CN113474699A - Laminate and display device - Google Patents
Laminate and display device Download PDFInfo
- Publication number
- CN113474699A CN113474699A CN202080016406.2A CN202080016406A CN113474699A CN 113474699 A CN113474699 A CN 113474699A CN 202080016406 A CN202080016406 A CN 202080016406A CN 113474699 A CN113474699 A CN 113474699A
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- China
- Prior art keywords
- meth
- layer
- adhesive
- adhesive layer
- laminate
- Prior art date
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- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- FFIUNPRXUCRYFU-UHFFFAOYSA-N tert-butyl pentaneperoxoate Chemical compound CCCCC(=O)OOC(C)(C)C FFIUNPRXUCRYFU-UHFFFAOYSA-N 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
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- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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]
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- 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
-
- 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; CALCULATING OR 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Theoretical Computer Science (AREA)
- Nonlinear Science (AREA)
- General Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Human Computer Interaction (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Polarising Elements (AREA)
Abstract
The purpose of the present invention is to provide a laminate which is capable of suppressing the occurrence of air bubbles and has excellent adhesive strength even when the front panel side is bent to the outside. The present invention provides a laminate comprising a front sheet, a1 st adhesive layer formed using a1 st adhesive composition, a polarizer layer, a2 nd adhesive layer formed using a2 nd adhesive composition, and a back sheet in this order, wherein the following relational expression (1) is satisfied if the shear stress relaxation rate at a temperature of 25 ℃ of the 1 st adhesive layer is R1 and the shear stress relaxation rate at a temperature of 25 ℃ of the 2 nd adhesive layer is R2: r1 is not less than R2 (1).
Description
Technical Field
The present invention relates to a laminate and a display device using the laminate.
Background
Jp 2018 a-28573 (patent document 1) describes a laminate for a flexible image display device having a plurality of adhesive layers.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2018-28573
Disclosure of Invention
In a display device including a laminate having a front panel and a plurality of adhesive layers, when the front panel side is repeatedly bent to the outside, air bubbles may be generated in the adhesive layers in the laminate. In addition, the adhesive force of the adhesive layer is weak, and floating or peeling may occur between the adhesive layer and the member to be bonded.
The purpose of the present invention is to provide a laminate which can suppress the occurrence of air bubbles and has excellent adhesion even when the front panel is repeatedly bent with the front panel side being the outer side, and a display device using the laminate.
The invention provides the following laminated body and display device.
[ 1] A laminate comprising a front sheet, a1 st adhesive layer formed using a1 st adhesive composition, a polarizer layer, a2 nd adhesive layer formed using a2 nd adhesive composition, and a back sheet in this order,
when the shear stress relaxation rate at a temperature of 25 ℃ of the 1 st pressure-sensitive adhesive layer is R1 and the shear stress relaxation rate at a temperature of 25 ℃ of the 2 nd pressure-sensitive adhesive layer is R2, the following relational expression (1) is satisfied:
R1≥R2 (1)。
[ 2] A laminate according to [ 1], wherein R represents a shear stress relaxation rate at 25 ℃ of a1 st reference adhesive layer having a thickness of 150 μm and formed using the 1 st adhesive composition01. The shear stress relaxation rate at 25 ℃ of a2 nd reference adhesive layer having a thickness of 150 μm formed using the 2 nd adhesive composition was R02, the following relational expressions (2) and (3) are satisfied:
0.02≤R01≤0.25 (2)
0.02≤R02≤0.25 (3)。
the laminate according to [ 1] or [ 2], wherein the 1 st adhesive composition and the 2 nd adhesive composition each contain a (meth) acrylic polymer.
The laminate according to [ 4] or [ 3], wherein the weight average molecular weight (Mw) of the (meth) acrylic polymer is 20 to 150 ten thousand.
The laminate according to [ 3] or [ 4], wherein the content of the constituent unit derived from the monomer having a reactive functional group in the (meth) acrylic polymer is less than 5% by mass based on the total mass of the polymer.
The laminate according to any one of [ 1] to [ 5 ], wherein the back panel is a touch sensor panel.
A display device comprising the laminate according to any one of [ 1] to [ 6 ].
[ 8 ] according to the display device described above in [ 7 ], the front panel side can be bent outward.
According to the present invention, a laminate which can suppress the generation of air bubbles and has excellent adhesive strength even when the front panel side is repeatedly bent to the outside, and a display device using the laminate can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of the laminate of the present invention.
Fig. 2 is a schematic cross-sectional view showing an example of the laminate of the present invention.
Fig. 3 is a schematic cross-sectional view showing an example of the laminate of the present invention.
Fig. 4 is a schematic diagram illustrating a method of the bending test.
Detailed Description
A laminate according to an embodiment of the present invention (hereinafter also simply referred to as "laminate") will be described below with reference to the drawings.
< laminate >
Fig. 1 is a schematic cross-sectional view of a laminate (optical laminate) according to an embodiment of the present invention. The laminate 100 includes a front panel 101, a1 st adhesive layer 102, a polarizer layer 103, a2 nd adhesive layer 104, and a back panel 105 in this order. The 1 st adhesive layer 102 is formed of a1 st adhesive composition, and the 2 nd adhesive layer 104 is formed of a2 nd adhesive composition. Hereinafter, the 1 st adhesive layer 102 and the 2 nd adhesive layer 104 may be collectively referred to as an adhesive layer.
The thickness of the laminate 100 is not particularly limited, and is, for example, 50 to 4000 μm, preferably 100 to 2000 μm, and more preferably 150 to 1000 μm, since it varies depending on the functions required for the laminate, the use of the laminate, and the like.
The shape of the laminate 100 in plan view may be, for example, a square shape, preferably a square shape having long sides and short sides, and more preferably a rectangle. When the shape of the laminate 100 in the plane direction is a rectangle, the length of the long side may be, for example, 10mm to 1400mm, and preferably 50mm to 600 mm. The length of the short side is, for example, 5mm to 800mm, preferably 30mm to 500mm, and more preferably 50mm to 300 mm. Each layer constituting the laminate may be subjected to a corner rounding process, or an end cutting process or a hole forming process.
The laminate 100 can be used for a display device or the like, for example. The display device is not particularly limited, and examples thereof include an organic electroluminescence (organic EL) display device, an inorganic electroluminescence (inorganic EL) display device, a liquid crystal display device, and an electroluminescence display device. The display device may have a touch panel function.
[ shear stress relaxation Rate of adhesive layer ]
In the laminate 100, if the shear stress relaxation rate at a temperature of 25 ℃ of the 1 st adhesive layer 102 is R1 and the shear stress relaxation rate at a temperature of 25 ℃ of the 2 nd adhesive layer 104 is R2, the following relational expression (1) is satisfied:
R1≥R2 (1)，
more preferably, the following relational expression (1') is satisfied:
R1＞R2 (1’)。
whether or not the relation (1) or (1') is satisfied is
i) A method of making a judgment based on each value of R1 and R2; and
ii) a method of judging based on other combinations having the same size relationship as the combination of R1 and R2.
Although the shear stress relaxation rate does not depend on the thickness of the adhesive layer, when the 1 st adhesive layer 102 and the 2 nd adhesive layer 104 are too thin, it may be difficult to accurately measure the shear stress relaxation rate. One of the methods for judging based on the other combinations of ii) is, for example, a method of comparing a1 st reference adhesive layer formed from a1 st adhesive composition with a2 nd reference adhesive layer formed from a2 nd adhesive composition. Shear stress relaxation rate R at 25 ℃ of temperature of No. 1 reference adhesive layer01 and 2 nd reference adhesive layer at a temperature of 25 ℃ and a shear stress relaxation rate R02 full ofThe following relational expression (1 a): r01≥R02(1a), the following relational expression (1' a) is satisfied: r01＞R02(1 'a) can be regarded as satisfying the relational expression (1'). The thickness of the 1 st and 2 nd reference adhesive layers may be 150 μm. Shear stress relaxation rate R at 25 ℃ of No. 1 reference adhesive layer and No. 2 reference adhesive layer having a thickness of 150 μm01、R02 was measured according to the measurement method described in the section of example.
The laminate 100 can be bent with the front panel 101 side facing outward. In a display device including a laminate, if the front panel side is repeatedly bent to the outside, air bubbles may be generated in the pressure-sensitive adhesive layer. The generation of such bubbles is particularly remarkable in the adhesive layer on the side away from the front panel, i.e., the 2 nd adhesive layer 104 in the laminate 100. As a result of studies by the present inventors, it was found that when the shear stress relaxation rates of the 1 st pressure-sensitive adhesive layer 102 and the 2 nd pressure-sensitive adhesive layer 104 satisfy the relational expression (1), bubbles generated in the pressure-sensitive adhesive layers in the laminate 100 can be suppressed even when the front panel 101 side is repeatedly bent outward. More specifically, even when the laminate 100 is repeatedly bent 2 ten thousand times so that the inner surface of the laminate 100 has a bending radius of 3mm, bubbles generated in the pressure-sensitive adhesive layer in the laminate 100 can be suppressed (hereinafter, the laminate is also referred to as having excellent "room-temperature bendability"). The room temperature flexibility can be evaluated according to the evaluation methods described in the section of examples described later. The laminate 100 can be bent with the front panel side being the inner side. The display device to which the laminate 100 is applied can be used as a flexible display which can be bent, rolled, or the like.
In the present specification, the bending includes a bending form in which a curved surface is formed at a bent portion, and a bending radius of an inner surface of the bending is not particularly limited. In addition, the bending also includes bending in which the bending angle of the inner surface is greater than 0 degrees and less than 180 degrees, and folding in which the bending radius of the inner surface is approximately zero or the bending angle of the inner surface is 0 degrees.
When the shear stress relaxation rates of the 1 st pressure-sensitive adhesive layer 102 and the 2 nd pressure-sensitive adhesive layer 104 satisfy the relational expression (1), even when left standing for a long time under constant temperature and humidity conditions, the adhesive layer and the member to be adhered hardly show changes in appearance such as floating, peeling, and foaming, and the adhesive durability at normal temperature is excellent. The room temperature adhesion durability can be evaluated according to the evaluation methods described in the section of examples described later.
