WO2010044466A1 - フラットパネルディスプレイ用透明粘着シート及びフラットパネルディスプレイ - Google Patents
フラットパネルディスプレイ用透明粘着シート及びフラットパネルディスプレイ Download PDFInfo
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- WO2010044466A1 WO2010044466A1 PCT/JP2009/067923 JP2009067923W WO2010044466A1 WO 2010044466 A1 WO2010044466 A1 WO 2010044466A1 JP 2009067923 W JP2009067923 W JP 2009067923W WO 2010044466 A1 WO2010044466 A1 WO 2010044466A1
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- Prior art keywords
- transparent
- adhesive sheet
- plate
- flat panel
- transparent adhesive
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- Ceased
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- 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
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4023—Coloured on the layer surface, e.g. ink
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- B32B2307/732—Dimensional properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/75—Printability
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2457/00—Electrical equipment
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- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/204—Plasma displays
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- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/206—Organic displays, e.g. OLED
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- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
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- 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
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
- G02F1/133311—Environmental protection, e.g. against dust or humidity
-
- 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
- G02F1/13338—Input devices, e.g. touch panels
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- 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
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
Definitions
- the present invention relates to a transparent adhesive sheet for a flat panel display, and particularly to a transparent adhesive sheet for a flat panel display that has excellent level difference absorbability and can be bonded to a plastic plate without foaming.
- a flat panel display such as a liquid crystal display
- a transparent plate such as an acrylic plate or a glass plate that protects the display panel so that the impact is not transmitted to the display panel.
- a protective panel including is provided with a certain gap.
- this gap is usually an air layer, the light reflection loss due to the difference in refractive index between the material constituting the display panel or the protection panel and the air layer is large, and good visibility is obtained. There is a problem that it cannot be obtained.
- a transparent pressure-sensitive adhesive sheet made of an acrylic pressure-sensitive adhesive (for example, an acrylate copolymer is epoxy-based, isocyanate-based, melamine-based)
- an acrylic pressure-sensitive adhesive for example, an acrylate copolymer is epoxy-based, isocyanate-based, melamine-based
- a protective transparent plate is bonded to the liquid crystal panel via a cross-linking agent of a metal or metal compound type, or a UV curable acrylic pressure-sensitive adhesive or the like processed into a sheet shape,
- Patent Document 1 A technique for tightly integrating a transparent plate is known (Patent Document 1, etc.).
- a protective transparent plate in a liquid crystal display acrylic as compared with a glass plate is used.
- Transparent plastic plates such as plates and polycarbonate plates are increasingly used.
- a black printing layer is usually formed on the outer peripheral edge of the protective transparent plate. The surface has a step due to the thickness of the printing layer.
- the transparent adhesive sheet is preferably soft in order to obtain excellent step absorbability, and the present inventors have proposed that the shear storage elastic modulus (G ′) of the adhesive sheet in order to soften the acrylic transparent adhesive sheet. Attempted to set a lower value.
- the acrylic transparent adhesive sheet with a low shear storage modulus (G ') showed excellent step absorbency, but foaming occurred on the adhesive surface to the protective transparent plate (transparent plastic plate), which occurred at that time. There was a problem that the visibility was lowered by the bubbles.
- the present invention has been made in view of the circumstances as described above, and the problem to be solved is a flat that does not cause foaming on an adhesive surface with a plastic plate while having excellent step absorbability. It is providing the transparent adhesive sheet for panel displays.
- the inventors of the present invention have a polyoxyalkylene polymer having at least one alkenyl group in one molecule (component A), and an average of two or more in one molecule.
- a polyoxyalkylene-based pressure-sensitive adhesive sheet obtained from a cured product of a composition containing a compound having a hydrosilyl group (component B) and a hydrosilylation catalyst (component C) has a relatively low shear storage modulus (G ′).
- G ′ shear storage modulus
- the present inventors have found that it can be bonded to a plastic plate without causing foaming, and have completed the present invention.
- a cured product of a composition containing the following components A to C, a shear storage modulus (G ′) at 25 ° C. and 1 Hz is 1.0 ⁇ 10 5 Pa or less, and a gel fraction is
- the transparent adhesive sheet for flat panel displays characterized by being 40% or more.
- C Hydrosilylation catalyst
- Flat panel The transparent adhesive sheet according to the above (1), wherein at least one layer in the front multilayer structure part of the display is used by being interposed between two adjacent layers which are a plastic plate or a plastic film.
- a touch panel is inserted between the protective transparent plate made of a transparent plastic plate or a transparent plastic film and the display panel, and between the transparent plastic plate on one outermost layer of the touch panel and the protective transparent plate, and A flat panel display obtained by interposing the transparent adhesive sheet described in (1) above between the transparent plastic plate on the other outermost layer of the touch panel and the display panel, and bonding and integrating the protective transparent plate, the touch panel, and the display panel.
- the transparent adhesive sheet of the present invention is excellent in flexibility and adheres to a plastic plate without causing foaming.
- a black printed layer is formed on the outer peripheral edge used as a protective transparent plate.
- Even a transparent plastic plate having a step on the surface can be bonded without causing a void and without causing foaming. Therefore, by using the transparent adhesive sheet of the present invention, a multilayer having at least a protective transparent plate made of a transparent plastic plate and a display panel formed on the front surface side of the flat panel display (that is, the display surface of the flat panel display). It is possible to realize a flat panel display in which there are no voids or bubbles that reduce visibility in the structure (front multi-layer structure), and adjacent layers in the front multi-layer structure are bonded and integrated.
- FIG. 1 is a schematic cross-sectional view of a liquid crystal display device in which a protective transparent plate made of a transparent plastic plate is bonded and integrated with a liquid crystal panel via a transparent adhesive sheet of the present invention. It is a schematic cross section of the liquid crystal display device which integrated the touch panel and the protective transparent board which consists of a transparent plastic board with respect to a liquid crystal display panel with the transparent adhesive sheet of this invention.
- the “flat panel display” in the present invention is a concept including a liquid crystal display (LCD), a plasma display (PDP), an organic or inorganic electroluminescence display (ELD), a surface electrolytic display (SED) and the like.
- the “display panel” refers to a panel body including a display material in various flat panel displays such as a panel body including a liquid crystal material (“liquid crystal panel”) in a liquid crystal display (LCD).
- a display module is a device in which a driver IC or the like is mounted on the body.
- the transparent pressure-sensitive adhesive sheet of the present invention is a polyoxyalkylene pressure-sensitive adhesive sheet made of a cured product obtained by curing a composition containing the following components A to C, and has a shear storage modulus (G ′) of 1 at 25 ° C. and 1 Hz. 0.0 ⁇ 10 5 Pa or less and the gel fraction is 40% or more.
- B Compound containing 2 or more and less than 5 hydrosilyl groups on average in one molecule
- C Hydrosilylation catalyst
- the transparent pressure-sensitive adhesive sheet of the present invention is excellent in flexibility and adheres to a plastic plate or plastic film with high adhesive force (peeling force) without causing foaming. Moreover, it adhere
- LCD liquid crystal display
- PDP plasma display
- ELD organic or inorganic electroluminescence display
- SED surface electrolysis display
- the two layers are bonded and integrated without generating bubbles between them.
