Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
  • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
• • 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
  • C09J7/10—Adhesives in the form of films or foils without carriers
• • 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
  • 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
  • G02F1/133528—Polarisers
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
• • 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
• • 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
  • H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements

Definitions

• the present invention relates to a laminated body and a display device using the same.
• Patent Document 1 Japanese Unexamined Patent Publication No. 20 18 _ 285 73
• Patent Document 1 describes a laminate for a flexible image display device having a plurality of pressure-sensitive adhesive layers.
• Patent Document 1 Japanese Patent Laid-Open No. 2 0 18 _ 2 8 5 7 3
• air bubbles may be generated in the pressure-sensitive adhesive layer in the laminate when the front plate side is inwardly bent repeatedly.
• the adhesive force of the pressure-sensitive adhesive layer was weak, and in some cases, floating or peeling occurred between the pressure-sensitive adhesive layer and the adherend.
• An object of the present invention is to provide a laminated body that suppresses the generation of bubbles even when repeatedly bent with the front plate side inward and has excellent adhesive strength, and a display device using the same. It is to be.
• the present invention provides the following laminated body and display device.
• the shear stress relaxation rate at a temperature of 25° of the first standard pressure-sensitive adhesive layer having a thickness of 150 formed by using the first pressure-sensitive adhesive composition is [[ 1.
• the shear stress relaxation rate at a temperature of 25 ° ⁇ of the second reference adhesive layer having a thickness of 150 and formed by using the second adhesive composition is [3 ⁇ 42, Relational expressions (2) and (3):
• the (meth)acrylic polymer has a weight average molecular weight Is not less than 200,000 and not more than 150 million, the laminate according to [3].
• the constitutional unit derived from a monomer having a reactive functional group is less than 5% by mass based on the total mass of the polymer, [3] or [4] Laminate.
• a display device including the laminate according to any one of [1] to [6].
• a laminated body in which generation of air bubbles is suppressed even when repeatedly bent with the front plate side facing inward and which has excellent adhesive strength, and a display device using the same. can do.
• Fig. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention.
• FIG. 2 A schematic cross-sectional view showing an example of a laminate according to the present invention. ⁇ 2020/175095 3 boxes (: 170? 2020 /004758
• FIG. 3 A schematic cross-sectional view showing an example of a laminate according to the present invention.
• FIG. 4 A schematic diagram illustrating a method of a bending test.
• laminate according to one embodiment of the present invention (hereinafter, also simply referred to as a "laminate") will be described.
• FIG. 1 shows a schematic sectional view of a laminate (optical laminate) according to one embodiment of the present invention.
• the laminate 100 includes a front plate 101, a first pressure-sensitive adhesive layer 102, a polarizer layer 103, a second pressure-sensitive adhesive layer 104, and a back plate 105. Include in order.
• the first pressure-sensitive adhesive layer 102 is formed from the first pressure-sensitive adhesive composition
• the second pressure-sensitive adhesive layer 104 is formed from the second pressure-sensitive adhesive composition.
• the first pressure-sensitive adhesive layer 102 and the second pressure-sensitive adhesive layer 104 may be collectively referred to as a pressure-sensitive adhesive layer.
• the thickness of the laminated body 100 is not particularly limited as it varies depending on the function required for the laminated body and the application of the laminated body, but is, for example, 50 or more and 400 or less, and preferably It is 100 or more and 200 or less, more preferably 1501 or more and 100 or less.
• the planar shape of the laminate 100 may be, for example, a rectangular shape, preferably a rectangular shape having a long side and a short side, and more preferably a rectangular shape.
• the long side has a length of, for example, 10
• the length of the short side is, for example, 5 Or less, preferably less than or equal to, more preferably 50 or more 3
• Each of the constituent layers may have a corner portion machined, an end portion cut-out machined, or a hole machined.
• the laminated body 100 can be used, for example, in a display device or the like.
• the display device is not particularly limited, and examples thereof include an organic electroluminescence (organic light !_) display device, an inorganic electroluminescent (inorganic light !_) display device, a liquid crystal display device, and an electroluminescent display device.
• the display device has a touch panel function ⁇ 2020/175095 4 ⁇ (: 170? 2020 /004758
• the laminated body 100 has a shear stress relaxation rate at a temperature of 25° ⁇ of the first adhesive layer 10 2 [3 ⁇ 4, and a shear stress at a temperature of 25° ⁇ of the second adhesive layer 10 4 If the relaxation rate is 2, the following relational expression (1):
• the shear stress relaxation rate does not depend on the thickness of the pressure-sensitive adhesive layer, the first pressure-sensitive adhesive layer 1
• the first standard pressure-sensitive adhesive layer formed by the first pressure-sensitive adhesive composition and the second standard pressure-sensitive adhesive layer formed by the second pressure-sensitive adhesive composition are used. 2 A method of comparing with a standard adhesive layer can be mentioned.
• the thickness of the first standard adhesive layer and the second standard adhesive layer may be 150.
• Shear stress relaxation rate of the 1st reference adhesive layer and the 2nd reference adhesive layer with a thickness of 150 at a temperature of 25°. 1, [3 ⁇ 4. 2 is measured according to the measuring method described in the section of Examples below.
• the laminated body 100 can be bent with the front plate 101 side facing inward.
• a display device including a laminate is repeatedly bent with the front plate side facing inward, bubbles may be generated in the adhesive layer.
• Such bubbles are generated in the pressure-sensitive adhesive layer close to the front plate side, that is, in the first pressure-sensitive adhesive layer 102 in the laminate 100. ⁇ 2020/175095 5 (: 170? 2020 /004758
• the front plate 10 1 side is placed inside. It was found that even when repeatedly bent, bubbles generated in the pressure-sensitive adhesive layer in the laminate 100 can be suppressed. More specifically, the bending radius of the inner surface of the laminate 100 is 3 It is possible to suppress the bubbles generated in the pressure-sensitive adhesive layer in the laminate 100 even after being repeatedly bent 100,000 times (hereinafter, also referred to as "having excellent room-temperature flexibility"). I found it.
• the room-temperature flexibility can be evaluated according to the evaluation method described in the section of Examples below.
• the laminate 100 may be bendable with the front plate side facing outward.
• a display device to which the laminated body 100 is applied can be used as a flexible display that can be bent or rolled.
• bending includes a bending state in which a curved surface is formed at a bending portion, and the bending radius of the bent inner surface is not particularly limited. Bending also includes refraction in which the inner surface has an angle of refraction greater than 0 degrees and less than 180 degrees, and bending in which the inner surface has a bending radius close to zero, or folding in which the inner surface has an angle of refraction of 0 degree.
• the shear stress relaxation rates of the first pressure-sensitive adhesive layer 102 and the second pressure-sensitive adhesive layer 104 satisfy the relational expression (1), they are allowed to stand for a long time under constant temperature and humidity conditions. However, it was found that there was almost no change in appearance such as floating, peeling, or foaming between the adhesive layer and the adherend, and that the adhesive durability was excellent at room temperature.
• the room temperature adhesion durability can be evaluated according to the evaluation method described in the Example section below.
• the first pressure-sensitive adhesive composition and the second pressure-sensitive adhesive composition are adjusted so that the shear stress relaxation rates of the first pressure-sensitive adhesive layer 102 and the second pressure-sensitive adhesive layer 104 satisfy the relational expression (1).
• the preparation method include forming the pressure-sensitive adhesive layer from the pressure-sensitive adhesive composition described below, changing the type of the monomer constituting the (meth)acrylic polymer 8 described later, or changing the type of the (meth)acrylic polymer 8 Examples thereof include a method of adjusting the molecular weight.
• the first pressure-sensitive adhesive layer 102 and the second pressure-sensitive adhesive layer 104 are, in one form, formed from a pressure-sensitive adhesive composition containing a (meth)acrylic polymer (hereinafter, also referred to as a pressure-sensitive adhesive composition 8). ..
• the pressure-sensitive adhesive composition may be an active energy ray curable type or a thermosetting type.
• the “(meth)acrylic polymer” means at least one selected from the group consisting of acrylic polymers and methacrylic polymers. The same applies to other terms with "(meta)".
• the (meth)acrylic polymer (hereinafter, also referred to as (meth)acrylic polymer 8) included in the pressure-sensitive adhesive composition 8 is )
• a constituent unit derived from an acrylic monomer can be included, and the (meth) acrylic monomer may be linear, branched or cyclic.
• the (meth)acrylic monomer may be, for example, (meth)acrylic acid ester, (meth)acrylic acid amide, or the like.