When the shear stress relaxation rate at 25 ℃ of the 1 st reference adhesive layer with the thickness of 150 μm is set as R01 and the shear stress relaxation rate at 25 ℃ of the 2 nd reference adhesive layer with a thickness of 150 μm is R02, the following relational expressions (2) and (3) are preferably satisfied:
0.02≤R01≤0.25 (2)
0.02≤R02≤0.25 (3)，
more preferably, the following relational expressions (2a) and (3a) are satisfied:
0.10≤R01≤0.20 (2a)
0.10≤R02≤0.20 (3a)。
examples of the method for producing the 1 st adhesive composition and the 2 nd adhesive composition so that the shear stress relaxation rates of the 1 st adhesive layer 102 and the 2 nd adhesive layer 104 satisfy the relational expression (1) include a method of forming an adhesive layer from the adhesive composition a described later, a method of changing the kind of monomers constituting the (meth) acrylic polymer a described later, or a method of adjusting the molecular weight of the (meth) acrylic polymer a described later.
[ adhesive composition ]
In one embodiment, the 1 st adhesive layer 102 and the 2 nd adhesive layer 104 are formed from an adhesive composition containing a (meth) acrylic polymer (hereinafter also referred to as an adhesive composition a). The adhesive composition a may be an active energy ray-curable type or a thermosetting type. In the present specification, "(meth) acrylic polymer" means at least 1 selected from acrylic polymers and methacrylic polymers. The same applies to other terms denoted by "(meth)".
(1) Active energy ray-curable adhesive composition
When the pressure-sensitive adhesive composition a is an active energy ray-curable pressure-sensitive adhesive composition, the (meth) acrylic polymer contained in the pressure-sensitive adhesive composition a (hereinafter also referred to as the (meth) acrylic polymer a) may contain a constituent unit derived from a (meth) acrylic monomer, and the (meth) acrylic monomer may be linear, branched, or cyclic. Examples of the (meth) acrylic monomer include (meth) acrylate and (meth) acrylic amide. Examples of the (meth) acrylic acid ester include butyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and the like. Examples of the (meth) acrylamide include (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-ethylacrylamide, and N- (2-hydroxyethyl) (meth) acrylamide. The (meth) acrylic polymer a may be a polymer or copolymer containing 1 or 2 or more monomers selected from the group consisting of the above-mentioned (meth) acrylic acid esters and (meth) acrylic acid amides. The content of the (meth) acrylic polymer a in the pressure-sensitive adhesive composition a may be, for example, 50 to 100 mass%, preferably 80 to 99.5 mass%, more preferably 88 to 99 mass%, and still more preferably 90 to 99 mass% with respect to 100 mass% of the solid content of the pressure-sensitive adhesive composition a.
The (meth) acrylic polymer contained in the adhesive composition a is preferably a (meth) acrylic polymer containing a constituent unit derived from a monomer that is a (meth) acrylate or a (meth) acrylic acid amide and contains a structure represented by the following formula (I).
(in the formula (I), Z1Is an oxygen atom or a nitrogen atom, Z2Is an oxygen atom, a nitrogen atom or a carbon atom, and Y is a hydrocarbon group. )
In the formula (I), Y may be a cyclic hydrocarbon group, or Y and Z may be1Or Z2Together forming a ring. Z1Or Z2May be an oxygen atom or a nitrogen atom bonded to the (meth) acryloyl group. From the viewpoint of improving durability, Y preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
At least one of the (meth) acrylic polymer a contained in the 1 st adhesive composition and the 2 nd adhesive composition preferably contains a constituent unit derived from a monomer that contains a structure represented by formula (I) and is a (meth) acrylate or a (meth) acrylic amide. By using the pressure-sensitive adhesive composition a containing such a (meth) acrylic polymer, the 1 st reference pressure-sensitive adhesive layer and the 2 nd reference pressure-sensitive adhesive layer satisfying the relational expressions (2) and (3) described above can be easily formed. The (meth) acrylic polymer a may contain, for example, 1 to 20 mass%, preferably 2 to 10 mass% of a constituent unit derived from a monomer containing a structure represented by formula (I) and being a (meth) acrylate or a (meth) acrylic amide, with respect to 100 mass% of the solid content of the (meth) acrylic polymer a.
Examples of the monomer having a structure represented by formula (I) and being a (meth) acrylate or a (meth) acrylamide include (meth) acrylic monomers represented by the following compounds of formulae (II) to (VI).
(wherein R represents a hydrogen atom or a methyl group.)
In the (meth) acrylic polymer a, the constituent unit derived from the monomer having a reactive functional group is preferably less than 5% by mass based on the total mass of the polymer, in addition to the constituent unit derived from the monomer containing the structure represented by the formula (I) and being a (meth) acrylate or a (meth) acrylamide. Examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amino group, an amide group, and an epoxy group. This increases the flexibility of the pressure-sensitive adhesive layer, and tends to prevent the generation of bubbles during bending. From the viewpoint of preventing the generation of bubbles, the constituent unit derived from the monomer having a reactive functional group in the (meth) acrylic polymer a is preferably 1% by mass or less, more preferably 0.01% by mass or less, even more preferably no constituent unit derived from the monomer having a reactive functional group, and even more preferably no hydroxyl group, carboxyl group, amino group, amide group, and epoxy group, based on the total mass of the polymer.
The weight average molecular weight (Mw) of the (meth) acrylic polymer a may be, for example, 30 to 70 ten thousand, and preferably 30 to 60 ten thousand from the viewpoint of suppressing bubbles at the time of bending. The weight average molecular weight (Mw) can be measured according to the measurement method described in the section of examples described later.
The adhesive composition a may contain 1 or 2 or more (meth) acrylic polymers a. The pressure-sensitive adhesive composition a may contain only the (meth) acrylic polymer a as a constituent component thereof, or may further contain a crosslinking agent. Examples of the crosslinking agent include metal ions having a valence of 2 or more which form a metal carboxylate with a carboxyl group; polyamine compounds forming amide bonds with carboxyl groups; polyepoxy compounds or polyols which form ester bonds with carboxyl groups; polyisocyanate compounds forming an amide bond with a carboxyl group, and the like. Among them, polyisocyanate compounds are preferable. When the pressure-sensitive adhesive composition a contains a crosslinking agent, the content of the crosslinking agent may be, for example, 5 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 part by mass or less, further preferably 0.1 part by mass or less, based on 100 parts by mass of the (meth) acrylic polymer a, and the pressure-sensitive adhesive composition a most preferably does not contain a crosslinking agent.
The active energy ray-curable adhesive composition means an adhesive composition having the following properties: the adhesive sheet is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam, has adhesive properties even before irradiation with an active energy ray, can be adhered to an adherend such as a film, and can be cured by irradiation with an active energy ray, thereby adjusting adhesion force and the like.
The active energy ray-curable adhesive composition is preferably an ultraviolet-curable adhesive composition.
When the pressure-sensitive adhesive composition a is an active energy ray-curable pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition a may further contain an active energy ray-polymerizable compound, a photopolymerization initiator, a photosensitizer, or the like.
Examples of the active energy ray-polymerizable compound include (meth) acrylate monomers having at least 1 (meth) acryloyloxy group in the molecule; a (meth) acrylic compound such as a (meth) acryloyloxy group-containing compound obtained by reacting 2 or more kinds of functional group-containing compounds and having at least 2 (meth) acryloyloxy groups in the molecule, e.g., a (meth) acrylate oligomer. The binder composition a may contain 0.1 to 10 parts by mass of the active energy ray-polymerizable compound per 100 parts by mass of the solid content of the binder composition a.
Examples of the photopolymerization initiator include benzophenone, benzildimethylketal, and 1-hydroxycyclohexylphenylketone. When the adhesive composition a contains a photopolymerization initiator, 1 or 2 or more species may be contained. When the adhesive composition a contains a photopolymerization initiator, the total content thereof may be, for example, 0.01 to 1.0 part by mass per 100 parts by mass of the solid content of the adhesive composition a.
The binder composition a may contain additives such as fine particles, beads (resin beads, glass beads, and the like), glass fibers, resins other than the base polymer, adhesion-imparting agents, fillers (metal powder, other inorganic powder, and the like), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, defoaming agents, and anticorrosive agents for imparting light scattering properties. From the viewpoint of preventing the problem of the reduction in durability caused by the residual solvent, the adhesive composition a preferably does not contain an organic solvent.
In the case where the adhesive layer is formed of the adhesive composition a, the adhesive layer may be formed by applying the adhesive composition a onto a substrate. In the case of using an active energy ray-curable pressure-sensitive adhesive composition, a cured product having a desired degree of curing can be produced by irradiating the formed pressure-sensitive adhesive layer with an active energy ray.
The adhesive composition a can be produced by mixing the respective components together by a known method, for example, using a mixer or the like.
(2) Heat-curable adhesive composition
When the adhesive composition a is a heat-curable adhesive composition, the (meth) acrylic polymer a preferably contains, as monomer units constituting the polymer, an alkyl (meth) acrylate having an alkyl group and 2 to 20 carbon atoms and a monomer having a reactive functional group in a molecule (reactive functional group-containing monomer).
The (meth) acrylic polymer A can exhibit preferable adhesiveness by containing an alkyl (meth) acrylate having an alkyl group and 2 to 20 carbon atoms as a monomer unit constituting the polymer. The alkyl (meth) acrylate having an alkyl group with 2 to 20 carbon atoms is preferably an alkyl (meth) acrylate having a glass transition temperature (Tg) of-40 ℃ or lower (hereinafter, may be referred to as "low Tg alkyl acrylate") as a homopolymer. By containing the low Tg alkyl acrylate as a constituent monomer unit, the flexibility of the pressure-sensitive adhesive layer is improved, floating or peeling between the pressure-sensitive adhesive layer and the member to be bonded is less likely to occur, and when the front panel side is repeatedly bent to the outside, the generation of bubbles in the pressure-sensitive adhesive layer tends to be more easily suppressed.
Examples of the low Tg alkyl acrylate include n-butyl acrylate (Tg of-55 ℃ C.), n-octyl acrylate (Tg of-65 ℃ C.), isooctyl acrylate (Tg of-58 ℃ C.), 2-ethylhexyl acrylate (Tg of-70 ℃ C.), isononyl acrylate (Tg of-58 ℃ C.), isodecyl acrylate (Tg of-60 ℃ C.), isodecyl methacrylate (Tg of-41 ℃ C.), n-lauryl methacrylate (Tg of-65 ℃ C.), tridecyl acrylate (Tg of-55 ℃ C.), and tridecyl methacrylate (Tg of-40 ℃ C.). Among them, from the viewpoint that the shear stress relaxation rate at 25 ℃ of the obtained adhesive is likely to fall within the above range, the low Tg alkyl acrylate having a homopolymer Tg of-45 ℃ or less is more preferable, and the low Tg alkyl acrylate having a homopolymer Tg of-50 ℃ or less is particularly preferable. Specifically, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. These may be used alone, or 2 or more of them may be used in combination.
