layer 16 include metal oxides, conductive fibers (fibers), and metals. Examples of the metal oxide include composite oxides. Examples of the composite oxide include indium zinc composite oxide (IZO), indium gallium zinc composite oxide (IGZO), indium gallium composite oxide (IGO), indium tin composite oxide (ITO), and antimonthine composite. Oxide (ATO) can be mentioned. Examples of conductive fibers include metal nanowires and carbon nanotubes. Metals include, for example, gold, platinum, silver, and copper. The conductive layer 16 integrally has a sensor electrode portion 18 located in the central portion in the plane direction and a drawer wiring portion 19 located in the periphery of the sensor electrode portion 18. Details of the conductive layer 16 are described in, for example, JP-A-2017-102443, JP-A-2014-113705, and JP-A-2014-219667.
＜基材層１７＞
　基材層１７は、導電層１６の裏面、および、粘着剤層１２の裏面に配置されている。基材層１７は、面方向に延びる。基材層１７は、例えば、樹脂層である。基材層１７の材料としては、オレフィン樹脂、ポリエステル樹脂、（メタ）アクリル樹脂、ポリカーボネート樹脂、ポリエーテルスルフォン樹脂、ポリアリレート樹脂、メラミン樹脂、ポリアミド樹脂、ポリイミド樹脂、セルロース樹脂、および、ポリスチレン樹脂が挙げられる。オレフィン樹脂として、例えば、ポリエチレン、ポリプロピレン、および、シクロオレフィンポリマー（ＣＯＰ）が挙げられる。ポリエステル樹脂としては、例えば、ＰＥＴ、ＰＢＴ、および、ＰＥＮが挙げられる。（メタ）アクリル樹脂としては、例えば、ポリ（メタ）アクリレート樹脂が挙げられる。基材層１７の詳細は、例えば、特開２０１８－１８１７２２号公報に記載される。 <Base layer 17>
The base material layer 17 is arranged on the back surface of the conductive layer 16 and the back surface of the pressure-sensitive adhesive layer 12. The base material layer 17 extends in the plane direction. The base material layer 17 is, for example, a resin layer. Examples of the material of the base material layer 17 include olefin resin, polyester resin, (meth) acrylic resin, polycarbonate resin, polyether sulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, and polystyrene resin. Can be mentioned. Examples of the olefin resin include polyethylene, polypropylene, and cycloolefin polymer (COP). Examples of the polyester resin include PET, PBT, and PEN. Examples of the (meth) acrylic resin include poly (meth) acrylate resins. Details of the base material layer 17 are described in, for example, Japanese Patent Application Laid-Open No. 2018-181722.
＜第２粘着剤層１４＞
　第２粘着剤層１４は、導電性フィルム１３の裏面に配置されている。具体的には、第２粘着剤層１４は、導電性フィルム１３の裏面に接触している。第２粘着剤層１４の材料は、粘着剤層１２の材料と同様である。 <Second adhesive layer 14>
The second pressure-sensitive adhesive layer 14 is arranged on the back surface of the conductive film 13. Specifically, the second pressure-sensitive adhesive layer 14 is in contact with the back surface of the conductive film 13. The material of the second pressure-sensitive adhesive layer 14 is the same as the material of the pressure-sensitive adhesive layer 12.
＜画像表示部材１５＞
　画像表示部材１５は、有機ＥＬ表示装置１０の裏面を形成する。画像表示部材１５は、導電性フィルム１３の裏側に第２粘着剤層１４を介して配置されている。画像表示部材１５は、面方向に延びる。画像表示部材１５は、具体的には、有機ＥＬ素子である。例えば、画像表示部材１５は、図示しないが、表示基板と、２つの電極と、２つの電極に挟まれる有機ＥＬ層と、封止層とを含む。なお、画像表示部材１５の構成および物性は、例えば、特開２０１８－２８５７３号公報に詳述される。 <Image display member 15>
The image display member 15 forms the back surface of the organic EL display device 10. The image display member 15 is arranged on the back side of the conductive film 13 via the second pressure-sensitive adhesive layer 14. The image display member 15 extends in the plane direction. Specifically, the image display member 15 is an organic EL element. For example, although not shown, the image display member 15 includes a display substrate, two electrodes, an organic EL layer sandwiched between the two electrodes, and a sealing layer. The configuration and physical properties of the image display member 15 are described in detail in, for example, Japanese Patent Application Laid-Open No. 2018-28873.