- a black printed layer (generally about 1 to 50 ⁇ m in thickness) is formed on the outer periphery. )
- G ′ shear storage modulus
- a black printed layer (generally about 1 to 50 ⁇ m in thickness) is formed on the outer periphery. )
- G ′ shear storage modulus
- a black printed layer (generally about 1 to 50 ⁇ m in thickness) is formed on the outer periphery. )
- plastic plate and “plastic film” are shown together, and “protective transparent plate” and “protective transparent film” are shown together, but “plate” and “film” are generally relatively thick in glass or plastic. Large sheet bodies are called “plates”, and sheets with relatively small thickness are often called “films”. Glass and plastic sheet bodies in the field of flat panel displays It is written together with the intention of including the whole. Therefore, in the following description, the description “plastic plate” is used as a concept including “plastic film”, and the description “protective transparent plate” is used as a concept including “protective transparent film”.
- the “front multi-layer structure” described above includes at least a display panel and a protective transparent plate on the front surface side of the flat panel display (that is, the display surface of the flat panel display). It means a multilayer structure (laminated structure) part including at least a display panel and a protective transparent plate, in which one or more functional layers other than the protective transparent plate may be provided between them.
- FIG. 1 is a schematic cross-sectional view of a liquid crystal display in which a protective transparent plate made of a transparent plastic plate is bonded and integrated with a liquid crystal display panel using the transparent adhesive sheet of the present invention.
- the transparent adhesive sheet 1 of the present invention is interposed between the liquid crystal display panel 2 and a protective transparent plate 3 made of a transparent plastic plate, and the transparent adhesive sheet 1 consists of the liquid crystal display panel 2 and a transparent plastic plate.
- the liquid crystal panel 2 and the protective transparent plate 3 are bonded and integrated with the protective transparent plate 3.
- symbol 5 in a figure is a black printing layer formed in the outer periphery of the protection transparent board 3, for example, and the transparent adhesive sheet 1 absorbs the level
- acrylic resin for example, PMMA
- PC polycarbonate
- PP polypropylene
- PP polyphenylene sulfide
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- TAC triacetyl cellulose
- the display panel in a liquid crystal display generally has a polarizing plate (polarizing filter) / transparent plate (glass plate, plastic plate) / liquid crystal material sandwiched between transparent electrodes / transparent plate (glass plate, plastic plate) / polarizing plate (although it is a panel body which has at least the laminated structure laminated
- the polarizing plate (polarizing filter) is usually formed by sandwiching a polyvinyl alcohol film (PVA) dyed with iodine between two pieces of triacetyl cellulose (TAC), and the TAC surface is untreated and hard-coated.
- PVA polyvinyl alcohol film
- TAC triacetyl cellulose
- the transparent adhesive sheet 1 of the present invention adheres to these materials with high adhesive force.
- the transparent adhesive sheet 1 of the present invention is interposed between a protective transparent plate 3 made of a transparent plastic plate and a polarizing plate (polarizing filter), and the two are closely integrated. I am letting.
- an impact-reducing film for example, polyethylene terephthalate (for example, polyethylene terephthalate)
- a flat panel display typified by a liquid crystal display
- an impact-reducing film for example, polyethylene terephthalate (for example, polyethylene terephthalate)
- the protective transparent plate to reduce the impact when the protective transparent plate receives an external impact.
- PET polyethylene naphthalate
- PC polycarbonate
- PP polypropylene
- PE polyethylene
- Optical compensation film for example, polycarbonate (PC) film, cycloolefin resin film, acrylic resin film, transparent film other than those described above and above in which a liquid crystal material is applied and oriented on the surface from the viewpoint of improving the contrast ratio
- a glass plate (film) may be inserted.
- an attachment mechanism such as a touch panel (a glass plate having a transparent electrode (detection electrode layer) / an adhesive layer / a glass plate having a transparent electrode (drive electrode layer)) between the display panel and the protective transparent plate.
- a touch panel a glass plate having a transparent electrode (detection electrode layer) / an adhesive layer / a glass plate having a transparent electrode (drive electrode layer)
- the transparent adhesive sheet of the present invention is made of various materials. Can be used for bonding two adjacent layers in the front multilayer structure.
- FIG. 2 is a schematic cross-sectional view of a liquid crystal display in which the transparent adhesive sheet of the present invention is used to perform interlayer adhesion in the front multilayer structure.
- the liquid crystal display 200 includes a touch panel (transparent plastic plate having a transparent electrode (detection electrode layer) / adhesive layer / transparent electrode (drive electrode layer)) between the liquid crystal display panel 2 and a protective transparent plate 3 made of a transparent plastic plate.
- the transparent adhesive sheet 1 of the present invention is inserted between the liquid crystal display panel 2 and the touch panel 4 and between the touch panel 4 and the protective transparent plate 3.
- the touch panel 4 and the protective transparent plate 3 are tightly integrated with the liquid crystal display panel 2.
- the transparent adhesive sheet 1 of this invention can be used also for the contact bonding layer which adhere
- symbol 5 in a figure is the black printing layer formed in the edge part of the outer periphery of the protection transparent board (transparent plastic board) 3.
- the touch panel is inserted between the display panel and the protective transparent plate made of a transparent plastic plate, and between the outermost transparent plastic plate and the protective transparent plate of the touch panel, and the outermost transparent plastic plate of the touch panel.
- the transparent adhesive sheet of the present invention By interposing the transparent adhesive sheet of the present invention between the display panel and the display panel, the transparent adhesive sheet has no transparent bubbles on the transparent plastic plate having the transparent electrode layer constituting the outermost layer of the touch panel. Bond with high adhesive strength. Therefore, it is possible to realize a flat panel display with a touch panel that is free from defects such as a reduction in the visibility of a display image and has excellent mechanical durability.
- the “polyoxyalkylene polymer having at least one alkenyl group in one molecule” of component A is not particularly limited, and various types can be used. It is preferable that the main chain of the polymer has a repeating unit represented by the following general formula (1).
- R 1 is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms.
- the repeating unit represented by the general formula (1) include —CH 2 O—, —CH 2 CH 2 O—, —CH 2 CH (CH 3 ) O—, —CH 2 CH (C 2 H 5 ) O—, —CH 2 C (CH 3 ) 2 O—, —CH 2 CH 2 CH 2 CH 2 O— and the like.
- the main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.
- a polymer having —CH 2 CH (CH 3 ) O— as the main repeating unit is preferred from the viewpoint of availability and workability.
- the main chain of the polymer may contain a repeating unit other than the oxyalkylene group.
- the total of oxyalkylene units in the polymer is preferably 80% by weight or more, and particularly preferably 90% by weight or more.
- the polymer of the component A may be a linear polymer or a branched polymer, and may be a mixture thereof. In order to obtain good adhesion, 50% by weight of the linear polymer is used. % Or more is preferable.
- the molecular weight of the polymer of component A is preferably 500 to 50,000, more preferably 5,000 to 30,000 in terms of number average molecular weight.
