WO2021084999A1 - 光学積層体及び表示装置 - Google Patents

光学積層体及び表示装置 Download PDF

Info

Publication number
WO2021084999A1
WO2021084999A1 PCT/JP2020/036642 JP2020036642W WO2021084999A1 WO 2021084999 A1 WO2021084999 A1 WO 2021084999A1 JP 2020036642 W JP2020036642 W JP 2020036642W WO 2021084999 A1 WO2021084999 A1 WO 2021084999A1
Authority
WO
WIPO (PCT)
Prior art keywords
optical laminate
adhesive layer
sensitive adhesive
pressure
resin
Prior art date
Application number
PCT/JP2020/036642
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
ボラム 片
大山 姜
Original Assignee
住友化学株式会社
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
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020217014962A priority Critical patent/KR102359353B1/ko
Priority to CN202080006638.XA priority patent/CN113167932A/zh
Publication of WO2021084999A1 publication Critical patent/WO2021084999A1/ja

Links

Images

Classifications

    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • B32B27/00—Layered products comprising a layer 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • 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

Definitions

  • the present invention relates to an optical laminate and a display device, and more particularly to an optical laminate that covers the display surface of a display panel and a display device having the optical laminate.
  • the flexibility display device can also be installed on a non-planar surface such as a curved surface and a bending surface. Further, the flexibility display device can be improved in portability by being folded or having a scroll shape. In such a flexibility display device, the optical laminate covering the display surface is also required to have flexibility.
  • the optical laminate used in the flexibility display device is required to have not only flexibility but also impact resistance. Furthermore, in addition to these, thinning and weight reduction of the optical laminate are desired not only for practical reasons but also for cost reduction and resource saving.
  • Patent Document 1 describes an optical laminate having a base material having a protective layer formed on one side thereof, a first transparent adhesive layer, and a first buffer layer (summary). A sample obtained by joining the optical laminate and the display panel with an adhesive sheet is said to have good impact resistance and bending resistance (paragraph [0118], paragraph [0125]).
  • the optical laminate of Patent Document 1 has sufficient characteristics, particularly bending resistance, and therefore, the appearance of an optical laminate with further improved bending resistance is desired.
  • the present invention solves the above problems, and an object of the present invention is to provide an optical laminate having excellent bending resistance and impact resistance.
  • the present invention is an optical laminate including a front plate, a first pressure-sensitive adhesive layer, an impact-resistant layer, and a second pressure-sensitive adhesive layer in this order from the visual side, and the second pressure-sensitive adhesive layer is 1.20 or less.
  • An optical laminate having tan ⁇ at 20 ° C., which means mechanical loss tangent, and is represented by tan ⁇ G "/ G'when the storage elastic modulus is G'and the loss elastic modulus is G". I will provide a.
  • the impact resistant layer and the second adhesive layer have a formula of 5.5 or less.
  • a is the thickness of the impact resistant layer
  • c is the thickness of the second pressure-sensitive adhesive layer.
  • It has a thickness ratio r represented by.
  • the impact resistant layer has a tan ⁇ at ⁇ 20 ° C. of 0.001 to 0.020.
  • the impact resistant layer has a tensile modulus of elasticity of 0.1 to 10 GPa.
  • the material of the impact resistant layer is selected from the group consisting of polycarbonate resin, polyimide resin and polyester resin.
  • the first pressure-resistant layer, the impact-resistant layer, and the second pressure-resistant layer have a total thickness of 120 to 190 ⁇ m.
  • the optical laminate has a thickness of 130-220 ⁇ m.
  • the optical laminate is subjected to 180 ° bending and stretching with the front plate inside under the conditions of a temperature of 25 ° C., a bending speed of 30 rpm, and a bending radius of 1.00 mm in a continuous bending test of 150,000 times or more. Indicates the number of times of bending resistance.
  • the present invention also provides a display device including any of the above optical laminates and a display unit in the internal direction of the optical laminate.
  • an optical laminate having excellent bending resistance and impact resistance, and further thinner is provided.
  • FIG. 1 is a cross-sectional view showing an example of the structure of the optical laminate of the present invention.
  • the optical laminate 10 shown in FIG. 1 includes a front plate 1, a first adhesive layer 2, an impact resistant layer 3, and a second adhesive layer 4 in this order from the visual side.
  • the front plate is on the inside.
  • the shape of the optical laminate in the plane direction may be, for example, a square shape, preferably a square shape having a long side and a short side, and more preferably a rectangle.
  • the length of the long side may be, for example, 10 to 1400 mm, preferably 50 to 600 mm.
  • the length of the short side is, for example, 5 to 800 mm, preferably 30 to 500 mm, and more preferably 50 to 300 mm.
  • Each layer constituting the optical laminate may have corners R-processed, end portions notched, or perforated.
  • the thickness of the optical laminate is preferably 100 to 200 ⁇ m. By adjusting the thickness of the optical laminate within this range, it becomes easy to improve the bending resistance while maintaining the impact resistance.
  • the thickness of the optical laminate is more preferably 100 to 180 ⁇ m, still more preferably 120 to 150 ⁇ m. In one embodiment, the thickness of the optical laminate is preferably 130-220 ⁇ m, more preferably 150-210 ⁇ m. By adjusting the thickness of the optical laminate within the above range, good impact resistance and good flexibility can be obtained.
  • the front plate 1 of the optical laminate is located in front of the optical laminate with reference to FIG. 1
  • the upward direction indicates the external direction in which the optical laminate is visually recognized
  • the downward direction indicates the internal direction in which the optical laminate is adhered to the display unit or the like.
  • the material of the front plate 1 is not limited as long as it is a plate-like body that can transmit light, but from the viewpoint of impact resistance and flexibility, a resin plate-like body (for example, a resin plate, a resin sheet, a resin) is used. It is preferable to use a film or the like).
  • the front plate may be composed of only one layer, or may be composed of two or more layers.
  • the material may be, for example, an acrylic resin such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; and a polyolefin-based material such as polyethylene, polypropylene, polymethylpentene and polystyrene.
  • Resins Cellular resins such as triacetyl cellulose, acetyl cellulose butyrate, propionyl cellulose, butyryl cellulose and acetyl propionyl cellulose; ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, etc.
  • sulfone resin such as polysulfone and polyether sulfone
  • ketone resin such as polyether ketone and polyether ether ketone
  • polyetherimide polycarbonate resin
  • polyester resin polyimide resin
  • polyamideimide resin polyamideimide resin
  • polyamide resin polyamide resin
  • Polycarbonate-based resin is a polymer containing a repeating structural unit having a carbonate group.
  • the polycarbonate resin include bisphenol A type polycarbonate, branched polycarbonate obtained by polymerizing trivalent phenol, and copolymerized polycarbonate obtained by copolymerizing an aliphatic or aromatic dicarboxylic acid and an aliphatic or alicyclic divalent alcohol. In the embodiment of the present invention, it can be appropriately selected and used from these.
  • a polyester resin is a polymer containing a repeating structural unit containing an ester bond.
  • the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethylterephthalate, polycyclohexanedimethylnaphthalate and the like. , In the embodiment of the present invention, it can be appropriately selected and used from these.
  • the polyimide-based resin represents a polymer containing any one or more selected from polyimide and polyamide-imide.
  • Polyimide represents a polymer containing a repeating structural unit having an imide group
  • polyamide-imide represents a polymer containing a repeating structural unit having an imide group and a repeating structural unit having an amide group.
  • the polyamide resin represents a polymer containing a repeating structural unit having an amide group.
  • the polyimide resin according to this embodiment has a repeating structural unit represented by the formula (10).
  • G represents a tetravalent organic group
  • A represents a divalent organic group.
  • G and / or A may include two or more different repeating structural units represented by the formula (10).
  • the polyimide-based resin according to the present embodiment has a repeating structure represented by any of the formulas (11), (12), and (13) as long as the various physical properties of the obtained transparent resin film are not impaired. It may contain any one or more of the units.
  • the main structural unit of the polyimide resin is the repeating structural unit represented by the formula (10) from the viewpoint of the strength and transparency of the transparent resin film.
  • the repeating structural unit represented by the formula (10) is preferably 40 mol% or more, more preferably 50 mol% or more, based on all the repeating structural units of the polyimide resin. It is even more preferably 70 mol% or more, even more preferably 90 mol% or more, and even more preferably 98 mol% or more.
  • the repeating structural unit represented by the formula (10) may be 100 mol%.