＜一実施形態の作用効果＞
　この光学積層体１は、４０μｍ以上、６０μｍ以下の厚みを有するガラス板２と、接着剤層３と、－１００℃から－５０℃におけるｔａｎδの平均が、０．０６以上であり、－１００℃から－５０℃における引張貯蔵弾性率Ｅ’の平均が、３ＧＰａ以上、６ＧＰａ以下であるフィルム４とを備え、さらに、粘着剤層１２をさらに備える。また、粘着剤層１２は、２０μｍ以下の厚みを有する。そのため、光学積層体１は、耐衝撃性に優れる。 <Action and effect of one embodiment>
The optical laminate 1 has a glass plate 2 having a thickness of 40 μm or more and 60 μm or less, an adhesive layer 3, and an average of tan δ from −100 ° C. to −50 ° C. of 0.06 or more, and −100 ° C. A film 4 having an average tensile storage elastic modulus E'at -50 ° C. of 3 GPa or more and 6 GPa or less is provided, and a pressure-sensitive adhesive layer 12 is further provided. Further, the pressure-sensitive adhesive layer 12 has a thickness of 20 μm or less. Therefore, the optical laminate 1 is excellent in impact resistance.
＜変形例＞
　以下の変形例において、上記した一実施形態と同様の部材および工程については、同一の参照符号を付し、その詳細な説明を省略する。また、変形例は、特記する以外、一実施形態態と同様の作用効果を奏することができる。 <Modification example>
In the following modification, the same members and processes as those in the above-described embodiment are designated by the same reference numerals, and detailed description thereof will be omitted. Further, the modified example can exhibit the same action and effect as that of one embodiment, except for special mention.
　一実施形態では、フィルム４は、単層であるが、フィルム４の層数は、限定されない。
　フィルム４は、複層でもよい。 In one embodiment, the film 4 is a single layer, but the number of layers of the film 4 is not limited.
The film 4 may have a plurality of layers.
　本発明の光学積層体は耐衝撃性に優れるので、厚みが４０μm以上、６０μｍ以下のガラス板でも十分な耐衝撃性を有する。厚みが４０μm以上、６０μｍ以下のガラス板は屈曲性に優れるため、本発明の光学積層体は、フォルダブルディスプレイおよびローラブルディスプレイなどのフレキシブルディスプレイにも好適に用いることができる。 Since the optical laminate of the present invention has excellent impact resistance, even a glass plate having a thickness of 40 μm or more and 60 μm or less has sufficient impact resistance. Since a glass plate having a thickness of 40 μm or more and 60 μm or less is excellent in flexibility, the optical laminate of the present invention can be suitably used for flexible displays such as foldable displays and rollable displays.
　図１の１点破線で示すように、光学積層体１は、機能層３７をさらに備えることができる。機能層３７は、ガラス板２の厚み方向他方面に配置される。機能層３７としては、例えば、ハードコート層、飛散防止層、防汚層、および、反射防止層が挙げられる。これらは、単層でもよく複数積層されてもよい。 As shown by the alternate long and short dash line in FIG. 1, the optical laminate 1 can further include a functional layer 37. The functional layer 37 is arranged on the other surface of the glass plate 2 in the thickness direction. Examples of the functional layer 37 include a hard coat layer, an anti-scattering layer, an anti-fouling layer, and an anti-reflection layer. These may be a single layer or a plurality of these may be laminated.
　以下の記載において用いられる配合割合（含有割合）、物性値、パラメータなどの具体的数値は、上記の「発明を実施するための形態」において記載されている、それらに対応する配合割合（含有割合）、物性値、パラメータなど該当記載の上限値（「以下」、「未満」として定義されている数値）または下限値（「以上」、「超過」として定義されている数値）に代替することができる。また、以下の記載において特に言及がない限り、「部」および「％」は質量基準である。 Specific numerical values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following description are the compounding ratios (content ratios) corresponding to those described in the above-mentioned "mode for carrying out the invention". ), Physical property values, parameters, etc., can be replaced with the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess"). can. In addition, unless otherwise specified in the following description, "part" and "%" are based on mass.
