WO2023190079A1 - 光学用粘着シート - Google Patents
光学用粘着シート Download PDFInfo
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- WO2023190079A1 WO2023190079A1 PCT/JP2023/011635 JP2023011635W WO2023190079A1 WO 2023190079 A1 WO2023190079 A1 WO 2023190079A1 JP 2023011635 W JP2023011635 W JP 2023011635W WO 2023190079 A1 WO2023190079 A1 WO 2023190079A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to an optical adhesive sheet.
- the present invention relates to an optical pressure-sensitive adhesive sheet suitable for manufacturing image display devices.
- Liquid crystal display devices and organic EL display devices are widely used as various image display devices such as smartphones, computer monitors, and televisions.
- a front transparent plate such as a transparent resin plate or a glass plate is provided on the viewing side of the image display panel for the purpose of preventing damage to the image display panel due to external impact.
- image display devices that include a touch panel on the viewing side of an image display panel are also becoming popular.
- an "interlayer filling structure" has been proposed in which the image display panel, the front transparent plate, the touch panel, etc. are bonded together via an adhesive sheet.
- an adhesive sheet may also be provided between the front transparent plate and the touch panel.
- the interlayer filling structure the gaps between the members are filled with the adhesive, so the refractive index difference at the interface is reduced, and a decrease in visibility due to reflection and scattering is suppressed.
- the members are pasted together and fixed using adhesive sheets, the advantage is that the members are less likely to peel off due to impacts such as drops, compared to cases where the members are fixed only to the casing. There is.
- bonding defects such as inclusion of air bubbles and misalignment of the bonding position may occur. If a bonding failure occurs, it is desirable to peel and remove the adhesive sheet from the image display panel and reuse the image display panel (herein sometimes referred to as "rework").
- static electricity is generated on the adhesive sheet when the adhesive sheet is peeled off from the image display panel in order to rework the image display panel.
- the generated static electricity affects the orientation of the display cells of the image display panel, causing display defects.
- thermal shock periodically repeating heating and cooling caused by repeatedly turning on and off the power of the image display device may cause voids to form at the interface between the adhesive sheet and the image display panel, and the haze of the adhesive sheet.
- the visibility of the image display device decreases over time due to an increase in the amount of image display.
- the present invention was conceived under the above circumstances, and an object of the present invention is to reduce static electricity when peeling an adhesive sheet from an image display panel in order to rework the image display panel.
- An object of the present invention is to provide an optical pressure-sensitive adhesive sheet capable of suppressing the occurrence of the problem.
- Another object of the present invention is to provide an optical pressure-sensitive adhesive sheet that can suppress deterioration of the visibility of an image display device over time due to thermal shock.
- a patterned transparent and conductive printed layer such as ITO (indium tin oxide) is formed on the surface of the touch panel, and furthermore, silver or copper routing wiring is formed in the periphery. Further, it is common to print a frame-shaped black concealing part on the peripheral edge of the front transparent plate. If various parts such as image display panels, front transparent plates, touch panels, etc. have uneven steps such as printed layers or wiring, the adhesive sheet that bonds them should have a sufficient adhesive layer on the steps. It is also required to exhibit characteristics (herein sometimes referred to as "level difference absorbency") that can be filled without leaving any bubbles or the like.
- level difference absorbency characteristics
- a first aspect of the present invention provides an optical adhesive sheet having a laminated structure in which a base material has a first surface and a second surface, and an adhesive layer is laminated on the first surface of the base material.
- the optical adhesive sheet of the first aspect of the present invention may be referred to as "the optical adhesive sheet of the present invention”.
- the adhesive layer constituting the optical adhesive sheet of the invention may be referred to as the "adhesive layer of the invention”
- the base material may be referred to as the "substrate of the invention”.
- the optical pressure-sensitive adhesive sheet of the present invention can be suitably used for manufacturing image display devices. That is, the adhesive layer of the present invention can be suitably used for bonding a front transparent plate, a touch panel, and other optical members (polarizing film, retardation film, etc.) to an image display panel constituting an image display device. It is. Further, the base material of the present invention can be various optical members used for manufacturing image display devices, such as front transparent plates, touch panels, and other optical members (polarizing film, retardation film, etc.). be.
- the adhesive layer of the present invention contains a liquid antistatic agent.