• (meth)acrylates include (meth)butyl acrylate, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)hexyl acrylate, (meth)octyl acrylate, (meth) ) Lauryl acrylate, (meth)isooctyl acrylate, (meth)isodecyl acrylate, (meth)2-ethylhexyl acrylate, (meth)hydroxypropyl acrylate, (meth)tetrahydrofurfuryl acrylate, (meth) ) Acrylic acid cyclohex ⁇ 2020/175095 7 ⁇ (: 170? 2020 /004758
• Examples thereof include sill and isobornyl (meth)acrylate.
• (meth)acrylic acid amides are (meth)acrylic amide, 1 ⁇ 1, 1 ⁇ 1-dimethyl (meth)acrylic amide, 1 ⁇ 1, 1 ⁇ 1_diethyl (meth)acrylic amide , 1 ⁇ 1 _ Isopropyryl (meth) acrylic amide, 1 ⁇ 1 _ Methoxyethyl (meth) acrylic amide, 1 ⁇ 1 ,1 ⁇ 1—Propyl (meth) acrylic amide, 1 ⁇ 1 — Ethyl acrylic amide And 1 ⁇ 1-(2-hydroxyethyl) (meth) acrylic amide.
• the (meth)acrylic polymer 8 may be a polymer or copolymer containing one or more monomers selected from the above-mentioned (meth)acrylic acid ester and (meth)acrylic acid amide as a monomer.
• the content of the (meth)acrylic polymer in the adhesive composition 8 may be, for example, 50% by mass or more and 100% by mass or less based on 100% by mass of the solid content of the adhesive composition. , Preferably 80 mass% or more and 99.5 mass% or less, more preferably 88 mass% or more and 99 mass% or less, and further preferably 90 mass% or more and 99 mass% or less.
• the (meth)acrylic polymer contained in the pressure-sensitive adhesive composition 8 is a (meth)acrylic acid ester or a (meth)acrylic acid amide and has the following formula ([]]: [0024] ]
• At least one of the (meth)acrylic polymer 8 contained in the first pressure-sensitive adhesive composition and the second pressure-sensitive adhesive composition contains a structure represented by the formula (I) (meth)acrylic acid ester Alternatively, it preferably contains a structural unit derived from a monomer which is (meth)acrylic acid amide.
• the pressure-sensitive adhesive composition containing such a (meth)acrylic polymer the first reference pressure-sensitive adhesive layer and the second reference pressure-sensitive adhesive layer satisfying the above relational expressions (2) and (3) can be easily formed. it can.
• the (meth)acrylic polymer 8 includes a structural unit derived from a monomer which is a (meth)acrylic acid ester or a (meth)acrylic acid amide containing a structure represented by the formula (I): For example, 1% by mass or more and 20% by mass or less, preferably 2% by mass or more and 10% by mass or less can be contained with respect to 100% by mass of the solid content of the polymer 8.
• Examples of the monomer containing the structure represented by I) include (meth)acrylic monomers represented by the following compound formulas (()) to (V).
• the structural unit derived from the monomer having a reactive functional group is preferably less than 5 mass% based on the total mass of the polymer.
• the reactive functional group include a hydroxyl group, a carboxyl group, an amino group, an amide group, and an epoxy group.
• Weight average molecular weight of acrylic polymer 8 May be, for example, 300,000 or more and 700,000 or less, and preferably 300,000 or more and 600,000 or less from the viewpoint of suppressing bubbles during bending.
• the weight average molecular weight (1 ⁇ /1) can be measured according to the measuring method described in the section of Examples below.
• the pressure-sensitive adhesive composition may contain one kind or two or more kinds of (meth)acrylic polymer. Further, the pressure-sensitive adhesive composition may contain only (meth)acrylic polymer 8 as its constituent component, or may further contain a crosslinking agent.
• a cross-linking agent a metal ion having a valence of 2 or more and forming a carboxylic acid metal salt with a carboxyl group; a polyamine compound forming an amide bond with a carboxyl group Compounds; polyepoxy compounds and polyols that form ester bonds with carboxyl groups; polyisocyanate compounds that form amido bonds with carboxyl groups, etc.
• polyisocyanate compounds are preferred.
• the content of the crosslinking agent may be, for example, 5 parts by mass or less, preferably 1 part by mass, relative to 100 parts by mass of the acrylic polymer. Parts or less, more preferably 0.5 parts by mass or less, and further preferably 0.1 parts by mass or less, and the pressure-sensitive adhesive composition contains no crosslinking agent. ⁇ 2020/175095 10 boxes (: 170? 2020 /004758
• An active energy ray-curable pressure-sensitive adhesive composition has a property of being cured by being irradiated with an active energy ray such as an ultraviolet ray or an electron beam, and has adhesiveness even before irradiation with an active energy ray. It is a pressure-sensitive adhesive composition having a property that it can be brought into close contact with an adherend such as a film and is cured by irradiation with an active energy ray to adjust the adhesive force.
• the active energy ray-curable pressure-sensitive adhesive composition is preferably an ultraviolet-curable type.
• the pressure-sensitive adhesive composition is an active energy ray-curable pressure-sensitive adhesive composition
• the pressure-sensitive adhesive composition may further contain an active energy ray-polymerizable compound, a photopolymerization initiator, a photosensitizer, and the like. it can.
• Examples of the active energy ray-polymerizable compound include (meth)acrylate monomers having at least one (meth)acryloyloxy group in the molecule; two or more kinds of functional group-containing compounds, which are obtained by reacting Examples thereof include (meth)acryl-based compounds such as (meth)acryloyloxy group-containing compounds such as (meth)acrylate oligomer_ having at least two (meth)acryloyloxy groups.
• the pressure-sensitive adhesive composition may contain an active energy ray-polymerizable compound in an amount of 0.1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the solid content of the adhesive composition.
• the photopolymerization initiator examples include benzophenone, benzyl dimethyl ketone, 1-hydroxycyclohexyl phenyl ketone, and the like.
• the pressure-sensitive adhesive composition contains a photopolymerization initiator, it may contain one kind or two or more kinds.
• the pressure-sensitive adhesive composition contains a photopolymerization initiator the total content thereof is, for example, 0.001 part by mass or more based on 100 parts by mass of the solid content of the adhesive composition. 0.0 parts by mass or less.
• the pressure-sensitive adhesive composition includes fine particles for imparting light-scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than base polymers, pressure-sensitive adhesives, fillers (metal powders). And other inorganic powders), antioxidants, UV absorbers ⁇ 2020/175095 1 1 ⁇ (: 170? 2020 /004758
• the pressure-sensitive adhesive composition preferably does not contain an organic solvent from the viewpoint of preventing the problem of durability deterioration due to the residual solvent.
• the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition 8 onto a substrate.
• the formed pressure-sensitive adhesive layer can be irradiated with an active energy ray to obtain a cured product having a desired degree of curing.
• the pressure-sensitive adhesive composition can be produced by a known method, for example, by collectively mixing the components using a mixer or the like.
• the (meth)acrylic polymer 8 is a (meth)acrylic polymer having an alkyl group with a carbon number of 2 to 20 as a monomer unit constituting the polymer. It is preferable to contain an acid alkyl ester and a monomer having a reactive functional group in the molecule (reactive functional group-containing monomer).
• the (meth)acrylic polymer 8 is preferable because it contains a (meth)acrylic acid alkyl ester having an alkyl group having 2 to 20 carbon atoms as a monomer unit constituting the polymer. It can develop tackiness.
• Alkyl group-containing (meth)acrylic acid alkyl esters having 2 to 20 carbon atoms are those having a glass transition temperature (C9) as a homopolymer of 140 ° C or less (hereinafter referred to as "low C9 alkyl acrylate"). ] Is preferred.) is preferred.
• the flexibility of the pressure-sensitive adhesive layer is improved so that the adhesive layer and the adherend are less likely to float or peel off, and the front plate side is When repeatedly bent inward, air bubbles tend to be suppressed in the pressure-sensitive adhesive layer.
• Examples of the low-dose 9 alkyl acrylate include n-butyl acrylate (Ding 9-55 ° ⁇ ), acrylate-octyl (Ding 9-65 ° ⁇ ), acrylate ⁇ 2020/175095 12 boxes (: 170? 2020 /004758
• Sooctyl (Cho 9-58° ⁇ ), 2-Ethylhexyl Acrylate (Cho 9-70° ⁇ ), Isononyl Acrylate (Cho 9-58° ⁇ ), Isodecyl Acrylate (Cho 9-60° ⁇ , Isodecyl Methacrylate) (Ding 9 - 4 1 ° ⁇ , methacrylic acid n - lauryl (Ding 9 -65 ° ⁇ , tridecyl acrylate (Ding 9 -55 ° ⁇ , main methacrylic acid tridecyl (Ding 9 -40 ° ⁇ ), and the like preferably Above all, from the viewpoint that the shear stress relaxation rate of the obtained adhesive at a temperature of 25 ° easily falls within the above range, as the low acrylate 9 alkyl acrylate, the homopolymer dex 9 is 145 ° C or less.