- the number average molecular weight is a value determined by a gel permeation chromatography (GPC) method.
- the polymer of component A preferably has a relatively narrow molecular weight distribution in which the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is 1.6 or less, and the Mw / Mn is 1.6 or less.
- Mw / Mn is more preferably 1.5 or less, and even more preferably 1.4 or less.
- Mw / Mn here is a value calculated
- the molecular weight measurement by the GPC method is a polystyrene conversion value measured using a GPC apparatus (HLC-8120GPC) manufactured by Tosoh Corporation, and the measurement conditions are as follows. Sample concentration: 0.2% by weight (THF solution) Sample injection volume: 10 ⁇ l Eluent: THF Flow rate: 0.6 ml / min Measurement temperature: 40 ° C Column: Sample column TSKgel GMH-H (S) Detector: Differential refractometer
- the alkenyl group is not particularly limited, but an alkenyl group represented by the following general formula (2) is preferable. It is.
- the bonding mode of the alkenyl group to the polyoxyalkylene polymer is not particularly limited, and examples thereof include a direct bond of an alkenyl group, an ether bond, an ester bond, a carbonate bond, a urethane bond, and a urea bond.
- R 4a in the formula specifically, -CH 2 -, - CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 -, - CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 OCH 2 CH 2 —, or —CH 2 CH 2 OCH 2 CH 2 CH 2 — and the like can be mentioned, but —CH 2 — is preferable from the viewpoint of ease of synthesis. .
- the alkenyl group may be present at least 1, preferably 1 to 5, more preferably 1.5 to 3 in one molecule of the component A polymer.
- the number of alkenyl groups contained in one molecule of the component A polymer is less than 1, the curability is insufficient, and when the number is more than 5, the network structure becomes too dense. May not be shown.
- the polymer of component A can be synthesized according to the method described in JP-A-2003-292926, and commercially available products can be used as they are.
- the B component “compound containing 2 or more and less than 5 hydrosilyl groups on average in one molecule” has an average of 2 or more hydrosilyl groups (groups having Si—H bonds) in one molecule, Any compound containing a hydrosilyl group that is less than 5 can be used without any particular limitation, but organohydrogenpolysiloxane modified with an organic component in particular from the standpoint of availability of raw materials and compatibility with component A Is preferred. Specifically showing the structure of polyorganohydrogensiloxane modified with such organic components, for example,
- R 6a is a hydrocarbon group having 2 to 20 carbon atoms in the main chain and one or more phenyl groups; Group may contain),
- R 6c is one or more hydrocarbon groups having 2 to 20 carbon atoms in the main chain. Or a chain-like or cyclic group represented by the above, or two or more of these units,
- R 6d is the backbone one or more phenyl groups with a hydrocarbon group having a carbon number of 2 to 20 2 ⁇ b 1 , m 4 ⁇ b 1 ⁇ 5, R 8a is a divalent to tetravalent organic group, R 7a is a divalent organic group, provided that R 7a is , Depending on the structure of R 8a ).
- R 6e is a hydrocarbon group having 2 to 20 carbon atoms in the main chain and one or more phenyl groups.
- R 8b is a divalent to tetravalent organic group
- R 7b is a divalent organic group, provided that R 7b is , Depending on the structure of R 8b ), or
- R 6f is a hydrocarbon group having 2 to 20 carbon atoms in the main chain, and one or more phenyl groups. 2 ⁇ b 3 , m 6 ⁇ b 3 ⁇ 5, R 8c is a divalent to tetravalent organic group, R 7c is a divalent organic group, provided that R 7c is , Depending on the structure of R 8c . And the like.
- the B component is preferably compatible with the A component and the C component or has good dispersion stability in the system.
- the viscosity of the whole system is low, if a component having low compatibility with the above components is used as the B component, phase separation may occur and poor curing may occur.
- B component having relatively good compatibility with the A component and the C component or relatively good dispersion stability include the following.
- R 6g is a hydrocarbon group having 8 or more carbon atoms.
- the component B include polymethylhydrogensiloxane.
- polymethylhydrogensiloxane In order to ensure compatibility with the component A and to adjust the amount of SiH, ⁇ -olefin, styrene, ⁇ -methylstyrene, allyl are used. Examples include compounds modified with alkyl ethers, allyl alkyl esters, allyl phenyl ethers, allyl phenyl esters, and the like, and examples thereof include the following structures.
- the B component can be synthesized by a known method, and commercially available products can be used as they are.
- the “hydrosilylation catalyst” of component C is not particularly limited, and any component can be used. Specifically, chloroplatinic acid; platinum alone; solid platinum supported on a carrier such as alumina, silica, carbon black; platinum-vinylsiloxane complex ⁇ eg, Pt n (ViMe 2 SiOSiMe 2 Vi) m , Pt [(MeViSiO) 4 ] m, etc.]; platinum-phosphine complexes ⁇ eg, Pt (PPh 3 ) 4 , Pt (PBu 3 ) 4 etc. ⁇ ; platinum-phosphite complexes ⁇ eg, Pt [P (OPh) 3 ] 4 , Pt [P (OBu) 3 ] 4 etc. ⁇ ; Pt (acac) 2 ; platinum-hydrocarbon complexes described in Ashby et al.
- Me represents a methyl group
- Bu represents a butyl group
- Vi represents a vinyl group
- Ph represents a phenyl group
- acac represents acetylacetonato
- n and m represent integers.
- catalysts other than platinum compounds include RhCl (PPh 3 ) 3 , RhCl 3 , Rh / Al 2 O 3 , RuCl 3 , IrCl 3 , FeCl 3 , AlCl 3 , PdCl 2 .2H 2 O, NiCl 2. , TiCl 4 and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-phosphine complex, platinum-vinylsiloxane complex, Pt (acac) 2 and the like are preferable.
- the amount of component C is not particularly limited, but is generally 1 ⁇ 10 ⁇ 1 mol or less with respect to 1 mol of alkenyl groups in component A, from the viewpoint of ensuring the pot life of the composition and the transparency of the sheet. Is 5.3 ⁇ 10 ⁇ 2 mol or less, more preferably 3.5 ⁇ 10 ⁇ 2 mol or less, particularly preferably 1.4 ⁇ 10 ⁇ 3 mol or less, particularly from the viewpoint of the transparency of the sheet. .
- the amount exceeds 1 ⁇ 10 ⁇ 1 mole relative to 1 mole of the alkenyl group in the component A, the finally obtained sheet tends to yellow, and the transparency of the sheet tends to be impaired.
- the amount of component C is based on 1 mole of alkenyl groups in component A. It is preferably 8.9 ⁇ 10 ⁇ 5 mol or more, more preferably 1.8 ⁇ 10 ⁇ 4 mol or more.
- the transparent adhesive sheet of the present invention has a shear storage modulus (G ′) at 25 ° C. and 1 Hz of 1.0 ⁇ 10 5 Pa or less and a gel fraction of 40% or more. is important.
- the shear storage modulus (G ′) at 25 ° C. and 1 Hz is 1.0 ⁇ 10 5 Pa or less
- the transparent pressure-sensitive adhesive sheet has excellent step absorbability.