　　実施例１
　厚み５０μｍのガラス板２（Ｇ－ｌｅａｆ）、厚み５０μｍのポリエチレンテレフタレートフィルムからなるフィルム４（ダイアホイルＳ１００、三菱ケミカル社製）を準備した。また、脂肪族脂環式エポキシ樹脂（セロキサイド２０２１Ｐ、エポキシ当量１２８～１３３ｇ／ｅｑ．、ダイセル化学社製）７０質量部、３官能脂肪族エポキシ樹脂（ＥＨＰＥ３１５０、エポキシ当量１７０～１９０ｇ／ｅｑ．、ダイセル化学社製）５質量部、オキセタン系樹脂（アロンオキセタン、東亜合成社製）１９質量部、シランカップリング剤（ＫＢＭ－４０３、３－グリシドキシプロピルトリメトキシシラン、信越化学工業社製）４質量部、光酸発生剤（ＣＰＩ１０１Ａ、トリアリールスルホニウム塩、サンアフロ社製）２質量部を配合して、エポキシ接着剤組成物を調製した。このエポキシ接着剤組成物をガラス板２とフィルム４とで挟み込んだ。 Example 1
A glass plate 2 (G-leaf) having a thickness of 50 μm and a film 4 (Diafoil S100, manufactured by Mitsubishi Chemical Corporation) made of a polyethylene terephthalate film having a thickness of 50 μm were prepared. In addition, 70 parts by mass of an aliphatic alicyclic epoxy resin (celloxide 2021P, epoxy equivalent 128 to 133 g / eq., Manufactured by Daicel Chemical Co., Ltd.), a trifunctional aliphatic epoxy resin (EHPE3150, epoxy equivalent 170 to 190 g / eq., Daicel). Chemical Co., Ltd.) 5 parts by mass, oxetane resin (Aron Oxetane, manufactured by Toa Synthetic Co., Ltd.) 19 parts by mass, silane coupling agent (KBM-403, 3-glycidoxypropyltrimethoxysilane, manufactured by Shinetsu Chemical Industry Co., Ltd.) 4 An epoxy adhesive composition was prepared by blending 2 parts by mass and 2 parts by mass of a photoacid generator (CPI101A, triarylsulfonium salt, manufactured by San Afro). This epoxy adhesive composition was sandwiched between the glass plate 2 and the film 4.
　その後、紫外線を、ガラス板２側から硬化型接着剤に照射した。これにより、ガラス板２およびフィルム４を強固に接着する硬化体からなる厚み１μｍの接着剤層３を形成した。ナノインデンター法で測定される２５℃における接着剤層３の弾性率は、４．９ＧＰａであった。 After that, the curable adhesive was irradiated with ultraviolet rays from the glass plate 2 side. As a result, an adhesive layer 3 having a thickness of 1 μm made of a cured body that firmly adheres the glass plate 2 and the film 4 was formed. The elastic modulus of the adhesive layer 3 at 25 ° C. measured by the nanoindenter method was 4.9 GPa.
　次いで、厚み１５μｍの粘着剤層１２をフィルム４の厚み方向一方面に、転写により配置した。粘着剤層１２は下記の通りに調製した。 Next, the pressure-sensitive adhesive layer 12 having a thickness of 15 μm was placed on one side of the film 4 in the thickness direction by transfer. The pressure-sensitive adhesive layer 12 was prepared as follows.
　ラウリルアクリレート（ＬＡ）４３質量部、２－エチルヘキシルアクリレート（２ＥＨＡ）４４質量部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）６質量部、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）７質量部、および、ＢＡＳＦ製「イルガキュア１８４」０．０１５質量部を配合し、紫外線を照射して重合し、ベースポリマー組成物（重合率：約１０％）を得た。 43 parts by mass of lauryl acrylate (LA), 44 parts by mass of 2-ethylhexyl acrylate (2EHA), 6 parts by mass of 4-hydroxybutyl acrylate (4HBA), 7 parts by mass of N-vinyl-2-pyrrolidone (NVP), and BASF. 0.015 parts by mass of "Irgacure 184" was blended and polymerized by irradiating with ultraviolet rays to obtain a base polymer composition (polymerization rate: about 10%).