- the antistatic agent imparts antistatic properties to the adhesive layer of the present invention, and the adhesive sheet is peeled off from the image display panel for rework in the event of poor adhesion to the image display panel. This is preferable in that it can suppress the generation of static electricity.
- the configuration in which the antistatic agent is in liquid form can impart an excellent antistatic effect to the adhesive layer of the present invention without impairing the adhesive properties of the adhesive layer of the present invention.
- the adhesion between the adhesive layer and the base material of the present invention is improved, and the adhesive layer of the present invention can be used even under harsh environments such as thermal shock (periodic repetition of heating and cooling). Characteristics that can maintain excellent optical properties by preventing voids from forming at the interface between the thermal shock resistance and the substrate (in this specification, such characteristics may be referred to as "thermal shock resistance”) ) is suitable.
- the surface resistance value of the pressure-sensitive adhesive layer of the present invention is less than 10 10 ⁇ .
- the configuration in which the adhesive layer of the present invention has a surface resistance value of less than 10 10 ⁇ means that the adhesive layer of the present invention exhibits an excellent antistatic effect and can be used in the event of poor bonding to an image display panel. This is suitable in that it is possible to suppress the generation of static electricity when the adhesive sheet is peeled off from the image display panel for rework.
- the haze of the optical adhesive sheet of the present invention after the following thermal shock test is 1% or less.
- the optical adhesive sheet of the present invention was subjected to thermal shock, with one cycle consisting of exposing it to an atmosphere of -40°C for 30 minutes, and then exposing it to an atmosphere of 80°C for 30 minutes. Apply 200 cycles using an impact tester.
- the configuration in which the optical adhesive sheet of the present invention has a haze of 1% or less after the above-mentioned thermal shock test means that the image display device of the present invention can maintain excellent visibility even in harsh environments such as thermal shock. So, it's preferable.
- the antistatic agent is preferably an ionic liquid.
- the configuration in which the antistatic agent is an ionic liquid can impart an excellent antistatic effect to the adhesive layer of the present invention without impairing the adhesive properties of the adhesive layer of the present invention. This is preferred because it improves the adhesion between the pressure-sensitive adhesive layer and the base material of the present invention and provides excellent thermal shock resistance.
- the ionic liquid preferably contains an anion component having 10 or less fluorine atoms.
- the configuration in which the ionic liquid contains an anion component having 10 or less fluorine atoms is due to the improved compatibility of the ionic liquid with the adhesive layer of the present invention and separation of the ionic liquid from the adhesive layer. This is preferable because it can suppress the increase in haze and improve the visibility of the image display device.
- the difference in haze of the optical adhesive sheet of the present invention before and after the above thermal shock test shall be 2% or less. is preferred.
- the configuration in which the difference in haze before and after the thermal shock test of the optical adhesive sheet of the present invention is 2% or less means that the image display device of the present invention maintains excellent visibility even in harsh environments such as thermal shock. This is preferable because it can be done.
- the difference in surface resistance of the adhesive layer of the present invention before and after the above thermal shock test is 1 log ⁇ or less, which indicates that the adhesive layer of the present invention has an excellent antistatic effect even in harsh environments such as thermal shock. For example, if a failure occurs such as a light emitting element not lighting up under the usage environment of the image display device, suppress the generation of static electricity when the adhesive sheet is peeled off from the image display panel for repair. This is suitable because it allows for
- the second surface of the base material is preferably subjected to antireflection treatment and/or antiglare treatment.
- the configuration in which the second surface of the base material is subjected to anti-reflection treatment and/or anti-glare treatment can prevent reflection from metal wiring, ITO wiring, etc. arranged on the substrate of the image display device, and improve visibility. This is preferable because it can be done.
- the adhesive layer is preferably an acrylic adhesive layer containing an acrylic polymer. This configuration is suitable for adjusting the properties (particularly, the level difference absorbability) of the pressure-sensitive adhesive layer.
- a second aspect of the present invention provides an image display device in which the optical pressure-sensitive adhesive sheet of the present invention and an image display panel are laminated.
- the image display device according to the second aspect of the present invention may be referred to as "the image display device of the present invention.” Since the image display device of the present invention has the optical adhesive sheet of the present invention in the laminated structure, the adhesive sheet is peeled off from the image display panel in order to rework when a bonding failure to the image display panel occurs. This is preferable in that it can suppress the generation of static electricity. It is also suitable because it can prevent the visibility of the image display device from deteriorating over time due to thermal shock, such as the formation of voids at the interface between the adhesive sheet and the image display panel and the increase in the haze of the adhesive sheet. It is.