- the shear storage modulus (G ′) is preferably 0.6 ⁇ 10 5 Pa or less. However, if the shear storage modulus (G ′) becomes too small, such a transparent pressure-sensitive adhesive sheet cannot maintain its shape as a sheet and tends to significantly impair workability. 1 ⁇ 10 5 Pa or more, more preferably 0.2 ⁇ 10 5 Pa or more.
- the transparent adhesive sheet has a gel fraction of 40% or more, it can be firmly bonded to a plastic surface or a surface of various materials without foaming.
- the gel fraction is preferably 45% or more.
- the upper limit is preferably 90% or less, more preferably 70% or less in order to show a tendency to damage.
- the shear storage elastic modulus (G ′) of the transparent adhesive sheet of the present invention is particularly related to the number of hydrosilyl groups in one molecule of the B component, and the shear storage elastic modulus (G ′) of the transparent adhesive sheet at 25 ° C. and 1 Hz. Is 1.0 ⁇ 10 5 Pa or less, it is important that the average number of hydrosilyl groups in one molecule of the B component is less than 5.
- the gel fraction of the transparent adhesive sheet of the present invention is particularly related to the ratio of the components A and B in the composition containing the components A to C, and the transparent adhesive sheet having a gel fraction of 40% or more.
- the amount of hydrosilyl groups in component B (total number of moles of hydrosilyl groups) is 0.50 or more in terms of the functional group ratio (molar ratio) to the amount of alkenyl groups in component A (total number of moles of alkenyl groups) It is important to adjust the amount ratio of the A component and the B component so that The upper limit of the functional group ratio (molar ratio) is preferably 1.0 or less in order to avoid stiffening of the transparent adhesive sheet when the gel fraction becomes too large.
- a storage stability improving agent may be blended for the purpose of improving storage stability.
- a known compound known as a storage stabilizer for the component B can be used without limitation.
- a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, or the like can be preferably used.
- the adhesion imparting agent for improving adhesiveness can be added as needed.
- the adhesion imparting agent include various silane coupling agents and epoxy resins.
- the catalyst for making a silyl group or an epoxy group react can be added together with a silane coupling agent and an epoxy resin.
- the influence with respect to hydrosilylation reaction must be considered.
- Various fillers, antioxidants, ultraviolet absorbers, pigments, surfactants, solvents, and silicon compounds may be added as appropriate.
- Specific examples of the filler include silica fine powder, calcium carbonate, clay, talc, titanium oxide, zinc white, diatomaceous earth, barium sulfate and the like.
- silica fine powder particularly fine powder silica having a particle size of about 50 to 70 nm (BET specific surface area of 50 to 380 m 2 / g) is preferable.
- hydrophobic silica subjected to surface treatment is preferable.
- a tackifying resin may be added as necessary.
- the tackifying resin include terpene resins, terpene phenol resins, petroleum resins, rosin esters, etc. It is possible to select freely according to.
- resins such as phenol resin, acrylic resin, styrene resin, xylene resin.
- adhesive components such as an acrylic adhesive, a styrene block adhesive, and an olefin adhesive, for the same purpose.
- the transparent pressure-sensitive adhesive sheet of the present invention exhibits a high adhesive force (peeling force) for various materials, for example, a peeling force for an acrylic plate (PMMA plate) of 3.5 N / 25 mm or more, and a polycarbonate (PC) plate
- peeling force with respect to the film shows 3.5 N / 25 mm or more
- PET polyethylene terephthalate
- PET polyethylene terephthalate
- the peeling force with respect to the glass plate shows 1.0 N / 25 mm or more.
- the peeling force refers to a 25 mm ⁇ 150 mm sample piece obtained by bonding a support (release liner) made of a 25 ⁇ m thick PET film to one side of a pressure sensitive adhesive sheet having a thickness of 200 ⁇ m.
- the sample piece is prepared and bonded to an adherend (PMMA plate, polycarbonate plate, polyethylene terephthalate film, glass plate) at a pressure of 2 kg, and the bonded sample piece is allowed to stand at 23 ° C. for 24 hours and then bonded. It is the value measured by peeling at a speed of 300 mm / min in the 90 ° direction with respect to the mating surfaces.
- the transparent adhesive sheet of this invention is manufactured with the following method, for example.
- a composition containing a polyoxyalkylene polymer as a main component (a composition containing at least the above-mentioned components A to C) is charged into an agitator equipped with a vacuum function together with an organic solvent as necessary, and is in a vacuum state (under vacuum) ), And the fluid after the vacuum defoaming is applied (cast) on various supports and heat-treated to form a sheet.
- the composition is heat-cured by heat treatment to obtain a sheet of a cured product.
- the coating on the support can be carried out by a known coating apparatus such as a roll coater such as gravure, kiss, or comma, a die coater such as slot or phantom, a squeeze coater, or a curtain coater.
- the heat treatment conditions at this time are preferably 50 to 200 ° C. (preferably 100 to 160 ° C.) and heated for about 0.01 to 24 hours (preferably 0.05 to 4 hours).
- a well-known stirring apparatus with a vacuum apparatus as a stirring apparatus provided with said vacuum function, Specifically, a planetary type (revolution / autorotation system) stirring deaerator and a deaerator with a disper Etc.
- the stirring time varies depending on the stirring device and the throughput of the fluid, it is generally preferably about 0.5 to 2 hours.
- the defoaming treatment there are substantially no bubbles in the sheet, and excellent optical properties (transparency) are exhibited.
- the haze value of the sheet measured by the test method described later is preferably 1.2% or less, more preferably 0.9% or less.
- the transparent pressure-sensitive adhesive sheet of the present invention is used for bonding two adjacent layers in the front multilayer structure portion of a flat panel display mounted on a small device such as a mobile phone, a portable game machine, or a car navigation system, the area is small.
- a first support (base separator) / cured layer of a composition containing the above components A to C (transparent adhesive) it is preferable to prepare a roll having a laminated structure of (sheet) / second support (cover separator) and perform punching while developing the roll.
- the roll is applied with a mold release treatment agent on a first support and subjected to a mold release treatment, while the composition containing the components A to C is stirred and vacuum degassed.
- the fluid is applied (cast) onto the first support, heat-treated into a sheet, and the second support subjected to the mold release treatment is bonded to it, and then wound into a roll. It is made with.
- first and second supports include, for example, an ionomer resin in which molecules of polyester such as polybutylene terephthalate (PBT) and ethylene-methacrylic acid copolymer are cross-linked with metal ions (Na + , Zn 2+, etc.).
- PBT polybutylene terephthalate
- metal ions Na + , Zn 2+, etc.
- EVA ethylene-vinyl acetate copolymer
- PVC polyvinyl chloride
- EEA ethylene-ethyl acrylate copolymer
- PE polyethylene
- PP polypropylene
- polyamide polybutyral, polystyrene, etc .