• Is more preferable and one having a temperature of 50° C. or less is particularly preferable.
• butyl acrylate and 2-ethylhexyl acrylate are particularly preferable.These may be used alone. However, two or more kinds may be used in combination.
• the (meth)acrylic polymer 8 preferably contains, as a lower limit, 85% by mass or more, and preferably 90% by mass or more, as a lower limit, a low-dose 9 alkyl acrylate as a monomer unit constituting the polymer. It is more preferable that the content be 95% by mass or more.
• the shear stress relaxation rate of the resulting pressure-sensitive adhesive at a temperature of 25 ° easily falls within the above range.
• the (meth)acrylic polymer 8 preferably contains the above-mentioned low alkyl acrylate as a monomer unit constituting the polymer, and its upper limit value is 99.9% by mass or less, and 99.5% by mass. % Or less, more preferably 99% by mass or less.
• the above low-alkyl acrylate By containing 99.9% by mass or less of the above low-alkyl acrylate, it is possible to introduce a suitable amount of another monomer component (particularly a reactive functional group-containing monomer) into the (meth)acrylic polymer 8. it can.
• the (meth)acrylic polymer 8 has a glass transition temperature (homopolymer) as a homopolymer in order to easily set the glass transition temperature (9) of the main polymer of the pressure-sensitive adhesive according to the present embodiment to the range described above. 9)
• the content of monomers exceeding 0 ° ⁇ (hereinafter sometimes referred to as “hard monomer”) should be reduced as much as possible. ⁇ 2020/175095 13 boxes (: 170? 2020 /004758
• the (meth)acrylic polymer 8 preferably has a hard monomer content of not more than 15% by mass as an upper limit, and not more than 10% by mass, as a monomer unit constituting the polymer. Is more preferable, and 5% by mass or less is further preferable.
• the hard monomer also contains a reactive functional group-containing monomer described later.
• Examples of the hard monomer such as methyl acrylate (sheets 9 1 0 ° ⁇ , methyl methacrylate (sheets 9 1 05 ° ⁇ , ethyl methacrylate (Ding 965 ° ⁇ ), methacrylic acid ⁇ -butyl (Ding 9 20° ⁇ ), isoptyl methacrylate (Cho 948° ⁇ , I-butyl methacrylate (Cha 9 07 07 ⁇ ), n-stearyl acrylate (Cha 9 30° ⁇ ), methacrylic acid-stearyl (Cha 9 38° ⁇ ), Cyclohexyl acrylate (Cho 9 15 ° ⁇ ), Cyclohexyl methacrylate (C 966 ° ⁇ , Phenoxyethyl acrylate (Cha 9 5 ° ⁇ ), Phenoxyethyl methacrylate (Cha 9 54 ° ⁇ ), Methacrylic acid benzyl (Ding 9 54 ° ⁇ ),
• the (meth)acrylic polymer 8 contains a reactive functional group-containing monomer as a monomer unit constituting the polymer, so that the reactive functional group derived from the reactive functional group-containing monomer is Through a thermal crosslinking agent described later, thereby forming a crosslinked structure (three-dimensional network structure), and a pressure-sensitive adhesive having a desired cohesive force is obtained.
• Examples of the reactive functional group-containing monomer contained in the (meth)acrylic polymer 8 as a monomer unit constituting the polymer include a monomer having a hydroxyl group in the molecule (hydroxyl group-containing monomer), Monomers having carboxy groups (carboxy group-containing monomers), Monomers having amino groups in the molecule (ami ⁇ 2020/175095 14 box (: 170? 2020 /004758
• the hydroxyl group-containing monomer is particularly preferable because many of them have a glass transition temperature (Choose 9) of 0 ° or less.
• Examples of the hydroxyl group-containing monomer include (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, and (meth)acrylic acid 2-hydroxybutyl. And (meth)acrylic acid hydroxyalkyl esters such as (meth)acrylic acid 3-hydroxybutyl and (meth)acrylic acid 4-hydroxybutyl.
• 2-hydroxy acrylate is preferable because of its glass transition temperature (9), reactivity of the hydroxyl group in the obtained (meth)acrylic polymer with the thermal crosslinking agent, and copolymerizability with other monomers. It is preferably at least one of ethyl, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. These may be used alone or in combination of two or more.
• carboxy group-containing monomer examples include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These may be used alone or in combination of two or more.
• carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These may be used alone or in combination of two or more.
• amino group-containing monomer examples include (meth)acrylic acid aminoethyl and (meth)acrylic acid butylaminoaminoethyl. These may be used alone or in combination of two or more.
• the (meth)acrylic polymer 8 preferably contains, as a monomer unit constituting the polymer, a reactive functional group-containing monomer as a lower limit of 0.1% by mass or more, and particularly It is preferably contained in an amount of 5% by mass or more, more preferably 1% by mass or more. Further, the upper limit value is preferably not more than 10% by mass, particularly preferably not more than 8% by mass, more preferably not more than 5% by mass, and less than 5% by mass. Most preferred.
• the (meth)acrylic polymer 8 is used as a monomer unit as described above. ⁇ 2020/175095 15 boxes (: 170? 2020 /004758
• the reactive functional group-containing monomer particularly the hydroxyl group-containing monomer
• the shear stress relaxation rate of the obtained pressure-sensitive adhesive layer at a temperature of 25 ° easily falls within the above range.
• the (meth)acrylic polymer 8 may not include, as a monomer unit constituting the polymer, a carboxy group-containing monomer, particularly acrylic acid which is also a hard monomer. Since the carboxy group is an acid component, it does not contain a carboxy group-containing monomer, so that the adhesive may cause problems with acid, such as a transparent conductive film such as tin-doped indium oxide ( ⁇ chome) or metal. Even when a film or metal mesh is present, it is possible to suppress their defects (corrosion, resistance value change, etc.) due to acid.
• a transparent conductive film such as tin-doped indium oxide ( ⁇ chome) or metal.
• the (meth)acrylic polymer 8 may optionally contain another monomer as a monomer unit constituting the polymer.
• a monomer that does not contain a reactive functional group is preferable because it does not hinder the action of the reactive functional group-containing monomer.
• Such other monomers include, for example, (meth)acrylic acid alkoxyalkyl esters such as (meth)methacrylic acid acrylate and (meth)acrylic acid ethoxyethyl, as well as the glass transition temperature as a homopolymer (Claim 9).
• Examples of the monomer include a monomer having a value of more than 40° and less than or equal to 0° (hereinafter, may be referred to as “Chacho 9 alkyl acrylate”).
• Examples of 9-alkyl acrylates include ethyl acrylate (Ding 9 _ 20 ° ⁇ , isoptyl acrylate (Ding 9-26 ° ⁇ , 2-ethyl hexyl methacrylate (Ding 9-10 ° ⁇ ), Acrylic acid lauryl (Ding 9-2 3 ° ⁇ )
• Isostearyl acrylate (Choose 9-18 ° C., etc. may be used singly or in combination of two or more kinds.
• the polymerization mode of the (meth)acrylic polymer 8 may be a random copolymer or a block copolymer.
• the lower limit of the weight average molecular weight of the (meth)acrylic polymer 8 is preferably 200,000 or more, particularly preferably 300,000 or more, and further preferably 400,000 or more. preferable.
• the weight average molecular weight in the present specification is a standard polystyrene conversion value measured by the gel permeation chromatography ( ⁇ ) method.
• the upper limit of the weight average molecular weight of the (meth)acrylic polymer 8 is 15
• the shear stress relaxation rate of the obtained pressure-sensitive adhesive layer at a temperature of 25° easily becomes within the above range.
• the (meth)acrylic polymer 8 may be used alone or in combination of two or more.
• the heat-crosslinking agent crosslinks the (meth)acryl-based polymer 8 to form a three-dimensional network structure.
• the cohesive force of the obtained pressure-sensitive adhesive is improved, and the shear stress relaxation rate of the obtained pressure-sensitive adhesive layer at a temperature of 25 ° easily becomes within the above-mentioned range.