  • G and G 1 independently represent a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbon atoms.
  • the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, in which case the hydrocarbon group and the fluorine-substituted hydrocarbon group preferably have 1 to 8 carbon atoms.
  • Examples of G and G 1 include formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), and formula (28).
  • Equation (20) to (29) in the * represents a bond
  • Z is a single bond, -O -, - CH 2 - , - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3 ) 2- , -C (CF 3 ) 2- , -Ar-, -SO 2- , -CO-, -O-Ar-O-, -Ar-O-Ar-, -Ar-CH 2 -Ar-, -Ar-C (CH 3 ) Represents 2- Ar- or -Ar-SO 2- Ar-.
  • Ar represents an arylene group having 6 to 20 carbon atoms which may be substituted with a fluorine atom, and specific examples thereof include a phenylene group.
  • G 2 represents a trivalent organic group, preferably a trivalent organic group having 4 to 40 carbon atoms.
  • the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, in which case the hydrocarbon group and the fluorine-substituted hydrocarbon group preferably have 1 to 8 carbon atoms.
  • the G 2, equation (20), equation (21), equation (22), equation (23), equation (24), equation (25), equation (26), equation (27), equation (28) or Examples thereof include a group in which any one of the bonds of the group represented by the formula (29) is replaced with a hydrogen atom, and a chain hydrocarbon group having a trivalent carbon number of 6 or less.
  • the example of Z in the formulas (20) to (29) is the same as the example of Z in the description regarding G.
  • G 3 represents a divalent organic group, preferably a divalent organic group having 4 to 40 carbon atoms.
  • the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, in which case the hydrocarbon group and the fluorine-substituted hydrocarbon group preferably have 1 to 8 carbon atoms.
  • the G 3 equation (20), equation (21), equation (22), equation (23), equation (24), equation (25), equation (26), equation (27), equation (28) or Among the group bonds represented by the formula (29), a group in which two non-adjacent groups are replaced with a hydrogen atom and a divalent chain hydrocarbon group having 6 or less carbon atoms can be mentioned.
  • the example of Z in the formulas (20) to (29) is the same as the example of Z in the description regarding G.
  • Examples of the organic group of G 3 include formula (20'), formula (21'), formula (22'), formula (23'), formula (24'), formula (25'), formula (26'), Equation (27'), Equation (28') and Equation (29'):
  • W 1 is synonymous with Z defined in equations (20) to (29), and * is defined in equations (20) to (29).
  • the divalent organic group represented by] is more preferable.
  • the polyimide resin has a structural unit in which G 3 in the formula (2) is represented by any of the above formulas (20') to (29'), Z in the formula (2) will be described later.
  • the polyimide resin has a structural unit represented by the formula (101')
  • the polyimide resin has the following formula (100): In addition to the structural unit.
  • R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms
  • R 2 is R 1.
  • Or -C ( O)-*, * represents a bond
  • It may further have a structural unit derived from a carboxylic acid represented by.
  • a polyimide resin having this structural unit is preferable because it tends to increase the fluidity of the resin varnish used in producing the transparent resin film.
  • R 1 an alkyl group having 1 to 6 carbon atoms, the aryl group an alkoxy group and 6 to 12 carbon atoms having 1 to 6 carbon atoms, respectively, include those exemplified in Formula (101) described later.
  • Polyimide resin may include a plurality of types of G 3 as G 3 in formula (2), G 3 of plural kinds may being the same or different.
  • G 3 is preferably of the formula (101):
  • R 3a and R 3b independently represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R 3a. And the hydrogen atoms contained in R 3b may be substituted with halogen atoms independently of each other.
  • R 9 is a hydrogen atom, a monovalent to 1 carbon atoms which may be ⁇ 12 substituted by a halogen atom
  • Represents a hydrocarbon group s is an integer from 0 to 4 t is an integer from 0 to 4 u is an integer from 0 to 4 * Represents a bond] It is represented by, more preferably the formula (101') :.
  • W independently of one another, a single bond, -O -, - CH 2 - , - CH 2 -CH 2 -, - CH (CH 3) -, - C ( CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- , -S-, -CO- or -N (R 9 )-, preferably from the viewpoint of bending resistance of the optical film. It represents —O— or —S—, more preferably —O—.
  • R 3a and R 3b independently represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and 2-methyl-.
  • Butyl group, 3-methyl-butyl group, 2-ethyl-propyl group, n-hexyl group and the like can be mentioned.
  • alkoxy group having 1 to 6 carbon atoms examples include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and a cyclohexyloxy group.
  • aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, a biphenyl group and the like.
  • R 3a and R 3b are independent of each other, preferably an alkyl group having 1 to 6 carbon atoms or a carbon number of carbon atoms. It represents an alkoxy group of 1 to 6, and more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
  • the hydrogen atoms contained in R 3a and R 3b may be substituted with halogen atoms independently of each other.
  • R 9 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom.
  • the monovalent hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group.
  • halogen atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • T and u in the formula (101) and the formula (101') are independently integers of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.
  • the A, A 1 , A 2 and A 3 all represent a divalent organic group, preferably a divalent organic group having 4 to 40 carbon atoms.
  • the organic group may be substituted with a hydrocarbon group or a hydrocarbon group having 1 to 8 carbon atoms substituted with fluorine, in which case the hydrocarbon group and the hydrocarbon group substituted with fluorine preferably have carbon atoms. It is 1 to 8.
  • Equation (30) to (38) in the * represents a bond, Z 1, Z 2 and Z 3, independently of one another, a single bond, -O -, - CH 2 - , - CH 2 -CH 2 -, -CH (CH 3 )-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -S-, -SO 2- , -CO- or -N (R 3 )- .
  • R 3 represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom.
  • R 3 represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom.
  • Z 1 and Z 2 and Z 2 and Z 3 are preferably located in the meta or para position with respect to each ring, respectively.
  • the resin composition forming the transparent resin film may be a polyamide-based resin.
  • the polyamide-based resin according to this embodiment is a polymer mainly composed of a repeating structural unit represented by the formula (13).
  • Preferred examples and specific examples of G 3, and A 3 in the polyamide resin is the same as the preferable examples and specific examples of G 3, and A 3 in the polyimide resin.
  • the polyamide resin may contain a repeating structural unit G 3, and / or A 3 is represented by two or more different formula (13).
  • the polyimide resin can be obtained, for example, by polycondensation of a diamine and a tetracarboxylic dian compound (tetracarboxylic dianhydride, etc.). It can be synthesized according to the method described.
  • examples of commercially available polyimide products include "Neoprim” (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Inc. and "KPI-MX300F” (trade name) manufactured by Kawamura Sangyo Co., Ltd.
  • the tetracarboxylic acid compound used for the synthesis of the polyimide resin examples include an aromatic tetracarboxylic acid and its anhydride, preferably an aromatic tetracarboxylic acid compound such as a dianhydride thereof, and an aliphatic tetracarboxylic acid and its anhydride. , Preferably an aliphatic tetracarboxylic acid compound such as the dianhydride thereof.
  • the tetracarboxylic acid compound may be a tetracarboxylic acid compound derivative such as a tetracarboxylic acid chloride compound as well as an anhydride, and these may be used alone or in combination of two or more.
  • aromatic tetracarboxylic dianhydride examples include a non-condensed polycyclic aromatic tetracarboxylic dianhydride, a monocyclic aromatic tetracarboxylic dianhydride, and a condensed polycyclic aromatic tetra. Examples include carboxylic dianhydride. Examples of the non-condensed polycyclic aromatic tetracarboxylic dianhydride include 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride and 2,2'.
  • 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propanedianhydride, 2,2-bis (2,3-dicarboxyphenyl) Phenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic dianhydride (6FDA) may be described.
  • 1,2,4,5-benzenetetracarboxylic dianhydride 1,2,4,5-benzenetetracarboxylic dianhydride
  • 1,2,4,5-benzenetetracarboxylic dianhydride examples thereof include 2,3,6,7-naphthalenetetracarboxylic dianhydride.
  • Examples of the aliphatic tetracarboxylic dianhydride include cyclic or acyclic aliphatic tetracarboxylic dianhydride.
  • the cyclic aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure, and specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic dianhydride.
  • Cycloalkanetetracarboxylic dianhydride such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2] .2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl-3,3', 4,4'-tetracarboxylic dianhydride and their positional isomers are listed. Be done. These can be used alone or in combination of two or more.
  • acyclic aliphatic tetracarboxylic dianhydride examples include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride and the like. These can be used alone or in combination of two or more. Further, a cyclic aliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride may be used in combination.
  • the alicyclic tetracarboxylic dianhydride or non-condensation polycyclic aromatic is preferable from the viewpoint of easily improving the tensile elasticity, bending resistance, and optical properties of the transparent resin film.
