CN111554184A - Laminate and image display device - Google Patents
Laminate and image display device Download PDFInfo
- Publication number
- CN111554184A CN111554184A CN202010084637.9A CN202010084637A CN111554184A CN 111554184 A CN111554184 A CN 111554184A CN 202010084637 A CN202010084637 A CN 202010084637A CN 111554184 A CN111554184 A CN 111554184A
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- CN
- China
- Prior art keywords
- adhesive layer
- laminate
- film
- pressure
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Images
Classifications
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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
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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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- 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
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/33—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Human Computer Interaction (AREA)
- Electroluminescent Light Sources (AREA)
- Polarising Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a laminated body which is not easy to generate cracks even under the condition of repeated bending. The laminate comprises a structure in which at least 1 optical members are laminated with an adhesive layer interposed therebetween, and the adhesive layer of at least 1 of the structures has a rate of change in thickness per unit number of bending [%/ten thousand ] < 10.
Description
Technical Field
The present invention relates to a laminate, and further relates to an image display device including the laminate.
Background
Documents of the prior art
Patent document
Patent document 1: korean patent No. 10-2017-
Patent document 2: korean patent No. 10-2013-7001791
Disclosure of Invention
In a laminate having a structure in which optical members are laminated with each other via an adhesive layer, cracks may occur when the laminate is repeatedly bent.
The invention aims to provide a laminated body which is not easy to generate cracks even under the condition of repeated bending.
The invention provides the following laminated body and image display device.
[1] A laminate comprising a structure in which at least 1 optical member is laminated with an adhesive layer interposed therebetween, wherein the adhesive layer of at least 1 structure satisfies the following formula (i).
The rate of change in thickness per unit number of bends [%/ten thousand ] < 10(i)
[2] The laminate according to [1], wherein the thickness of the adhesive layer satisfying the formula (i) is 5 μm or more.
[3] The laminate according to [1] or [2], wherein the adhesive layers of the structure each satisfy the formula (i).
[4] The laminate according to any one of [1] to [3], wherein the structure in which the optical members are laminated with each other via an adhesive layer is a structure in which 2 optical members selected from a front panel, a polarizing plate, a touch sensor panel, an organic EL display element, and a retardation film are laminated with the adhesive layer.
[5] An image display device comprising the laminate according to any one of [1] to [4 ].
[6] The image display device according to [5], which has flexibility.
According to the present invention, a laminate that is less likely to crack even when repeatedly bent 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 sectional view schematically showing an example of the method for producing an optical laminate according to the present invention.
Fig. 5 is a schematic diagram for explaining a method of the bending test.
Description of the symbols
1. 4, 7, 100 laminates, 2, 5, 8 optical members, 3, 6, 9, 21, 22, 23 adhesive layers, 10 adhesive layers, 11 front panels, 12 polarizing plates, 13 touch sensor panels, 14 organic EL display elements, 501, 502 mounting tables.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the embodiments below. In all the drawings below, the scale is appropriately adjusted to facilitate understanding of each component, and the scale of each component shown in the drawings does not necessarily coincide with the scale of the actual component.
< laminate >
Fig. 1 is a schematic cross-sectional view of a laminate (hereinafter, also referred to as "laminate" as omitted) according to an embodiment of the present invention. The laminate 1 shown in fig. 1 includes an optical member 2, a pressure-sensitive adhesive layer 3, and an optical member 2 in this order. The laminate 1 is a laminate including a structure in which 1 optical member is laminated with a pressure-sensitive adhesive layer interposed therebetween, and is a laminate including a structure in which only optical members are laminated with a pressure-sensitive adhesive layer interposed therebetween.
The laminate has flexibility. The flexible property means that the laminate can be bent without causing cracks or fractures when the laminate is bent. Having flexibility preferably means that cracks and fractures do not occur even in the case of performing 3 ten thousand times of bending with a bending radius of 2.5mm of the inner surface of the laminate.
The thickness of the laminate 1 varies depending on the functions required for the laminate 1, the application of the laminate 1, and the like, and is not particularly limited, and may be, for example, 50 μm or more and 1000 μm or less, preferably 100 μm or more and 500 μm or less, and more preferably 100 μm or more and 300 μm or less.
The shape of the laminate 1 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 laminate 1 has a rectangular shape in plan view, 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 or more and 800mm or less, preferably 30mm or more and 500mm or less, and more preferably 50mm or more and 300mm or less.
When the laminate 1 has a square shape in plan view, the lengths of the sides of the layers constituting the laminate 1 may be the same. Each layer constituting the laminate 1 may be subjected to R processing at a corner, or grooving or drilling at an end.
In the present specification, a planar view means a view from the thickness direction of the layer.
As described above, in the laminate 1, when repeated bending is performed in at least one direction in the plane so that the bending radius of the inner surface of the laminate 1 is 2.5mm, it is preferable that cracks and fractures do not occur even if the number of bending times is 3 ten thousand.
In the laminate 1, when repeated bending is performed so that the bending radius of the inner surface of the laminate 1 becomes 2.5mm in at least one direction in the plane, cracking and breaking do not occur even if the number of bending is more preferably 5 ten thousand, even more preferably 10 ten thousand, and even more preferably 30 ten thousand. In the laminate 1, it is preferable that the number of bending times in which cracks and breaks do not occur when the above repeated bending is performed is in the above range with respect to at least one direction in the plane and a direction orthogonal thereto.
In the present specification, the bending includes a bent form in which a curved surface is formed at a bent portion. In the bent form, the bending radius of the inner surface of the bend is not particularly limited. The bend includes a bent form in which the inner surface has a bend angle of more than 0 degrees and less than 180 degrees, and a folded form in which the inner surface has a bend radius of approximately zero or the inner surface has a bend angle of 0 degrees.
In the structure in which the optical members are laminated with the adhesive layer interposed therebetween, for example, when the optical member, the adhesive layer, and the optical member are formed into a unit structure (hereinafter, also referred to as a structure 1), the optical member may be formed into a single structure 1 or may be formed into a plurality of structures 1. In the case of a structure including a plurality of structures 1, 2 or more structures 1 may be stacked via an adhesive layer, or one optical member constituting the structure 1 may be bonded to another optical member via an adhesive layer. The optical members may be of the same kind or different kinds, but preferably are of different kinds. The adhesive layers may have the same composition or different compositions, but preferably have the same composition.
The structure in which the optical members are laminated with the adhesive layer interposed therebetween may include a structure in a polarizing plate and a structure between retardation films, which will be described later. For example, the polarizer included in the polarizing plate may be laminated with the retardation film or the retardation layer via an adhesive layer, laminated with the retardation film and the retardation layer via an adhesive layer, or laminated with the retardation films or the retardation layers via an adhesive layer. More specifically, there are a structure in which a polarizer contained in a polarizing plate and a λ/4 plate are laminated via an adhesive layer, a structure in which a λ/4 plate and a positive C plate or a λ/2 plate are laminated via an adhesive layer, and the like.