• the above-mentioned thermal cross-linking agent may be any as long as it reacts with the reactive group of the (meth) acrylic polymer 8, and examples thereof include an isocyanate cross-linking agent, an epoxy cross-linking agent, an amine cross-linking agent, and a melamine-based cross-linking agent.
• Cross-linking agent aziridine-based cross-linking agent, hydrazine-based cross-linking agent, aldehyde-based cross-linking agent, oxazoline-based cross-linking agent, metal alkoxide-based cross-linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, ammonium salt-based cross-linking agent Etc.
• the reactive group of the (meth)acrylic polymer 8 is a hydroxyl group
• the thermal crosslinking agents may be used alone or in combination of two or more.
• the isocyanate crosslinking agent contains at least a polyisocyanate compound.
• polyisocyanate compound for example, tolylene diisocyanate, ⁇ 2020/175095 17 ⁇ (: 170? 2020/004758
• Aromatic polyisocyanates such as diphenylmethane diisocyanate and xylylene diisocyanate, Aliphatic polyisocyanates such as hexamethylene diisocyanate, Isophorone diisocyanate, Alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, etc., and their pyrurets Examples thereof include isocyanurates, and adducts which are reaction products with low molecular weight active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
• trimethylolpropane-modified aromatic polyisocyanates particularly trimethylolpropane-modified tolylene diisocyanate and trimethylolpropane-modified xylylene diisocyanate are preferred from the viewpoint of reactivity with hydroxyl groups.
• epoxy-based cross-linking agent examples include 1,3-bis (1 ⁇ 1, 1 ⁇ 1-diglycidyl aminomethyl) cyclohexane, 1 ⁇ 1, 1 ⁇ 1, 1 ⁇ 1, 1 ⁇ 1, tetra- Glycidyl xylylenediamine, ethylene glycol diglycidyl ether, 1,
• 6-hexanediol diglycidyl ether 6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine and the like can be mentioned.
• the content of the thermal crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.01% by mass or more based on 100% by mass of the (meth)acrylic polymer, and 0.0
• the content is more preferably 5% by mass or more, and further preferably 0.1% by mass or more.
• the content is preferably 1 mass% or less, more preferably 0.8 mass% or less, and further preferably 0.5 mass% or less.
• the pressure-sensitive adhesive composition preferably contains a silane coupling agent.
• the obtained pressure-sensitive adhesive layer has improved adhesion to each member in the laminate to be the adherend, and more excellent durability against bending. ⁇ 2020/175095 18 boxes (: 170? 2020 /004758
• the silane coupling agent is an organosilicon compound having at least one alkoxysilyl group in the molecule, which has good compatibility with the (meth)acrylic polymer 8 and has light transmittance. Is preferred.
• silane coupling agent for example, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane and other polyunsaturated group-containing silicon compounds, 3-glycidoxypropyltrimethoxysilane, 2-(3 , 4-Epoxycyclohexyl) silicon compounds having an epoxy structure such as ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercapto group-containing silicon compounds such as 3-mercaptopropyldimethoxymethylsilane, 3- Aminopropyltrimethoxysilane, 1 ⁇ !— (2-aminoethyl)-1,3-aminopropyltrimethoxysilane, 1 ⁇ !— (2-aminoethyl)-1,3-aminopropylmethyldimethoxysilane and other amino group-containing silicon compounds, 3
• the content of the silane coupling agent in the pressure-sensitive adhesive composition is preferably 0.01% by mass or more based on 100% by mass of the (meth)acryl-based polymer. It is more preferably at least 0.5% by mass, further preferably at least 0.1% by mass. Further, the content is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less. When the content of the silane coupling agent is within the above range, the obtained pressure-sensitive adhesive layer has more preferable adhesiveness with each member in the laminate to be the adherend.
• the polymerization solvent and diluent solvent should not be included in the additives that make up the pressure-sensitive adhesive composition. ⁇ 2020/175095 19 ⁇ (: 170? 2020/004758
• the (meth)acrylic polymer 8 can be produced by polymerizing a mixture of monomers constituting the polymer by a usual radical polymerization method.
• the (meth)acrylic polymer is preferably polymerized by a solution polymerization method, optionally using a polymerization initiator.
• the polymerization solvent include ethyl acetate, 1 ⁇ !-butyl acetate, isoptyl acetate, toluene, acetone, hexane, methyl ethyl ketone, and the like, and two or more kinds may be used in combination.
• Examples of the polymerization initiator include azo compounds and organic peroxides, and two or more kinds may be used in combination.
• Examples of the azo compound include 2,2'-azobis isoptylonitrile, 2,2'-azobis (2-methylptyronitrile),
• 1, 1,'-Azobis (cyclohexane 1-carbonitrile), 2, 2'-Azobis (2, 4-dimethylvaleronitrile), 2, 2'-Azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-Azobis (2-methylpropionate), 4,4'-Azobis (4-cyanovaleric acid), 2,2'-Azobis (2-hydroxymethylpropionitrile),
• organic peroxide examples include benzoyl peroxide, 1-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di _ ⁇ _ propyl peroxydicarbonate, di( 2-ethoxyethyl) peroxydicarbonate, I _ butyl peroxy neodecanoate,
• the weight average molecular weight of the obtained polymer can be adjusted by adding a chain transfer agent such as 2-mercaptoethanol.
• a heat crosslinking agent, a silane coupling agent, and optionally an additive and a diluting solvent are added to the solution of No. 8 and mixed sufficiently to obtain a pressure-sensitive adhesive composition (coating solution) diluted with the solvent.
• any of the above components is used in a solid state, or when precipitation occurs when mixed with other components in an undiluted state, the component is used alone. May be dissolved or diluted in a diluting solvent in advance and then mixed with other components.
• diluent solvent examples include aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol and propanol.
• Butanol alcohols such as 1-methoxy_2-propanol, acetone, methyl ethyl ketone, 2-pentanone, isophorone, ketones such as cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolves such as ethyl cellosolve.
• a solvent or the like is used.
• the concentration/viscosity of the coating solution thus prepared may be within a coatable range and is not particularly limited and may be appropriately selected depending on the situation.
• the pressure-sensitive adhesive composition is diluted to a concentration of 10 to 60% by mass.
• addition of a diluent solvent or the like is not a necessary condition, and if the pressure-sensitive adhesive composition has a coatable viscosity or the like, the diluent solvent may not be added.
• the pressure-sensitive adhesive composition 8 is a coating solution using the (meth)acrylic polymer polymerization solvent as a diluting solvent.
• a preferable pressure-sensitive adhesive as the pressure-sensitive adhesive according to the present embodiment is obtained by crosslinking the pressure-sensitive adhesive composition.
• the pressure-sensitive adhesive composition 8 can be crosslinked by heat treatment.
• the heat treatment can also be used as a drying treatment when the diluent solvent or the like is volatilized from the coating film of the pressure-sensitive adhesive composition 8 applied to a desired object.
• the heating temperature of the heat treatment is preferably from 50 to 150°, and from 70 to 1
• the heating time is preferably 10 seconds to 10 minutes, more preferably 50 seconds to 2 minutes. ⁇ 2020/175095 21 ⁇ (: 170? 2020 /004758
• a curing period of about 2 weeks may be provided. If this curing period is required, after the curing period has elapsed, if the curing period is not required, the adhesive will be formed after the heat treatment is completed.
• the (meth)acrylic polymer is sufficiently crosslinked via the crosslinking agent to form a crosslinked structure, and a pressure-sensitive adhesive is obtained.
• the pressure-sensitive adhesive layer formed from such a pressure-sensitive adhesive easily has a shear stress relaxation rate at a temperature of 25 ° C. within the above-mentioned range.
• a pressure-sensitive adhesive sheet according to the present invention includes a pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive composition according to the present invention.
• the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition onto a substrate.
• heat treatment and curing
• the conditions for heat treatment and curing are as described above.
• the substrate may be a release film that has been subjected to a release treatment.
• the pressure-sensitive adhesive sheet can be prepared by forming a layer of a pressure-sensitive adhesive in a sheet shape on a release film, and further laminating another release film on the pressure-sensitive adhesive layer.
• a method of applying the coating liquid of the pressure-sensitive adhesive composition for example, a bar coating method, a knife coating method, a mouth coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
• the front plate 101 is not limited in material and thickness as long as it is a plate that can transmit light, and may be composed of only one layer, or may be composed of two or more layers. Examples thereof include a resin plate (for example, a resin plate, a resin sheet, a resin film, etc.), a glass plate (for example, a glass plate, a glass film, etc.), and a touch sensor panel described later.