- polystyrene series Polyolefin, polydiene, vinyl chloride, polyurethane, polyester, polyamide, fluorine, chlorinated polyethylene, polynorbornene, polystyrene / polyolefin copolymer, (hydrogenated) polystyrene / butadiene copolymer,
- thermoplastic elastomers exhibiting rubber elasticity such as styrene / vinylpolyisoprene copolymer system
- single layer film (sheet) made of polyolefin such as polyethylene and polypropylene blended with thermoplastic elastomer, polyolefin (polypropylene ( PP
- multilayer (laminate) films such as composite multilayer (laminate) in which the blend ratio of polyolefin + thermoplastic elastomer is changed.
- impregnated paper, coated paper, fine paper, craft paper, cloth, acetate cloth, non-woven cloth, glass cloth, and the like can be given.
- Examples of the release treatment agent used for the first and second supports include a silicone release treatment agent, a fluorine release treatment agent, a long-chain alkyl release treatment agent, and the like.
- a silicone-based mold release treatment agent is preferable, and a curing method such as ultraviolet irradiation or electron beam irradiation is preferably used as the curing method.
- cationically polymerizable UV-curable silicone release treatment agents are preferable.
- the cationic polymerizable UV curable silicone release treatment agent is a mixture containing a cationic polymerization type silicone (polyorganosiloxane having an epoxy functional group in the molecule) and an onium salt photoinitiator.
- the photoinitiator is made of a boron photoinitiator, and a cationically polymerizable UV-curable silicone release agent in which such an onium salt photoinitiator is made of a boron photoinitiator is used.
- a cationically polymerizable UV-curable silicone release agent in which such an onium salt photoinitiator is made of a boron photoinitiator is used.
- the cationic polymerization type silicone polyorganosiloxane having an epoxy functional group in the molecule
- has at least two epoxy functional groups in one molecule, and is linear or branched or A mixture thereof may be used.
- the type of epoxy functional group contained in the polyorganosiloxane is not particularly limited as long as ring-opening cationic polymerization proceeds with an onium salt photoinitiator. Specific examples include ⁇ -glycidyloxypropyl group, ⁇ - (3,4-epoxycyclohexyl) ethyl group, ⁇ - (4-methyl-3,4-epoxycyclohexyl) propyl group, and the like.
- Such cationic polymerization type silicone (polyorganosiloxane having an epoxy functional group in the molecule) is commercially available, and a commercially available product can be used.
- Examples include 62-7634A, Poly200, Poly201, RCA200, RCA250, and RCA251 manufactured by Arakawa Chemical Co., Ltd.
- polyorganosiloxanes having the following structural units (A) to (C) are particularly preferable.
- the composition ratio ((A) :( B) :( C)) of the structural units (A) to (C) is 50 to 95: Those having 2 to 30: 1 to 30 (mol%) are particularly preferred, and those having 50 to 90: 2 to 20: 2 to 20 (mol%) are particularly preferred.
- Polyorganosiloxanes comprising such structural units (A) to (C) are available as Poly200, Poly201, RCA200, X-62-7622, X-62-7629, and X-62-7660.
- onium salt photoinitiators can be used without particular limitation. Specific examples include, for example, (R 1 ) 2 I + X ⁇ , ArN 2 + X ⁇ , or (R 1 ) 3 S + X ⁇ , wherein R 1 is an alkyl group and / or an aryl group.
- Ar represents an aryl group
- X ⁇ represents [B (C 6 H 5 ) 4 ] ⁇ , [B (C 6 F 5 ) 4 ] ⁇ , [B (C 6 H 4 CF 3 ) 4 ] ⁇ , [ (C 6 F 5 ) 2 BF 2 ] ⁇ , [C 6 F 5 BF 3 ] ⁇ , [B (C 6 H 3 F 2 ) 4 ] ⁇ , BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , HSO 4 -, or ClO 4 -.
- an antimony (Sb) -based initiator As an onium salt-based photoinitiator, an antimony (Sb) -based initiator is conventionally known. However, when an antimony (Sb) -based initiator is used, delamination occurs, and the transparent adhesive sheet is removed from the separator. It tends to be difficult to peel.
- the amount of the onium salt photoinitiator used is not particularly limited, but is preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the cationic polymerization type silicone (polyorganosiloxane). If the amount used is less than 0.1 parts by weight, the silicone release layer may be insufficiently cured. If the amount used is more than 10 parts by weight, it is not practical in terms of cost.
- the onium salt initiator may be dissolved or dispersed in an organic solvent and mixed with the polyorganosiloxane.
- organic solvent examples include alcohol solvents such as isopropyl alcohol and n-butanol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate.
- coating of a mold release processing agent can be performed using common coating apparatuses, such as a roll coater method, a reverse coater method, a doctor blade method, for example.
- the coating amount (solid content) of the mold release treatment agent is not particularly limited, but is generally about 0.05 to 6 mg / cm 2 .
- liquid crystal display in a portable game machine, a digital video camera, a car navigation system, a small music player, a small video player, a mobile phone, etc.
- the display on the liquid crystal screen is held on the front surface of the liquid crystal panel.
- the transparent adhesive sheet of the present invention is brought into contact with the glass or plastic film on which the transparent electrode layer is formed, but the transparent adhesive sheet of the present invention is made of ITO, TO ( Excellent non-transparent conductive material corrosiveness (especially non-ITO corrosion) that does not corrode the transparent conductive material even when in contact with transparent conductive material such as tin oxide, ZnO (zinc oxide), CTO (tin cadmium oxide) Therefore, it works advantageously when a touch panel is interposed between the protective transparent plate and the display module.
- ITO Excellent non-transparent conductive material corrosiveness (especially non-ITO corrosion) that does not corrode the transparent conductive material even when in contact with transparent conductive material such as tin oxide, ZnO (zinc oxide), CTO (tin cadmium oxide) Therefore, it works advantageously when a touch panel is interposed between the protective transparent plate and the display module.
- the thickness of the transparent adhesive sheet of the present invention varies depending on the type of flat panel display, etc., it is usually used at a thickness of 1000 ⁇ m or less, further 500 ⁇ m or less from the viewpoint of thinning the flat panel display. However, if the thickness is too thin, it is not preferable in terms of step absorbability of the printed portion formed on the protective panel, and therefore the lower limit of the thickness is preferably 10 ⁇ m or more. A more preferred thickness is 15 to 300 ⁇ m, and particularly preferred is 25 to 250 ⁇ m.
- the transparent pressure-sensitive adhesive sheet of the present invention can be basically produced without a solvent, and has a low molecular weight and a low volatile oligomer component or monomer component. There is also an advantage that even if it is used for a device equipped with a flat panel display that has come to be used, there is little adverse effect on the human body.
- Adhesive sheets with an adhesive layer thickness of 10 to 250 ⁇ m are laminated and laminated to a thickness of about 0.5 to 1 mm, and the laminated sheet is punched into a circular shape with a diameter of 7.9 mm as a measurement sample. Measured by the following method. Measuring device: ARES manufactured by Rheometric Scientific Measurement conditions: Measurement temperature 25 ° C Measurement frequency 1 Hz (6.28 rad / sec)
- Step absorbency A PET film (thickness 25 ⁇ m) was bonded to a substrate-less transparent double-sided tape (adhesion layer thickness 12 ⁇ m) to prepare a step tape having a total thickness of 37 ⁇ m.