  • examples include tetracarboxylic dianhydride. More preferred specific examples are 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3). , 4-Dicarboxyphenyl) propane dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic acid dianhydride (6FDA). These can be used alone or in combination of two or more.
  • the polyimide-based resin according to the present embodiment has a tetracarboxylic acid, a tricarboxylic acid compound, and a dicarboxylic acid in addition to the tetracarboxylic acid anhydride used in the above-mentioned polyimide synthesis, as long as the various physical properties of the obtained transparent resin film are not impaired. Acid compounds, their anhydrides and their derivatives may be further reacted.
  • the tricarboxylic acid compound examples include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, acid chloride compounds related thereto, acid anhydrides, and the like, and two or more of these may be used in combination.
  • Specific examples thereof include an anhydride of 1,2,4-benzenetricarboxylic acid, an acid chloride compound of 1,3,5-benzenetricarboxylic acid, and 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride.
  • examples thereof include compounds in which phthalic anhydride and benzoic acid are single-bonded, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or phenylene group linked. ..
  • dicarboxylic acid compound examples include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, acid chloride compounds related thereto, acid anhydrides, and the like, and two or more of these may be used in combination.
  • R 9 represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom.
  • the ratio of the tetracarboxylic acid compound to the total of the tetracarboxylic acid compound, the tricarboxylic acid compound, and the dicarboxylic acid compound is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol%.
  • the above is more preferably 90 mol% or more, and particularly preferably 98 mol% or more.
  • diamine used for synthesizing the polyimide resin examples include aliphatic diamines, aromatic diamines, and mixtures thereof.
  • aromatic diamine represents a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic group or other substituent may be contained in a part of the structure.
  • the aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. Among these, a benzene ring is preferable.
  • the "aliphatic diamine” represents a diamine in which an amino group is directly bonded to an aliphatic group, and an aromatic ring or other substituent may be contained as a part of the structure thereof.
  • aliphatic diamine examples include an acyclic aliphatic diamine such as hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, norbornanediamine, 4,4'.
  • acyclic aliphatic diamine such as hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, norbornanediamine, 4,4'.
  • -Cyclic aliphatic diamines such as diaminodicyclohexylmethane can be mentioned, and these can be used alone or in combination of two or more.
  • aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylene diamine, p-xylylene diamine, 1,5-diaminonaphthalene, and 2,6-diamino.
  • Aromatic amines with one aromatic ring such as naphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-Aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) Phen
  • aromatic diamine preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-Diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (Trifluoromethyl) -4,4'-diaminodiphenyl (TFMB),
  • the diamine may also have a fluorine-based substituent.
  • fluorine-based substituent include a perfluoroalkyl group having 1 to 5 carbon atoms such as a trifluoromethyl group and a fluoro group.
  • one or more selected from the group consisting of aromatic diamines having a biphenyl structure are preferably mentioned, and specific examples thereof include 2,2'-.
  • One or more selected from the group consisting of dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB) and 4,4'-bis (4-aminophenoxy) biphenyl Can be mentioned.
  • TFMB 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl
  • TFMB 2,2'-bis (4-aminophenoxy
  • the polyimide-based resin is represented by the formula (10), which is formed by polycondensation of a diamine and a tetracarboxylic acid compound (including a tetracarboxylic acid compound derivative such as an acid chloride compound and a tetracarboxylic acid dianhydride). It is a condensation type polymer containing a repeating structural unit.
  • tricarboxylic acid compounds including tricarboxylic acid compound derivatives such as acid chloride compounds and tricarboxylic acid anhydrides
  • dicarboxylic acid compounds including derivatives such as acid chloride compounds
  • the polyamide resin is a condensed polymer containing a repeating structural unit represented by the formula (13), which is formed by polycondensation of a diamine and a dicarboxylic acid compound (including a derivative such as an acid chloride compound). is there.
  • the repeating structural units represented by the formulas (10) and (11) are usually derived from diamines and tetracarboxylic acid compounds.
  • the repeating structural unit represented by the formula (12) is usually derived from a diamine and a tricarboxylic acid compound.
  • the repeating structural unit represented by the formula (13) is usually derived from a diamine and a dicarboxylic acid compound. Specific examples of the diamine, the tetracarboxylic acid compound, the tricarboxylic acid compound and the dicarboxylic acid compound are as described above.
  • the molar ratio of the diamine to the carboxylic acid compound such as the tetracarboxylic acid compound can be appropriately adjusted in the range of 0.9 mol or more and 1.1 mol or less of the tetracarboxylic acid with respect to 1.00 mol of the diamine. Since the obtained polyimide resin preferably has a high molecular weight in order to exhibit high folding resistance, it is more preferably 0.98 mol or more and 1.02 mol of tetracarboxylic acid with respect to 1.00 mol of diamine. It is more preferably 0.99 mol or more and 1.01 mol or less.
  • the ratio of amino groups in the obtained polymer terminal is low, and the carboxylic acid compound such as the tetracarboxylic acid compound with respect to 1.00 mol of diamine It is preferably 1.00 mol or more.
  • the amount of fluorine in the obtained polyimide resin is 1% by mass or more and 5 by mass based on the mass of the polyimide resin. It can be mass% or more, 10 mass% or more, and 20 mass% or more. Since the raw material cost tends to increase as the proportion of fluorine increases, the upper limit of the amount of fluorine is preferably 40% by mass or less.
  • the fluorinated substituents may be present in either the diamine or the carboxylic acid compound, or in both. In particular, the YI value may be reduced by including a fluorine-based substituent.
  • the polyimide resin according to the present embodiment may be a copolymer containing a plurality of the above-mentioned repeating structural units of different types.
  • the weight average molecular weight of the polyimide resin in terms of standard polystyrene is usually 100,000 to 800,000.
  • the weight average molecular weight of the polyimide resin is large, the flexibility at the time of film formation is improved, so that it is preferably 200,000 or more, more preferably 250,000 or more, and further preferably 280,000 or more. Is.
  • a varnish having an appropriate concentration and viscosity can be obtained and the film forming property tends to be improved, it is preferably 750,000 or less, more preferably 600,000 or less, and further preferably 500,000. It is as follows. Two or more types of polyimide resins having different weight average molecular weights may be used in combination. Further, other polymer materials may be mixed as long as the physical properties are not impaired.
  • the polyimide-based resin and the polyamide-based resin tend to have an improved tensile elastic modulus and a reduced YI value when they are formed into a film by containing a fluorine-containing substituent.
  • the polyimide resin and the polyamide resin preferably have a fluorine-containing substituent.
  • the fluorine-containing substituent include a fluoro group and a trifluoromethyl group.
  • the content of fluorine atoms in the polyimide resin and the mixture of the polyimide resin and the polyamide resin is preferably based on the mass of the polyimide resin or the total of the mass of the polyimide resin and the mass of the polyamide resin, respectively. It is 1% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 40% by mass or less.
  • the content of fluorine atoms is in the above range, the YI value at the time of film formation tends to be further reduced and the transparency tends to be further improved.
  • the content of the polyimide resin and / or the polyamide resin in the resin composition constituting the transparent resin film is preferably 40% by mass or more, more preferably 50% by mass, based on the solid content of the resin composition. % Or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 100% by mass.
  • the solid content refers to the total amount of the components excluding the solvent from the resin composition.
  • the imidization ratio of the polyimide resin and the polyamide-imide resin is preferably 90% or more, more preferably 93% or more, still more preferably 96% or more. From the viewpoint of easily increasing the optical homogeneity of the optical film and / or the optical laminate, the imidization ratio is preferably at least the above lower limit. The upper limit of the imidization rate is 100% or less.
  • the imidization ratio indicates the ratio of the molar amount of imide bond in the polyimide resin and the polyamide-imide resin to the value twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin or the polyamide-imide resin.
  • the value is twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin and the polyamide-imide resin, and the value is derived from the tricarboxylic acid compound.