　別途、メタクリル酸ジシクロペンタニル（ＤＣＰＭＡ）６０質量部、メタクリル酸メチル（ＭＭＡ）４０質量部、α－チオグリセロール３．５質量部、および、トルエン１００質量部を混合し、窒素雰囲気下にて７０℃で１時間撹拌した。次に、２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２質量部を投入し、７０℃で２時間反応させた後、８０℃に昇温して２時間反応させた。その後、反応液を１３０℃に加熱して、トルエン、連鎖移動剤および未反応モノマーを乾燥除去して、固形状のアクリル系オリゴマーを得た。アクリル系オリゴマーの重量平均分子量は５１００であった。ガラス転移温度（Ｔｇ）は１３０℃であった。 Separately, 60 parts by mass of dicyclopentanyl methacrylate (DCPMA), 40 parts by mass of methyl methacrylate (MMA), 3.5 parts by mass of α-thioglycerol, and 100 parts by mass of toluene are mixed and subjected to a nitrogen atmosphere. The mixture was stirred at 70 ° C. for 1 hour. Next, 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) was added and reacted at 70 ° C. for 2 hours, then heated to 80 ° C. and reacted for 2 hours. Then, the reaction solution was heated to 130 ° C., and toluene, the chain transfer agent and the unreacted monomer were dried and removed to obtain a solid acrylic oligomer. The weight average molecular weight of the acrylic oligomer was 5100. The glass transition temperature (Tg) was 130 ° C.
　ベースポリマー組成物の固形分１００質量部に対して、１，６－ヘキサンジオールジアクリレート（ＨＤＤＡ）０．０７質量部、アクリル系オリゴマー１質量部、シランカップリング剤（信越化学製「ＫＢＭ４０３」）０．３質量部を添加した後、これらを均一に混合して、粘着剤組成物を調製した。 0.07 parts by mass of 1,6-hexanediol diacrylate (HDDA), 1 part by mass of acrylic oligomer, silane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by mass of the solid content of the base polymer composition. After adding 0.3 parts by mass, these were uniformly mixed to prepare a pressure-sensitive adhesive composition.
　粘着剤組成物を、ＰＥＴフィルム（三菱ケミカル製「ダイアホイルＭＲＦ７５」）からなる剥離シートの表面に塗布し、その後、別のＰＥＴフィルム（三菱ケミカル製「ダイアホイルＭＲＦ７５」）からなる剥離シートを塗膜に貼り合わせた。その後、塗膜に紫外線を照射して、厚み１５μｍの粘着剤層１２を調製した。この粘着剤層１２の２５℃におけるせん断貯蔵弾性率Ｇ’は、０．０３ＭＧＰａであった。測定方法は、以下の通りである。粘着剤層１２を円盤状に外形加工し、パラレルプレートに挟み込み、Ｒｈｅｏｍｅｔｒｉｃ　Ｓｃｉｅｎｔｉｆｉｃ社製「Ａｄｖａｎｃｅｄ　Ｒｈｅｏｍｅｔｒｉｃ　Ｅｘｐａｎｓｉｏｎ　Ｓｙｓｔｅｍ（ＡＲＥＳ）」を用いて、以下の条件の動的粘弾性測定により、粘着剤層１２の２５℃におけるせん断貯蔵弾性率Ｇ’を求めた。 The pressure-sensitive adhesive composition is applied to the surface of a release sheet made of PET film (Mitsubishi Chemical "Diafoil MRF75"), and then a release sheet made of another PET film (Mitsubishi Chemical "Diafoil MRF75") is applied. It was attached to the film. Then, the coating film was irradiated with ultraviolet rays to prepare an adhesive layer 12 having a thickness of 15 μm. The shear storage elastic modulus G'at 25 ° C. of the pressure-sensitive adhesive layer 12 was 0.03 MGPa. The measurement method is as follows. The pressure-sensitive adhesive layer 12 is externally processed into a disk shape, sandwiched between parallel plates, and the pressure-sensitive adhesive layer 12 is measured by dynamic viscoelasticity measurement under the following conditions using "Advanced Shearometric Exhibition System (ARES)" manufactured by Shearetic Scientific. The shear storage elastic modulus G'at 25 ° C. was determined.
　［条件］
　モード：ねじり
　温度：－４０℃から１５０℃
　昇温速度：５℃／分
　周波数：１Ｈｚ [conditions]
Mode: Torsion temperature: -40 ° C to 150 ° C
Temperature rise rate: 5 ° C / min Frequency: 1Hz
　これにより、ガラス板２と、接着剤層３と、フィルム４と、粘着剤層１２とを備える光学積層体１を製造した。 As a result, an optical laminate 1 including a glass plate 2, an adhesive layer 3, a film 4, and an adhesive layer 12 was manufactured.