- the step tape was attached in a frame shape to the periphery along the four sides of the main surface of the rectangular glass plate to make a stepped glass plate. After sticking an adhesive sheet on the entire surface of the stepped glass plate to which the step tape has been applied, and performing autoclaving (50 ° C., 0.5 MPa, 15 minutes), the adhesive layer floating at the step portion was visually observed. Observed with. In the evaluation, a state in which the lift of the adhesive layer was not confirmed at a stepped portion was determined as pass ( ⁇ ), and a state in which the lift was confirmed was determined as reject (x).
- Example 1 A polyoxyalkylene polymer having two alkenyl groups in one molecule as component A (number average molecular weight: about 20,000), a hydrosilyl compound as component B (average number of hydrosilyl groups in one molecule is 2 or more, 5
- the hydrosilylation catalyst which is a component (C) and component C is such that the component A and component B have a hydrosilyl group content of component B of 0.58 in terms of functional group ratio (molar ratio) to the amount of component alkenyl groups.
- a composition (manufactured by Kaneka Co., Ltd.) that is blended in a quantitative ratio and blended in such an amount that C component is 0.9 ⁇ 10 ⁇ 3 mol per 1 mol of alkenyl groups in component A is stirred with a vacuum device. It put into the apparatus (Chitech mini-dappo), and deaerated by stirring for 1 hour in a vacuum state (100 Pa). Next, the vacuum degassed composition is used at room temperature on a base separator (support) made of a polyester film (thickness: 100 ⁇ m) which has been subjected to a release treatment using a roll coater, so that the composition has a thickness of 200 ⁇ m. Application (casting) was performed.
- Curing is carried out by heating at 130 ° C. for 10 minutes in a heating oven, and a cover separator (release liner) made of a polyester film (thickness: 100 ⁇ m) which has been similarly subjected to a release treatment is bonded to the cured sheet thus obtained.
- a cover separator release liner
- a transparent adhesive sheet thickness: 199 ⁇ m
- the obtained transparent adhesive sheet had a haze value of 0.3%, a shear storage modulus (G ′) at 25 ° C. of 0.2 ⁇ 10 5 (Pa), and a gel fraction of 41%. And the level
- Example 2 The amount of the hydrosilyl compound as the component B in the composition containing the components A to C was changed to an amount such that the amount of the hydrosilyl group was 0.68 in terms of the functional group ratio (molar ratio) with respect to the amount of the alkenyl group of the component A. Except for this, a transparent adhesive sheet (thickness: 199 ⁇ m) was obtained in the same manner as in Example 1. The obtained transparent adhesive sheet had a haze value of 0.4%, a shear storage modulus (G ′) at 25 ° C. of 0.6 ⁇ 10 5 (Pa), and a gel fraction of 65%. And the level
- Comparative Example 1 97 parts by weight of butyl acrylate (hereinafter abbreviated as “parts”), 3 parts of acrylic acid and 0.4 parts of azobisisobutyronitrile are dissolved in 100 parts of ethyl acetate and reacted at about 60 ° C. with stirring.
- a photopolymerization composition was prepared by blending 0.05 part of a polymerization initiator (Irgacure 651 trade name, manufactured by Ciba Specialty Chemicals).
- This photopolymerized composition was applied (cast) onto a polyester film (thickness 75 ⁇ m) subjected to a release treatment so that the thickness of the composition became 200 ⁇ m, and a polyester film (for covering)
- an ultraviolet curable acrylic pressure-sensitive adhesive sheet was formed by irradiating it with 2000 mJ / cm 2 of ultraviolet rays and photopolymerizing with an ultraviolet lamp.
- the pressure-sensitive adhesive sheet had a shear storage modulus (G ′) at 25 ° C. of 0.4 ⁇ 10 5 (Pa) and a gel fraction of 25%.
- step difference absorbency and foaming resistance of this transparent adhesive sheet were evaluated. Table 1 shows the results.