  • the ratio of the molar amount of the imide bond in the polyimide resin and the polyamide-imide resin to the total amount of the molar amount of the constituent unit to be formed is shown.
  • the imidization rate can be determined by an IR method, an NMR method, or the like. For example, in the NMR method, it can be measured by the method described in Examples.
  • the resin composition forming the transparent resin film may further contain an inorganic material such as inorganic particles in addition to the above-mentioned polyimide-based resin and / or polyamide-based resin.
  • the inorganic material include inorganic particles such as silica particles, titanium particles, aluminum hydroxide, zirconia particles, and barium titanate particles, and silicon compounds such as quaternary alkoxysilane such as tetraethyl orthosilicate. From the viewpoint of the stability of the varnish and the dispersibility of the inorganic material, silica particles, aluminum hydroxide, zirconia particles, and more preferably silica particles are preferable.
  • the average primary particle size of the inorganic material particles is preferably 10 to 100 nm, more preferably 10 to 90 nm, still more preferably 10 to 50 nm, and even more preferably 10 to 30 nm.
  • the average primary particle size of the silica particles is 100 nm or less, the transparency tends to be improved.
  • the average primary particle size of the silica particles is 10 nm or more, the cohesive force of the silica particles is weakened, so that the silica particles tend to be easy to handle.
  • the silica particles may be a silica sol in which silica particles are dispersed in a solvent or the like, or silica fine particle powder produced by the vapor phase method may be used, but the silica particles are produced by the liquid phase method because they are easy to handle. It is preferably a silica sol.
  • the average primary particle size of the silica particles in the transparent resin film can be determined by observation with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the particle size distribution of the silica particles before forming the transparent resin film can be obtained by a commercially available laser diffraction type particle size distribution meter.
  • the content thereof when the resin composition contains an inorganic material, the content thereof is preferably 0.001% by mass or more and 90% by mass or less, more preferably 0.% by mass, based on the solid content of the resin composition. It is 001% by mass or more and 60% by mass or less, and more preferably 0.001% by mass or more and 40% by mass or less.
  • the solid content refers to the total amount of the components excluding the solvent from the resin composition.
  • the resin composition constituting the transparent resin film may further contain other components in addition to the components described above.
  • Other components include, for example, antioxidants, mold release agents, light stabilizers, bluing agents, flame retardants, lubricants and leveling agents.
  • the content of the other components is preferably 0.001% or more with respect to the total mass of the transparent resin film. It is 20% by mass or less, more preferably 0.001% or more and 10% by mass or less.
  • the transparent resin film is, for example, a reaction solution of a polyimide resin and / or a polyamide resin obtained by selecting and reacting with the tetracarboxylic acid compound, the diamine and the other raw materials, if necessary. It can be produced from a resin varnish prepared by adding a solvent to a resin composition containing an inorganic material and other components, mixing and stirring.
  • a solution of the purchased polyimide resin or the like or a solution of the purchased solid polyimide resin or the like may be used instead of the reaction solution of the polyimide resin or the like.
  • the solvent that can be used for preparing the resin varnish a solvent capable of dissolving or dispersing a resin component such as a polyimide resin can be appropriately selected.
  • the boiling point of the solvent is preferably 120 to 300 ° C., more preferably 120 to 270 ° C., still more preferably 120 to 250 ° C., and particularly preferably 120 to 120 ° C. It is 230 ° C.
  • Such a solvent include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; and lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone; Ketone solvents such as cyclohexanone, cyclopentanone and methyl ethyl ketone; acetate solvents such as butyl acetate and amyl acetate; sulfur-containing solvents such as dimethyl sulfoxide, dimethyl sulfoxide and sulfolane, carbonate solvents such as ethylene carbonate and propylene carbonate, etc. Can be mentioned.
  • amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone
  • lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone
  • Ketone solvents such as cyclohexanone, cyclopent
  • N N-dimethylacetamide (boiling point: 165 ° C.), ⁇ -butyrolactone (boiling point: 204 ° C.), N-methylpyrrolidone (boiling point: 202 ° C.) because of its excellent solubility in polyimide-based resin and polyamide-based resin.
  • the solvent one type may be used alone, or two or more types may be used in combination. When two or more kinds of solvents are used, it is preferable to select the type of solvent so that the boiling point of the solvent having the highest boiling point among the solvents used falls within the above range.
  • the amount of the solvent may be selected so as to have a viscosity that allows the resin varnish to be handled, and is not particularly limited.
  • the amount of the solvent is preferably 50 to 95% by mass, more preferably 70 to 95, based on the total amount of the resin varnish. It is by mass, more preferably 80 to 95% by mass.
  • the transparent resin film of the present invention can be obtained by applying the above resin varnish on a support and pre-drying it.
  • the transparent resin film is releasably laminated on the support.
  • the fact that the film can be peeled off means that the shape of the film can be maintained and the film can be peeled off from the support without breaking.
  • it means that the solvent is dried by pre-drying so that an appropriate amount of solvent remains.
  • the amount of residual solvent is too large, the shape of the film cannot be maintained, and if the amount of residual solvent is too small, the adhesion to the support becomes too high and the film breaks at the time of peeling.
  • the appropriate amount of residual solvent varies depending on the type of resin composition, solvent, and support of the transparent resin film, and needs to be adjusted as appropriate.
  • the content of the solvent in the transparent resin film is 0.1% by mass or more with respect to the total mass of the transparent resin film.
  • the upper limit of the solvent content in the transparent resin film is not particularly limited as long as the shape can be maintained as a film, but is usually 50% by mass or less with respect to the total mass of the transparent resin film.
  • the thickness of the resin plate-like body is preferably 10 to 200 ⁇ m. By adjusting the thickness of the resin plate-like body within this range, it becomes easy to improve the bending resistance while maintaining the impact resistance.
  • the thickness of the resin plate-like body is more preferably 20 to 100 ⁇ m, still more preferably 30 to 80 ⁇ m.
  • the yellowness (YI value) of the transparent resin film is preferably 3.0 or less, more preferably 2.7 or less, still more preferably 2.5 or less, and particularly preferably 2.0 or less.
  • the yellowness is usually ⁇ 5 or more, preferably ⁇ 2 or more, more preferably 0 or more, still more preferably 0.3 or more, still more preferably 0.5 or more, and particularly preferably 0.7 or more.
  • the total light transmittance of the transparent resin film is preferably 80% or more, more preferably 85% or more, still more preferably 89%, and even more preferably 90% or more.
  • the upper limit of the total light transmittance is usually 100% or less.
  • the total light transmittance can be measured using a haze computer in accordance with, for example, JIS K 7361-1: 1997.
  • the haze of the transparent resin film is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, even more preferably 0.5% or less, and particularly preferably 0.3%. It is as follows. When the haze of the transparent resin film is not more than the above upper limit, the transparency is good, and when it is used for the front plate of an image display device, for example, the visibility of an image can be easily improved.
  • the lower limit of haze is usually 0.01% or more.
  • the haze can be measured using a haze computer in accordance with JIS K 7136: 2000.
  • the front plate 1 may be a film having a hard coat layer provided on at least one surface of the base film to further improve the hardness.
  • a film made of the above resin can be used as the base film.
  • the hard coat layer may be formed on one surface of the base film or may be formed on both surfaces. By providing the hard coat layer, a resin film having improved hardness and scratchability can be obtained.
  • the hard coat layer is, for example, a cured layer of an ultraviolet curable resin. Examples of the ultraviolet curable resin include acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, epoxy resin and the like.
  • the hard coat layer may contain additives to improve strength. Additives are not limited, and examples thereof include inorganic fine particles, organic fine particles, and mixtures thereof.
  • the front plate 1 may have a function as a window film in the display device.
  • the front plate 1 may have a blue light cut function, a viewing angle adjusting function, and the like.
  • the front plate 1 can be a layer constituting the outermost surface of the display device.
  • the thickness of the front plate 1 is preferably 20 to 220 ⁇ m. By adjusting the thickness of the front plate 1 within this range, it becomes easy to improve the bending resistance while maintaining the impact resistance, and it is also possible to impart hardness.