The (meth) acrylic polymer a preferably contains the low Tg alkyl acrylate in an amount of 85 mass% or more, more preferably 90 mass% or more, and still more preferably 95 mass% or more, in terms of the lower limit of the amount of the monomer units constituting the polymer. When the temperature is in this range, the shear stress relaxation rate at 25 ℃ of the obtained adhesive is likely to fall within the above range.
The low Tg alkyl acrylate is preferably contained in the (meth) acrylic polymer a in an amount of 99.9 mass% or less, more preferably 99.5 mass% or less, and still more preferably 99 mass% or less, as the upper limit of the monomer unit constituting the polymer. By containing 99.9 mass% or less of the low Tg alkyl acrylate, an appropriate amount of other monomer components (particularly, a monomer having a reactive functional group) can be introduced into the (meth) acrylic polymer a.
In order to easily set the glass transition temperature (Tg) of the main polymer of the adhesive of the present embodiment to the above range, the content of a monomer having a glass transition temperature (Tg) exceeding 0 ℃ as a homopolymer (hereinafter, sometimes referred to as "hard monomer") is preferably reduced as much as possible in the (meth) acrylic polymer a. Specifically, in the (meth) acrylic polymer a, the content of the hard monomer as a monomer unit constituting the polymer is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less, as the upper limit value. The hard monomer also includes a reactive functional group-containing monomer described later.
Examples of the hard monomer include methyl acrylate (Tg of 10 ℃ C.), methyl methacrylate (Tg of 105 ℃ C.), ethyl methacrylate (Tg of 65 ℃ C.), n-butyl methacrylate (Tg of 20 ℃ C.), isobutyl methacrylate (Tg of 48 ℃ C.), tert-butyl methacrylate (Tg of 107 ℃ C.), n-stearyl acrylate (Tg of 30 ℃ C.), n-stearyl methacrylate (Tg of 38 ℃ C.), cyclohexyl acrylate (Tg of 15 ℃ C.), cyclohexyl methacrylate (Tg of 66 ℃ C.), phenoxyethyl acrylate (Tg of 5 ℃ C.), phenoxyethyl methacrylate (Tg of 54 ℃ C.), benzyl methacrylate (Tg of 54 ℃ C.), isobornyl acrylate (Tg of 94 ℃ C.), isobornyl methacrylate (Tg of 180 ℃ C.), acryloylmorpholine (Tg of 145 ℃ C.), adamantyl acrylate (Tg of 115 ℃ C.), and so forth, Acrylic monomers such as adamantyl methacrylate (Tg of 141 ℃ C.), acrylic acid (Tg of 103 ℃ C.), dimethylacrylamide (Tg of 89 ℃ C.), acrylamide (Tg of 165 ℃ C.), vinyl acetate (Tg of 32 ℃ C.), styrene (Tg of 80 ℃ C.), and the like.
The (meth) acrylic polymer a contains a reactive functional group-containing monomer as a monomer unit constituting the polymer, and thus forms a crosslinked structure (three-dimensional network structure) by reacting a thermal crosslinking agent described later with the reactive functional group derived from the reactive functional group-containing monomer through the reactive functional group, thereby obtaining an adhesive having a desired cohesive force.
Examples of the reactive functional group-containing monomer contained as a monomer unit constituting the (meth) acrylic polymer a include a monomer having a hydroxyl group in the molecule (hydroxyl group-containing monomer), a monomer having a carboxyl group in the molecule (carboxyl group-containing monomer), and a monomer having an amino group in the molecule (amino group-containing monomer). Among these, monomers having a glass transition temperature (Tg) of 0 ℃ or lower are more preferable, and hydroxyl group-containing monomers are particularly preferable.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Among them, at least one of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate is preferable from the viewpoint of the glass transition temperature (Tg), the reactivity of the hydroxyl group in the obtained (meth) acrylic polymer a with a thermal crosslinking agent and the copolymerizability with other monomers. These may be used alone, or 2 or more of them may be used in combination.
Examples of the carboxyl group-containing monomer 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 2 or more of them may be used in combination.
Examples of the amino group-containing monomer include aminoethyl (meth) acrylate, n-butylaminoethyl (meth) acrylate, and the like. These may be used alone, or 2 or more of them may be used in combination.
The (meth) acrylic polymer a preferably contains the reactive functional group-containing monomer in an amount of 0.1 mass% or more, particularly preferably 0.5 mass% or more, and more preferably 1 mass% or more, as the lower limit of the monomer unit constituting the polymer. The content of the above-mentioned limit is preferably 10% by mass or less, particularly preferably 8% by mass or less, further preferably 5% by mass or less, and most preferably less than 5% by mass. When the (meth) acrylic polymer a contains the reactive functional group-containing monomer, particularly the hydroxyl group-containing monomer, as a monomer unit in the above-mentioned amount, the shear stress relaxation rate at a temperature of 25 ℃ of the obtained pressure-sensitive adhesive layer tends to fall within the above-mentioned range.
In the (meth) acrylic polymer a, as a monomer unit constituting the polymer, a carboxyl group-containing monomer, particularly acrylic acid, which is also a hard monomer, may not be contained. Since the carboxyl group is an acid component, since the carboxyl group-containing monomer is not contained, even when there are components that cause troubles due to an acid, for example, a transparent conductive film such as tin-doped indium oxide (ITO), a metal film, a metal mesh, or the like in the object to which the adhesive is attached, it is possible to suppress the troubles (corrosion, change in resistance value, or the like) caused by an acid.
The (meth) acrylic polymer a may contain other monomers as the monomer unit constituting the polymer, if necessary. As the other monomer, a monomer containing no reactive functional group is also preferable in order not to hinder the action of the reactive functional group-containing monomer. Examples of the other monomer include, in addition to alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, monomers having a glass transition temperature (Tg) of more than-40 ℃ and not more than 0 ℃ as a homopolymer (hereinafter, sometimes referred to as "medium Tg alkyl acrylate"), and the medium Tg alkyl acrylates include, for example, ethyl acrylate (Tg of-20 ℃), isobutyl acrylate (Tg of-26 ℃), 2-ethylhexyl methacrylate (Tg of-10 ℃), n-lauryl acrylate (Tg of-23 ℃), isostearyl acrylate (Tg of-18 ℃) and the like, and these may be used alone or in combination of 2 or more.
The polymerization system of the (meth) acrylic polymer a may be a random copolymer or a block copolymer.
The lower limit of the weight average molecular weight of the (meth) acrylic polymer a is preferably 20 ten thousand or more, particularly preferably 30 ten thousand or more, and more preferably 40 ten thousand or more. When the lower limit of the weight average molecular weight of the (meth) acrylic polymer a is not less than the above range, troubles such as bleeding out of the adhesive can be suppressed. The weight average molecular weight in the present specification is a value in terms of standard polystyrene measured by a Gel Permeation Chromatography (GPC) method.
The upper limit of the weight average molecular weight of the (meth) acrylic polymer a is preferably 150 ten thousand or less, particularly preferably 135 ten thousand or less, and more preferably 120 ten thousand or less. When the upper limit of the weight average molecular weight of the (meth) acrylate polymer a is not more than the above range, the shear stress relaxation rate at a temperature of 25 ℃ of the pressure-sensitive adhesive layer to be obtained easily falls within the above range.
In the adhesive composition a, 1 kind of the (meth) acrylic polymer a may be used alone, or 2 or more kinds may be used in combination.
When the adhesive composition A containing a thermal crosslinking agent is heated, the thermal crosslinking agent crosslinks the (meth) acrylic polymer A to form a three-dimensional network structure. This improves the cohesive force of the resulting pressure-sensitive adhesive, and the shear stress relaxation rate at a temperature of 25 ℃ of the resulting pressure-sensitive adhesive layer tends to fall within the above range.
The thermal crosslinking agent is a compound having a structure similar to that of the (meth) acrylic polymer AThe reactive group of (3) may be reacted with a thermal crosslinking agent, and examples thereof include an isocyanate crosslinking agent, an epoxy crosslinking agent, an amine crosslinking agent, a melamine crosslinking agent, an aziridine crosslinking agent, a hydrazine crosslinking agent, an aldehyde crosslinking agent, an amine crosslinking agent, a melamine crosslinking agent, an aziridine crosslinking agent, a hydrazine crosslinking agent, an aldehyde crosslinking agent, a melamine crosslinking agent, a polyester resin, a copolymer, and a copolymer, and a copolymer, and a copolymer, and a copolymer, a,
An oxazoline-based crosslinking agent, a metal alkoxide-based crosslinking agent, a metal chelate-based crosslinking agent, a metal salt-based crosslinking agent, an ammonium salt-based crosslinking agent, and the like. Among the above, when the reactive group of the (meth) acrylic polymer a is a hydroxyl group, an isocyanate-based crosslinking agent having excellent reactivity with the hydroxyl group is preferably used. The thermal crosslinking agent may be used alone in 1 kind, or in combination of 2 or more kinds.
The isocyanate-based crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; and biuret or isocyanurate adducts thereof, and adducts thereof as reaction products with low-molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane and castor oil. Among them, trimethylolpropane-modified aromatic polyisocyanates are preferable from the viewpoint of reactivity with hydroxyl groups, and trimethylolpropane-modified tolylene diisocyanate and trimethylolpropane-modified xylylene diisocyanate are particularly preferable.
Examples of the epoxy-based crosslinking agent include 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N' -tetraglycidylmethylenem-xylylenediamine, ethylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, and diglycidylamine.
The content of the thermal crosslinking agent in the adhesive composition a is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and still more preferably 0.1 mass% or more, with respect to 100 mass% of the (meth) acrylic polymer a. The content is preferably 1% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.5% by mass or less. When the content of the thermal crosslinking agent is in the above range, the shear stress relaxation rate of the obtained pressure-sensitive adhesive layer at a temperature of 25 ℃ is likely to fall within the above range.
The adhesive composition a preferably contains a silane coupling agent. This improves the adhesion between the pressure-sensitive adhesive layer obtained and each member in the laminate to be adhered, and further improves the durability against bending.
The silane coupling agent is preferably an organosilicon compound having at least 1 alkoxysilyl group in the molecule, and has good compatibility with the (meth) acrylic polymer a and light transmittance.