- the transparent adhesive sheet of the example since the transparent adhesive sheet of the example has excellent level difference absorbability, it does not cause foaming on the adhesive surface with the plastic plate. Therefore, between the adjacent layers in the front multilayer structure portion of the flat panel display. It can be seen that a transparent adhesive sheet extremely suitable for bonding is realized.
- the transparent adhesive sheet of the present invention By using the transparent adhesive sheet of the present invention, it is possible to realize a high-performance flat panel display in which the display surface is protected and the display image is excellent in visibility.
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Abstract
Description
(1)下記A~C成分を含む組成物の硬化物からなり、25℃、1Hzでのせん断貯蔵弾性率(G’)が1.0×105Pa以下であり、かつ、ゲル分率が40%以上であることを特徴とする、フラットパネルディスプレイ用透明粘着シート。
A:1分子中に少なくとも1個のアルケニル基を有するポリオキシアルキレン系重合体
B:1分子中に平均2個以上、5個未満のヒドロシリル基を有する化合物
C:ヒドロシリル化触媒
(2)フラットパネルディスプレイの前面多層構造部内の少なくとも一方の層がプラスチック板もしくはプラスチックフィルムである隣接する2つの層間に介在させて使用されるものである、上記(1)記載の透明粘着シート。
(3)少なくとも一方の層がプラスチック板もしくはプラスチックフィルムである隣接する2つの層が、透明プラスチック板もしくは透明プラスチックフィルムからなる保護透明板と表示パネルである、上記(2)記載の透明粘着シート。
(4)25℃、1Hzでのせん断貯蔵弾性率(G’)が0.1×105Pa以上である、上記(1)記載の透明粘着シート。
(5)ゲル分率が90%以下である、上記(1)記載の透明粘着シート。
(6)透明プラスチック板もしくは透明プラスチックフィルムからなる保護透明板と表示パネルとの間に上記(1)に記載の透明粘着シートを介在させて、保護透明板と表示パネルとを接着一体化してなる、フラットパネルディスプレイ。
(7)透明プラスチック板もしくは透明プラスチックフィルムからなる保護透明板と表示パネルとの間に、タッチパネルが挿入されており、タッチパネルの一方の最外層の透明プラスチック板と保護透明板との間、及び、タッチパネルの他方の最外層の透明プラスチック板と表示パネルとの間に上記(1)記載の透明粘着シートを介在させて、保護透明板、タッチパネル及び表示パネルを接着一体化してなる、フラットパネルディスプレイ。
本発明でいう「フラットパネルディスプレイ」とは、液晶ディスプレイ(LCD)、プラズマディスプレイ(PDP)、有機又は無機エレクトロルミネッセンスディスプレイ(ELD)、表面電解ディスプレイ(SED)等を含む概念である。
また、「表示パネル」とは、例えば、液晶ディスプレイ(LCD)における液晶材料を含むパネル体(「液晶パネル」)等の各種フラットパネルディスプレイにおける、表示材料を含むパネル体のことであり、該パネル体に駆動用のドライバIC等を実装したものが「表示モジュール」である。
A:1分子中に少なくとも1個のアルケニル基を有するポリオキシアルキレン系重合体
B:1分子中に平均2個以上、5個未満のヒドロシリル基を含有する化合物
C:ヒドロシリル化触媒
(式中、R1はアルキレン基である)
サンプル濃度:0.2重量%(THF溶液)
サンプル注入量:10μl
溶離液:THF
流速:0.6ml/min
測定温度:40℃
カラム:サンプルカラム TSKgel GMH-H(S)
検出器:示差屈折計
(式中、R2は水素原子又はメチル基である)
一般式(3):{H2C=C(R3a)-R4a-O}a1R5a
(式中、R3aは水素原子又はメチル基、R4aは炭素数1~20の2価の炭化水素基であって、1個以上のエーテル基が含まれていてもよい、R5aはポリオキシアルキレン系重合体残基であり、a1は正の整数である。)
で示される重合体が挙げられる。式中のR4aは、具体的には、-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH(CH3)CH2-、-CH2CH2CH2CH2-,-CH2CH2OCH2CH2-、または-CH2CH2OCH2CH2CH2-などを挙げることができるが、合成の容易さからは-CH2-が好ましい。
(式中、R3b、R4b、R5b及びa2は、それぞれR3a、R4a、R5a、a1と同義である。)で示されるエステル結合を有する重合体が挙げられる。
(式中、R3c、R5c及びa3は、それぞれR3a、R5a、a1と同義である。)
で示される重合体も挙げられる。
(式中、R3d、R4d、R5d及びa4は、それぞれR3a、R4a、R5a及びa1と同義である。)
で示されるカーボネート結合を有する重合体も挙げられる。
又は、
等で示されるものが挙げられる。
これらの触媒は単独で使用してもよく、2種以上併用しても構わない。触媒活性の点から、塩化白金酸、白金-ホスフィン錯体、白金-ビニルシロキサン錯体、Pt(acac)2等が好ましい。
ポリオキシアルキレン系重合体を主体成分とする組成物(少なくとも上記A~C成分を含む組成物)を、必要に応じて有機溶剤とともに、真空機能を備えた攪拌装置に仕込み、真空状態(真空下)で攪拌することで脱泡を行い、該真空脱泡後の流動物を各種の支持体上に塗布(流延)し、熱処理してシート化する。熱処理によって組成物は加熱硬化され、硬化物によるシートが得られる。支持体上への塗布は、例えば、グラビア、キス、コンマ等のロールコーター、スロット、ファンテン等のダイコーター、スクイズコーター、カーテンコーター等の公知の塗布装置によって行うことができる。この際の熱処理条件としては50~200℃(好ましくは100~160℃)で、0.01~24時間(好ましくは0.05~4時間)程度加熱するのが好ましい。なお、上記の真空機能を備えた攪拌装置としては、公知の真空装置付攪拌装置を使用すればよく、具体的には、遊星式(公転/自転方式)攪拌脱泡装置やディスパー付脱泡装置等が挙げられる。また、真空脱泡を行う際の減圧の程度としては、10kPa以下が好ましく、3kPa以下がより好ましい。また、攪拌時間は攪拌装置や流動物の処理量によっても異なるが、概ね、0.5~2時間程度が好ましい。脱泡処理により、シート内には実質的に気泡(ボイド)が存在せず、優れた光学的特性(透明性)を示す。例えば、後述の試験方法で測定されるシートのヘイズ値が好ましくは1.2%以下、より好ましくは0.9%以下を示す。
粘着層の厚みが10~250μmの粘着シートを貼り合せて、厚みが約0.5~1mmとなるように積層し、積層されたシートをφ7.9mmの円形に打抜いたものを測定試料とし、以下の方法で測定した。
測定装置:Rheometric Scientific社製 ARES
測定条件:測定温度 25℃
測定周波数 1Hz(6.28rad/sec)
粘着層の厚さが200μmの粘着シートを50mm×25mmの大きさに切り取って試料片とし、これをガラス基板(松浪硝子社製 S-1111 商品名)に貼り合わせ、測定試料とした。ヘイズ値の測定は、ヘイズメーター(村上色彩研究所製 HM-150 商品名)を用い、装置の受光面側にサンプルが位置するように設置し、試料片のセパレーター(支持体)を剥離して、JIS K 7136に準拠して測定を行った。
粘着層の厚さが200μmの粘着シートを50mm×50mmの大きさに切り取った試料片をセパレータから剥がし、重量がわかっているスクリュー管(重量A)へ入れ、スクリュー管ごと重量を測定し(重量B)、この後、スクリュー管を酢酸エチルで満たし、1週間(168時間)静置した。その後、内容物をメッシュでろ過し、重量のわかっているアルミシャーレ(重量C)にゲルを移し、アルミシャーレを乾燥機に入れ、130℃で2時間加熱して、取り出し、約20分冷却した後、乾燥重量(重量D)を測定した。以上の操作後、下記式によりゲル分率を算出した。
ゲル分率=(D-C)×100/(B-A) [%]
基材レス透明両面テープ(粘着層の厚み12μm)にPETフィルム(厚み25μm)を貼り合わせ、総厚37μmの段差テープを作製した。矩形のガラス板の主面の四辺に沿う周縁に上記段差テープを額縁状に貼り付けて、段差付きガラス板を作った。この段差付きガラス板の段差テープを貼付した面の全面に対し、粘着シートを貼り付け、オートクレーブ処理(50℃、0.5MPa、15分)を行なった後、段差部分の粘着層の浮きを目視で観察した。