  • the thickness of the front plate 1 is more preferably 35 to 110 ⁇ m, still more preferably 40 to 90 ⁇ m.
  • the tensile elastic modulus of the front plate is preferably 3 GPa or more, more preferably 4 GPa or more, further preferably 5 GPa or more, preferably 10 GPa or less, and more preferably 9 GPa or less.
  • the tensile elastic modulus may satisfy at least one of MD (Machine Direction, film forming direction) or TD (Transverse Direction, direction perpendicular to MD), and it is preferable that both of them satisfy the above range.
  • the pressure-sensitive adhesive layer is located between the non-adhesive layers constituting the optical laminate or between the non-adhesive layer constituting the optical laminate and an adherend such as a display unit.
  • the pressure-sensitive adhesive layer is a layer that connects members existing on both sides thereof.
  • the optical laminate 10 has a first pressure-sensitive adhesive layer 2 and a second pressure-sensitive adhesive layer 4.
  • the first pressure-sensitive adhesive layer 2 is located between the front plate 1 and the impact-resistant layer 3 described later, and binds the two.
  • the second pressure-sensitive adhesive layer is located on the inner surface of the impact-resistant layer 3 and bonds the impact-resistant layer and the adherend. Examples of the adherend include a polarizing plate of a display unit, a circular polarizing plate, a touch sensor, and the like.
  • Each pressure-sensitive adhesive layer may be made of the same material or different materials.
  • the pressure-sensitive adhesive layer can be composed of a pressure-sensitive adhesive composition containing a resin as a main component, such as (meth) acrylic-based, rubber-based, urethane-based, ester-based, silicone-based, and polyvinyl ether-based. Among them, a pressure-sensitive adhesive composition using a (meth) acrylic resin having excellent transparency, weather resistance, heat resistance and the like as a base polymer is preferable.
  • the pressure-sensitive adhesive composition may be an active energy ray-curable type or a thermosetting type.
  • Examples of the (meth) acrylic resin (base polymer) used in the pressure-sensitive adhesive composition include butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2- (meth) acrylate.
  • a polymer or copolymer containing one or more (meth) acrylic acid esters such as ethylhexyl as a monomer is preferably used. It is preferable that the base polymer is copolymerized with a polar monomer.
  • Examples of the polar monomer include (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and glycidyl ().
  • Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group and the like, such as meta) acrylate.
  • the pressure-sensitive adhesive composition may contain only the above-mentioned base polymer, but usually further contains a cross-linking agent.
  • the cross-linking agent is a divalent or higher metal ion that forms a carboxylic acid metal salt with a carboxyl group; a polyamine compound that forms an amide bond with a carboxyl group; poly.
  • the active energy ray-curable pressure-sensitive adhesive composition has a property of being cured by being irradiated with active energy rays such as ultraviolet rays and electron beams, and has adhesiveness even before irradiation with active energy rays. It is a pressure-sensitive adhesive composition having the property of being able to adhere to an adherend such as, etc., and being cured by irradiation with active energy rays to adjust the adhesion force.
  • the active energy ray-curable pressure-sensitive adhesive composition is preferably an ultraviolet-curable type.
  • the active energy ray-curable pressure-sensitive adhesive composition further contains an active energy ray-polymerizable compound in addition to the base polymer and the cross-linking agent. Further, if necessary, a photopolymerization initiator, a photosensitizer, or the like may be contained.
  • the pressure-sensitive adhesive composition includes fine particles for imparting light scattering, beads (resin beads, glass beads, etc.), glass fibers, resins other than the base polymer, pressure-sensitive adhesives, fillers (metal powders and other inorganic powders). Etc.), antioxidants, UV absorbers, dyes, pigments, colorants, antifoaming agents, corrosion inhibitors, photopolymerization initiators and other additives may be included.
  • the formed pressure-sensitive adhesive layer can be irradiated with active energy rays to obtain a cured product having a desired degree of curing.
  • the adhesive layer has viscoelasticity and has a function of alleviating the impact applied to the optical laminate.
  • the bending resistance is improved by appropriately adjusting the viscoelasticity of the pressure-sensitive adhesive layer or selecting a pressure-sensitive adhesive layer having appropriate viscoelasticity.
  • the static viscoelasticity measurement method is a method for measuring the response time and temperature change in response to steady strain and stress, and specifically.
  • stress relaxation measurement which measures the stress by applying a constant strain to the measurement sample
  • creep & recovery method which measures the strain by applying a constant stress.
  • the dynamic viscoelasticity measurement is a method of applying a strain of a sinusoidal waveform to a measurement sample and measuring the corresponding strain or stress signal.
  • the temperature dependence of the glass transition temperature and elastic modulus can be analyzed by the temperature dispersion measurement.
  • various relaxation phenomena including glass transition can be observed, and knowledge about the molecular structure and molecular motion of the polymer can be obtained.
  • the elastic modulus G * which is the ratio of stress and strain, is expressed by the following equation in the range where response signals of the same frequency are observed.
  • G' represents the storage elastic modulus
  • ⁇ represents the measurement frequency
  • G'( ⁇ ) is a measure of the energy stored in a given strain
  • G'( ⁇ ) is a measure of the rate at which energy is dissipated due to phase shift due to the viscous behavior of the sample.
  • the energy applied to the system by repeated dynamic deformation such as bending resistance test is consumed as the deformation energy of the system or dissipated as heat.
  • the deformation energy of the system is consumed in part as elastic energy and in another part in the destruction of the system.
  • the energy that is mechanically dissipated as elastic energy or the like as described above is usually released by molecular relaxation of the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer. It is stored in the stratified system. This causes the temperature of the pressure-sensitive adhesive layer to rise, and as a result and / or the stored energy contributes to the destruction of the system as interfacial peeling energy, so that the pressure-sensitive adhesive layer and the adherend layer are separated from each other. Is considered to be even more likely to occur.
  • the bending resistance of the optical laminate of the present invention is affected by the tan ⁇ of the pressure-sensitive adhesive layer and its position in the laminated structure. That is, it was found that the lower the tan ⁇ of the pressure-sensitive adhesive layer located on the outer side when bending the optical laminate, the more effective it is for improving the bending resistance.
  • the tan ⁇ of the second pressure-sensitive adhesive layer of the optical laminate of the present invention at ⁇ 20 ° C. is less than 1.23.
  • the tan ⁇ of the second pressure-sensitive adhesive layer at ⁇ 20 ° C. is preferably 0.01 to 1.20, more preferably 0.06 to 0.8.
  • the tan ⁇ of the second pressure-sensitive adhesive layer of the optical laminate at ⁇ 20 ° C. is preferably 0.03 to 1.00, more preferably 0.05 to 0.80, still more preferably 0.06 to 0.06. It is 0.70.
  • the storage elastic modulus of the second pressure-sensitive adhesive layer at ⁇ 20 ° C. is preferably 0.01 to 25.00 MPa.
  • the storage elastic modulus of the second pressure-sensitive adhesive layer at ⁇ 20 ° C. is 0.01 MPa or more, the impact resistance of the optical laminate is improved, and when it is 25.00 MPa or less, the bending resistance of the optical laminate is improved.
  • the storage elastic modulus of the second pressure-sensitive adhesive layer at ⁇ 20 ° C. is preferably 0.01 to 25.00 MPa, more preferably 0.10 to 25.00 MPa.
  • the storage elastic modulus of the second pressure-sensitive adhesive layer at 25 ° C. has a storage elastic modulus of 0.01 to 0.80 MPa.
  • the storage elastic modulus of the pressure-sensitive adhesive layer is 0.01 MPa or more, the impact resistance of the optical laminate is improved, and when it is 0.80 MPa or less, the flexibility of the optical laminate is improved. It is preferably 0.02 to 0.75 MPa, more preferably 0.03 to 0.70 MPa.
  • the thickness of the second pressure-sensitive adhesive layer is preferably 5 to 100 ⁇ m. When the thickness of the second pressure-sensitive adhesive layer is 5 ⁇ m or more, the impact resistance of the optical laminate is improved, and when the thickness of the second pressure-sensitive adhesive layer is 100 ⁇ m or less, the flexibility is improved.
  • the thickness of the second pressure-sensitive adhesive layer is more preferably 5 to 85 ⁇ m, still more preferably 15 to 85 ⁇ m, and may be 25 to 50 ⁇ m.
  • the tan ⁇ of the first pressure-sensitive adhesive layer at ⁇ 20 ° C. is preferably 0.1 to 1.2, more preferably 0.1 to 1.0.
  • the storage elastic modulus of the first pressure-sensitive adhesive layer at ⁇ 20 ° C. is preferably 0.01 to 25.00 MPa, more preferably 0.10 to 25.00 MPa.
  • the storage elastic modulus of the first pressure-sensitive adhesive layer at 25 ° C. has a storage elastic modulus of 0.01 to 0.80 MPa.
  • the thickness of the first pressure-sensitive adhesive layer is preferably 5.0 to 50.0 ⁇ m, more preferably 5.0 to 25.0 ⁇ m.
  • the impact-resistant layer 3 is located in the internal direction of the front plate, and has a function of alleviating the impact when an impact is applied to the front surface of the display device and preventing damage to the wiring of the display panel, elements, and the like.