Examples of the silane coupling agent include silicon compounds containing a polymerizable unsaturated group such as vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane and the like; silicon compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; mercapto group-containing silicon compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, etc.; amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, or a condensate of at least one of these with an alkyl-containing silicon compound such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, or ethyltrimethoxysilane. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The content of the silane coupling agent in the adhesive composition a is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more, based on 100% by mass of the (meth) acrylic polymer a. The content is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more 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 adhesion to each member in the laminate as an adherend.
Various additives may be added to the adhesive composition a as needed. The additives constituting the adhesive composition a do not include a polymerization solvent and a dilution solvent.
The (meth) acrylic polymer a can be produced by polymerizing a mixture of monomers constituting the polymer by a general radical polymerization method. The polymerization of the (meth) acrylic polymer a is preferably carried out by a solution polymerization method using a polymerization initiator as needed. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone, and 2 or more kinds thereof may be used in combination.
The polymerization initiator may be an azo compound, an organic peroxide, or the like, and 2 or more kinds may be used in combination. Examples of the azo compound include 2,2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), 1 ' -azobis (cyclohexane 1-carbonitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2 ' -azobis (2-methylpropionate), 4 ' -azobis (4-cyanovaleric acid), 2 ' -azobis (2-hydroxymethylpropionitrile), and 2,2 ' -azobis [2- (2-imidazolin-2-yl) propane ].
Examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxyvalerate, (3,5, 5-trimethylhexanoyl) peroxide, dipropionylperoxide, and diacetyl peroxide.
In the polymerization step, a chain transfer agent such as 2-mercaptoethanol is added to adjust the weight average molecular weight of the obtained polymer.
After obtaining the (meth) acrylic polymer a, a thermal crosslinking agent, a silane coupling agent, and if necessary, an additive and a diluting solvent are added to a solution of the (meth) acrylic polymer a and sufficiently mixed to obtain a binder composition a (coating solution) diluted with a solvent.
In the case where a solid component is used or a precipitate is generated when the solid component is mixed with another component in an undiluted state, any of the above components may be dissolved or diluted in a diluting solvent alone and then mixed with another component.
Examples of the diluting solvent include aliphatic hydrocarbons such as hexane, heptane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; alcohols such as methanol, ethanol, propanol, butanol, and 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; and cellosolve-based solvents such as ethyl cellosolve.
The concentration and viscosity of the coating solution prepared in this manner are not particularly limited as long as the coating solution can be applied, and may be appropriately selected according to the situation. For example, the binder composition A is diluted so that the concentration thereof is 10 to 60 mass%. The addition of a diluting solvent or the like is not an essential condition when obtaining a coating solution, and the diluting solvent may not be added if the adhesive composition a has a viscosity capable of being coated or the like. In this case, the pressure-sensitive adhesive composition a is a coating solution in which the polymerization solvent of the (meth) acrylic polymer a is directly used as a dilution solvent.
A preferable pressure-sensitive adhesive as the pressure-sensitive adhesive of the present embodiment is a pressure-sensitive adhesive composition a obtained by crosslinking. Crosslinking of the adhesive composition a may be performed by heat treatment. The heat treatment may be used in combination with a drying treatment when a diluent solvent or the like is volatilized from a coating film of the pressure-sensitive adhesive composition a applied to a desired object.
The heating temperature of the heating treatment is preferably 50 to 150 ℃, and more preferably 70 to 120 ℃. The heating time is preferably 10 seconds to 10 minutes, and more preferably 50 seconds to 2 minutes.
After the heat treatment, if necessary, a curing period of about 1 to 2 weeks may be set at normal temperature (e.g., 23 ℃ C., 50% RH). In the case where the curing period is required, the adhesive is formed after the curing period, and in the case where the curing period is not required, the adhesive is formed after the heat treatment is completed.
By the heat treatment (and curing), the (meth) acrylic polymer a is sufficiently crosslinked via the crosslinking agent to form a crosslinked structure, thereby obtaining an adhesive. The shear stress relaxation rate at a temperature of 25 ℃ of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive is likely to fall within the above range.
The adhesive sheet of the present invention comprises an adhesive layer formed from the adhesive composition a of the present invention described above. The adhesive layer may be formed by applying the adhesive composition a to a substrate. When a thermosetting adhesive composition is used as the adhesive composition a, the adhesive layer formed is subjected to heat treatment (and curing) to produce a cured product having a desired degree of curing. The conditions of the heat treatment and the aging are as described above.
The substrate may be a release film subjected to a release treatment. The pressure-sensitive adhesive sheet can be produced by forming a layer made of a pressure-sensitive adhesive into a sheet shape on a release film in advance and further bonding another release film to the pressure-sensitive adhesive layer.
As a method for applying the coating liquid of the adhesive composition a, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
[ front panel ]
The front panel 101 is not limited in material and thickness as long as it is a plate-like body that can transmit light, and may be composed of only 1 layer, or 2 or more layers. Examples thereof include a plate-like body made of resin (for example, a resin plate, a resin sheet, a resin film, etc.), a plate-like body made of glass (for example, a glass plate, a glass film, etc.), and a touch sensor panel described later. The front panel may constitute the outermost surface of the display device.
The thickness of the front plate 101 may be, for example, 10 to 500. mu.m, preferably 30 to 200. mu.m, and more preferably 50 to 100. mu.m. In the present invention, the thickness of each layer can be measured by the thickness measurement method described in the examples described below.
When the front panel 101 is a resin plate-like body, the resin plate-like body is not limited as long as light can be transmitted therethrough. Examples of the resin constituting the plate-like body made of a resin such as a resin film include films made of polymers such as triacetyl cellulose, cellulose acetate butyrate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, levulinyl cellulose, polyester, polystyrene, polyamide, polyetherimide, poly (meth) acrylic acid, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyetherketone, polyetheretherketone, polyethersulfone, polymethylmethacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, and polyamideimide. These polymers may be used alone or in combination of 2 or more. From the viewpoint of improving strength and transparency, a resin film made of a polymer such as polyimide, polyamide, polyamideimide, or the like is preferable.
From the viewpoint of enhancing the hardness, the front panel 101 is preferably a film in which a hard coat layer is provided on at least one surface of a base film. As the base film, a film formed of the above resin can be used. The hard coat layer may be formed on one surface of the substrate film or on both surfaces. By providing the hard coat layer, a resin film having improved hardness and scratch resistance can be produced. The hard coat layer is a cured layer of, for example, an ultraviolet curable resin. Examples of the ultraviolet curable resin include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins. To increase the hardness, the hard coating may contain additives. The additive is not limited, and examples thereof include inorganic fine particles, organic fine particles, and a mixture thereof.
When the front panel 101 is a glass plate, a strengthened glass for display is preferably used as the glass plate. The thickness of the glass plate may be, for example, 10 to 1000. mu.m. By using the glass plate, the front panel 101 having excellent mechanical strength and surface hardness can be configured.
When the laminate 100 is used in a display device, the front panel 101 may be a front panel having a function of protecting the front surface (screen) of the display device (a function as a window film), a function as a touch sensor, a blue light cut-off function, a viewing angle adjustment function, and the like.
[ 1 st adhesive layer ]
The 1 st adhesive layer 102 is a layer interposed between the front panel 101 and the polarizer layer 103 and bonded to each other, and may be a layer made of, for example, an adhesive or a bonding agent, or a layer obtained by subjecting the layer to some treatment. The 1 st adhesive layer may be an adhesive layer disposed closest to the front panel among the adhesive layers constituting the laminate. Adhesives are also known as pressure sensitive adhesives. In the present specification, the "adhesive" refers to an adhesive other than an adhesive (pressure-sensitive adhesive), and is clearly distinguished from an adhesive. The 1 st adhesive layer 102 may be composed of 1 layer, or may be composed of 2 or more layers, preferably 1 layer.
The 1 st adhesive layer 20 may be formed directly from the adhesive composition or using an adhesive sheet having an adhesive layer formed using the adhesive composition. The adhesive composition is preferably the adhesive composition a described above. The pressure-sensitive adhesive composition other than the pressure-sensitive adhesive composition a (hereinafter also referred to as the pressure-sensitive adhesive composition B) may be, for example, a pressure-sensitive adhesive composition containing a resin such as a rubber-based, urethane-based, ester-based, silicone-based, or polyvinyl ether-based resin as a main component. Among them, the pressure-sensitive adhesive composition B is preferably a pressure-sensitive adhesive composition having excellent transparency, weather resistance, heat resistance and the like. The adhesive composition B may be an active energy ray-curable type.
When the adhesive composition B is an active energy ray-curable adhesive composition, the active energy ray-curable adhesive composition further contains an active energy ray-polymerizable compound in addition to the base polymer. Further, a photopolymerization initiator, a photosensitizer, or the like may be contained as necessary. In addition, the adhesive composition B may contain additives. Examples of the active energy ray-polymerizable compound and the photopolymerization initiator are the same as those of the active energy ray-polymerizable compound and the photopolymerization initiator described in the description of the (meth) acrylic polymer a.
In the case where the 1 st adhesive layer 102 is formed from the adhesive composition B, the formation method thereof may be the same as the method of forming the 1 st adhesive layer 102 from the adhesive composition a described above.
The thickness of the 1 st pressure-sensitive adhesive layer 102 is, for example, preferably 3 μm to 100 μm, more preferably 5 μm to 50 μm, and may be 20 μm or more.
[ polarizer layer ]
Examples of the polarizer layer 103 include a stretched film or a stretched layer having a dichroic dye adsorbed thereon, and a layer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound. As the dichroic dye, specifically, iodine or a dichroic organic dye can be used. The dichroic organic dye includes a dichroic direct dye composed of a bisazo compound such as c.i. direct RED (c.i. direct RED)39, and a dichroic direct dye composed of a compound such as a trisazo compound or a tetrazo compound.
Examples of the polarizer layer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound include 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 dichroic dye having liquid crystallinity or a composition containing a dichroic dye and a polymerizable liquid crystal.
The polarizing layer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound is preferable to the stretched film or the stretched layer having the dichroic dye adsorbed thereon because the polarizing layer has no limitation in the bending direction.
[ polarizer layer as stretched film or stretched layer ]
The polarizer layer as a stretched film having a dichroic dye adsorbed thereon can be generally produced through the following steps: a step of uniaxially stretching a polyvinyl alcohol resin film; a step of adsorbing a dichroic dye by dyeing a polyvinyl alcohol resin film with the dichroic dye; treating the polyvinyl alcohol resin film having the dichroic dye adsorbed thereon with an aqueous boric acid solution; and a step of washing the substrate with water after the treatment with the aqueous boric acid solution.