- a third aspect of the present invention provides a tiling display in which a plurality of image display devices of the present invention are arranged.
- the tiling display according to the third aspect of the present invention may be referred to as "the tiling display of the present invention".
- the tiling display of the present invention is suitable as a large-screen image display device such as an advertisement display or a signage such as a bulletin board.
- the optical adhesive sheet of the present invention By using the optical adhesive sheet of the present invention in the production of image display devices, static electricity is generated when the adhesive sheet is peeled off from the image display panel in order to perform rework in the event of poor adhesion to the image display panel. This is preferable in that it can suppress the occurrence of. Furthermore, since it is possible to impart an excellent antistatic effect to the adhesive layer of the present invention without impairing the adhesive properties of the adhesive layer of the present invention, the adhesive layer of the present invention and the base material of the present invention can be The adhesion of the adhesive sheet is improved, excellent thermal shock resistance is obtained, and the visibility of the image display device is reduced over time due to the formation of voids at the interface between the adhesive sheet and the image display panel, and the increase in the haze of the adhesive sheet. This is preferable in that it can prevent a decrease in the temperature.
- FIG. 1 is a schematic diagram (cross-sectional view) showing one embodiment of the optical pressure-sensitive adhesive sheet of the present invention.
- FIG. 2 is a schematic diagram (cross-sectional view) showing another embodiment of the optical pressure-sensitive adhesive sheet of the present invention.
- FIG. 3 is a schematic diagram (cross-sectional view) showing an embodiment of the image display device of the present invention in which the optical adhesive sheet of FIG. 2 is laminated.
- FIG. 4 is a schematic diagram (perspective view) showing an embodiment of the tiling display of the present invention.
- the optical pressure-sensitive adhesive sheet of the present invention has a laminated structure in which a base material has a first surface and a second surface, and a pressure-sensitive adhesive layer is laminated on the first surface of the base material.
- adhesive sheet includes the meaning of "adhesive tape.” That is, the optical pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive sheet having a tape-like form.
- the image display device of the present invention is an image display device in which the optical adhesive sheet of the present invention and an image display panel are laminated. Further, the tiling display of the present invention is a tiling display in which a plurality of image display devices of the present invention are arranged side by side.
- FIG. 1 is a schematic diagram (cross-sectional view) showing one embodiment of the optical pressure-sensitive adhesive sheet of the present invention.
- an optical adhesive sheet 10A has a laminated structure in which a base material 1 and an adhesive layer 2 are laminated.
- the base material 1 has a first surface 1a and a second surface 1b, and an adhesive layer 2 is laminated on the first surface 1a of the base material 1.
- the optical adhesive sheet 10B has a laminated structure in which a base material 1 and an adhesive layer 2 are laminated.
- the base material 1 has a first surface 1a and a second surface 1b, and an adhesive layer 2 is laminated on the first surface 1a of the base material 1.
- the second surface 1b of the base material 1 is subjected to an antireflection treatment and/or an antiglare treatment 3.
- FIG. 3 is a schematic diagram (cross-sectional view) showing one embodiment of the image display device of the present invention.
- an image display panel 4 is laminated on the adhesive layer 2 of the optical adhesive sheet 10B.
- FIG. 4 is a schematic diagram (perspective view) showing an embodiment of the tiling display of the present invention.
- the tiling display 30 is formed by arranging nine image display devices 20 (the laminated structure is not shown) in a tile shape on a support substrate 31 in a 3 ⁇ 3 arrangement. Each configuration will be explained below.
- optical adhesive sheet in the optical adhesive sheet of the present invention means that it is used for optical purposes, and more specifically, it means that it is used for manufacturing products using optical members (optical products). do.
- optical products include image display devices, input devices such as touch panels, liquid crystal image display devices, self-luminous image display devices (e.g. organic EL (electroluminescence) image display devices, LED image display devices), etc. ) and the like.
- the optical adhesive sheet of the present invention is suitable for manufacturing self-luminous image display devices.
- the form of the optical pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as the pressure-sensitive adhesive layer of the present invention is laminated on the first surface of the base material of the present invention.
- the adhesive sheet may be a single-sided adhesive sheet in which only one side is adhesive, or a double-sided adhesive sheet in which both sides are adhesive.