• the front plate may constitute the outermost surface of the display device. ⁇ 2020/175095 22 ⁇ (: 170? 2020 /004758
• the thickness of the front plate 101 may be, for example, 10 or more and 500 or less, preferably 30 or more and 200 or less, and more preferably 50 or more and 100 or less.
• the thickness of each layer can be measured according to the thickness measuring method described in Examples below.
• the resin plate is not limited as long as it can transmit light.
• the resin that constitutes the resin-made plate-shaped body such as a resin film
• the resin that constitutes the resin-made plate-shaped body such as a resin film
• the front plate 101 is preferably a film in which a hard coat layer is provided on at least one surface of the base film from the viewpoint of increasing hardness.
• a film made of the above resin can be used as the substrate film.
• the hard coating layer may be formed on one surface of the substrate film, or may be formed on both surfaces. By providing the hard coat layer, it is possible to obtain a resin film having improved hardness and scratch resistance.
• the hard coat layer is, for example, a cured layer of an ultraviolet curable resin. Examples of UV curable resins include acrylic resins, silicone resins, polyester resins, urethane resins. ⁇ 0 2020/175095 23 ⁇ (: 17 2020 /004758
• the hard coat layer may contain an additive in order to improve the hardness.
• the additive is not limited, and may be inorganic fine particles, organic fine particles, or a mixture thereof.
• the front plate 101 is a glass plate
• a reinforced glass for display is preferably used as the glass plate.
• the glass plate may have a thickness of, for example, 10 or more and 100 or less.
• the front plate 10 1 having excellent mechanical strength and surface hardness can be formed.
• the front plate 1101 has not only a function of protecting the front surface (screen) of the display device (function as a window film) but also a touch sensor. Function, blue light cut function, viewing angle adjustment function, and the like.
• the first pressure-sensitive adhesive layer 102 is a layer which is interposed between the front plate 10 1 and the polarizer layer 10 3 to bond them together.
• a layer formed of a pressure-sensitive adhesive or an adhesive or It may be a layer obtained by subjecting the layer to some treatment.
• the first pressure-sensitive adhesive layer may be the pressure-sensitive adhesive layer arranged closest to the front plate among the pressure-sensitive adhesive layers constituting the laminated body.
• Adhesives are also called pressure sensitive adhesives. In the present specification, the “adhesive” refers to an adhesive other than a pressure-sensitive adhesive (pressure-sensitive adhesive) and is clearly distinguished from the pressure-sensitive adhesive.
• the first pressure-sensitive adhesive layer 102 may be composed of one layer, or may be composed of two or more layers, but is preferably one layer.
• the first pressure-sensitive adhesive layer 102 can be formed directly from the pressure-sensitive adhesive composition or by using a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition.
• the adhesive composition is preferably the above-mentioned adhesive composition.
• Adhesive Compositions Other than the eight, other adhesive compositions include, for example, rubber-based, urethane-based, ester-based, silicone-based, polyvinyl ether ⁇ 2020/175095 24 ⁇ (: 170? 2020 /004758
• the pressure-sensitive adhesive composition is preferably a pressure-sensitive adhesive composition having excellent transparency, weather resistance, heat resistance and the like.
• the pressure-sensitive adhesive composition may be an active energy ray-curable type.
• the active energy ray-curable pressure-sensitive adhesive composition when the pressure-sensitive adhesive composition is an active energy ray-curable pressure-sensitive adhesive composition, the active energy ray-curable pressure-sensitive adhesive composition further contains an active energy ray-polymerizable compound in addition to the base polymer. .. Further, if necessary, a photopolymerization initiator, a photosensitizer or the like may be contained. Moreover, the pressure-sensitive adhesive composition may contain an additive. Examples of the active energy ray-polymerizable compound and the photopolymerization initiator are the same as those described above in the description of the (meth)acrylic polymer 8.
• the forming method is the same as the method for forming the first pressure-sensitive adhesive layer 102 from the pressure-sensitive adhesive composition described above. You can
• the thickness of the first pressure-sensitive adhesive layer 102 is, for example, preferably 3 or more and 100 or less, more preferably 5 or more and 50 or less, and may be 2001 or more.
• the polarizer layer 103 examples include a stretched film or a stretched layer having a dichroic dye adsorbed thereon, and a layer obtained by coating and curing a composition containing a dichroic dye and a polymerizable compound.
• the dichroic pigment specifically, iodine or a dichroic organic dye is used.
• dichroic organic dyes there are ⁇ . ⁇ .0 ⁇
• the dichroic direct dyes composed of disazo compounds such as 39 and the dichroic direct dyes composed of compounds such as trisazo and tetrakisazo are included.
• the polarizer layer obtained by coating and curing a composition containing a dichroic dye and a polymerizable compound includes a composition containing a dichroic dye having liquid crystallinity, or a dichroic dye and a polymerizable liquid crystal.
• a polarizer layer containing a cured product of a polymerizable liquid crystal compound such as a layer obtained by applying and curing a composition containing
• a polarizer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound. ⁇ 2020/175095 25 boxes (: 170? 2020 /004758
• the layer is preferable because there is no limitation in the bending direction as compared with the stretched film or stretched layer on which the dichroic dye is adsorbed.
• the polarizer layer which is a stretched film with a dichroic dye adsorbed, is usually produced by the process of uniaxially stretching a polyvinyl alcohol-based resin film, and by diluting the polyvinyl alcohol-based resin film with a dichroic dye It can be manufactured through a step of adsorbing a chromogenic dye, a step of treating a polyvinyl alcohol-based resin film on which a dichroic pigment is adsorbed with a boric acid aqueous solution, and a step of washing with water after the treatment with the boric acid aqueous solution.
• the thickness of the polarizer layer 103 is, for example, 2 or more and 40 or less.
• the thickness of the polarizer layer 103 may be 5 or more, and may be 200! or less, further 15 or less, and still further 10 or less.
• the polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin.
• a polyvinyl acetate-based resin in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer that can be copolymerized with it is used.
• examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth)acrylic amides having an ammonium group. ..
• the degree of saponification of the polyvinyl alcohol resin is usually about 85 mol% or more and 100 mol% or less, and preferably 98 mol% or more.
• the polyvinyl alcohol resin may be modified, and for example, polyvinyl formal modified with aldehydes or polyvinyl acetal may be used.
• the polymerization degree of the polyvinyl alcohol-based resin is usually 100 or more and 100 or less, preferably 150 or more and 500 or less.
• the polarizer layer which is a stretched layer on which a dichroic dye is adsorbed, is usually a step of applying a coating liquid containing the above polyvinyl alcohol-based resin onto a base film, and the obtained laminated film is _axis -stretched.
• the base film may be peeled and removed from the polarizer layer.
• the material and thickness of the base film may be the same as the material and thickness of the thermoplastic resin film described later.
• the polarizer layer which is a stretched film or a stretched layer, may be incorporated in a laminate in a form in which a thermoplastic resin film is attached to one side or both sides thereof.
• This thermoplastic resin film can function as a protective film for the polarizer layer 103 or as a retardation film.
• the thermoplastic resin film is, for example, a polyolefin resin such as a chain polyolefin resin (such as polypropylene resin) or a cyclic polyolefin resin (such as norbornene resin); a cellulose resin such as triacetyl cellulose; polyethylene.
• the film may be a polyester resin such as terephthalate, polyethylene naphthalate, or polypropylene terephthalate; a polycarbonate resin; a (meth)acrylic resin; or a mixture thereof.
• the thickness of the thermoplastic resin film is generally 300 or less, preferably 200 or less, more preferably 100 or less, and further preferably 80 or less. And still more preferably 60 or less, usually 5 or more, and preferably 200! or more.
• thermoplastic resin film may or may not have a retardation.
• thermoplastic resin film can be attached to the polarizer layer 103 using an adhesive layer, for example.
• a polarizer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound. ⁇ 2020/175095 27 ⁇ (: 170? 2020 /004758
• a composition containing a polymerizable dichroic dye having liquid crystallinity or a composition containing a dichroic dye and a polymerizable liquid crystal on a base film and curing the composition
• examples include a polarizer layer containing a cured product of a liquid crystalline compound.
• the base film may be peeled off from the polarizer layer.
• the material and thickness of the base film may be the same as the material and thickness of the thermoplastic resin film described above.
• the polarizer layer may include an alignment film. The alignment film may be peeled off.
• thermoplastic resin film obtained by coating and curing a composition containing a dichroic dye and a polymerizable compound is incorporated into an optical laminate in a form in which a thermoplastic resin film is attached to one or both sides of the polarizer layer.
• thermoplastic resin film the same one as the thermoplastic resin film that can be used for the stretched film or the polarizer layer which is the stretched layer can be used.