The thickness of the polarizer layer 103 is, for example, 2 μm to 40 μm. The thickness of the polarizer layer 103 may be 5 μm or more, 20 μm or less, further 15 μm or less, and further 10 μm or less.
The polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith may be used. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
The saponification degree of the polyvinyl alcohol resin is usually about 85 mol% to 100 mol%, and preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The polymerization degree of the polyvinyl alcohol resin is usually 1000 to 10000, preferably 1500 to 5000.
The polarizer layer as the stretched layer having the dichroic dye adsorbed thereon can be generally produced through the following steps: a step of applying a coating liquid containing the polyvinyl alcohol resin onto a base film; a step of uniaxially stretching the obtained laminated film; a step of dyeing the polyvinyl alcohol resin layer of the uniaxially stretched laminated film with a dichroic dye to adsorb the dichroic dye to produce a polarizer; treating the film having the dichroic dye adsorbed thereon with an aqueous boric acid solution; and a step of washing the substrate with water after the treatment with the aqueous boric acid solution.
The substrate film may be peeled off from the polarizer layer as necessary. The material and thickness of the base film may be the same as those of the thermoplastic resin film described later.
The polarizer layer as the stretched film or the stretched layer may be assembled in a laminate in a form in which a thermoplastic resin film is bonded to one surface or both surfaces thereof. The thermoplastic resin film can function as a protective film or a retardation film for the polarizer layer 103. The thermoplastic resin film may be formed of a polyolefin resin such as a chain polyolefin resin (e.g., a polypropylene resin) or a cyclic polyolefin resin (e.g., a norbornene resin); cellulose resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate; a polycarbonate-based resin; (meth) acrylic resins; or a mixture thereof.
From the viewpoint of thinning, the thickness of the thermoplastic resin film is usually 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less, further preferably 80 μm or less, further preferably 60 μm or less, and usually 5 μm or more, preferably 20 μm or more.
The thermoplastic resin film may or may not have a phase difference.
The thermoplastic resin film may be bonded to the polarizer layer 103 using an adhesive layer, for example.
[ polarizer layer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound ]
Examples of the polarizer layer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound include 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 liquid crystal-polymerizable dichroic dye or a composition containing a dichroic dye and a polymerizable liquid crystal to a base film.
The substrate film may be peeled off from the polarizer layer as necessary. The material and thickness of the base film may be the same as those of the thermoplastic resin film described above. The polarizer layer may be provided with an orientation film. The alignment film may be peeled off.
The polarizer layer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound may be incorporated in the optical laminate in a form in which a thermoplastic resin film is bonded to one or both surfaces thereof. As the thermoplastic resin film, the same thermoplastic resin film as that usable for the stretched film or the polarizer layer of the stretched layer can be used. The thermoplastic resin film may be bonded to the polarizer layer using an adhesive layer, for example.
The polarizer layer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound may have an Overcoat (OC) layer formed on one or both surfaces thereof as a protective layer. Examples thereof include photocurable resins and water-soluble polymers. Examples of the photocurable resin include a (meth) acrylic resin, a urethane resin, a (meth) acrylic urethane resin, an epoxy resin, and a silicone resin. Examples of the water-soluble polymer include poly (meth) acrylamide polymers; vinyl alcohol polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, (meth) acrylic acid or anhydride thereof-vinyl alcohol copolymers; a carboxyvinyl polymer; polyvinylpyrrolidone; starches; sodium alginate; polyethylene oxide polymers, and the like. The thickness of the OC layer is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and may be 5 μm or less, and may be 0.05 μm or more, and may be 0.5 μm or more.
The thickness of the polarizer layer obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound is usually 10 μm or less, preferably 0.5 to 8 μm, and more preferably 1 to 5 μm.
[2 nd adhesive layer ]
The 2 nd adhesive layer 104 is an adhesive layer disposed between the polarizer layer 103 and the back surface plate 105. The 2 nd adhesive layer may be an adhesive layer disposed closest to the back surface plate among the adhesive layers constituting the laminate. The 2 nd adhesive layer 104 may be 1 layer, or may be composed of 2 or more layers, and preferably 1 layer.
The composition and blending components of the pressure-sensitive adhesive composition constituting the 2 nd pressure-sensitive adhesive layer 104, the type of the pressure-sensitive adhesive composition (whether it is active energy ray-curable or thermosetting, etc.), additives that can be blended in the pressure-sensitive adhesive composition, the method for producing the 2 nd pressure-sensitive adhesive layer, and the thickness of the 2 nd pressure-sensitive adhesive layer are the same as those described in the above description of the 1 st pressure-sensitive adhesive layer 102.
The 2 nd adhesive layer 104 may be the same as or different from the 1 st adhesive layer 102 in composition, blending components, thickness, and the like of the adhesive composition.
[ Back Panel ]
As the back plate 105, a plate-like body that can transmit light, a component used in a general display device, or the like can be used.
The thickness of back plate 105 may be, for example, 5 μm to 2000 μm, preferably 10 μm to 1000 μm, and more preferably 15 μm to 500 μm.
The plate-like body used for rear plate 105 may be formed of only 1 layer or 2 or more layers, and the plate-like body exemplified for the plate-like body described in front plate 101 may be used.
Examples of the constituent elements used in a typical display device used for the back panel 105 include a touch sensor panel and an organic EL display element. Examples of the order of stacking the components in the display device include a window film, a circularly polarizing plate, a touch sensor panel, an organic EL display element, a window film, a touch sensor panel, a circularly polarizing plate, and an organic EL display element.
(touch sensor panel)
The touch sensor panel is not limited to a detection method as long as it is a sensor capable of detecting a touched position, and examples thereof include touch sensor panels of a resistive film method, a capacitive coupling method, an optical sensor method, an ultrasonic wave method, an electromagnetic induction coupling method, a surface acoustic wave method, and the like. From the viewpoint of low cost, a touch sensor panel of a resistive film type or a capacitive coupling type can be preferably used.
An example of a resistive touch sensor panel includes a pair of substrates arranged to face each other, an insulating spacer sandwiched between the pair of substrates, a transparent conductive film provided as a resistive film on an inner front surface of each of the substrates, and a touch position detection circuit. In an image display device provided with a resistive touch sensor panel, if a surface of a front panel is touched, an opposing resistive film is short-circuited, and a current flows through the resistive film. The touch position detecting circuit detects the voltage change at this time, thereby detecting the touched position.
An example of a capacitive coupling type touch sensor panel includes a substrate, a position detection transparent electrode provided on the entire surface of the substrate, and a touch position detection circuit. In an image display device provided with a capacitive coupling type touch sensor panel, if the front surface of the front panel is touched, the transparent electrode is grounded via the capacitance of a human body at the touched point. The touch position detection circuit detects the grounding of the transparent electrode, thereby detecting the touched position.
The thickness of the touch sensor panel may be, for example, 5 to 2000 μm, or 5 to 100 μm.
[ phase difference layer ]
The laminate 100 may further include 1 or 2 or more retardation layers. The phase difference layer is typically disposed between the polarizer layer 103 and the back panel 105. The retardation layer may be laminated on the 1 st pressure-sensitive adhesive layer 102 or the 2 nd pressure-sensitive adhesive layer 104, or may be laminated on another layer (including another retardation layer) via a layer (hereinafter, also referred to as a laminating layer) made of a pressure-sensitive adhesive or an adhesive other than these layers.
[ adhesive layer ]
The laminating layer is a layer disposed between the 1 st adhesive layer 102 and the 2 nd adhesive layer 104, and is a layer made of an adhesive or an adhesive. The adhesive constituting the laminating layer may be the same adhesive as exemplified for the adhesive composition constituting the 1 st adhesive layer 102 or the 2 nd adhesive layer, or may be another adhesive such as a (meth) acrylic adhesive, a styrene-based adhesive, a silicone-based adhesive, a rubber-based adhesive, a urethane-based adhesive, a polyester-based adhesive, an epoxy-based copolymer adhesive, or the like.
The adhesive constituting the adhesive layer may be formed by combining 1 or 2 or more kinds of water-based adhesives, active energy ray-curable adhesives, pressure-sensitive adhesives, and the like. Examples of the aqueous adhesive include a polyvinyl alcohol resin aqueous solution and an aqueous two-pack type urethane emulsion adhesive. The active energy ray-curable adhesive is an adhesive that is cured by irradiation with an active energy ray such as ultraviolet ray, and examples thereof include an adhesive containing a polymerizable compound and a photopolymerization initiator, an adhesive containing a photoreactive resin, and an adhesive containing a binder resin and a photoreactive crosslinking agent. Examples of the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy monomer, a photocurable acrylic monomer, and a photocurable urethane monomer, and oligomers derived from these monomers. Examples of the photopolymerization initiator include photopolymerization initiators containing active species that generate neutral radicals, anionic radicals, cationic radicals, and the like by irradiation with active energy rays such as ultraviolet rays.
The thickness of the adhesive layer may be, for example, 1 μm or more, preferably 1 to 25 μm, more preferably 2 to 15 μm, and still more preferably 2.5 to 5 μm.
The laminate 100 shown in fig. 2 includes a front plate 101, a1 st adhesive layer 102, a polarizer layer 103, a2 nd adhesive layer 104, a back plate 105, and further includes a bonding layer 108 and a1 st retardation layer 106.
The laminate 100 shown in fig. 3 includes a front plate 101, a1 st adhesive layer 102, a polarizer layer 103, a2 nd adhesive layer 104, and a back plate 105, and further includes a bonding layer 108, a1 st retardation layer 106, a bonding layer 109, and a2 nd retardation layer 107.
Examples of the retardation layer include a positive a plate and a positive C plate such as a λ/4 plate and a λ/2 plate.
The retardation layer may be, for example, a retardation film that can be formed of the thermoplastic resin film, or a layer obtained by curing a polymerizable liquid crystal compound, that is, a layer containing a cured product of a polymerizable liquid crystal compound, and the latter is preferable.
The thickness of the retardation film may be the same as that of the thermoplastic resin film described above. The thickness of the retardation layer obtained by curing the polymerizable liquid crystal compound is, for example, 0.1 to 10 μm, preferably 0.5 to 8 μm, and more preferably 1 to 6 μm.
The retardation layer obtained by curing the polymerizable liquid crystal compound can be formed by applying a composition containing the polymerizable liquid crystal compound to a substrate film and curing the composition. An alignment layer may also be formed between the substrate film and the coating layer. The material and thickness of the base film may be the same as those of the thermoplastic resin film described above.