  • the impact resistant layer 3 preferably has a function of improving the bending resistance of the optical laminate.
  • the deformation energy applied to the material reaches the threshold value, and the material is damaged such as breakage, cracks or wrinkles.
  • the impact-resistant layer is preferably a material having a large tolerance for deformation energy, for example, a thermoplastic resin that is hard and tenacious (that is, has a large toughness).
  • a thermoplastic resin that is hard and tenacious (that is, has a large toughness).
  • resins include polycarbonate-based resins, polyimide-based resins, polyamide-based resins, polyamide-imide-based resins, and polyester-based resins.
  • a resin having excellent translucency preferably optically transparent.
  • the impact resistant layer preferably has a tensile elastic modulus of 0.1 to 10 GPa.
  • the tensile elastic modulus of the impact-resistant layer is 0.1 GPa or more, the impact resistance of the optical laminate is improved, and when it is 10 GPa or less, the flexibility of the optical laminate is improved.
  • the tensile elastic modulus of the impact-resistant layer is preferably 1.0 to 8.0 GPa, and more preferably 3.0 to 7.0 GPa.
  • the tensile elastic modulus may satisfy at least one of MD (Machine Direction, film forming direction) or TD (Transverse Direction, direction perpendicular to MD), and it is preferable that both of them satisfy the above range.
  • the impact resistant layer may be an impact resistant layer having an optical function such as a retardation film or a brightness improving film.
  • a retardation film to which an arbitrary retardation value is imparted by stretching a film made of the thermoplastic resin (uniaxial stretching, biaxial stretching, etc.) or forming a liquid crystal layer or the like on the film. can be.
  • the tan ⁇ of the impact resistant layer at ⁇ 20 ° C. is 0.001 to 0.020. If the tan ⁇ of the impact-resistant layer at ⁇ 20 ° C. is less than 0.001, the impact resistance of the optical laminate tends to decrease, and if it exceeds 0.020, the bending resistance of the optical laminate tends to decrease.
  • the tan ⁇ of the impact resistant layer at ⁇ 20 ° C. is preferably 0.001 to 0.020, more preferably 0.005 to 0.020.
  • the impact resistant layer has a thickness of 5 to 140 ⁇ m.
  • the thickness of the impact resistant layer is preferably 10 to 120 ⁇ m, more preferably 40 to 100 ⁇ m.
  • the optical laminate of the present invention is produced by bonding a front plate and an impact-resistant layer using an adhesive layer and forming an adhesive layer on the inner surface of the impact-resistant layer.
  • an adhesive layer may be formed on the bonding surface of one layer and then the other layer may be laminated, or the adhesive layer may be adhered to the bonding surface of both layers.
  • the pressure-sensitive adhesive layers may be combined with each other.
  • the method of forming the pressure-sensitive adhesive layer on the surface to which the layers are bonded may be formed by using the pressure-sensitive adhesive composition as described above, or a sheet-like pressure-sensitive adhesive that can be handled independently is prepared and used. It may be formed by sticking it on the surface.
  • the optical laminate includes, for example, a front plate 1, a first adhesive layer 2, an impact resistant layer 3, and a second adhesive layer 4 in this order from the visual side, it is resistant.
  • the ratio r of the impact layer thickness a to the thickness c of the second pressure-sensitive adhesive layer is preferably 5.5 or less from the viewpoint of bending resistance of the optical laminate.
  • the ratio r is preferably 5.5 or less, more preferably 5.0 or less, and even more preferably 1 to 4.
  • the total thickness of the first pressure-sensitive adhesive layer, the impact-resistant layer, and the second pressure-sensitive adhesive layer is 100 to 200 ⁇ m.
  • the total thickness of the pressure-sensitive adhesive layer and the impact-resistant layer is 100 ⁇ m or more, the impact resistance of the optical laminate is improved, and when it is 200 ⁇ m or less, the bending resistance of the optical laminate is improved.
  • the total thickness is preferably 100 ⁇ m to 190 ⁇ m, more preferably 120 to 180 ⁇ m, and may be 120 to 190 ⁇ m.
  • the optical laminate has excellent bending resistance.
  • the bending resistance refers to a characteristic that the adhesive layer does not peel or break at the bent portion when the front plate of the optical laminate is bent inside.
  • the bending radius at the time of bending is, for example, 5 mm or less, preferably 3 mm or less, and more preferably 1 mm or less.
  • the bending speed at the time of bending is, for example, 30 to 60 rpm, preferably 30 rpm or less. The number of times of bending may decrease when the bending speed is slow, but the optical laminate in the present invention has high bending resistance even when the bending speed is slow.
  • the optical laminate is usually 100,000 times when a continuous flexibility test is performed in which the impact resistant layer and the second pressure-sensitive adhesive layer are continuously bent and stretched by 180 ° with the front plate inside until peeling occurs.
  • the bending resistance is preferably 150,000 times or more, more preferably 200,000 times or more.
  • the conditions of the continuous bending test are a temperature of 25 ° C., a bending speed of 30 rpm, and a bending radius of 1.00 mm.
  • FIG. 2 is a cross-sectional view showing an example of the structure of the display device of the present invention.
  • the display device 20 has an optical laminate 10 arranged on the front surface (visual side) thereof, and a display unit 5.
  • the display unit may be configured to be foldable with the surface on the viewing side inside, or may be configured to be retractable. Further, the display unit may be configured as a touch panel type display device.
  • Specific examples of the display unit include a laminated body in which a touch sensor layer and a polarizing layer are formed on the display surface of the display element.
  • Specific examples of the display element include a liquid crystal display element, an organic EL display element, an inorganic EL display element, a plasma display element, and a field emission type display element.
  • the display device 20 can be used as a mobile device such as a smartphone or tablet, a television, a digital photo frame, an electronic signage, a measuring instrument or an instrument, an office device, a medical device, a computer device, or the like.
  • a mobile device such as a smartphone or tablet, a television, a digital photo frame, an electronic signage, a measuring instrument or an instrument, an office device, a medical device, a computer device, or the like.
  • the unit "part" of the ratio of the substance to be blended is based on mass unless otherwise specified.
  • TFMB 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl
  • DMAc N, N-dimethylacetamide
  • the temperature inside the container was raised to 70 ° C. using an oil bath, maintained at 70 ° C., and stirred for another 3 hours to obtain a reaction solution.
  • the obtained reaction solution was cooled to room temperature and poured into a large amount of methanol in the form of filaments to precipitate a precipitate.
  • the precipitated precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C. to obtain a polyamide-imide resin 1.
  • the weight average molecular weight of the obtained polyamide-imide resin 1 was 400,000, and the imidization rate was 99.0%.
  • the imidization ratio was determined by 1 H-NMR measurement as follows. (1) Pretreatment method A sample was dissolved in deuterated dimethyl sulfoxide (DMSO-d 6 ) to prepare a 2% by mass solution, which was used as a measurement solution.
  • DMSO-d 6 deuterated dimethyl sulfoxide
  • ⁇ Manufacturing example 2 Production of Optical Film for Front Plate
  • GBL ⁇ -butyrolactone
  • the thickness of the self-supporting film is 55 ⁇ m on the smooth surface of the polyester base material (“A4100” (trade name) manufactured by Toyobo Co., Ltd.). It was applied, saliva-molded, and a varnish coating was formed. At this time, the linear velocity was 0.8 m / min.
  • ⁇ Manufacturing example 4 Manufacture of front plate Roll-to-roll the photocurable resin composition prepared in Production Example 3 on one side of the polyamide-imide film (optical film) produced in Production Example 2 so that the thickness after drying is 10 ⁇ m. It was painted by the method. Then, the coating film was dried in an oven at 80 ° C. for 3 minutes, and the coating film was irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the photocurable resin composition to obtain a front plate. The integrated light intensity of the irradiated ultraviolet rays was set to 500 mJ / cm 2 . The thickness of the hard coat layer on the front plate was 10 ⁇ m. The tensile elastic modulus of the obtained front plate (including the hard coat layer) was 6.5 GPa.
  • ⁇ Manufacturing example 5> A reactor equipped with a silica gel tube, a stirrer and a thermometer in a synthetic separable flask made of polyimide (PI) resin, and an oil bath were prepared. In this flask, 75.52 g of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB) 54.44 g was added. While stirring this at 400 rpm, 519.84 g of N, N-dimethylacetamide (DMAc) was added, and stirring was continued until the contents of the flask became a uniform solution.
  • 6FDA 4,4'-(hexafluoroisopropylidene) diphthalic anhydride
  • TFMB 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl
  • stirring was continued for another 20 hours while adjusting the temperature inside the container to be in the range of 20 to 30 ° C. using an oil bath, and the reaction was carried out to generate a polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the reaction system temperature was returned to room temperature, and 649.8 g of DMAc was added to adjust the polymer concentration to 10% by mass. Further, 32.27 g of pyridine and 41.65 g of acetic anhydride were added, and the mixture was stirred at room temperature for 10 hours for imidization. The polyimide varnish was taken out from the reaction vessel.