- the optical adhesive sheet of the present invention is a double-sided adhesive sheet
- the optical adhesive sheet of the present invention may have a form in which both adhesive surfaces are provided by the adhesive layer of the present invention. , even if one adhesive surface is provided by the adhesive layer of the present invention and the other adhesive surface is provided by an adhesive layer other than the adhesive layer of the present invention (another adhesive layer). good.
- the optical adhesive sheet of the present invention constitutes the outermost surface of an optical product, a single-sided adhesive sheet is preferred, and when adherends (optical members) are bonded together, a double-sided adhesive sheet is preferred.
- the optical pressure-sensitive adhesive sheet of the present invention may include other layers, such as a base material other than the base material of the present invention, to the extent that the effects of the present invention are not impaired.
- a base material other than the base material of the present invention to the extent that the effects of the present invention are not impaired.
- an adhesive layer other than the adhesive layer of the present invention, an intermediate layer, an undercoat layer, an antistatic layer, a release liner, a surface protection film, etc. may be provided on the surface or between arbitrary layers.
- the haze of the optical pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 1% or less. It is preferable that the optical pressure-sensitive adhesive sheet of the present invention has a haze of 1% or less because the image display device of the present invention exhibits excellent visibility. Since the image display device of the present invention exhibits excellent visibility, the haze of the optical adhesive sheet of the present invention is preferably 0.8% or less, more preferably 0.5% or less, or 0.4% or less. It may be.
- the lower limit of the haze of the optical pressure-sensitive adhesive sheet of the present invention is not particularly limited, and is preferably as low as possible, but may be 0.01% or more.
- the haze of the optical adhesive sheet of the present invention after the following thermal shock test is 1% or less.
- the optical adhesive sheet of the present invention was subjected to thermal shock, with one cycle consisting of exposing it to an atmosphere of -40°C for 30 minutes, and then exposing it to an atmosphere of 80°C for 30 minutes. Apply 200 cycles using an impact tester.
- the configuration in which the optical adhesive sheet of the present invention has a haze of 1% or less after the above-mentioned thermal shock test means that the image display device of the present invention can maintain excellent visibility even in harsh environments such as thermal shock. So, it's preferable. Since the image display device of the present invention can maintain excellent visibility, the haze of the optical adhesive sheet of the present invention after the above thermal shock test is preferably 0.8% or less, and more preferably 0.5% or less. It is preferable or may be 0.4% or less.
- the lower limit of the haze of the optical pressure-sensitive adhesive sheet of the present invention after the thermal shock test is not particularly limited, and is preferably as low as possible, but may be 0.01% or more.
- the difference in haze of the optical adhesive sheet of the present invention before and after the above thermal shock test (haze of the optical adhesive sheet after the thermal shock test - haze of the optical adhesive sheet before the thermal shock test) is 2% or less. It is preferable.
- the configuration in which the difference in haze before and after the thermal shock test of the optical adhesive sheet of the present invention is 2% or less means that the image display device of the present invention maintains excellent visibility even in harsh environments such as thermal shock. This is preferable because it can be done. Since the image display device of the present invention can maintain excellent visibility, the difference in haze of the optical adhesive sheet of the present invention before and after the above thermal shock test is more preferably 1.8% or less, and 1.5%. The following is more preferable, or it may be 1 or less.
- the haze of the optical adhesive sheet of the present invention, the haze of the optical adhesive sheet of the present invention after the above thermal shock test, and the difference thereof can be measured in accordance with JIS K 7136, and specifically, It can be measured by the method described in Examples below.
- the haze of the optical adhesive sheet of the present invention, the haze of the optical adhesive sheet of the present invention after the above thermal shock test, and the difference thereof are determined by the type and thickness of the resin and glass constituting the base material of the present invention, and the haze of the optical adhesive sheet of the present invention after the above thermal shock test. It can be adjusted by the type and thickness of the resin constituting the adhesive layer of the invention, the type and amount of the antistatic agent, and by applying antireflection treatment and/or antiglare treatment to the surface of the base material.
- the visible light transmittance of the optical adhesive sheet of the present invention is not particularly limited, but is preferably 90% or more. It is preferable that the visible light transmittance of the optical pressure-sensitive adhesive sheet of the present invention is 90% or more, since excellent visibility can be obtained in the image display device of the present invention, and more preferably 90.5% or more. , 91% or more.
- the upper limit of the visible light transmittance of the optical adhesive sheet of the present invention is not particularly limited, but may be 95% or less.