The retardation layer obtained by curing the polymerizable liquid crystal compound may be incorporated in the laminate 100 in a form having an alignment layer and/or a substrate film. The back panel 105 may also be a substrate film coated with the above composition.
As described above, the adhesive or the adhesive may be used for the adhesion layer 108. The adhesive may be the adhesive composition a or the adhesive composition B described above.
As the adhesive, an aqueous adhesive or an active energy ray-curable adhesive can be used. Examples of the aqueous adhesive include an adhesive composed of a polyvinyl alcohol resin aqueous solution, and an aqueous two-pack type urethane emulsion adhesive.
The active energy ray-curable adhesive is an adhesive that is cured by irradiation with an active energy ray such as ultraviolet ray, and examples thereof include an adhesive containing a polymerizable compound and a photopolymerization initiator, an adhesive containing a photoreactive resin, and an adhesive containing a binder resin and a photoreactive crosslinking agent.
Examples of the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy monomer, a photocurable (meth) acrylic monomer, and a photocurable urethane monomer, and oligomers derived from a photopolymerizable monomer.
Examples of the photopolymerization initiator include photopolymerization initiators containing active species that generate neutral radicals, anionic radicals, and cationic radicals by irradiation with active energy rays such as ultraviolet rays. As the active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator, an active energy ray-curable adhesive containing a photocurable epoxy monomer and a photocationic polymerization initiator can be preferably used.
[ method for producing laminate ]
The laminate 100 can be manufactured by a method including the following steps: the layers constituting the laminate 100 are bonded to each other via an adhesive layer or further via an adhesive layer. When the layers are bonded to each other via an adhesive layer or an adhesive layer, one or both of the bonding surfaces are preferably subjected to a surface activation treatment such as corona treatment in order to improve the adhesion.
The polarizer layer 103 may be formed directly on a thermoplastic resin film or a base film, which may be incorporated in the laminate 100, or may be separated from the polarizer layer 103 without being a constituent of the laminate.
< display device >
The display device of the present invention includes the laminate 100 of the present invention described above. The display device is not particularly limited, and examples thereof include image display devices such as an organic EL display device, an inorganic EL display device, a liquid crystal display device, and an electroluminescence display device. The display device may have a touch panel function. The optical laminate is suitable for a flexible display device which can be bent or bent.
In the display device, the optical laminate is disposed on the viewing side of the display element included in the display device such that the front panel faces outward (the side opposite to the display element side, i.e., the viewing side).
The display device of the present invention can be used as a mobile device such as a smart phone or a tablet computer, a television, a digital photo frame, an electronic sign, a measuring instrument, an office machine, a medical machine, a computer machine, or the like.
< adhesive composition >
The pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic polymer containing a constituent unit derived from a monomer which is a (meth) acrylate or a (meth) acrylamide and which contains a structure represented by the above formula (I), and the pressure-sensitive adhesive composition of the present invention is preferably the pressure-sensitive adhesive composition a.
< adhesive sheet >
The adhesive sheet of the present invention preferably includes an adhesive layer formed from an adhesive composition containing a (meth) acrylic polymer containing a constituent unit derived from a monomer which is a (meth) acrylate or a (meth) acrylic amide and which includes the structure represented by formula (I). The adhesive layer may be formed by applying the adhesive composition to a substrate. When an active energy ray-curable pressure-sensitive adhesive composition is used as the pressure-sensitive adhesive composition, a cured product having a desired degree of curing can be obtained by irradiating the pressure-sensitive adhesive layer thus formed with active energy rays.
The substrate may be a release film subjected to a release treatment. The pressure-sensitive adhesive sheet can be produced by forming a layer made of a pressure-sensitive adhesive on a release film in a sheet form in advance, and further laminating another release film on the pressure-sensitive adhesive layer.
The adhesive layer of the adhesive sheet of the present invention has excellent adhesion. When the shear stress relaxation rate at 25 ℃ of a reference adhesive layer having a thickness of 150 μm and formed from the adhesive composition used for forming the adhesive layer is R0Then, the following relational expression (4) is preferably satisfied:
0.02≤R0≤0.25 (4)，
more preferably, the following relational expression (4a) is satisfied:
0.10≤R0≤0.20 (4a)。
by using the pressure-sensitive adhesive composition satisfying the above relational expression, a pressure-sensitive adhesive sheet having excellent room-temperature adhesion durability can be produced.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
< preparation of (meth) acrylic polymers A1-A4 >
The monomers shown in table 1 were mixed and copolymerized to obtain (meth) acrylic polymers a1 to a 4. The monomer amounts in the table are parts by mass. The measured weight average molecular weight (Mw) is shown in table 1.
< preparation of adhesive compositions B1-B4 >
100 parts by mass (solid content equivalent; the same applies hereinafter) of the (meth) acrylic polymer obtained in the above step, trimethylolpropane-modified xylylene diisocyanate (product name "TD-75" manufactured by Soken chemical Co., Ltd.) as a thermal crosslinking agent, and 3-glycidoxypropyltrimethoxysilane (product name "KBM 403" manufactured by shin-Etsu chemical Co., Ltd.) as a silane coupling agent were mixed in amounts (parts by mass) shown in Table 1 and sufficiently stirred. The mixture was diluted with methyl ethyl ketone to obtain coating solutions of adhesive compositions B1 to B4.
[ Table 1]
The abbreviations in table 1 represent the following meanings.
BA: acrylic acid n-butyl ester
2 EHA: 2-ethylhexyl acrylate
4 HBA: acrylic acid 4-hydroxybutyl ester
< production of adhesive sheet >
The coating solutions of the adhesive compositions B1 to B4 were applied to the release-treated surface of a release film a (product name "SP-PET 752150" manufactured by linetec) by a knife coater. Then, the coating layer was heat-treated at 90 ℃ for 1 minute to form a coating layer. Then, the coating layer on the release film A obtained above was bonded to a release film B (manufactured by Lintec, product name "SP-PET 382120") so that the release-treated surface of the release sheet was in contact with the coating layer, and the resultant was cured at 23 ℃ and 50% RH for 7 days to prepare a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer with a thickness of 25 μm, that is, a pressure-sensitive adhesive sheet having a structure of release film A/pressure-sensitive adhesive layer (thickness: 25 μm)/release film B. The thickness of the pressure-sensitive adhesive layer is a value measured by a method described later. Using the obtained adhesive sheet, a reference adhesive layer was prepared by the method described later, and the shear stress relaxation rate was measured. The results are shown in Table 1.
< preparation of (meth) acrylic polymers A5-A8 >
Production example A5
After a monomer mixture comprising 70 mass% of 2-ethylhexyl acrylate (2-EHA) monomer, 9.9 mass% of hydroxypropyl methacrylate (HPMA) monomer, and 20 mass% of Lauryl Acrylate (LA) monomer was charged into a 1L reactor equipped with a cooling device to reflux nitrogen gas and facilitate temperature adjustment, the temperature was maintained at 80 ℃ after refluxing nitrogen gas for 1 hour to remove oxygen. After the monomer mixture was uniformly mixed, 0.05 mass% of benzildimethylketal (I-651) and 0.05 mass% of 1-hydroxycyclohexylphenylketone (I-184) as photopolymerization initiators were added. Subsequently, a UV lamp (10mW) was irradiated with the resulting mixture while stirring to produce a (meth) acrylate polymer A5 having a weight-average molecular weight (Mw) of 40 ten thousand.
Production example A6
A 1L reactor equipped with a cooling device to reflux nitrogen gas and easily adjusted in temperature was charged with a monomer mixture comprising 75 mass% of 2-ethylhexyl acrylate (2-EHA) monomer, 4.9 mass% of tetrahydrofurfuryl methacrylate (THFMA) monomer, and 20 mass% of Lauryl Acrylate (LA) monomer, and then the mixture was refluxed with nitrogen gas for 1 hour to remove oxygen and maintained at 80 ℃. After the monomer mixture was uniformly mixed, 0.05 mass% of benzildimethylketal (I-651) and 0.05 mass% of 1-hydroxycyclohexylphenylketone (I-184) as photopolymerization initiators were added. Subsequently, a UV lamp (10mW) was irradiated with the resulting mixture while stirring to produce a (meth) acrylate polymer A6 having a weight-average molecular weight (Mw) of 45 ten thousand.
Production example A7
After a monomer mixture comprising 70 mass% of 2-ethylhexyl acrylate (2-EHA) monomer, 2.5 mass% of cyclohexyl methacrylate (CHMA) monomer and 27.4 mass% of Lauryl Acrylate (LA) monomer was charged into a 1L reactor equipped with a cooling device to reflux nitrogen gas and facilitate temperature adjustment, the temperature was maintained at 80 ℃ after refluxing nitrogen gas for 1 hour to remove oxygen. After the monomer mixture was uniformly mixed, 0.05 mass% of benzildimethylketal (I-651) and 0.05 mass% of 1-hydroxycyclohexylphenylketone (I-184) as photopolymerization initiators were added. Subsequently, a UV lamp (10mW) was irradiated with the resulting mixture while stirring to produce a (meth) acrylate polymer A7 having a weight-average molecular weight (Mw) of 50 ten thousand.
Production example A8
A 1L reactor equipped with a cooling device to reflux nitrogen gas and easily adjusted in temperature was charged with a monomer mixture comprising 87 mass% of 2-ethylhexyl acrylate (2-EHA) monomer, 3.0 mass% of hydroxypropyl methacrylate (HPMA) monomer, 3.0 mass% of tetrahydrofurfuryl methacrylate (THFMA) monomer, and 6.9 mass% of Lauryl Acrylate (LA) monomer, and then the mixture was refluxed with nitrogen gas for 1 hour to remove oxygen and maintained at 80 ℃. After the monomer mixture was uniformly mixed, 0.05 mass% of benzildimethylketal (I-651) and 0.05 mass% of 1-hydroxycyclohexylphenylketone (I-184) as photopolymerization initiators were added. Subsequently, a UV lamp (10mW) was irradiated with the resulting mixture while stirring to produce a (meth) acrylate polymer A8 having a weight-average molecular weight (Mw) of 35 ten thousand.
The compositions and weight average molecular weights (Mw) of production examples A5 to A8 are summarized in Table 2.
[ Table 2]
Each abbreviation of table 2 indicates the following meaning.