  • the obtained polyimide varnish was dropped into methanol for reprecipitation, and the obtained powder was heated and dried to remove the solvent to obtain a transparent polyimide resin as a solid content.
  • the weight average molecular weight was 360,000.
  • PI Polyimide
  • the thickness of the free-standing film is 85 ⁇ m on the smooth surface of the polyester base material (“A4100” (trade name) manufactured by Toyobo Co., Ltd.).
  • A4100 trade name
  • the obtained coating film was peeled off from the polyester substrate to obtain a self-supporting film.
  • the free-standing film was fixed to a gold frame and further dried in the atmosphere at 200 ° C. for 40 minutes to obtain a polyimide film (optical film) having a thickness of 80 ⁇ m.
  • Example 1 Production of Optical Laminate A polyimide (PI) film having a thickness of 80 ⁇ m and a tensile elastic modulus of 4.0 GPa obtained in Production Example 6 was prepared as an impact resistant layer.
  • the PI film had a tan ⁇ of 0.014 at ⁇ 20 ° C.
  • the first pressure-sensitive adhesive layer As the first pressure-sensitive adhesive layer, a (meth) acrylic pressure-sensitive adhesive layer having a storage elastic modulus of 0.1 MPa at 25 ° C. was prepared.
  • the pressure-sensitive adhesive layer had a thickness of 25 ⁇ m, a storage elastic modulus at ⁇ 20 ° C. of 0.21 MPa, and a tan ⁇ at ⁇ 20 ° C. of 0.64.
  • a (meth) acrylic pressure-sensitive adhesive layer having a storage elastic modulus of 0.1 MPa at 25 ° C. was prepared.
  • the pressure-sensitive adhesive layer had a thickness of 25 ⁇ m, a storage elastic modulus at ⁇ 20 ° C. of 0.21 MPa, and a tan ⁇ at ⁇ 20 ° C. of 0.64.
  • the front plate obtained in Production Example 4 and the impact resistant layer were laminated via the first pressure-sensitive adhesive layer.
  • the second pressure-sensitive adhesive layer was laminated on the surface on which the first pressure-sensitive adhesive layer of the impact-resistant layer was not laminated to prepare an optical laminate.
  • Example 2 Example 1 and Example 1 except that a polyethylene terephthalate (PET) film having a thickness of 80 ⁇ m (tensile elastic modulus 4.6 GPa, tan ⁇ at -20 ° C: 0.007) was used as the impact resistant layer instead of the polyimide film. In the same manner, an optical laminate was produced.
  • PET polyethylene terephthalate
  • Example 3 As the second pressure-sensitive adhesive layer, a layer having a storage elastic modulus at ⁇ 20 ° C. of 0.11 MPa and a tan ⁇ at ⁇ 20 ° C. of 0.63 was used in the same manner as in Example 2. An optical laminate was produced.
  • Example 4 As the second pressure-sensitive adhesive layer, a layer having a storage elastic modulus at ⁇ 20 ° C. of 0.19 MPa and a tan ⁇ at ⁇ 20 ° C. of 0.06 was used in the same manner as in Example 2. An optical laminate was produced.
  • Example 5 As the second pressure-sensitive adhesive layer, a layer having a storage elastic modulus at ⁇ 20 ° C. of 4.03 MPa and a tan ⁇ at ⁇ 20 ° C. of 0.80 was used in the same manner as in Example 2. An optical laminate was produced.
  • Example 6 As the first pressure-sensitive adhesive layer, a layer having a storage elastic modulus at ⁇ 20 ° C. of 28.06 MPa and a tan ⁇ at ⁇ 20 ° C. of 1.23 was used in the same manner as in Example 2. An optical laminate was produced.
  • Example 7 As the impact resistant layer, a PET film having a thickness of 50 ⁇ m and a tensile elastic modulus of 4.6 GPa was used instead of the polyimide film, and as the second adhesive layer, the storage elastic modulus at ⁇ 20 ° C. was 0.09 MPa. , An optical laminate was produced in the same manner as in Example 1 except that the tan ⁇ at ⁇ 20 ° C. was 0.52.
  • Example 8> As the impact resistant layer, a PET film having a thickness of 100 ⁇ m and a tensile elastic modulus of 4.6 GPa was used instead of the polyimide film, and as the second adhesive layer, the storage elastic modulus at ⁇ 20 ° C. was 0.18 MPa. , An optical laminate was produced in the same manner as in Example 1 except that the tan ⁇ at ⁇ 20 ° C. was 0.93.
  • ⁇ Comparative example 1> As the second pressure-sensitive adhesive layer, a layer having a storage elastic modulus at ⁇ 20 ° C. of 28.06 MPa and a tan ⁇ at ⁇ 20 ° C. of 1.23 was used in the same manner as in Example 2. An optical laminate was produced.
  • thermoplastic polyurethane (TPU) film was prepared instead of the polyethylene terephthalate film.
  • This TPU film had a thickness of 150 ⁇ m, a tensile elastic modulus of 0.03 GPa, and a tan ⁇ of 0.022 at ⁇ 20 ° C.
  • the first pressure-sensitive adhesive layer As the first pressure-sensitive adhesive layer, a (meth) acrylic pressure-sensitive adhesive layer having a storage elastic modulus of 0.14 MPa at 25 ° C. was prepared.
  • the pressure-sensitive adhesive layer had a thickness of 25 ⁇ m, a storage elastic modulus at ⁇ 20 ° C. of 28.06 MPa, and a tan ⁇ at ⁇ 20 ° C. of 1.23.
  • a (meth) acrylic pressure-sensitive adhesive layer having a storage elastic modulus of 0.1 MPa at 25 ° C. was prepared.
  • the pressure-sensitive adhesive layer had a thickness of 25 ⁇ m, a storage elastic modulus at ⁇ 20 ° C. of 28.06 MPa, and a tan ⁇ at ⁇ 20 ° C. of 1.23.
  • the front plate obtained in Production Example 4 and the impact resistant layer were laminated via the first pressure-sensitive adhesive layer.
  • the second pressure-sensitive adhesive layer was laminated on the surface on which the first pressure-sensitive adhesive layer of the impact-resistant layer was not laminated to prepare an optical laminate.
  • the yellowness (Yellow Index: YI value) of the optical film was measured using a spectrocolorimeter CM-3700A manufactured by Konica Minolta Co., Ltd. Specifically, after performing background measurement in the absence of a sample, an optical laminate is set in a sample holder, transmittance measurement for light of 300 to 800 nm is performed, and tristimulus values (X, Y, Z) are performed. ) was calculated, and the YI value was calculated based on the following formula.
  • Total light transmittance The total light transmittance (Tt) was measured by a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. in accordance with JIS K 7105: 1981.
  • a pressure image analysis system (“FPD-8010J” (trade name) manufactured by FUJIFILM Corporation) was used to measure the bottom pressure.
  • the weight had a mass of 5.6 g and was spherical.
  • the point where the weight collided with the optical laminate was a circle with a diameter of 0.75 mm. This test was performed 3 times.
  • the average value of the bottom pressure obtained in the three measurements was evaluated according to the following criteria.
  • the bending resistance test was performed at a temperature of 25 ° C.
  • the optical laminates obtained in Examples and Comparative Examples were cut into a size of 10 mm width using a dumbbell cutter.
  • the cut optical laminate is set on the jig of a surface-state no-load U-shaped expansion / contraction tester ("DMLHB-FS" (trade name) manufactured by Yuasa System Co., Ltd.) so that it can be bent with the front plate inside.
  • the operation of bending and extending by 180 ° was repeated so that the distance between the facing front plates was 2.0 mm (bending radius of 1 mm).
  • the bending speed was 30 rpm.
  • the number of times the optical laminate was bent between the impact-resistant layer and the pressure-sensitive adhesive layer until it was peeled off and whitened was recorded as the number of times of bending.
  • the number of bending resistances was evaluated as follows.
  • Bending resistance is 200,000 or more ⁇ ... Bending resistance is 150,000 or more and less than 200,000 ⁇ ... Bending resistance is 100,000 or more and less than 150,000 ⁇ ... Bending resistance is less than 100,000
  • ⁇ Tension modulus> The impact-resistant layer and the front plate used in Examples and Comparative Examples were cut into strips of 10 mm ⁇ 100 mm using a dumbbell cutter to obtain samples. Using "Autograph AG-IS" (trade name) manufactured by Shimadzu Corporation, the tensile elastic modulus of this sample was measured by measuring the SS curve under the conditions of a distance between chucks of 500 mm and a tensile speed of 10 mm / min, and its inclination. The tensile elastic modulus of the impact-resistant layer was calculated from. The tensile elastic modulus was measured in an environment with a temperature of 23 ° C. and a relative humidity of 55%.
  • ⁇ Dynamic viscoelastic property (tan ⁇ of impact resistant layer)> From the tan ⁇ curve of the loss elastic modulus and the storage elastic modulus measured in the following measurement modes using a dynamic viscoelasticity measuring device (“DMA Q800” (trade name) manufactured by TA Instrument), at -20 ° C. The tan ⁇ was calculated. Sample: Length 5-15 mm, Width 5 mm Experimental mode: DMA Multi-Frequency-Strin
  • the condition is that the frequency is 1.0 Hz, the deformation amount is 1%, and the temperature rise rate is 5 ° C / min in the temperature range of -20 ° C to 100 ° C in the state of being adhered to the measurement chip.
  • the storage elastic modulus values at ⁇ 20 ° C. and 25 ° C. were confirmed.
  • the thickness of the hard coat layer was measured using a "F20 desktop film thickness system” (trade name) manufactured by Filmetics.
  • Example 6 a pressure-sensitive adhesive composition having a tan ⁇ of 1.23 at ⁇ 20 ° C. was used for the first pressure-sensitive adhesive layer, but no decrease in bending resistance was observed.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Liquid Crystal (AREA)
  • Polarising Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Electroluminescent Light Sources (AREA)
PCT/JP2020/036642 2019-10-28 2020-09-28 光学積層体及び表示装置 WO2021084999A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020217014962A KR102359353B1 (ko) 2019-10-28 2020-09-28 광학 적층체 및 표시장치
CN202080006638.XA CN113167932A (zh) 2019-10-28 2020-09-28 光学层叠体和显示装置