• the thermoplastic resin film can be attached to the polarizer layer using, for example, an adhesive layer.
• a polarizer layer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound may have a bar coat ( ⁇ layer) formed as a protective layer on one side or both sides thereof.
• the photocurable resin include water-soluble polymers, etc.
• the photocurable resin include (meth)acrylic resin, urethane resin, (meth)acrylic urethane resin, epoxy resin, and silicone resin.
• water-soluble polymers include poly(meth)acrylic amide-based polymers; polyvinyl alcohol, and ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, (meth)acrylic acid or anhydrides thereof.
• vinyl alcohol-based polymers such as vinyl alcohol copolymers; carboxyvinyl-based polymers; polyvinylpyrrolidone; starches; sodium alginate; polyethylene oxide-based polymers, etc.
• Layer thickness is 20 or less. Preferably, it is 15 or less, more preferably, 10 or less, more preferably 5 or less, and is 0.05 or more, 0.5. It may be more than ⁇ !
• a polarizer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound. ⁇ 2020/175095 28 ⁇ (: 170? 2020 /004758
• the thickness of the layer is usually 10 or less, preferably 0.5 or more and 801 or less, and more preferably 1 or more and 5 or less.
• the second pressure-sensitive adhesive layer 104 is a pressure-sensitive adhesive layer arranged between the polarizer layer 103 and the back plate 105.
• the second pressure-sensitive adhesive layer can be a pressure-sensitive adhesive layer that is disposed closest to the back plate among the pressure-sensitive adhesive layers that form the laminate.
• the second pressure-sensitive adhesive layer 104 may be one layer, or may be composed of two or more layers, but is preferably one layer.
• the additives that can be mixed in the adhesive composition, the method for producing the second pressure-sensitive adhesive layer, and the thickness of the second pressure-sensitive adhesive layer are the same as those described above in the description of the first pressure-sensitive adhesive layer 102. is there.
• the second pressure-sensitive adhesive layer 104 may be the same as or different from the first pressure-sensitive adhesive layer 102 in terms of composition, compounding components, thickness, etc. of the pressure-sensitive adhesive composition.
• the back plate 105 it is possible to use a plate that can transmit light, a component used in a normal display device, or the like.
• the thickness of the back plate 105 may be, for example, 5 or more and 200 or less, preferably 10 or more and 100 or less, and more preferably 1 5 or more.
• the plate-like body used for the back plate 105 may be composed of only one layer, or may be composed of two or more layers. What was illustrated about can be used.
• Examples of components used in a normal display device used for the back plate 105 include a touch sensor panel, an organic display element, and the like.
• the stacking order of the components in the display device is, for example, window film/circular polarizing plate/batch sensor panel/organic display element, window film/touch sensor. ⁇ 2020/175095 29 ⁇ (: 170? 2020 /004758
• Examples include panel/circular polarizer/organic mirror 1_display element.
• the detection method is not limited, and a resistance film method, a capacitive coupling method, an optical sensor method, an ultrasonic method, an electromagnetic induction method.
• a touch sensor panel such as a coupling type or a surface acoustic wave type. Because of its low cost, a resistive film type or electrostatic capacity coupling type touch sensor panel is preferably used.
• An example of a capacitive coupling type touch sensor panel includes a substrate, a transparent electrode for position detection provided on the entire surface of the substrate, and a touch position detection circuit.
• the transparent electrode In the image display device provided with the capacitive coupling type touch sensor panel, when the surface of the front plate is touched, the transparent electrode is grounded via the electrostatic capacitance of the human body at the touched point.
• the touch position detection circuit detects the grounding of the transparent electrode, and the touched position is detected.
• the thickness of the touch sensor panel may be, for example, 5 or more and 200 or less, and may be 50! or more and 100 or less.
• the laminated body 100 can further include one layer or two or more retardation layers.
• the retardation layer is usually arranged between the polarizer layer 103 and the back plate 105.
• the phase difference layer includes the first pressure-sensitive adhesive layer 102, the second pressure-sensitive adhesive layer 104, or a layer composed of a pressure-sensitive adhesive or an adhesive other than these layers (hereinafter, also referred to as a bonding layer).
• the laminating layer is a layer arranged between the first pressure-sensitive adhesive layer 102 and the second pressure-sensitive adhesive layer 104, and is a layer composed of a pressure-sensitive adhesive or an adhesive.
• the adhesive constituting the laminating layer may be the same agent as exemplified for the pressure-sensitive adhesive composition constituting the first pressure-sensitive adhesive layer 102 or the second pressure-sensitive adhesive layer, or may be another pressure-sensitive adhesive.
• Agent for example, (meth)acrylic adhesive, styrene adhesive, silicone adhesive, rubber adhesive, urethane adhesive, polyester adhesive, epoxy copolymer adhesive, etc. ..
• the adhesive constituting the bonding layer for example, one or two or more of an aqueous adhesive, an active energy ray-curable adhesive, a pressure-sensitive adhesive and the like can be formed in combination.
• the water-based adhesive include a polyvinyl alcohol-based resin aqueous solution and a water-based two-component urethane-based emulsion adhesive.
• the active energy ray-curable adhesive agent is an adhesive agent that is cured by irradiation with active energy rays such as ultraviolet rays. And those containing a binder resin and a photoreactive crosslinking agent.
• Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable urethane monomers, and oligomers derived from these monomers.
• Examples of the photopolymerization initiator include those containing a substance that emits active species such as neutral radicals, anion radicals, and cation radicals upon irradiation with active energy rays such as ultraviolet rays.
• the thickness of the bonding layer may be, for example, 1 or more, and preferably 1 or more.
• It is 25 or less, more preferably 2 or more and 15 or less, still more preferably 2.5 or more and 5 or less.
• the laminated body 100 shown in Fig. 2 has a front plate 101, a first pressure-sensitive adhesive layer 102, a polarizer layer 103, a second pressure-sensitive adhesive layer 104, and a back plate 105. And further includes a bonding layer 108 and a first retardation layer 106.
• the laminate 100 shown in Fig. 3 includes a front plate 101, a first pressure-sensitive adhesive layer 102, and a polarizer. ⁇ 2020/175095 31 ⁇ (: 170? 2020 /004758
• a layer 103, a second pressure-sensitive adhesive layer 104, and a back plate 105 are provided, and a laminating layer 108, a first retardation layer 1 06, a laminating layer 10 9 and a second retardation layer. 10 7 is further provided.
• Examples of the retardation layer include positive eight plates such as S/4 plate and S/2 plate, and positive O plate.
• the retardation layer may be, for example, a retardation film that can be formed from the above-mentioned thermoplastic resin film, or a layer formed by curing a polymerizable liquid crystal compound, that is, a cured product of the polymerizable liquid crystal compound.
• the layer may be included, but the latter is preferable.
• the thickness of the retardation film may be the same as the thickness of the thermoplastic resin film described above.
• the thickness of the retardation layer formed by curing the polymerizable liquid crystal compound is, for example, 0. 1 0 1 or more and 10 or less, preferably 0. 5 0! or more and 8 0! or less, and more preferably 1 or more. It is less than 60!
• the retardation layer formed by curing the polymerizable liquid crystal compound can be formed by applying a composition containing the polymerizable liquid crystal compound onto a substrate film and curing the composition.
• An alignment layer may be formed between the base film and the coating layer.
• the material and thickness of the base film may be the same as the material and thickness of the thermoplastic resin film described above.
• the retardation layer formed by curing the polymerizable liquid crystal compound may be incorporated in the laminate 100 in a form having an alignment layer and/or a base film.
• the back plate 105 may be a base film to which the above composition is applied.
• the bonding layer 108 may use a pressure-sensitive adhesive or an adhesive.
• This pressure-sensitive adhesive may be the pressure-sensitive adhesive composition or pressure-sensitive adhesive composition described above.
• a water-based adhesive or an active energy ray curable adhesive can be used.
• the water-based adhesive include an adhesive composed of a polyvinyl alcohol-based resin aqueous solution and a water-based two-component urethane-based emulsion adhesive.
• the active energy ray-curable adhesive refers to an adhesive that is cured by irradiation with active energy rays such as ultraviolet rays, and includes, for example, a polymerizable compound and a photopolymerization initiator. ⁇ 2020/175095 32 units (: 170? 2020 /004758
• those containing a photoreactive resin those containing a binder resin and a photoreactive crosslinking agent, and the like.
• Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable (meth)acrylic monomers, and photocurable urethane monomers, and oligomers derived from photopolymerizable monomers.