2-EHA: 2-ethylhexyl acrylate (Tokyo chemical Co., Ltd., Japan),
HPMA: hydroxypropyl methacrylate (Tokyo chemical industry Co., Ltd., Japan),
THFMA: tetrahydrofurfuryl methacrylate (Tokyo Kasei Kogyo Co., Ltd., Japan),
CHMA: cyclohexyl methacrylate (Tokyo chemical industry Co., Ltd., Japan),
LA: lauryl acrylate (Tokyo chemical industry Co., Ltd., Japan),
i-651: benzildimethylketal (photopolymerization initiator, BASF, germany),
i-184: 1-Hydroxycyclohexyl phenyl ketone (photopolymerization initiator, BASF, Germany).
< preparation of adhesive compositions B5-B8 >
Adhesive compositions B1 to B6 were prepared by mixing the components and the ratios shown in table 2. The amounts added in the table are mass%.
[ Table 3]
Each abbreviation of table 3 indicates the following meaning.
BA: butyl acrylate (Tokyo chemical industry Co., Ltd., Japan),
BPO: benzophenone (tokyo chemical industry co., japan).
< production of adhesive sheet >
The pressure-sensitive adhesive compositions B5 to B8 were applied to a light release film A (polyethylene terephthalate film, thickness 38 μm) coated with a silicon release agent so that the thickness became 25 μm. A heavy release film B (polyethylene terephthalate film, 38 μm thick) was bonded thereto, and UV irradiation was performed to prepare a pressure-sensitive adhesive sheet composed of a release film A/a pressure-sensitive adhesive layer/a release film B. Using the obtained adhesive sheet, a reference adhesive layer was prepared by the method described later, and the shear stress relaxation rate was measured. The results are shown in Table 3.
[ measurement of weight average molecular weight (Mw) ]
The weight average molecular weight (Mw) of the (meth) acrylic polymer was determined as a number average molecular weight (Mn) in terms of polystyrene, and the mobile phase was obtained by the Size Exclusion Chromatography (SEC) described below using tetrahydrofuran. The measured (meth) acrylic polymer was dissolved in tetrahydrofuran at a concentration of about 0.05 mass%, and 10. mu.L of the solution was injected into SEC. The mobile phase flowed at a rate of 1.0 mL/min. As the column, PLGel MIXED-B (manufactured by Polymer Laboratories) was used. The detector used was a UV-VIS detector (trade name: Agilent GPC).
[ thickness of layer ]
The film thickness was measured using a contact type film thickness measuring apparatus ("MS-5C" manufactured by Nikon corporation).
The polarizer layer and the alignment film were measured using a laser microscope ("OLS 3000" manufactured by Olympus corporation).
[ shear stress relaxation Rate ]
The shear stress relaxation rate was measured by using a viscoelasticity measuring apparatus (MCR-301, Anton Paar Co.). The adhesive sheet was cut into a width of 20mm × a length of 20mm, and a plurality of sheets were laminated to a thickness of 150 μm by peeling off the release film, and then bonded to a glass plate. The test piece was bonded to the test piece, and the deformation was stopped at a temperature of 25 ℃ so that the Normal force (Normal force) was 1N and the deformation amount was 10%, and the shear modulus after 300 seconds was measured. Based on these measured values, the shear stress relaxation rate R was calculated from the following formula0。
R0Shear modulus after 300 seconds/shear modulus after 0.1 seconds
[ laminates of examples 1 to 6 and comparative example 1]
< 1 st adhesive layer 102 and 2 nd adhesive layer 104 >
As the psa sheets including the 1 st psa layer 102 and the 2 nd psa layer 104, psa sheets formed from the psa compositions shown in tables 1 and 3 were prepared. Hereinafter, the psa sheet for the 1 st psa layer 102 is referred to as the 1 st psa sheet, and the psa sheet for the 2 nd psa layer 104 is referred to as the 2 nd psa sheet.
< front panel 101 >
For the window film as the front panel 101, a polyimide film having a hard coat layer on one surface (HC-PI, thickness of the whole: 60 μm, thickness of the hard coat layer: 10 μm, thickness of the polyimide film: 50 μm) was prepared.
< polarizer layer 103 >
[ laminate having polarizer layer ]
(polymerizable liquid Crystal Compound)
As the polymerizable liquid crystal compound, 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 also referred to as Compound (1-7) ] were used.
The compounds (1-6) and (1-7) were synthesized by the method described in Lub et al, Recl, Trav, Chim, Pays-Bas, 115, 321-328 (1996).
(dichroic dye)
As the dichroic dye, azo dyes described in examples of Japanese patent application laid-open No. 2013-101328 represented by the following formulae (2-1a), (2-1b) and (2-3a) are used.
(composition for Forming polarizer layer)
The composition for forming the polarizer layer was prepared by: 75 parts by mass of the compound (1-6), 25 parts by mass of the compound (1-7), 2.5 parts by mass of each of the azo dyes represented by the above formulae (2-1a), (2-1b) and (2-3a) as dichroic dyes, 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (Irgacure369, manufactured by BASF Japan) as a polymerization initiator and 1.2 parts by mass of a polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) as a leveling agent were mixed with 400 parts by mass of toluene as a solvent, and the resulting mixture was stirred at 80 ℃ for 1 hour.
(composition for Forming alignment film)
The polymer 1 is a polymer having a photoreactive group and composed of the following structural units.
The molecular weight of the polymer 1 obtained according to GPC measurement showed a number average molecular weight of 28200, Mw/Mn of 1.82, and a monomer content of 0.5%.
A solution obtained by dissolving the polymer 1 in cyclopentanone at a concentration of 5 mass% was used as the alignment film forming composition.
(composition for protective layer)
The composition for a protective layer was prepared by mixing 3 parts by mass of a polyvinyl alcohol resin powder (manufactured by Kuraray Co., Ltd., average polymerization degree 18000, trade name: KL-318) and 1.5 parts by mass of a polyamide epoxy resin (a crosslinking agent, manufactured by Suzuki Chemtex Co., Ltd., trade name: SR650(30)) with 100 parts by mass of water.
(production of laminate having polarizer layer)
The composition for forming an alignment film was applied to a triacetyl cellulose (TAC) film (thickness 25 μm) subjected to corona treatment (output 0.3kW, treatment speed 3 m/min) by a bar coating method, and heat-dried in a drying oven at 80 ℃ for 1 minute. The obtained dried coating film was subjected to polarized UV irradiation treatment to form a1 st alignment film (AL 1). The polarized light UV treatment was carried out by passing light irradiated by a UV irradiation device ("SPOT CURE SP-7" manufactured by Ushio Motor Co., Ltd.) through a wire grid ("UIS-27132 #") and measuring the cumulative quantity of light at a wavelength of 365nm of 100mJ/cm2Under the conditions of (1). The thickness of the 1 st alignment film (AL1) was 100 nm.
The composition for forming a polarizer layer was applied to the 1 st alignment film (AL1) formed by a bar coating method, dried by heating in a drying oven at 120 ℃ for 1 minute, and then cooled to room temperature. Using the UV irradiation apparatus described above, the cumulative light amount was 1200mJ/cm2The dried coating film was irradiated with ultraviolet light (365nm basis), thereby forming a polarizer layer (pol). The thickness of the resulting polarizer layer was 1.8 μm.
The composition for protective layer was coated on the formed polarizer layer by a bar coating method, coated so that the thickness after drying became 1.0 μm, and dried at a temperature of 80 ℃ for 3 minutes. In this manner, a laminate composed of TAC film/1 st alignment film (AL 1)/polarizer layer/protective layer was obtained.
< 1 st retardation layer 106 >
[ laminate having retardation layer ]
(composition for Forming retardation layer)
The following components were mixed, and the resulting mixture was stirred at 80 ℃ for 1 hour to obtain a composition for forming a retardation layer.
A compound b-1 represented by the following formula: 80 parts by weight
A compound b-2 represented by the following formula: 20 parts by weight of
Polymerization initiator (Irgacure369, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one manufactured by BASF Japan): 6 parts by mass
Leveling agent (BYK-361N, polyacrylate compound, BYK-Chemie Co., Ltd.): 0.1 part by mass
Solvent (cyclopentanone): 400 parts by mass
(production of a laminate having a retardation layer)
A polyethylene terephthalate (PET) film having a thickness of 100 μm was prepared as a substrate, and the above-mentioned composition for forming an alignment film was applied to the film by a bar coating method and dried by heating in a drying oven at 80 ℃ for 1 minute. The obtained dried film was subjected to polarized UV irradiation treatment to form a2 nd alignment film (AL 2). The polarized light UV treatment was carried out by using the above UV irradiation apparatus, and the cumulative quantity of light measured at a wavelength of 365nm was 100mJ/cm2Under the conditions of (1). The polarization direction of the polarized light UV is set to 45 ° with respect to the absorption axis of the polarizer layer.
The retardation layer-forming composition was applied to the obtained 2 nd alignment film (AL2) by a bar coating method, dried by heating in a drying oven at 120 ℃ for 1 minute, and then cooled to room temperature. The obtained dried film was irradiated with a cumulative light amount of 1000mJ/cm using the UV irradiation device2Ultraviolet rays (365nm basis), thereby forming a retardation layer. Measurement was carried out by a laser microscope (OLS 3000 manufactured by Olympus Co., Ltd.)The thickness of the resulting retardation layer was 2.0. mu.m. The phase difference layer is a lambda/4 plate (QWP) exhibiting a phase difference value of lambda/4 in the in-plane direction. In this manner, a laminate composed of the substrate (PET)/the 2 nd alignment film (AL 2)/the retardation layer (QWP) was obtained.
< laminating layer 108 >
The following components were reacted at 55 ℃ while stirring under a nitrogen atmosphere, thereby obtaining an acrylic resin.
Butyl acrylate: 70 portions of
Methyl acrylate: 20 portions of
Acrylic acid: 2.0 part by weight
Radical polymerization initiator (2, 2' -azobisisobutyronitrile): 0.2 part
The following ingredients were mixed to obtain an adhesive composition.
The acrylic resin: 100 portions of
Crosslinking agent ("Coronate L" manufactured by tokyo corporation): 1.0 part
Silane coupling agent (X-12-981, manufactured by shin-Etsu silicon Co., Ltd.): 0.5 portion
Ethyl acetate was added so that the total solid content concentration became 10%, to obtain an adhesive composition.