When the laminate includes 2 or more structures 1, these structures may be bonded via an adhesive layer or a bonding layer described later.
The pressure-sensitive adhesive layer of at least 1 structure among the structures in which the optical members are laminated with the pressure-sensitive adhesive layer interposed therebetween satisfies the following formula (i).
The rate of change in thickness per unit number of bends [%/ten thousand ] < 10(i)
From the viewpoint of improving the bendability, the rate of change [%/ten thousand times ] in the thickness per unit number of bending of at least 1 of the optical members stacked via the adhesive layer is preferably 5 or less, more preferably 4 or less, and even more preferably 2 or less. From the viewpoint of improving the bendability, it is preferable that the pressure-sensitive adhesive layers of the structure in which the optical members are laminated via the pressure-sensitive adhesive layer satisfy formula (i).
So-called per unit bendRate of change in thickness of degree [%/ten thousand]When the laminate was repeatedly bent 1 ten thousand times so that the inner surface had a bending radius of 2.5mm, the thickness of the pressure-sensitive adhesive layer at the initial stage, that is, the thickness of the pressure-sensitive adhesive layer at 0 bending times was T0When the thickness of the pressure-sensitive adhesive layer obtained by repeating the bending 1 ten thousand times is T1, it can be obtained according to the following equation.
Rate of change in thickness per unit number of bends [%/ten thousand times]＝│T1－T0│/T0×100
The thickness of the pressure-sensitive adhesive layer and the rate of change [%/ten thousand times of the thickness per unit number of bending of the pressure-sensitive adhesive layer can be determined by the methods described in the examples section below.
The present inventors have found that, when the laminate is repeatedly bent, the adhesive layer included in the structure in which the optical members are laminated via the adhesive layer tends to increase in thickness. The present inventors have studied the relationship between the rate of change in the thickness of the pressure-sensitive adhesive layer and the flexibility, and as a result, they have found that the smaller the rate of change in the thickness per unit number of bending, the better the flexibility of the laminate. This is presumably because if the thickness of the pressure-sensitive adhesive layer is increased, stress generated in the laminate when the laminate is bent increases, and cracks and fractures are likely to occur.
In order to make the rate of change [%/ten thousand times ] in thickness per unit number of bending less than 10, for example, adjustment of the production conditions of the pressure-sensitive adhesive layer, selection of the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer, and the like can be performed. As the adjustment of the production conditions of the pressure-sensitive adhesive layer, for example, when the pressure-sensitive adhesive layer is formed from an active energy ray-curable pressure-sensitive adhesive composition, if the irradiation amount of active energy rays is increased to increase the degree of curing of the active energy ray-curable pressure-sensitive adhesive composition, the rate of change [%/ten thousand times ] in thickness per unit number of bending tends to be small. In addition, if the amount of the crosslinking agent in the adhesive composition is increased, the rate of change in thickness per unit number of bending [%/ten thousand ] tends to be easily decreased.
Further, when a pressure-sensitive adhesive having a large storage elastic modulus [ MPa ] or a high recovery rate is used, the rate of change [%/ten thousand times ] in thickness per unit number of bending tends to be small. The thickness of the pressure-sensitive adhesive layer satisfying the above formula (i) may be, for example, 5 μm or more.
The storage elastic modulus [ MPa ] of the pressure-sensitive adhesive layer at a temperature of 25 ℃ and a relative humidity of 55% may exceed, for example, 0.02MPa, preferably 0.03MPa or more, and more preferably 0.05MPa or more. On the other hand, the storage elastic modulus [ MPa ] of the pressure-sensitive adhesive layer is preferably 0.1MPa or less, and more preferably 0.08MPa or less. When the storage elastic modulus [ MPa ] of the laminate is in the above range, the change in the thickness of the pressure-sensitive adhesive layer tends to be small even when the laminate is repeatedly bent. The storage elastic modulus [ MPa ] of the laminate can be measured by the method described in the examples section below.
The recovery rate [% ] of the pressure-sensitive adhesive layer at a temperature of 25 ℃ and a relative humidity of 55% may be, for example, 25% or more, preferably 30% or more. On the other hand, the adhesive layer usually has a recovery rate [% ] of, for example, 70% or less, preferably 60% or less. When the recovery rate [% ] of the laminate is within the above range, the change in thickness of the pressure-sensitive adhesive layer tends to be small even when the laminate is repeatedly bent. The recovery rate [% ] of the laminate can be measured according to the method described in the following examples.
Fig. 2 is a schematic cross-sectional view showing still another example of the laminate of the present invention. The laminate 4 shown in fig. 2 includes an optical member 5, a pressure-sensitive adhesive layer 6, and an optical member 5 in this order. The laminate 4 is a laminate including the above-described structure 1, and is a laminate having a structure in which only optical members are laminated with each other via a pressure-sensitive adhesive layer.
Fig. 3 is a schematic cross-sectional view showing still another example of the laminate of the present invention. The laminate 7 shown in fig. 3 includes an optical member 8, an adhesive layer 9, an optical member 8, a bonding layer 10, an optical member 8, an adhesive layer 9, and an optical member 8 in this order. The laminate 7 is a laminate including 2 optical members laminated via an adhesive layer, and the optical members are bonded to each other via the bonding layer 10.
[ optical Member ]
Examples of the optical member include a front panel, a polarizing plate, a retardation film, a touch sensor panel, and an organic EL display device.
Specific examples of the above-mentioned structure 1 include the following structures.
A front panel/an adhesive layer/a polarizer,
polarizer/adhesive layer/touch sensor panel,
touch sensor panel/adhesive layer/organic EL display element.
When the optical member has a structure in which a plurality of structures 1 are laminated with an adhesive layer interposed therebetween, specific examples thereof include the following structures.
Front panel/adhesive layer/polarizer/adhesive layer/touch sensor panel,
front panel/adhesive layer/touch sensor panel/adhesive layer/polarizer,
polarizer/adhesive layer/touch sensor panel/adhesive layer/organic EL display element,
front panel/adhesive layer/polarizer/adhesive layer/touch sensor panel/adhesive layer/organic EL display element,
front panel/adhesive layer/touch sensor panel/adhesive layer/polarizer/adhesive layer/organic EL display element.
[ front panel ]
The front panel is preferably a plate-like body capable of transmitting light. The front panel may be composed of only 1 layer, or may be composed of 2 or more layers. The front panel may constitute the outermost surface of the image display device.