評価は、段差のある部分にて粘着層の浮きが確認されない状態を合格(○)とし、浮きが確認される状態を不合格(×)とした。
50mm×50mmの偏向板と50mm×50mmのプラスチック板(PMMA板、PC板、PET板)の間に粘着シート(サンプル)を挟んで、オートクレーブ処理(50℃、0.5MPa、15分)を行なった。気泡が抜けたことを確認した後、かかる偏向板/粘着シート/プラスチック板一体型サンプルを80℃、0%rhの環境に150時間(hr)投入し、150時間経過後のサンプル内の外観を目視にて確認を行なった。
評価は、プラスチック板側からサンプルを目視にて観察した際に、目視で確認できる気泡がない状態を良好(○)、1mmφ以下の気泡(気泡数2つ以下)が存在する状態を可(△)、1mmφを超える気泡(気泡数が2つ以上)が存在する状態を不可(×)とした。
A成分である1分子中に2個のアルケニル基を有するポリオキシアルキレン系重合体(数平均分子量:約20000)、B成分であるヒドロシリル化合物(1分子中の平均のヒドロシリル基数が2以上、5個未満)及びC成分であるヒドロシリル化触媒が、A成分とB成分とが、B成分のヒドロシリル基量がA成分のアルケニル基量に対して官能基比(モル比)で0.58となる量比で配合され、かつ、C成分がA成分中のアルケニル基1モルに対して0.9×10-3モルとなる量で配合された組成物(株式会社カネカ製)を真空装置付攪拌装置(シーテック社製ミニダッポー)に投入し、真空状態(100Pa)で1時間攪拌して脱泡をおこなった。次いで、真空脱泡された組成物を室温下でロールコーターを用い、離型処理が施されたポリエステルフィルム(厚さ100μm)からなるベースセパレーター(支持体)上に、組成物の厚みが200μmになるように塗布(流延)した。加熱オーブンで130℃で10分間加熱することで硬化させ、こうして得られた硬化シートに、同様に離型処理が施されたポリエステルフィルム(厚さ100μm)からなるカバーセパレーター(剥離ライナー)を貼り合せることによって透明粘着シート(厚み:199μm)を得た。
A~C成分を含む組成物におけるB成分であるヒドロシリル化合物の量を、そのヒドロシリル基量がA成分のアルケニル基量に対して官能基比(モル比)で0.68となる量に変更した以外は、実施例1と同様にして、透明粘着シート(厚み:199μm)を得た。得られた透明粘着シートのヘイズ値は0.4%、25℃におけるせん断貯蔵弾性率(G’)は0.6×105(Pa)、ゲル分率は65%であった。そして、この透明粘着シートの段差吸収性及び耐発泡性を評価した。表1にその結果を示す。
アクリル酸ブチル97重量部(以下、「部」と略称する)、アクリル酸3部、アゾビスイソブチロニトリル0.4部を酢酸エチル100部に溶解させて攪拌下に約60℃で反応させて得たアクリル系ポリマーの溶液に、イソシアネート系架橋剤3部を配合し、これを厚さ25μmのポリエステル系のベースセパレーター(支持体)上に塗布し、加熱乾燥し、粘着剤(塗布乾燥物)の厚みが20μmになるようにポリエステル系のカバーセパレーター(剥離ライナー)を貼り合わせ、粘着剤厚み20μmの粘着シートを得た。この粘着剤厚みが20μmの粘着シートを貼り合わせて粘着剤厚み200μmの粘着シートを作製した。該粘着シートの25℃におけるせん断貯蔵弾性率(G’)は2.3×105(Pa)、ゲル分率は64%であった。そして、この粘着シートの段差吸収性及び耐発泡性を評価した。表1にその結果を示す。
冷却管、窒素導入管、温度計、紫外線照射装置及び拡販装置を備えた反応容器に、アクリル酸2-エチルへキシル(東亞合成社製)100重量部(以下、「部」と略称する)、アクリル酸2-ヒドロキシエチル(東亞合成社製 アクリックス HEA 商品名)15部、光重合開始剤(チバ・スペシャリティケミカルズ社製 イルガキュア184 商品名)0.15部、光重合開始剤(チバ・スペシャリティケミカルズ社製 イルガキュア651 商品名)0.05部を入れ、紫外線照射により重合処理して、重合率約10重量%の重合体、単量体組成物からなる粘性液体を得た。次に、この粘性液体に、トリメチロールプロパントリアクリレート(大阪有機化学社製 V♯295)0.15部、光重合開始剤(チバ・スペシャリティケミカルズ社製 イルガキュア184 商品名)0.15部、光重合開始剤(チバ・スペシャリティケミカルズ社製 イルガキュア651 商品名)0.05部を配合して、光重合組成物を調製した。この光重合組成物を、剥離処理が施されたポリエステルフィルム(厚さ75μm)上に、組成物の厚みが200μmになるように塗布(流延)し、さらにこの上にカバー用のポリエステルフィルム(厚さ50μm)を被せた後、紫外線ランプにて、2000mJ/cm2の紫外線を照射して、光重合させることにより、紫外線硬化型アクリル系粘着剤シートを形成した。該粘着シートの25℃におけるせん断貯蔵弾性率(G’)は0.4×105(Pa)、ゲル分率は25%であった。そして、この透明粘着シートの段差吸収性及び耐発泡性を評価した。表1にその結果を示す。
2 液晶表示パネル
3 保護透明板
4 タッチパネル
5 黒色印刷層
100、200 フラットパネルディスプレイ
Claims (7)
- 下記A~C成分を含む組成物の硬化物からなり、25℃、1Hzでのせん断貯蔵弾性率(G’)が1.0×105Pa以下であり、かつ、ゲル分率が40%以上であることを特徴とする、フラットパネルディスプレイ用透明粘着シート。
A:1分子中に少なくとも1個のアルケニル基を有するポリオキシアルキレン系重合体
B:1分子中に平均2個以上、5個未満のヒドロシリル基を有する化合物
C:ヒドロシリル化触媒 - フラットパネルディスプレイの前面多層構造部内の少なくとも一方の層がプラスチック板もしくはプラスチックフィルムである隣接する2つの層間に介在させて使用されるものである、請求項1記載の透明粘着シート。
- 少なくとも一方の層がプラスチック板もしくはプラスチックフィルムである隣接する2つの層が、透明プラスチック板もしくは透明プラスチックフィルムからなる保護透明板と表示パネルである、請求項2記載の透明粘着シート。
- 25℃、1Hzでのせん断貯蔵弾性率(G’)が0.1×105Pa以上である、請求項1記載の透明粘着シート。
- ゲル分率が90%以下である、請求項1記載の透明粘着シート。
- 透明プラスチック板もしくは透明プラスチックフィルムからなる保護透明板と表示パネルとの間に請求項1に記載の透明粘着シートを介在させて、保護透明板と表示パネルとを接着一体化してなる、フラットパネルディスプレイ。
- 透明プラスチック板もしくは透明プラスチックフィルムからなる保護透明板と表示パネルとの間に、タッチパネルが挿入されており、タッチパネルの一方の最外層の透明プラスチック板と保護透明板との間、及び、タッチパネルの他方の最外層の透明プラスチック板と表示パネルとの間に請求項1に記載の透明粘着シートを介在させて、保護透明板、タッチパネル及び表示パネルを接着一体化してなる、フラットパネルディスプレイ。
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| JPWO2014073316A1 (ja) * | 2012-11-09 | 2016-09-08 | 三菱樹脂株式会社 | 画像表示装置用両面粘着シート、離形フィルム付画像表示装置用両面粘着シート及びこれらを用いてなる画像表示装置 |
| US9650546B2 (en) | 2012-11-09 | 2017-05-16 | Mitsubishi Plastics, Inc. | Double-sided adhesive sheet for image display device, double-sided adhesive sheet with release film for image display device, and image display device using same |
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| JP2017027079A (ja) * | 2016-10-24 | 2017-02-02 | 三菱電機株式会社 | 表示装置 |
| JP2018092177A (ja) * | 2018-01-24 | 2018-06-14 | 三菱電機株式会社 | 表示装置 |
| US20230279279A1 (en) * | 2020-07-02 | 2023-09-07 | Lg Chem, Ltd. | Pressure-Sensitive Adhesive and Liquid Crystal Cell |
| US11976224B2 (en) * | 2020-07-02 | 2024-05-07 | Lg Chem, Ltd. | Pressure-sensitive adhesive and liquid crystal cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102187381A (zh) | 2011-09-14 |
| JP2010097070A (ja) | 2010-04-30 |
| US20110254790A1 (en) | 2011-10-20 |
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