　　比較例１
　実施例１と同様にして、光学積層体１を製造した。但し、粘着剤層１２の厚みを２５μｍに変更した。 Comparative Example 1
The optical laminate 1 was manufactured in the same manner as in Example 1. However, the thickness of the pressure-sensitive adhesive layer 12 was changed to 25 μm.
　　比較例２
　実施例１と同様にして、光学積層体１を製造した。但し、ガラス板２の厚みを７０μｍに変更した。 Comparative Example 2
The optical laminate 1 was manufactured in the same manner as in Example 1. However, the thickness of the glass plate 2 was changed to 70 μm.
　　比較例３
　実施例１と同様にして、光学積層体１を製造した。但し、フィルム４として、厚み４０μｍのトリアセチルセルロースフィルム（ＫＣ４ＵＹＷ、コニカミノルタ製）を用いた。 Comparative Example 3
The optical laminate 1 was manufactured in the same manner as in Example 1. However, as the film 4, a triacetyl cellulose film (KC4UYW, manufactured by Konica Minolta) having a thickness of 40 μm was used.
　　比較例４
　実施例１と同様にして、光学積層体１を製造した。但し、フィルム４として、厚み８０μｍのトリアセチルセルロースフィルム（ＫＣ８ＵＡＷ、コニカミノルタ製）を用いた。 Comparative Example 4
The optical laminate 1 was manufactured in the same manner as in Example 1. However, as the film 4, a triacetyl cellulose film (KC8UAW, manufactured by Konica Minolta) having a thickness of 80 μm was used.
　＜評価＞
　各実施例および比較例について、下記の事項を測定および評価した。それらの結果を表１に記載する。 <Evaluation>
The following items were measured and evaluated for each Example and Comparative Example. The results are shown in Table 1.
　＜フィルム４のｔａｎδおよび引張貯蔵弾性率Ｅ’＞
　各実施例および比較例で準備したフィルム４を動的粘弾性試験に供した。装置および条件を下に記載する。 <Tan δ of film 4 and tensile storage elastic modulus E'>
The films 4 prepared in each Example and Comparative Example were subjected to a dynamic viscoelasticity test. The equipment and conditions are described below.
　装置：日立ハイテクサイエンス社製　多機能動的粘弾性測定装置　ＤＭＳ６１００
　温度範囲　：－１００～２００℃
　昇温速度　：２℃／ｍｉｎ
　モード　：引張
　サンプル幅　：１０ｍｍ
　チャック間距離　：２０ｍｍ
　周波数　：１０Ｈｚ
　歪振幅　：１０μｍ
　雰囲気　：大気（２５０ｍｌ／ｍｉｎ）
　データの取得間隔：０．５ｍｉｎ（１℃毎） Equipment: Hitachi High-Tech Science Multifunctional Dynamic Viscoelasticity Measuring Equipment DMS6100
Temperature range: -100 to 200 ° C
Temperature rise rate: 2 ° C / min
Mode: Tensile sample width: 10 mm
Distance between chucks: 20 mm
Frequency: 10Hz
Strain amplitude: 10 μm
Atmosphere: Atmosphere (250 ml / min)
Data acquisition interval: 0.5 min (every 1 ° C)
　－１００℃から－５０℃におけるフィルム４の引張貯蔵弾性率Ｅ’の平均のそれぞれは、－１００℃から－５０℃における上記した取得したすべてのデータの総和をデータの数で割って、算出した。－１００℃から－５０℃におけるフィルム４のｔａｎδの平均のそれぞれは、－１００℃から－５０℃における上記した取得したすべてのデータの総和をデータの数で割って、算出した。 Each of the average tensile storage elastic moduli E'of the film 4 from -100 ° C to -50 ° C was calculated by dividing the sum of all the above acquired data from -100 ° C to -50 ° C by the number of data. .. Each of the averages of tan δ of film 4 from −100 ° C. to −50 ° C. was calculated by dividing the sum of all the above-mentioned acquired data from −100 ° C. to −50 ° C. by the number of data.