Examples of the front panel include a glass plate (e.g., a glass plate, a glass film, etc.) and a resin plate (e.g., a resin plate, a resin sheet, a resin film, etc.). Among the above, from the viewpoint of flexibility of the laminate and the image display device including the same, a plate-like body made of a resin such as a resin film is preferable.
Examples of the thermoplastic resin constituting the plate-like body made of a resin such as a resin film include polyolefin resins such as a chain polyolefin resin (e.g., a polyethylene resin, a polypropylene resin, and a polymethylpentene resin) and 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 resin; ethylene-vinyl acetate-based resin; a polystyrene-based resin; a polyamide resin; a polyetherimide resin; (meth) acrylic resins such as polymethyl (meth) acrylate resins; a polyimide-based resin; a polyether sulfone-based resin; a polysulfone-based resin; a polyvinyl chloride resin; a polyvinylidene chloride resin; a polyvinyl alcohol resin; a polyvinyl acetal resin; a polyether ketone resin; a polyether ether ketone resin; a polyether sulfone-based resin; polyamide-imide resins, and the like.
The thermoplastic resin may be used alone or in combination of 2 or more.
Among them, polyimide-based resins, polyamide-based resins, and polyamideimide-based resins are preferably used as the thermoplastic resin constituting the front panel from the viewpoint of flexibility, strength, and transparency.
The front panel may be a film having a hard coat layer provided on at least one surface of the base film to further increase the hardness. As the base film, the above resin film 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, hardness and scratch resistance can be improved. The thickness of the hard coat layer may be, for example, 0.1 μm or more and 30 μm or less, preferably 1 μm or more and 20 μm or less, and more preferably 5 μm or more and 15 μm or less.
The hard coat layer is a cured layer of, for example, an ultraviolet curable resin. Examples of the ultraviolet curable resin include (meth) acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins. To improve strength, the hard coating may be added with additives. The additive is not limited, and examples thereof include inorganic fine particles, organic fine particles, and a mixture thereof.
The front panel may have not only a function of protecting the front (screen) of the image display device (a function as a window film), but also a function as a touch sensor, a blue light cut-off function, a viewing angle adjustment function, and the like.
The thickness of the front plate may be, for example, 20 μm to 2000 μm, preferably 25 μm to 1500 μm, more preferably 30 μm to 1000 μm, still more preferably 40 μm to 500 μm, particularly preferably 40 μm to 200 μm, and yet still more preferably 40 μm to 100 μm.
[ polarizing plate ]
Examples of the polarizing plate include a stretched film or a stretched layer having a dichroic dye adsorbed thereon, and a film including a polarizer obtained by coating and curing a polymerizable compound containing a dichroic dye thereon. When the pigment is dispersed and oriented in a medium having anisotropy, the pigment may look colored in a certain direction and almost colorless in a direction perpendicular to the direction. A dye exhibiting such a phenomenon is referred to as a dichroic dye. 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 disazo compound such as c.i. direct red 39, and a dichroic direct dye composed of a compound such as trisazo or tetraazo.
Examples of the film obtained by applying and curing a polymerizable compound containing a dichroic dye include a film 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.
A film obtained by applying and curing a polymerizable compound containing a dichroic dye is preferable because the film is not limited in the bending direction as compared with a stretched film or a stretched layer having a dichroic dye adsorbed thereon. Therefore, in order to obtain a laminate in which the number of times of bending in which cracks are not generated when the repeated bending is performed in at least one direction in the plane and in the direction orthogonal thereto, and further in all the directions in the plane is in the above range, it is preferable that the polarizing plate includes a film as a polarizer, which is obtained by applying and curing a polymerizable compound containing a dichroic dye.
(1) Polarizing plate comprising polarizer as stretched film or stretched layer
A polarizer as a stretched film having a dichroic dye adsorbed thereon can be generally produced through the following steps: the method for producing a polyvinyl alcohol film comprises a step of uniaxially stretching a polyvinyl alcohol resin film, a step of dyeing the polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye, a step of treating the polyvinyl alcohol resin film adsorbed with the dichroic dye with an aqueous boric acid solution, and a step of washing the polyvinyl alcohol resin film with water after the treatment with the aqueous boric acid solution. The polarizer may be used as it is, or a polarizing plate obtained by laminating a transparent protective film on one or both surfaces thereof may be used. The thickness of the polarizer is preferably 2 μm or more and 40 μm or less.
The polyvinyl alcohol resin is 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 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal obtained by modifying an aldehyde may be used. The polymerization degree of the polyvinyl alcohol resin is usually 1000 or more and 10000 or less, and preferably 1500 or more and 5000 or less.
The polarizer as the stretched layer having the dichroic dye adsorbed thereon can be generally produced through the following steps: the method for producing a polarizer includes 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 a polyvinyl alcohol resin layer of the uniaxially stretched laminated film with a dichroic dye to adsorb the dichroic dye to produce a polarizer, a step of treating the film adsorbed with the dichroic dye with an aqueous boric acid solution, and a step of washing the film with water after the treatment with the aqueous boric acid solution.
The substrate film may be peeled off from the polarizer 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 as the stretched film or the stretched layer may be incorporated in the optical 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 polarizers.
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 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 using an adhesive layer, for example.
(2) Polarizing plate having polarizer made of film obtained by coating and curing polymerizable compound containing dichroic dye
Examples of the film obtained by applying and curing the polymerizable compound containing a dichroic dye include a film containing a cured product of a polymerizable liquid crystal compound, such as a layer obtained by applying and curing a composition containing a polymerizable dichroic dye having liquid crystallinity or a composition containing a dichroic dye and a polymerizable liquid crystal onto a base film (or an alignment film formed on a base film).
The film can be used as a polarizing plate by peeling off the substrate or using it together with the substrate. The material and thickness of the base film may be the same as those of the thermoplastic resin film described above.
The film obtained by applying and curing the polymerizable compound containing the dichroic dye may be incorporated in the laminate in a form in which a thermoplastic resin film is bonded to one surface or both surfaces thereof. As the thermoplastic resin film, the same thermoplastic resin film as that usable for a polarizer as a stretched film or a stretched layer can be used.
The thermoplastic resin film may be bonded to the polarizer using an adhesive layer, for example. Specific examples of the film obtained by applying and curing a polymerizable compound containing a dichroic dye include films described in japanese patent laid-open publication No. 2012-33249 and the like.
The thickness of the film obtained by applying and curing the polymerizable compound containing the dichroic dye is usually 10 μm or less, preferably 0.5 μm or more and 8 μm or less, and more preferably 1 μm or more and 5 μm or less.