The pressure-sensitive adhesive composition was applied by an applicator to the release-treated surface of release-treated heavy release film B (polyethylene terephthalate film, thickness 38 μm) so that the dried thickness became 5 μm. The coating layer was dried at 100 ℃ for 1 minute to obtain a film having an adhesive layer. Then, a light release film A (polyethylene terephthalate film, 38 μm thick) subjected to a mold release treatment was laminated on the exposed surface of the pressure-sensitive adhesive layer. Thereafter, the mixture was aged at 23 ℃ and 50% RH relative humidity for 7 days to obtain an adhesive sheet.
< Back surface plate 105 >
As the rear plate 105, a polyethylene terephthalate substrate (thickness 38 μm) or a glass substrate was prepared.
< production of laminate 100 >
The laminates of examples 1 to 6 and comparative example 1 were produced by the following procedure. In the formation of the 1 st adhesive layer and the 2 nd adhesive layer, adhesive sheets formed from the adhesive compositions shown in tables 1 and 3 were used in combination shown in table 4.
First, the release film a of the adhesive sheet for adhesive layer was peeled off, and then the exposed adhesive layer was subjected to corona treatment. The surface of the laminate including the polarizer layer on the protective layer side is subjected to corona treatment. The pressure-sensitive adhesive sheet for a pressure-sensitive adhesive layer was bonded to a laminate including the polarizer layer so that the corona-treated surface became a bonding surface, to obtain a laminate a 1.
After the other release film B of the adhesive sheet for adhesive layer was peeled off from the laminate a1, the exposed adhesive layer was subjected to corona treatment. Laminate a1 was laminated to the laminate including the retardation layer so that the surface on the retardation layer side of the laminate including the retardation layer was subjected to corona treatment and the surface subjected to corona treatment became the lamination surface, to obtain laminate a 2.
The PET film was peeled from the laminate a2, and the surface on the retardation layer side was subjected to corona treatment. The release film a of the adhesive sheet 2 was peeled off, and the surface of the adhesive layer was subjected to corona treatment. Laminate a2 was bonded to the 2 nd adhesive layer so that the corona-treated surface became the bonding surface, resulting in laminate A3.
The release film a was peeled from the 1 st adhesive sheet, and the surface of the adhesive layer was subjected to corona treatment.
The surface of the front panel on the PI side was also subjected to corona treatment, and the 1 st adhesive layer was bonded to the front panel so that the corona-treated surface became a bonding surface, to obtain a laminate a 4.
The surface of the laminate a3 on the TAC film side was subjected to corona treatment. The release film B of the laminate a4 was peeled off, and the surface of the 1 st adhesive layer was subjected to corona treatment. Laminate A3 was bonded to laminate a4 so that the corona-treated surface became the bonding surface, and laminate a5 was obtained.
The release film B of the laminate a5 was peeled off, and the laminate was bonded to a polyethylene terephthalate substrate to prepare a laminate for ordinary temperature bendability evaluation.
The release film B of the laminate a5 was peeled off and bonded to a glass substrate to prepare a laminate for room-temperature adhesion durability test.
A laminated body composed of a window film/1 st adhesive layer/TAC film layer/1 st alignment film (AL 1)/polarizer layer/protective layer/adhesive layer/2 nd alignment film (AL 2)/phase difference layer/2 nd adhesive layer/back surface plate was produced in this manner.
Corona treatment was all at the output: 0.3KW, speed: at 3 m/min.
The laminates of examples 1 to 6 and comparative example 1 were evaluated for room temperature bendability and room temperature adhesion durability. The results are shown in Table 4.
[ Table 4]
[ Normal temperature bendability ]
The laminate was subjected to an evaluation test for confirming room-temperature bendability using a bending evaluation apparatus (STS-VRT-500, manufactured by Science Town). Fig. 4 is a diagram schematically showing the method of the evaluation test. As shown in fig. 4, two independently movable mounting tables 501 and 502 are arranged so that the gap C becomes 6mm (the bending radius is 3mm), the center in the width direction is positioned at the center of the gap C, and the laminate is fixed and arranged so that the polyethylene terephthalate substrate is positioned on the upper side (fig. 4 (a)). Then, the two tables 501 and 502 are rotated upward by 90 degrees around the position P1 and the position P2 as the center of the rotation axis, and a bending force is applied to the region of the laminated body corresponding to the gap C of the tables (fig. 4 (b)). Thereafter, the two tables 501 and 502 are returned to their original positions (fig. 4 (a)). The above series of operations was completed, and the number of times of application of the bending force was counted as 1 time. 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 of the laminate corresponding to the gap C of the mounting tables 501 and 502. The moving speed of the mounting tables 501 and 502 and the step of applying the bending force are the same in the evaluation test of any laminate.
A: no bubble was generated even if the number of bending force applications reached 10 ten thousand.
B: bubbles are generated when the number of times of applying the bending force is 5 ten thousand or more and less than 10 ten thousand.
C: bubbles are generated when the number of times of applying the bending force is 2 ten thousand or more and less than 5 ten thousand.
D: bubbles are generated when the number of times of application of the bending force is 1 ten thousand or more and less than 2 ten thousand.
E: bubbles are generated when the number of times of application of the bending force is less than 1 ten thousand.
[ Normal temperature adhesion durability ]
Room temperature adhesion durability a laminate obtained by bonding a glass substrate instead of a polyethylene terephthalate substrate as described above was used for the test. Specifically, the laminate a5 was cut so as to have a width of 100mm × a length of 100mm, and the release film B was peeled off from the 2 nd pressure-sensitive adhesive layer and bonded to an alkali-free glass substrate to prepare a laminate for room-temperature adhesion durability test. The test piece was treated with an autoclave at 50 ℃ and 5 atm for 20 minutes and then kept at constant temperature and humidity (23 ℃ and 50% relative humidity) for 4 hours. Thereafter, after being left in an oven at 25 ℃ for 250 hours, the test piece was observed for the presence or absence of floating, peeling and bubbling. The evaluation criteria are as follows.
A: the appearance change such as floating, peeling, foaming and the like was hardly observed.
B: the appearance change such as floating, peeling, foaming and the like is slightly conspicuous.
C: the appearance changes such as floating, peeling, foaming and the like are obviously seen.
Examples 1 to 6 satisfy "R01≥R02 ", and therefore, it can be judged that the relation" R1 ≧ R2 "is satisfied. On the other hand, comparative example 1 is "R01＜R02 ", and thus can be judged as" R1 < R2 ".
Description of the symbols
100 laminate, 101 front panel, 102 1 st adhesive layer, 103 polarizer layer, 104 nd 2 nd adhesive layer, 105 back panel, 106 st 1 st retardation layer, 107 nd 2 nd retardation layer, 108, 109 bonding layer, 501, 502 mounting table.
Claims (8)
1. A laminate comprising, in this order, a front sheet, a1 st adhesive layer formed using a1 st adhesive composition, a polarizer layer, a2 nd adhesive layer formed using a2 nd adhesive composition, and a back sheet,
if the shear stress relaxation rate at a temperature of 25 ℃ of the 1 st adhesive layer is R1 and the shear stress relaxation rate at a temperature of 25 ℃ of the 2 nd adhesive layer is R2, the following relational expression (1) is satisfied:
R1≥R2 (1)。
2. the laminate according to claim 1, wherein R represents a shear stress relaxation rate at 25 ℃ of a1 st reference adhesive layer having a thickness of 150 μm and formed using the 1 st adhesive composition01. The shear stress relaxation rate at 25 ℃ of a2 nd reference adhesive layer having a thickness of 150 μm formed by using the 2 nd adhesive composition was R02, the following relational expressions (2) and (3) are satisfied:
0.02≤R01≤0.25 (2)
0.02≤R02≤0.25 (3)。
3. the laminate of claim 1 or 2, wherein the 1 st adhesive composition and the 2 nd adhesive composition each comprise a (meth) acrylic polymer.
4. The laminate according to claim 3, wherein the weight average molecular weight (Mw) of the (meth) acrylic polymer is 20 to 150 ten thousand.
5. The laminate according to claim 3 or 4, wherein the (meth) acrylic polymer has less than 5% by mass of a constituent unit derived from a monomer having a reactive functional group, based on the total mass of the polymer.
6. The laminate according to any one of claims 1 to 5, wherein the back sheet is a touch sensor panel.
7. A display device comprising the laminate according to any one of claims 1 to 6.
8. The display device according to claim 7, wherein the front panel side can be bent to an outer side.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019034146A JP2020140010A (en) | 2019-02-27 | 2019-02-27 | Laminate and display device |
| JP2019-034146 | 2019-02-27 | ||
| PCT/JP2020/004761 WO2020175098A1 (en) | 2019-02-27 | 2020-02-07 | Laminate and display device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113474699A true CN113474699A (en) | 2021-10-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202080016406.2A Pending CN113474699A (en) | 2019-02-27 | 2020-02-07 | Laminate and display device |
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| Country | Link |
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| JP (2) | JP2020140010A (en) |
| KR (1) | KR20210130175A (en) |
| CN (1) | CN113474699A (en) |
| TW (1) | TW202031477A (en) |
| WO (1) | WO2020175098A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6792736B1 (en) * | 2019-11-20 | 2020-11-25 | 住友化学株式会社 | Optical laminate and display device |
| JP7406977B2 (en) * | 2019-12-23 | 2023-12-28 | 住友化学株式会社 | Method for manufacturing optical laminates |
| JP2022094078A (en) * | 2020-12-14 | 2022-06-24 | 住友化学株式会社 | Foldable polarizing plate |
| CN114373394B (en) * | 2022-01-20 | 2023-11-28 | 武汉华星光电半导体显示技术有限公司 | Display device and method for manufacturing display device |
| JP2024014626A (en) * | 2022-07-22 | 2024-02-01 | 日東電工株式会社 | Adhesive sheet and optical laminate |
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2019
- 2019-02-27 JP JP2019034146A patent/JP2020140010A/en active Pending
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2020
- 2020-02-07 CN CN202080016406.2A patent/CN113474699A/en active Pending
- 2020-02-07 WO PCT/JP2020/004761 patent/WO2020175098A1/en active Application Filing
- 2020-02-07 KR KR1020217028954A patent/KR20210130175A/en unknown
- 2020-02-20 TW TW109105519A patent/TW202031477A/en unknown
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- 2021-06-30 JP JP2021108502A patent/JP2021184091A/en active Pending
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| Publication number | Publication date |
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| JP2020140010A (en) | 2020-09-03 |
| KR20210130175A (en) | 2021-10-29 |
| WO2020175098A1 (en) | 2020-09-03 |
| JP2021184091A (en) | 2021-12-02 |
| TW202031477A (en) | 2020-09-01 |
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