　＜ペンドロップ割れ試験＞
　各実施例および比較例の光学積層体１について、下記のペンドロップ割れ試験を実施した。図１の仮想線で示すように、まず、ガラス板２が上側を向くように、光学積層体１を樹脂フィルム３４の表面に置いた。具体的には、粘着剤層１２を樹脂フィルム３４の表面に貼着した。樹脂フィルム３４は、プレスケール（富士フィルム製　プレスケールＭＳ中圧用モノシートタイプ、厚み９５μｍ）である。樹脂フィルム３４は、図示しない水平台の表面に配置されている。次いで、ガラス板２から５ｃｍの高さから７ｇのペン２９（Ｐｅｎｔｅｌボールペン　ＢＫ４０７黒、ボール径０．７ｍｍ）を落下させるペンドロップ割れ試験を実施する。上記した高さ５ｃｍは、ガラス板２の厚み方向一方面と、ペン２９の先端部３２との距離である。先端部３２は、下側を向き、尖っている。この光学積層体１では、ペン２９の上記した落下で、ガラス板２に割れが発生すれば、ペンドロップ割れ試験の高さＨ１は、５ｃｍとなる。ガラス板２に割れが発生しなれば、１ｃｍずつ高さを段階的に引き上げる。これにより、ガラス板２に割れが発生したときの高さＨ１を得る。 <Pen drop crack test>
The following pen drop cracking test was carried out for the optical laminate 1 of each Example and Comparative Example. As shown by the virtual line in FIG. 1, first, the optical laminate 1 was placed on the surface of the resin film 34 so that the glass plate 2 faces upward. Specifically, the pressure-sensitive adhesive layer 12 was attached to the surface of the resin film 34. The resin film 34 is a prescale (a monosheet type for prescale MS medium pressure manufactured by Fujifilm, thickness 95 μm). The resin film 34 is arranged on the surface of a horizontal table (not shown). Next, a pen drop cracking test is carried out in which a 7 g pen 29 (Pentel ballpoint pen BK407 black, ball diameter 0.7 mm) is dropped from a height of 5 cm from the glass plate 2. The height of 5 cm described above is the distance between one side of the glass plate 2 in the thickness direction and the tip portion 32 of the pen 29. The tip portion 32 faces downward and is sharp. In this optical laminate 1, if the glass plate 2 is cracked by the above-mentioned drop of the pen 29, the height H1 of the pen drop cracking test becomes 5 cm. If the glass plate 2 does not crack, the height is gradually increased by 1 cm. As a result, the height H1 when the glass plate 2 is cracked is obtained.
＜各実施例および比較例の対比＞
＜粘着剤層１２の厚みの評価＞
　粘着剤層１２の厚みを評価する。実施例１と比較例１とを対比する。実施例１の粘着剤層１２の厚みは、１５μｍである。一方、比較例１の粘着剤層１２の厚みは、２５μｍである。比較例１のペンドロップ割れ試験の高さＨ１　１０ｃｍに対して、実施例１のペンドロップ割れ試験の高さＨ１　２０ｃｍは、高い。そのため、粘着剤層１２の厚みを２０μｍ以下にすることにより、光学積層体１の耐衝撃性が向上することが分かる。 <Comparison of each example and comparative example>
<Evaluation of the thickness of the adhesive layer 12>
The thickness of the pressure-sensitive adhesive layer 12 is evaluated. Example 1 and Comparative Example 1 are compared. The thickness of the pressure-sensitive adhesive layer 12 of Example 1 is 15 μm. On the other hand, the thickness of the pressure-sensitive adhesive layer 12 of Comparative Example 1 is 25 μm. The height H1 20 cm of the pen drop cracking test of Example 1 is higher than the height H1 10 cm of the pen drop cracking test of Comparative Example 1. Therefore, it can be seen that the impact resistance of the optical laminate 1 is improved by reducing the thickness of the pressure-sensitive adhesive layer 12 to 20 μm or less.
　＜ガラス板２の厚みの評価＞
　ガラス板２の厚みを評価する。実施例１と比較例２とを対比する。実施例１のガラス板２の厚みは、５０μｍである。比較例２のガラス板２の厚みは、７０μｍである。比較例２のペンドロップ割れ試験の高さＨ１　７ｃｍに対して、実施例１のペンドロップ割れ試験の高さＨ１　２０ｃｍは、高い。そのため、ガラス板２の厚みを６０ｃｍ以下にすることによって、光学積層体１の耐衝撃性が向上することが分かる。 <Evaluation of the thickness of the glass plate 2>
The thickness of the glass plate 2 is evaluated. Example 1 and Comparative Example 2 are compared. The thickness of the glass plate 2 of Example 1 is 50 μm. The thickness of the glass plate 2 of Comparative Example 2 is 70 μm. The height H1 20 cm of the pen drop cracking test of Example 1 is higher than the height H17 cm of the pen drop cracking test of Comparative Example 2. Therefore, it can be seen that the impact resistance of the optical laminate 1 is improved by reducing the thickness of the glass plate 2 to 60 cm or less.