The thickness of the polarizing plate is, for example, 2 μm or more and 100 μm or less, and preferably 10 μm or more and 60 μm or less.
The polarizing plate may further include a retardation film. The retardation film may include 1 or 2 or more retardation layers. The retardation layer may be a positive A plate such as a λ/4 plate or a λ/2 plate, or a positive C plate. The retardation layer may be formed of a resin film exemplified as a material of the above-described protective film, or may be formed of a layer obtained by curing a polymerizable liquid crystal compound. The retardation film may further include an alignment film and a substrate film.
If the polarizer and the retardation film are disposed so that the absorption axis of the polarizer and the slow axis of the retardation film form a predetermined angle, a laminate comprising the polarizing plate and the retardation film has an antireflection function, that is, the laminate can function as a circular polarizing plate. When the retardation film is a retardation film comprising a λ/4 plate as a retardation layer, the angle formed by the absorption axis of the polarizer and the slow axis of the λ/4 plate may be 45 ° ± 10 °.
The polarizing plate and the retardation film may be bonded to each other through a bonding layer or an adhesive layer described later. The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive composition described later, or may be a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive composition other than the pressure-sensitive adhesive layer. The thickness of the pressure-sensitive adhesive layer may be, for example, 0.5 μm or more and 25 μm or less, and preferably 1 μm or more and 25 μm or less.
The thickness of the circularly polarizing plate is, for example, 10 μm or more and 200 μm or less, and preferably 10 μm or more and 100 μm or less.
[ touch sensor Panel ]
The touch sensor panel is not limited to any detection method as long as it is a sensor capable of detecting a touched position, and examples thereof include a resistive film type, a capacitive coupling type, an optical sensor type, an ultrasonic wave type, an electromagnetic induction coupling type, a surface acoustic wave type, 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 as a resistive film provided on the inner front surface of each substrate, 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 detection circuit detects a change in voltage at that time, and detects a 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, a transparent electrode is grounded at the touched point via the capacitance of a human body. The touch position detection circuit detects the grounding of the transparent electrode and detects the touch position.
The thickness of the touch sensor panel may be, for example, 5 μm to 2000 μm, preferably 5 μm to 100 μm, and more preferably 5 μm to 50 μm.
The touch sensor panel may form a touch sensor pattern on a substrate film. Examples of the base film may be the same as those in the description of the protective film. The thickness of the touch sensor pattern may be, for example, 1 μm or more and 40 μm or less.
[ organic EL display element ]
The organic EL display device may be a conventionally known organic EL display device, and is preferably an organic EL display device that can be used for a flexible image display device. The thickness of the organic EL display element may be, for example, 5 μm or more and 2000 μm or less, preferably 5 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less.
[ retardation film ]
The retardation film may include 1 or 2 or more retardation layers. The retardation layer may be a positive A plate such as a λ/4 plate or a λ/2 plate, or a positive C plate. The retardation layer may be formed of a resin film exemplified as a material of the above-described protective film, or may be formed of a layer obtained by curing a polymerizable liquid crystal compound. The retardation film may further include an alignment film and a substrate film.
The thickness of the retardation film formed of the resin 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 μm or more and 10 μm or less, preferably 0.5 μm or more and 8 μm or less, and more preferably 1 μm or more and 6 μm or less.
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 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 films or the retardation layers, or the retardation films and the retardation layers may be bonded to each other via a bonding layer or an adhesive layer described later. The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive composition described later, or may be a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive composition other than the pressure-sensitive adhesive layer. The thickness of the pressure-sensitive adhesive layer may be, for example, 0.5 μm or more and 25 μm or less, and preferably 1 μm or more and 25 μm or less.
[ adhesive layer ]
The pressure-sensitive adhesive layer is contained in a structure in which optical members are laminated with each other with the pressure-sensitive adhesive layer interposed therebetween. The pressure-sensitive adhesive layer may include a pressure-sensitive adhesive layer in a structure in which a polarizing plate and a retardation film or a retardation layer are laminated with a pressure-sensitive adhesive layer therebetween, and a structure in which a retardation film and a retardation layer or a retardation film and a retardation layer are laminated with each other, or a retardation layer and a retardation layer are laminated with a pressure-sensitive adhesive layer therebetween.
The adhesive layer may be composed of 1 layer or 2 or more layers, but is preferably composed of 1 layer.
The pressure-sensitive adhesive layer may be composed of a pressure-sensitive adhesive composition containing a resin such as a (meth) acrylic, rubber, urethane, ester, silicone, or polyvinyl ether resin as a main component. Among them, preferred is an adhesive composition containing a (meth) acrylic resin as a base polymer, which is excellent in transparency, weather resistance, heat resistance and the like. The adhesive composition may be an active energy ray-curable type or a thermosetting type.
As the (meth) acrylic resin (base polymer) used in the adhesive composition, for example, a polymer or copolymer containing 1 or 2 or more kinds of (meth) acrylic esters such as 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, and isobornyl (meth) acrylate as monomers can be preferably used.
In the base polymer, it is preferable to copolymerize a polar monomer. Examples of the polar monomer include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like, such as (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamide, N-dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate.
The weight average molecular weight (Mw) of the (meth) acrylic resin may be, for example, 70 to 250 ten thousand, or 100 to 200 ten thousand. The molecular weight distribution indicated by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) may be 10 or less, 8 or less, or 6 or less. The weight average molecular weight (Mw) can be determined by Size Exclusion Chromatography (SEC) as follows. As for the weight average molecular weight (Mw), tetrahydrofuran was used for the mobile phase, and the measured (meth) acrylic resin was dissolved in tetrahydrofuran at a concentration of about 0.05 mass%, and 10 μ L was injected into SEC. The mobile phase flowed at a rate of 1.0 mL/min. The weight average molecular weight (Mw) is a value calculated from polystyrene conversion. As the column, PLGel MIXED-B (manufactured by Polymer Laboratories) was used. As the detector, a UV-VIS detector (trade name: Agilent GPC) can be used.
The adhesive composition may comprise only the above-mentioned base polymer, but usually further contains a crosslinking agent. Examples of the crosslinking agent include metal ions having a valence of 2 or more and a metal carboxylate salt formed between the crosslinking agent and a carboxyl group; a polyamine compound and a substance forming an amide bond with a carboxyl group; a polyepoxy compound, a polyhydric alcohol, and a substance forming an ester bond with a carboxyl group; a polyisocyanate compound and a substance forming an amide bond with a carboxyl group. Among them, polyisocyanate compounds are preferable.