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019195592 2019-10-28
JP2019-195592 2019-10-28
JP2020-136374 2020-08-12
JP2020136374A JP6869409B2 (ja) 2019-10-28 2020-08-12 光学積層体及び表示装置

Publications (1)

Publication Number Publication Date
WO2021084999A1 true WO2021084999A1 (ja) 2021-05-06

Family

ID=75712372

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/036642 WO2021084999A1 (ja) 2019-10-28 2020-09-28 光学積層体及び表示装置

Country Status (5)

Country Link
JP (2) JP6869409B2 (enrdf_load_stackoverflow)
KR (1) KR102359353B1 (enrdf_load_stackoverflow)
CN (1) CN113167932A (enrdf_load_stackoverflow)
TW (1) TW202132100A (enrdf_load_stackoverflow)
WO (1) WO2021084999A1 (enrdf_load_stackoverflow)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7092232B1 (ja) 2021-04-19 2022-06-28 東洋インキＳｃホールディングス株式会社 導電材分散液、およびそれを用いた二次電池電極用組成物、電極膜、二次電池。
KR102839164B1 (ko) * 2021-10-28 2025-07-25 엘지디스플레이 주식회사 표시 장치
WO2024024409A1 (ja) * 2022-07-28 2024-02-01 Ａｇｃ株式会社 積層板および光学素子

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001109361A (ja) * 1999-10-08 2001-04-20 Dainippon Printing Co Ltd 体積ホログラム積層体、および体積ホログラム積層体作製用ラベル
JP2010260880A (ja) * 2009-04-09 2010-11-18 Dic Corp 両面粘着テープ
JP2015030765A (ja) * 2013-07-31 2015-02-16 日東電工株式会社 粘着シート、粘着層付き光学フィルム、および画像表示装置
WO2016093133A1 (ja) * 2014-12-10 2016-06-16 積水化学工業株式会社 衝撃吸収シート、衝撃吸収粘着シート、前面板固定用衝撃吸収両面粘着シート、背面板固定用衝撃吸収両面粘着シート、及び、バックライトユニット固定用衝撃吸収両面粘着シート
JP2018193558A (ja) * 2013-11-22 2018-12-06 日東電工株式会社 両面粘着シート
WO2019026577A1 (ja) * 2017-08-02 2019-02-07 バンドー化学株式会社 光学透明粘着シート、積層体、及び、貼り合わせ構造物

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005049795A (ja) * 2003-07-31 2005-02-24 Dainippon Printing Co Ltd スクリーン用レンズシート
JP4645074B2 (ja) 2004-06-24 2011-03-09 Ｄｉｃ株式会社 両面粘着テープとこれを用いた液晶表示モジュールユニット
JP2008037018A (ja) * 2006-08-08 2008-02-21 Sekisui Chem Co Ltd 透明積層体
JP5428158B2 (ja) * 2007-12-27 2014-02-26 Ｄｉｃ株式会社 両面粘着テープ
JP5130928B2 (ja) * 2008-01-31 2013-01-30 凸版印刷株式会社 光学部材及びバックライトユニット並びにディスプレイ装置
WO2016121788A1 (ja) * 2015-01-30 2016-08-04 日東電工株式会社 低粘着性発泡シート
JP6505518B2 (ja) * 2015-06-22 2019-04-24 積水化学工業株式会社 両面粘着テープ
KR102031556B1 (ko) * 2015-06-26 2019-10-14 동우 화인켐 주식회사 적층 필름 및 이를 포함하는 화상 표시 장치
JP6804310B2 (ja) * 2016-03-07 2020-12-23 日東電工株式会社 光学用粘着シート、粘着剤層付偏光フィルム、および液晶表示装置
JPWO2017204248A1 (ja) * 2016-05-25 2019-03-28 王子ホールディングス株式会社 積層粘着シート
KR20180034056A (ko) 2016-09-27 2018-04-04 삼성전자주식회사 표시 장치용 윈도우 및 표시 장치
JP6807234B2 (ja) * 2017-01-10 2021-01-06 日東電工株式会社 粘着シート
WO2018134974A1 (ja) * 2017-01-20 2018-07-26 住友化学株式会社 樹脂フィルム、積層体、光学部材、ガスバリア材及びタッチセンサー基材
JP7185396B2 (ja) 2017-12-19 2022-12-07 リンテック株式会社 粘着シート、繰り返し屈曲積層部材および繰り返し屈曲デバイス
JP7076217B2 (ja) * 2018-01-30 2022-05-27 日東電工株式会社 粘着シートおよびその製造方法、ならびに画像表示装置の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001109361A (ja) * 1999-10-08 2001-04-20 Dainippon Printing Co Ltd 体積ホログラム積層体、および体積ホログラム積層体作製用ラベル
JP2010260880A (ja) * 2009-04-09 2010-11-18 Dic Corp 両面粘着テープ
JP2015030765A (ja) * 2013-07-31 2015-02-16 日東電工株式会社 粘着シート、粘着層付き光学フィルム、および画像表示装置
JP2018193558A (ja) * 2013-11-22 2018-12-06 日東電工株式会社 両面粘着シート
WO2016093133A1 (ja) * 2014-12-10 2016-06-16 積水化学工業株式会社 衝撃吸収シート、衝撃吸収粘着シート、前面板固定用衝撃吸収両面粘着シート、背面板固定用衝撃吸収両面粘着シート、及び、バックライトユニット固定用衝撃吸収両面粘着シート
WO2019026577A1 (ja) * 2017-08-02 2019-02-07 バンドー化学株式会社 光学透明粘着シート、積層体、及び、貼り合わせ構造物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHIMADA TETSUYA: "High fonctional adhesive", SANYO KEISEI NEWS, vol. 516, 2019, pages 1 - 4 *

Also Published As

Publication number Publication date
JP2021070315A (ja) 2021-05-06
JP2021075057A (ja) 2021-05-20
KR102359353B1 (ko) 2022-02-08
KR20210080455A (ko) 2021-06-30
TW202132100A (zh) 2021-09-01
JP6869409B2 (ja) 2021-05-12
JP7053904B2 (ja) 2022-04-12
CN113167932A (zh) 2021-07-23

Similar Documents

Publication Publication Date Title
JP7118651B2 (ja) フィルム、樹脂組成物およびポリアミドイミド樹脂の製造方法
TWI758399B (zh) 光學膜及光學膜之製造方法
CN110191910B (zh) 聚酰胺酰亚胺树脂及包含该聚酰胺酰亚胺树脂的光学构件
CN108373543B (zh) 聚酰亚胺膜
JP7249732B2 (ja) 光学フィルムおよび光学フィルムの製造方法
KR102475756B1 (ko) 폴리이미드계 필름 및 적층체
TWI748038B (zh) 聚醯胺醯亞胺樹脂及含有該聚醯胺醯亞胺樹脂而成的光學構件
JP7053904B2 (ja) 光学積層体及び表示装置
JP7584548B2 (ja) 光学積層体及び表示装置
CN111381295A (zh) 光学膜

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 20217014962

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20881510

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20881510

Country of ref document: EP

Kind code of ref document: A1