　＜フィルム４のｔａｎδの平均の評価＞
　フィルム４のｔａｎδの平均を評価する。実施例１と比較例３と比較例４とを対比する。実施例１のフィルム４のｔａｎδの平均は、０．０６２である。比較例３と比較例４とのそれぞれのフィルム４のｔａｎδの平均は、０．０４７μｍである。比較例３と比較例４とのそれぞれのペンドロップ割れ試験の高さＨ１　７ｃｍと１０ｃｍとに対して、実施例１のペンドロップ割れ試験の高さＨ１　２０ｃｍは、高い。そのため、フィルム４のｔａｎδの平均を０．０６以上にすることによって、光学積層体１の耐衝撃性が向上することが分かる。
Figure JPOXMLDOC01-appb-T000001
 <Evaluation of the average of tan δ of film 4>
The average of tan δ of film 4 is evaluated. Example 1, Comparative Example 3 and Comparative Example 4 are compared. The average of tan δ of the film 4 of Example 1 is 0.062. The average of tan δ of each film 4 of Comparative Example 3 and Comparative Example 4 is 0.047 μm. The height H1 20 cm of the pen drop cracking test of Example 1 is higher than the height H17 cm and 10 cm of the pen drop cracking test of Comparative Example 3 and Comparative Example 4, respectively. Therefore, it can be seen that the impact resistance of the optical laminate 1 is improved by setting the average of tan δ of the film 4 to 0.06 or more.
Figure JPOXMLDOC01-appb-T000001
　なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示に過ぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記請求の範囲に含まれる。 Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be construed in a limited manner. Modifications of the invention that are apparent to those skilled in the art are included in the claims below.
　光学積層体は、画像表示装置に備えられる。 The optical laminate is provided in the image display device.
１ 光学積層体
２ ガラス板
３ 接着剤層
４ フィルム
１２ 粘着剤層 1 Optical laminate 2 Glass plate 3 Adhesive layer 4 Film 12 Adhesive layer

Claims (1)

  1. 　ガラス板と、接着剤層と、フィルムと、粘着剤層とを厚み方向一方側に向かって順に備え、
    　前記ガラス板は、４０μｍ以上、６０μｍ以下の厚みを有し、
    　周波数１０Ｈｚ、昇温速度２℃／ｍｉｎ、引張モードの動的粘弾性試験により求められる－１００℃から－５０℃における前記フィルムのｔａｎδの平均が、０．０６以上であり、
    　前記動的粘弾性試験により求められる－１００℃から－５０℃における前記フィルムの引張貯蔵弾性率Ｅ’の平均が、３ＧＰａ以上、６ＧＰａ以下であり、
    　前記粘着剤層は、２０μｍ以下の厚みを有する、光学積層体。     A glass plate, an adhesive layer, a film, and an adhesive layer are provided in order toward one side in the thickness direction.
    The glass plate has a thickness of 40 μm or more and 60 μm or less, and has a thickness of 40 μm or more and 60 μm or less.
    The average tan δ of the film at a frequency of 10 Hz, a heating rate of 2 ° C./min, and a dynamic viscoelasticity test in a tensile mode from -100 ° C to -50 ° C is 0.06 or more.
    The average tensile storage elastic modulus E'of the film at −100 ° C. to −50 ° C. determined by the dynamic viscoelasticity test is 3 GPa or more and 6 GPa or less.
    The pressure-sensitive adhesive layer is an optical laminate having a thickness of 20 μm or less.
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WO2023163151A1 (en) * 2022-02-28 2023-08-31 日東電工株式会社 Optical laminate for oled display device

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JP2019025899A (en) * 2017-07-28 2019-02-21 株式会社ダイセル Laminate, and flexible device comprising the laminate
WO2019087938A1 (en) * 2017-10-30 2019-05-09 日東電工株式会社 Laminate for image display devices

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JP2019025899A (en) * 2017-07-28 2019-02-21 株式会社ダイセル Laminate, and flexible device comprising the laminate
WO2019087938A1 (en) * 2017-10-30 2019-05-09 日東電工株式会社 Laminate for image display devices

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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