Examples of the polyisocyanate-based compound include an aliphatic isocyanate-based compound (e.g., hexamethylene diisocyanate), an alicyclic isocyanate-based compound (e.g., isophorone diisocyanate), hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and an aromatic isocyanate-based compound (e.g., toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate). The polyisocyanate compound may be an adduct (adduct) of the above isocyanate compound with a polyol compound [ for example, an adduct of glycerin, trimethylolpropane or the like ], an isocyanurate compound, a biuret compound, a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like, or the like. The polyisocyanate compounds may be used alone or in combination of 2 or more. Among these, toluene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and polyol compounds thereof or isocyanurate compounds thereof are preferable from the viewpoint of durability.
The proportion of the crosslinking agent may be, for example, 0.01 part by mass or more and 10 parts by mass or less, preferably 0.1 part by mass or more and 3 parts by mass or less, and more preferably 0.1 part by mass or more and 1 part by mass or less, relative to 100 parts by mass of the base polymer.
The active energy ray-curable pressure-sensitive adhesive composition is a pressure-sensitive adhesive composition having a property of being cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam, and having a property of having adhesiveness even before irradiation with an active energy ray to enable the pressure-sensitive adhesive composition to be adhered to an adherend such as a film, and being cured by irradiation with an active energy ray to enable adjustment of adhesion force and the like.
The active energy ray-curable adhesive composition is preferably an ultraviolet-curable adhesive composition. The active energy ray-curable adhesive composition further contains an active energy ray-polymerizable compound in addition to the base polymer and the crosslinking agent. Further, a photopolymerization initiator, a photosensitizer and the like may be contained as necessary.
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 such as a (meth) acrylate oligomer obtained by reacting 2 or more kinds of functional group-containing compounds and having at least 2 (meth) acryloyloxy groups in the molecule.
The adhesive composition may further comprise a silane compound. By containing the silane compound, the adhesion between the pressure-sensitive adhesive layer and the stacked layer can be improved. More than 2 silane compounds may be used.
Examples of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
In addition, the silane compound may contain an oligomer derived from the above silane compound.
The content of the silane compound in the adhesive composition is usually 0.01 part by mass or more and 10 parts by mass or less, preferably 0.03 part by mass or more and 5 parts by mass or less, more preferably 0.05 part by mass or more and 2 parts by mass or less, and further preferably 0.1 part by mass or more and 1 part by mass or less, with respect to 100 parts by mass of the base polymer.
The adhesive composition may contain additives such as fine particles, beads (resin beads, glass beads, and the like), glass fibers, resins other than the base polymer, tackifiers, fillers (metal powders, other inorganic powders, and the like), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, defoamers, preservatives, and photopolymerization initiators for imparting light scattering properties.
The adhesive layer can be formed by applying, for example, a diluted solution of the above adhesive composition in an organic solvent to a substrate and drying it. When an active energy ray-curable pressure-sensitive adhesive composition is used, a cured product having a desired degree of curing can be obtained by irradiating the pressure-sensitive adhesive layer formed with an active energy ray.
The thickness of the pressure-sensitive adhesive layer may be, for example, 1 μm or more and 100 μm or less, preferably 2 μm or more and 70 μm or less, and more preferably 3 μm or more and 50 μm or less.
[ adhesive layer ]
The adhesive layer is a layer having a function of bonding the structures 1 to each other or bonding another optical member to the structure 1. The adhesive or adhesive may be used for the adhesive layer. The adhesive used in the laminating layer may be an adhesive composition used in the adhesive layer. 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. When the adhesive composition used in the adhesive layer is used for a laminating layer, the laminating layer satisfies the above formula (i). On the other hand, when an adhesive layer is used as the pressure-sensitive adhesive layer, the adhesive layer may or may not satisfy the above formula (i).
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 those 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 >
A method for manufacturing a laminate will be described with reference to the drawings. The embodiment shown in fig. 4 includes the following steps.
1) Step of preparing front plate 11 (FIG. 4(a))
2) Step of Forming adhesive layer 21 on front plate 11 (FIG. 4(b))
3) Step of bonding polarizing plate 12 to the surface of adhesive layer 21 opposite to front plate 11 (FIG. 4(c))
4) A step of forming an adhesive layer 22 on the surface of the polarizing plate 12 opposite to the adhesive 11 side and bonding the touch sensor panel 13 to the surface of the adhesive layer 22 opposite to the polarizing plate 12 side (FIG. 4(d))
5) A step of forming an adhesive layer 23 on the surface of the touch sensor panel 13 opposite to the adhesive layer 22 side, and bonding the organic EL display element 14 to the surface of the adhesive layer 23 opposite to the touch sensor panel 13 side (fig. 4(e))
When the pressure-sensitive adhesive layer is bonded to each optical member, the bonding surface may be subjected to a treatment such as corona treatment or plasma treatment.
The adhesive layer can be formed, for example, by: the pressure-sensitive adhesive composition is dissolved or dispersed in an organic solvent such as toluene or ethyl acetate to prepare a pressure-sensitive adhesive liquid, a layer made of a pressure-sensitive adhesive is formed in a sheet form on a release film subjected to a release treatment in advance, another release film is further bonded to the pressure-sensitive adhesive layer to prepare a pressure-sensitive adhesive sheet, the release film is removed from the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet is bonded to an optical member, and the remaining release film is removed.
< image display device >
An image display device of the present invention includes the laminate of the present invention. The image display device is not particularly limited, and examples thereof include an organic EL display device, an inorganic EL display device, a liquid crystal display device, an electroluminescence display device, and the like. The image display device may have a touch panel function. The laminate is suitable for an image display device having flexibility such as bending or bending. In the image display device, when the laminate has the front panel, the laminate is disposed on the viewing side of the image display device with the front panel facing outward (the side opposite to the image display element side, i.e., the viewing side).
The image display device of the present invention can be used as mobile devices such as smart phones and tablet computers, televisions, digital photo frames, electronic signs, measuring instruments, office equipment, medical equipment, and computer equipment. The image display device of the present invention is suitable for a flexible display or the like because of its excellent flexibility.
The present invention will be further specifically explained by way of examples and comparative examples, but the present invention is not limited to these examples. In the examples, "%" and "part(s)" are% by mass and part(s) by mass unless otherwise specified. The test and measurement were carried out as follows.