• photopolymerizable monomers such as photocurable epoxy monomers, photocurable (meth)acrylic monomers, and photocurable urethane monomers, and oligomers derived from photopolymerizable monomers.
• the photopolymerization initiator examples include those containing substances that generate active species such as neutral radicals, anion radicals, and cation radicals upon irradiation with active energy rays such as ultraviolet rays.
• active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator an adhesive containing a photocurable epoxy monomer and a photocationic polymerization initiator can be preferably used.
• the laminated body 100 can be manufactured by a method including a step of laminating the layers constituting the laminated body 100 with a pressure-sensitive adhesive layer or an adhesive layer.
• a pressure-sensitive adhesive layer or an adhesive layer When laminating layers via an adhesive layer or an adhesive layer, surface activation treatment such as corona treatment is applied to one or both of the laminating surfaces to enhance adhesion. It is preferable.
• the polarizer layer 103 can be directly formed on the thermoplastic resin film or the base film, and the thermoplastic resin film or the base film may be incorporated in the laminate 100, Alternatively, it may be separated from the polarizer layer 103 and not be a constituent element of the laminate.
• a display device includes the layered product 100 according to the present invention.
• the display device is not particularly limited, and examples thereof include an image display device such as an organic display device, an inorganic display device, a liquid crystal display device, and an electroluminescent display device.
• the display device may have a touch panel function.
• the optical layered body is suitable for a flexible display device that can be bent or bent.
• the optical laminate is arranged on the viewing side of the display element of the display device with the front plate facing outward (the side opposite to the display element side, that is, the viewing side).
• the display device according to the present invention can be used as a smartphone, a mobile device such as a tablet, a television, a digital photo frame, an electronic signboard, a measuring instrument or measuring instrument, an office device, a medical device, a computer device, or the like. it can.
• the pressure-sensitive adhesive composition according to the present invention is a (meth)acrylic acid ester or a (meth)acrylic acid amide, and contains a structural unit derived from a monomer having a structure represented by the above formula (). )
• the pressure-sensitive adhesive sheet according to the present invention is a (meth)acrylic acid ester or a (meth)acrylic acid amide, and contains a structural unit derived from a monomer having a structure represented by the above formula (). )
• a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing an acrylic polymer, and preferably a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
• the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition onto a substrate.
• an active energy ray-curable pressure-sensitive adhesive composition is used as the pressure-sensitive adhesive composition, the formed pressure-sensitive adhesive layer can be irradiated with an active energy ray to obtain a cured product having a desired degree of curing. ..
• the base material may be a release film that has been subjected to a release treatment.
• the pressure-sensitive adhesive sheet can be prepared by forming a layer made of a pressure-sensitive adhesive in a sheet shape on a release film, and further laminating another release film on the pressure-sensitive adhesive layer.
• the adhesive layer of the adhesive sheet according to the present invention has excellent adhesiveness. Temperature of the standard adhesive layer having a thickness of 150, which is formed by the adhesive composition used for forming the adhesive layer Then, preferably, the following relational expression (4):
• the monomers shown in Table 1 were mixed and copolymerized to obtain (meth)acrylic polymers 81 to 86.
• the amounts of monomers in the table are parts by mass. Also, the measured weight average molecular weight Are shown in Table 1.
• a sheet that is, a pressure-sensitive adhesive sheet having a structure of release film 8/adhesive layer (thickness: 25)/release film, was prepared.
• the thickness of the pressure-sensitive adhesive layer is a value measured by the method described below.
• a standard pressure-sensitive adhesive layer was prepared by the method described below, and the shear stress relaxation rate was measured. The results are shown in Table 1.
• the photopolymerization initiator benzyl dimethyl ketal ( ⁇ _ 6 5 1) ⁇ 0.05% by mass and 1 — hydroxycyclohexyl phenyl ketone ( ⁇ 1 184) ⁇ 0.5 mass% was added. Then, the mixture was irradiated with an II V lamp (10) with stirring to produce a (meth)acrylate polymer (89) having a weight average molecular weight (1 ⁇ /1) of 500,000.
• the temperature was maintained at 80 ° .
• the photopolymerization initiator benzyl dimethyl ketal (1 65 1) 0.05% by mass and 1-hydroxycyclohexyl phenyl ketone (1 _ 1 8 4) 0. 5% by mass was added.
• the mixture was irradiated with an II V lamp (10) with stirring to produce a (meth)acrylate polymer (8 10) with a weight average molecular weight (! ⁇ /!) of 350,000.
• Adhesive compositions No. 7 to No. 10 were applied to a light release film 8 (polyethylene terephthalate film, thickness 3801) coated with a silicone release agent to a thickness of 25.
• a heavy release film film (polyethylene terephthalate film, thickness 3800) was bonded onto it, and irradiated/irradiated to produce an adhesive sheet consisting of release film 8/adhesive layer/release film film.
• the adhesive sheet was used to prepare a reference adhesive layer by the method described below, and the shear stress relaxation rate was measured.
• (Meth) Weight average molecular weight of acrylic polymer was calculated as the polystyrene-equivalent number average molecular weight (M n ) using tetrahydrofuran as the mobile phase and the following size exclusion chromatography (3).
• the (meth)acrylic polymer to be measured was dissolved in tetrahydrofuran at a concentration of about 0.05% by mass, and was injected at a volume of 3 (10 to 3).
• the mobile phase was flown at a flow rate of 1.0.
• 1_966 I IV! IX ⁇ 0— ⁇ manufactured by Polymer Laboratories
• Three detectors (trade name: 89 9 ⁇ 6 1 ⁇ ⁇ ⁇ ) were used.
• the polarizer layer and the alignment film were measured using a laser microscope ("O1_33000" manufactured by Olympus Corporation).
• the shear stress relaxation rate was measured using a viscoelasticity measuring device (MC R_301, Anton ⁇ ⁇ "Sha”). It was cut into pieces, the release film was peeled off, multiple layers were laminated to a thickness of 150, and they were bonded to a glass plate. When bonded to the measuring chip, at a temperature of 25 ° ⁇ ⁇ ”013 ⁇ Dry ⁇ ” ⁇ 6 1 1 ⁇ 1, deform to a deformation of 10% and stop.
• MC R_301 Anton ⁇ ⁇ "Sha”
• the shear elastic modulus was measured after 300 seconds. Based on these measured values, the shear stress relaxation rate o was calculated from the following formula.
• pressure-sensitive adhesive sheet including the first pressure-sensitive adhesive layer 102 and the second pressure-sensitive adhesive layer 104
• pressure-sensitive adhesive sheets formed from the pressure-sensitive adhesive compositions shown in Table 1 and Table 3 were prepared.
• the pressure-sensitive adhesive sheet for the first pressure-sensitive adhesive layer 102 is referred to as a first pressure-sensitive adhesive sheet
• the pressure-sensitive adhesive sheet for the second pressure-sensitive adhesive layer 104 is referred to as a second pressure-sensitive adhesive sheet.
• a polyimide film having a hard coat layer on one side (1 to 10 1 layer, total thickness: 60, thickness of hard coat layer: 1 0 1 ,polyimide) Film thickness: 50 000 was prepared.
• the polymerizable liquid crystal compound includes a polymerizable liquid crystal compound represented by the formula (1 _6) [hereinafter also referred to as compound (1 _6)] and a polymerizable liquid crystal compound represented by the formula (1 _7) [hereinafter, compound (1 _6) —7) Also called].
• the dichroic dye has the following formula The azo dyes described in Examples of JP-A No. 2013-101 328 represented by (2-113) and (2-33) were used.
• composition for forming a polarizer layer comprises: compound (1 _6) 75 parts by mass, compound (1 _7) 25 parts by mass, the above formula (2_ 1 3 ) as a dichroic dye, (2 _ 1 ⁇ ), (
• Polymer 1 is a polymer having a photoreactive group consisting of the following structural units.
• the molecular weight of the obtained polymer 1 is number average molecular weight 28200, 82, and the monomer content was 0.5%.
• a solution prepared by dissolving Polymer 1 at a concentration of 5 mass% in cyclopentanone was used as a composition for forming an alignment film.
• the composition for the protective layer is polyvinyl alcohol resin powder (produced by Kuraray Co., Ltd., average degree of polymerization: 18000, trade name: ⁇ !__3 18) with respect to 100 parts by mass of water.
• polyamide epoxy resin crosslinking agent, manufactured by Sumika Chemtex Co., Ltd., trade name: 38650 (30)
• Corona treatment (output ⁇ .