Examples
[ evaluation of flexibility ]
A bending evaluation apparatus (U-shaped planar body no-load stretching test, DLDMLH-FS, manufactured by Yuasa System) was used. Fig. 5 is a diagram schematically showing the method of the evaluation test. As shown in fig. 5, two tables 501 and 502 that can be moved apart are disposed so that the gap C becomes 5.0mm (2.5R), and the laminate is fixed and disposed so that the center in the width direction is located at the center of the gap C (fig. 5 (a)). At this time, the laminate is disposed so that the front panel is upward. Then, the two tables 501 and 502 are rotated upward by 90 degrees about the positions P1 and P2 as the centers of the rotation axes, and a bending force is applied to the region of the laminated body corresponding to the gap C of the tables (fig. 5 (b)). Then, the two tables 501 and 502 are returned to their original positions (fig. 5 a). The above series of operations was completed, and the number of times of addition of the bending force was counted as 1 time. After repeating this operation at room temperature, the presence or absence of cracks in the regions of the laminate corresponding to the gaps C of the mounting tables 501 and 502 was confirmed. The moving speed of the mounting tables 501 and 502 and the applying speed of the bending force (90 times/min) were the same in the evaluation test of any laminate. The number of times of bending in which cracks were generated was counted for each laminate after bending each laminate.
[ method for measuring thickness ]
The laminate obtained when the laminate was bent 1 ten thousand times in the same bending test as described above and the center in the width direction (bending position) of the laminate before the bending test were sliced in a direction perpendicular to the width direction by a microtome, and the cross section was observed with a transmission electron microscope (SU 8010; manufactured by horiba, ltd.) to measure the thickness of each layer from the obtained observation image.
[ thickness Change Rate per bending count ]
The thickness T of the pressure-sensitive adhesive layer before flexibility evaluation, which was determined as described above0And the thickness T of the adhesive layer at 1 ten thousand times of bending1The rate of change [%/ten thousand times of thickness per unit bending time was obtained according to the following formula]。
Rate of change in thickness per unit number of bends [%/ten thousand times]＝|T1－T0|/T0×100
[ method for measuring storage modulus of elasticity ]
The storage elastic modulus of the adhesive layer at a temperature of 25 ℃ was measured using a viscoelasticity measuring apparatus (MCR-301, AntonPaar Co.). An adhesive sheet having a thickness of 25 μm, which was the same as the adhesive layer used in the examples and comparative examples, was cut into a width of 30mm × a length of 30 mm. The release film was peeled off, and a plurality of the films were laminated and bonded to a glass plate so as to have a thickness of 150 μm, and then the film was bonded to a measurement chip and measured in a temperature range of-20 ℃ to 100 ℃ under conditions of a frequency of 1.0Hz, a deformation amount of 1%, and a temperature rise rate of 5 ℃/min, and a storage elastic modulus at a temperature of 25 ℃ was measured.
[ method for measuring recovery Rate ]
The recovery rate was measured using a viscoelasticity measuring apparatus (MCR-301, Anton Paar Co.) A pressure-sensitive adhesive sheet having a thickness of 25 μm, which was the same as the pressure-sensitive adhesive layer used in the examples and comparative examples, was cut into a width of 20mm × mm and a length of 20mm, a release film was peeled off, and a plurality of sheets were laminated and bonded to a glass plate so that the thickness became 200 μm.A measurement was performed under a load condition of a torque of 1200 μ Nm at a temperature of 25 ℃ in a state of being bonded to a measurement chip, and after measuring the shear deformation amount at 1200 seconds, the measurement was continued under a condition of changing to a torque of 0 μ Nm, and the shear deformation amount at 1206 seconds was measured0[％]Calculated by the following equation.
R0[％](1200-1206 seconds shear deformation)/1200 seconds shear deformation × 100
< production example 1 >
A mixed solution of 81.8 parts of acetone, 98.4 parts of butyl acrylate, 0.6 part of acrylic acid and 1.0 part of 2-hydroxyethyl acrylate was charged into a reactor equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirrer, and the internal temperature was raised to 55 ℃ while the atmosphere in the apparatus was replaced with nitrogen gas so as not to contain oxygen. Then, a solution prepared by dissolving 0.14 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of acetone was added in the total amount. After 1 hour of the initiator addition, the reactor was kept at an internal temperature of 54 to 56 ℃ for 12 hours while continuously adding acetone to the reactor at an addition rate of 17.3 parts/hr so that the concentration of the acrylic resin from which monomers were removed became 35%, and finally ethyl acetate was added so that the concentration of the acrylic resin became 20%. The weight-average molecular weight Mw of the obtained acrylic resin was 1650000 and Mw/Mn was 4.3.
< production example 2 >
An acrylic resin solution was obtained in the same manner as in production example 1, except that the monomer composition was changed to 0.4 parts of acrylic acid. The Mw of the resulting acrylic resin was 1270000 and the Mw/Mn was 5.0.
< production example 3 >
A mixed solution of 100 parts of ethyl acetate, 98.9 parts of butyl acrylate and 1.1 parts of acrylic acid was charged into a reactor equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, and while the atmosphere in the apparatus was replaced with nitrogen gas so as to exclude oxygen, a solution prepared by dissolving 0.2 parts of azobisisobutyronitrile into 10 parts of ethyl acetate was added in the whole amount, and the internal temperature was raised to 70 ℃ for 6 hours and further raised to 70 ℃ for 2 hours. Then, a solution prepared by dissolving 0.4 part of azobisisobutyronitrile in 20 parts of ethyl acetate was added dropwise over 1 hour, and ethyl acetate was further added thereto so that the acrylic resin concentration was adjusted to 20%. The viscosity of the resulting acrylic resin solution was 9.8 pas, the weight-average molecular weight Mw of the acrylic resin was 710000, and the Mw/Mn was 12.0.
< production example 4 >
An acrylic resin solution was obtained in the same manner as in production example 3, except that the monomer composition was changed to 0.6 parts of acrylic acid. The weight-average molecular weight Mw of the obtained acrylic resin was 710000 and Mw/Mn was 12.
< production example 5 >
An acrylic resin solution was obtained in the same manner as in production example 3, except that the monomer composition was changed to 0.5 parts of acrylic acid. The weight-average molecular weight Mw of the obtained acrylic resin was 710000 and Mw/Mn was 12.
(1) Preparation of adhesive composition
< preparation of adhesive composition A >
To 100 parts of the solid content of the acrylic resin [ the obtained acrylic resin obtained in production example 1], was mixed a polyisocyanate compound [ Coronate L: 0.5 part of an ethyl acetate solution (solid content concentration: 75%) of a trimethylolpropane adduct of tolylene diisocyanate, obtained from Polyurethane industries, Japan, and 0.5 part of a silane compound [ KBM403, 3-glycidoxypropyltrimethoxysilane, obtained from shin-Etsu chemical industries, Ltd ]. Ethyl acetate was added so that the total solid content concentration became 10%, to obtain a pressure-sensitive adhesive composition a.
< preparation of adhesive composition B >
An adhesive composition B was obtained in the same manner as in the preparation of the adhesive composition a except that the acrylic resin was the acrylic resin obtained in production example 2 and 0.4 part of the polyisocyanate compound was used.
< preparation of adhesive composition C >
An adhesive composition C was obtained in the same manner as in the preparation of the adhesive composition a except that the acrylic resin was the acrylic resin obtained in production example 3 and 0.05 part of the polyisocyanate compound was used.
< preparation of adhesive composition D >
A pressure-sensitive adhesive composition D was obtained in the same manner as in the preparation of the pressure-sensitive adhesive composition a except that the acrylic resin was the acrylic resin obtained in production example 4.
< preparation of adhesive composition E >
An adhesive composition E was obtained in the same manner as in the preparation of the adhesive composition a except that the acrylic resin was the acrylic resin obtained in production example 5 and the polyisocyanate compound was 0.03 parts.
< preparation of adhesive composition F >
An adhesive composition F was obtained in the same manner as in the preparation of the adhesive composition a except that the acrylic resin was the acrylic resin obtained in production example 5 and 0.02 part of the polyisocyanate compound was used.
(2) Production of adhesive sheet
The pressure-sensitive adhesive composition A was applied by an applicator to the release-treated surface of a polyethylene terephthalate film (thickness: 38 μm) which had been subjected to release treatment so that the dried thickness became 25 μm or 5 μm. The coated layer was dried at 100 ℃ for 1 minute to obtain a film having an adhesive layer A with a thickness of 25 μm or 5 μmm. Then, another polyethylene terephthalate film (thickness 38 μm) subjected to a mold release treatment was attached to the adhesive layer. Then, the mixture was aged at 23 ℃ and 50% RH relative humidity for 7 days.
Thus, a pressure-sensitive adhesive sheet a composed of a release film a/a pressure-sensitive adhesive layer a/a release film B was produced.
Adhesive sheets B to F were produced in the same manner except that the adhesive composition a was replaced with the adhesive compositions B to F. Storage elastic modulus and recovery rate were measured for each adhesive sheet. The results are shown in Table 1.
(3) Preparation of polarizing plate
A photo-alignment film was formed on a triacetyl cellulose (TAC) film (thickness 25 μm). A composition containing a dichroic dye and a polymerizable liquid crystal compound was applied to a photo-alignment film, and the film was aligned and cured to obtain a polarizer having a thickness of 2 μm. A resin composition containing polyvinyl alcohol and water was applied to the polarizer so that the thickness after drying became 1.0 μm, and dried at a temperature of 80 ℃ for 3 minutes to form a hard coat layer, thereby obtaining a polarizing plate.
(4) Optical member
The following optical members were used. The optical members are the same size as the front panel.
A front panel: front panel (thickness 70 μm, longitudinal 110mmm × transverse 20mm) having hard coat layer (thickness 10 μm) formed on both sides of base film (polyimide resin film, thickness 50 μm)
Polarizing plate: the polarizing plate described above (thickness of about 28 μm)
Phase difference film: a retardation film comprising a layer obtained by polymerizing and curing a liquid crystal compound [ thickness 11 μm, layer composition: lambda/4 plate (thickness 3 μm)/adhesive layer (thickness 5 μm) comprising layer obtained by curing liquid crystal compound and alignment film/Positive C plate (thickness 3 μm) comprising layer obtained by curing liquid crystal compound and alignment film
Touch sensor panel: thickness 33 μm, layer composition: touch sensor pattern (laminate of cured layer of ITO and acrylic resin composition, thickness 7 μm)/adhesive layer (thickness 3 μm)/cycloolefin resin film (thickness 23 μm)
Organic EL panel: thickness 38 μm
< example 1 >
The surface of the front panel bonded to the pressure-sensitive adhesive layer and the surface of the front panel bonded to the 1 st pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive layer a having a thickness of 25 μm were subjected to corona treatment. Then, the front panel was bonded to the 1 st adhesive layer to obtain a front panel with an adhesive layer.
The retardation film was laminated on the surface of the hard coat layer of the polarizing plate via a 2 nd pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive layer A having a thickness of 5 μm, to prepare a circularly polarizing plate (having a thickness of 43.5 μm).
Then, the surface of the front panel on which the adhesive layer was formed and the TAC-side surface of the circularly polarizing plate were subjected to corona treatment, and then the front panel with the adhesive layer and the circularly polarizing plate were laminated so that these surfaces were located inside, and were bonded to each other using a roll bonding machine. Further, the touch sensor panel was laminated on the surface of the circularly polarizing plate opposite to the side to which the front panel was bonded, with the cycloolefin-based resin film as a surface layer, via the 3 rd pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive layer a having the thickness of 25 μm described above.
Next, the organic EL panel was bonded to the surface of the cycloolefin resin film side through the 4 th adhesive layer composed of the adhesive layer a having the thickness of 25 μm. The evaluation results of the obtained laminate are shown in table 2.
< example 2 >
A laminate of example 2 was produced in the same manner as in example 1, except that in example 1, the adhesive layer B was used in place of the adhesive layer a used in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer, and the 4 th adhesive layer, in place of the adhesive layer a used in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer, and the 4 th adhesive layer. The evaluation results of the obtained laminate are shown in table 2.
< example 3 >
A laminate of example 3 was produced in the same manner as in example 1, except that in example 1, the adhesive layer C was used in place of the adhesive layer a used in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer, and the 4 th adhesive layer, instead of the adhesive layer a used in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer, and the 4 th adhesive layer. The evaluation results of the obtained laminate are shown in table 2.
< example 4 >
A laminate of example 4 was produced in the same manner as in example 1, except that in example 1, the adhesive layer C for the 1 st adhesive layer, the 3 rd adhesive layer and the 4 th adhesive layer and the adhesive layer D for the 2 nd adhesive layer were used instead of the adhesive layer a for the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer and the 4 th adhesive layer. The evaluation results of the obtained laminate are shown in table 2.
< example 5 >
A laminate of example 5 was produced in the same manner as in example 1, except that in example 1, the adhesive layer D was used in place of the adhesive layer a used in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer and the 4 th adhesive layer, instead of the adhesive layer a used in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer and the 4 th adhesive layer. The evaluation results of the obtained laminate are shown in table 2.
< example 6 >
A laminate of example 6 was produced in the same manner as in example 1, except that in example 1, the adhesive layer E was used in place of the adhesive layer a used in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer and the 4 th adhesive layer, in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer and the 4 th adhesive layer. The evaluation results of the obtained laminate are shown in table 2.
< comparative example 1 >
A laminate of comparative example 1 was produced in the same manner as in example 1, except that in example 1, the adhesive layer F was used in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer, and the 4 th adhesive layer instead of the adhesive layer a was used in the 1 st adhesive layer, the 2 nd adhesive layer, the 3 rd adhesive layer, and the 4 th adhesive layer. The evaluation results of the obtained laminate are shown in table 2.