• a composition for forming an alignment film was applied onto a triacetylcellulose (Chaukei) film (thickness 25) with a processing speed of 3/min) by the percoat method, and heated and dried in a drying oven at 80° for 1 minute. ..
• the obtained dried coating film was irradiated with polarized light V to form a first alignment film (1_ 1 ).
• the polarized light V treatment is performed by changing the light emitted from the II V irradiation device (“3 0 3 7 17” manufactured by Ushio Electric Co., Ltd.) ⁇ 2020/175095 42 ⁇ (: 170? 2020 /004758
• [1) 1 3-27 1 32##”) manufactured by Sai Denki Co., Ltd. was transmitted, and the integrated light quantity measured at a wavelength of 365 was 100”/ ⁇ 2 .
• the thickness of the first alignment film (8!_ 1) is Met.
• the composition for forming a polarizer layer was applied on the formed first alignment film (8 1_1) by a bar coating method, and was heated and dried in a drying oven at 120 ° ⁇ for 1 minute, and then allowed to reach room temperature. Cooled. Using the above II V irradiation device, the accumulated light amount is 1 200 The ultraviolet (365 n m reference), by irradiating the dried coating to form a polarizer layer ( ⁇ ). The thickness of the obtained polarizer layer was 1.8.
• composition for protective layer was applied onto the formed polarizer layer by a bar coating method, so that the thickness after drying was 1.0, and dried at a temperature of 80 ° for 3 minutes. .. In this way, a laminated body consisting of the 80 film/first alignment film (8!_ 1)/polarizer layer/protective layer was obtained.
• a polyethylene terephthalate film having a thickness of 1001 (Mending) was prepared, and the composition for forming an alignment film described above was coated on the film by a bar coating method, and then in a dry oven at 80 ° Heat dried for minutes.
• the obtained dried film was subjected to polarized light irradiation treatment to form a second alignment film (!_ 2).
• the polarized II V treatment was performed by using the above II V irradiator, and the accumulated light amount measured at a wavelength of 365 n was 100 ”/ ⁇ . It was performed under the condition of 2 .
• the polarization direction of polarized light II V was set to be 45° with respect to the absorption axis of the polarizer layer.
• a composition for forming a retardation layer was applied on the obtained second alignment film (eight!_2) by a bar coating method, and was dried by heating in a drying oven at 120 ° ⁇ for 1 minute, and then at room temperature. It was cooled down. The dry film thus obtained was subjected to an integrated light amount of 1
• the retardation layer was formed by irradiating (365 nm standard) ultraviolet rays.
• the thickness of the obtained retardation layer was measured by a laser microscope (01-33000 manufactured by Olympus Corporation), and it was 2.0.
• the phase difference layer was a S/4 plate ( ⁇ ) showing a phase difference value of S/4 in the in-plane direction.
• the base material (Ming)/the second alignment film (8 1_2)/position A laminate comprising the retardation layer ( ⁇ ) was obtained.
• An acrylic resin was obtained by reacting the following components at 55 ° with stirring under a nitrogen atmosphere.
• Butyl acrylate 70 parts ⁇ 2020/175095 44 ⁇ (: 170? 2020 /004758
• Cross-linking agent (Coronate!-" manufactured by Tosoh Corporation): 1.0 part
• Silane coupling agent (Shin-Etsu Silicon Co., Ltd. " ⁇ _ 1 2-9 8 1")
• Ethyl acetate was added so that the total solid content concentration was 10% to obtain a pressure-sensitive adhesive composition.
• the thickness after drying was 5 using an applicator. Applied. The coating layer was dried at 100° for 1 minute to obtain a film having an adhesive layer. Then, a light release film 8 (polyethylene terephthalate film, thickness 38) that had been subjected to a mold release treatment was laminated on the exposed surface of the adhesive layer. Then temperature 23 ° ⁇ , relative humidity The adhesive sheet was obtained by curing for 7 days under the above conditions.
• a polyethylene terephthalate substrate (thickness 38) or a glass substrate was prepared.
• Laminates of Examples 1 to 5 and Comparative Examples 1 and 2 were manufactured by the following procedure.
• pressure-sensitive adhesive sheets formed from the pressure-sensitive adhesive compositions shown in Tables 1 and 3 were used in the combinations shown in Table 4.
• the pressure-sensitive adhesive sheet for laminated layers and the laminate containing the above-mentioned polarizer layer were attached to each other to obtain a laminate 81.
• the other adhesive film for the bonding layer was subjected to corona treatment on the exposed bonding layer.
• Corona treatment is applied to the surface of the layered product including the retardation layer on the retardation layer side, and the layered product 1 and the layered product including the retardation layer are processed so that the corona-treated surface becomes the bonding surface.
• Lamination was performed to obtain a laminated body 82.
• the Mingo film was peeled from the laminate 82, and the surface on the retardation layer side was subjected to corona treatment.
• the release film 8 of the second pressure-sensitive adhesive sheet was peeled off, and the surface of the pressure-sensitive adhesive layer was subjected to corona treatment.
• the laminate 8 2 and the second pressure-sensitive adhesive layer were attached to each other so that the surface subjected to the corona treatment was the attachment surface to obtain a laminate 8 3.
• Release film 8 was peeled from the first pressure-sensitive adhesive sheet, and the surface of the pressure-sensitive adhesive layer was subjected to corona treatment.
• Corona treatment was also applied to the front side of the front plate, and the first pressure-sensitive adhesive layer and the front plate were bonded together so that the corona-treated surface became the bonding surface to obtain a laminated body 84.
• the surface of the laminate 83 on the film side was subjected to corona treatment.
• the release film underlayer of the laminated body 84 was peeled off, and the surface of the first pressure-sensitive adhesive layer was subjected to corona treatment.
• the layered product 3 and the layered product 4 were attached to each other so that the surface subjected to the corona treatment was the attachment surface to obtain a layered product 85.
• the laminated film 85 of the laminated body 85 was peeled off, and the laminated body was laminated with a polyethylene terephthalate substrate to obtain a laminated body for evaluation of room-temperature flexibility.
• the release film Maw of the laminate 85 was peeled off and bonded to a glass substrate to obtain a laminate for a normal temperature adhesive durability test.
• the window film/first adhesive layer/chome film layer/first alignment film (8!_1)/polarizer layer/protective layer/laminating layer/second alignment film ( A laminate consisting of eight !_ 2 )/retardation layer/second adhesive layer/back plate was prepared.
• FIG. 4 is a diagram schematically showing the method of this evaluation test. As shown in Fig. 4, two individually movable mounting tables 50 1 and 5 (Bending radius 3 01 01) so that the center in the width direction is located at the center of the gap ⁇ and the window film is located on the upper side. (Fig. 4 (3)).
• the two mounting tables 50 1 and 50 2 are rotated upward 90 degrees about the position 1 and the position 2 as the center of the rotation axis, and bent into the region of the stacked body corresponding to the space 0 between the mounting tables.
• Force was applied (Fig. 4 (13)).
• the two mounting tables 50 1 and 50 2 were returned to their original positions (Fig. 4 (3)).
• the number of times the bending force was applied was counted as 1. After repeating this at a temperature of 25°, it was confirmed whether or not air bubbles were generated in the pressure-sensitive adhesive layer in the region corresponding to the space ⁇ of the stacking tables 50 1 and 50 2.
• the moving speeds of the mounting tables 50 1 and 50 2 and the pace of applying the bending force were set to the same conditions in the evaluation test for any of the laminates.
• ⁇ Bubbles were generated when the bending force was applied more than 10,000 and less than 50,000.
• Mami Bubbles were generated when the bending force was applied less than 10,000.
• the room temperature adhesion durability was tested by using a laminate in which a glass substrate was bonded instead of the polyethylene terephthalate substrate as described above.
• the laminate 8 After cutting so that the release film was peeled off from the second pressure-sensitive adhesive layer, it was bonded to a non-alkali glass substrate to obtain a laminate for a room temperature adhesion durability test.
• the test piece was treated in an autoclave at a temperature of 5°C and a pressure of 5 atm for 20 minutes, and then kept under constant temperature and humidity conditions (temperature of 23°C and relative humidity of 50%) for 4 hours. Then, after leaving it for 25 hours at a temperature of 25°, it floated on the test piece and was observed for peeling and air bubbles.
• the evaluation criteria are as follows.
• ⁇ Appearance changes such as floating, peeling and foaming are noticeable.
• Comparative Examples 1 and 2 have a relationship of "[3 ⁇ 4 0 1 >[3 ⁇ 4 0 2”, and thus can be determined to have a relationship of "[3 ⁇ 4 1 >[3 ⁇ 4 2".

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