[ Table 1]
| Adhesive layer | Storage modulus of elasticity [ MPa ]] | Percent recovery [% ]] |
| A | 0.07 | 50 |
| B | 0.03 | 40 |
| C | 0.03 | 25 |
| D | 0.02 | 25 |
| E | 0.02 | 15 |
| F | 0.007 | 7 |
[ Table 2]
Claims (6)
1. A laminate comprising a structure in which at least 1 optical members are laminated with an adhesive layer interposed therebetween, wherein the adhesive layer of at least 1 structure satisfies the following formula (i),
the rate of change in thickness per unit number of bends is < 10(i), in%/ten thousand.
2. The laminate according to claim 1, wherein the thickness of the adhesive layer satisfying the formula (i) is 5 μm or more.
3. The laminate of claim 1 or 2, wherein the adhesive layers of the structure each satisfy the formula (i).
4. The laminate according to any one of claims 1 to 3, wherein the structure in which the optical members are laminated with each other via an adhesive layer is a structure in which 2 optical members selected from a front panel, a polarizing plate, a touch sensor panel, an organic EL display element, and a retardation film are laminated with the adhesive layer.
5. An image display device comprising the laminate according to any one of claims 1 to 4.
6. The image display device according to claim 5, which has flexibility.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2019022514 | 2019-02-12 | ||
| JP2019-022514 | 2019-02-12 |
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| CN111554184A true CN111554184A (en) | 2020-08-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP (2) | JP7183207B2 (en) |
| KR (1) | KR20200098418A (en) |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015047013A1 (en) * | 2013-09-30 | 2015-04-02 | 주식회사 엘지화학 | Optical device |
| CN105899568A (en) * | 2014-01-10 | 2016-08-24 | 三菱化学株式会社 | Thermosetting resin composition, cured member and overcoat layer formed using same, polarizing element provided with said overcoat layer, and image display device |
| CN107357459A (en) * | 2017-07-12 | 2017-11-17 | 业成科技（成都）有限公司 | Flexible structure |
| CN107531028A (en) * | 2015-04-10 | 2018-01-02 | 富士胶片株式会社 | Hyaline membrane, polarizer and image display device |
| JP2018028974A (en) * | 2016-08-15 | 2018-02-22 | 日東電工株式会社 | Adhesive composition for organic el display device, adhesive layer for organic el display device, polarizing film with adhesive layer for organic el display device, and organic el display device |
| JP2018028573A (en) * | 2016-08-15 | 2018-02-22 | 日東電工株式会社 | Laminate for Flexible Image Display Device and Flexible Image Display Device |
| CN108351547A (en) * | 2015-10-13 | 2018-07-31 | 康宁股份有限公司 | Flexible electronic-component module, product and its manufacturing method |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104837945B (en) * | 2012-12-14 | 2017-08-25 | 综研化学株式会社 | Pressure-sensitive adhesive for optical films composition, adhesive optical film and laminated body |
| KR101822700B1 (en) * | 2014-12-23 | 2018-01-30 | 삼성에스디아이 주식회사 | Adhesive composition, adhesive film prepared by the same and display member comprising the same |
| KR102494986B1 (en) * | 2016-01-11 | 2023-02-03 | 삼성디스플레이 주식회사 | Foldable display device |
| JP6932420B2 (en) * | 2016-08-15 | 2021-09-08 | 日東電工株式会社 | Adhesive composition for flexible image display device, adhesive layer for flexible image display device, laminate for flexible image display device, and flexible image display device |
| JP6932421B2 (en) * | 2016-08-15 | 2021-09-08 | 日東電工株式会社 | Adhesive layer for flexible image display device, laminate for flexible image display device, and flexible image display device |
| KR20180045108A (en) * | 2016-10-24 | 2018-05-04 | 삼성디스플레이 주식회사 | Display apparatus |
| JP6807234B2 (en) * | 2017-01-10 | 2021-01-06 | 日東電工株式会社 | Adhesive sheet |
| WO2019026760A1 (en) * | 2017-07-31 | 2019-02-07 | 日東電工株式会社 | Layered body for flexible image display device, and flexible image display device |
| KR20220134663A (en) * | 2017-07-31 | 2022-10-05 | 닛토덴코 가부시키가이샤 | Layered body for flexible image display device, and flexible image display device |
| JP7489755B2 (en) | 2018-03-29 | 2024-05-24 | リンテック株式会社 | Repeatedly bent device, manufacturing method thereof, and method for suppressing flexion marks |
-
2020
- 2020-01-31 TW TW109103054A patent/TW202030084A/en unknown
- 2020-02-07 JP JP2020019692A patent/JP7183207B2/en active Active
- 2020-02-10 CN CN202010084637.9A patent/CN111554184A/en active Pending
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-
2021
- 2021-11-22 JP JP2021189544A patent/JP2022047539A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015047013A1 (en) * | 2013-09-30 | 2015-04-02 | 주식회사 엘지화학 | Optical device |
| CN105899568A (en) * | 2014-01-10 | 2016-08-24 | 三菱化学株式会社 | Thermosetting resin composition, cured member and overcoat layer formed using same, polarizing element provided with said overcoat layer, and image display device |
| CN107531028A (en) * | 2015-04-10 | 2018-01-02 | 富士胶片株式会社 | Hyaline membrane, polarizer and image display device |
| CN108351547A (en) * | 2015-10-13 | 2018-07-31 | 康宁股份有限公司 | Flexible electronic-component module, product and its manufacturing method |
| JP2018028974A (en) * | 2016-08-15 | 2018-02-22 | 日東電工株式会社 | Adhesive composition for organic el display device, adhesive layer for organic el display device, polarizing film with adhesive layer for organic el display device, and organic el display device |
| WO2018034151A1 (en) * | 2016-08-15 | 2018-02-22 | 日東電工株式会社 | Adhesive composition for organic electroluminescent display devices, adhesive layer for organic electroluminescent display devices, polarizing film equipped with adhesive layer for organic electroluminescent display devices, and organic electroluminescent display device |
| JP2018028573A (en) * | 2016-08-15 | 2018-02-22 | 日東電工株式会社 | Laminate for Flexible Image Display Device and Flexible Image Display Device |
| CN107357459A (en) * | 2017-07-12 | 2017-11-17 | 业成科技（成都）有限公司 | Flexible structure |
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| KR20200098418A (en) | 2020-08-20 |
| TW202030084A (en) | 2020-08-16 |
| JP7183207B2 (en) | 2022-12-05 |
| JP2020134939A (en) | 2020-08-31 |
| JP2022047539A (en) | 2022-03-24 |
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