- the visible light transmittance of the optical adhesive sheet of the present invention can be measured in accordance with JIS K7361-1.
- the visible light transmittance of the optical adhesive sheet of the present invention is determined by the resin constituting the base material of the present invention, the type and thickness of glass, the type and thickness of the resin constituting the adhesive layer of the present invention, and the antistatic agent. It can be adjusted by the type and amount of , and by applying antireflection treatment and/or antiglare treatment to the surface of the base material.
- the L * defined by the L * a * b * color system of the optical pressure-sensitive adhesive sheet of the present invention is not particularly limited, but it is preferably 90 or more in terms of obtaining excellent visibility in the image display device of the present invention.
- 92 or more, preferably 94 or more, and a * and b * are not particularly limited, but may be the same or different, and are preferably from -5 to 5, more preferably from -3 to 3, particularly preferably in the range of -1 to 1 (in particular 0 or nearly 0).
- the amount of change ( ⁇ b * ) in b * in the L * a * b * color system before and after the thermal shock test of the optical adhesive sheet of the present invention is not particularly limited, but the optical adhesive sheet of the present invention In terms of exhibiting excellent thermal shock resistance, it is preferably 0.1 or less, and preferably 0.05 or less.
- L * a * b * color system refers to a color space called the Commission Internationale de l'Eclairage (CIE) 1976 color system, and is measured in accordance with JIS Z 8781-4 (2013). can do.
- L * , a * , b * , and ⁇ b * defined in the L * a * b * color system are based on the type and thickness of the resin and glass that constitute the base material of the present invention, and the adhesive layer of the present invention. It can be adjusted by the type and thickness of the resin constituting the resin, the type and amount of the antistatic agent, and by applying antireflection treatment and/or antiglare treatment to the surface of the base material.
- the adhesive strength of the optical pressure-sensitive adhesive sheet of the present invention against an acrylic plate when peeled off at a peeling rate of 300 mm/min at 23° C. at a peeling angle of 180° is not particularly limited, but is sufficient to ensure sufficient adhesion between the base material of the present invention and the image display panel. From the viewpoint of performance, it is preferably 3N/25mm or more, more preferably 5N/25mm or more, even more preferably 7N/25mm or more.
- the optical pressure-sensitive adhesive sheet of the present invention exhibits good adhesion to the base material of the present invention when it has a peeling strength of 3N/25mm at a peeling angle of 180° at a peeling rate of 300mm/min at 23°C.
- the upper limit of the peeling adhesive force of the optical adhesive sheet of the present invention to an acrylic plate at 23° C. and a peeling angle of 180° at a peeling speed of 300 mm/min is not particularly limited, but is, for example, 40 N/20 mm, and more Preferably it is 60N/20mm.
- the amount of peeling charge when the optical adhesive sheet of the present invention is peeled off from an acrylic plate at 23° C. at a peeling speed of 5 mm/min at a peeling angle of 150° is not particularly limited, but if poor adhesion to an image display panel occurs. It is preferably within ⁇ 2 kV, more preferably within ⁇ 1.5 kV, and even more preferably within ⁇ 1 kV, in terms of suppressing the generation of static electricity when peeling the adhesive sheet from the image display panel for rework. .
- the adhesive strength of the optical adhesive sheet of the present invention against an acrylic plate at 23°C when peeled at a peeling angle of 180° at a peeling speed of 300 mm/min and the peeling charge amount when peeled at a peeling angle of 150° at a peeling speed of 5 mm/min at 23°C are as follows: , as measured by adhesive force and peel charge amount measurement in Examples described below.
- the adhesive force of the adhesive layer of the present invention on an acrylic plate when peeled at 180° at a peeling speed of 300 mm/min at 23°C and the peeling charge amount when peeled at 150° at a peeling speed of 5 mm/min at 23°C are as follows: Composition of the adhesive composition for forming the adhesive layer of the present invention (e.g., type and molecular weight of base polymer, amount used, monomer composition, type and amount of functional group, type and amount of antistatic agent, crosslinking agent) (type and amount), curing conditions (heating conditions, radiation irradiation conditions), etc.
- Composition of the adhesive composition for forming the adhesive layer of the present invention e.g., type and molecular weight of base polymer, amount used, monomer composition, type and amount of functional group, type and amount of antistatic agent, crosslinking agent) (type and amount), curing conditions (heating conditions, radiation irradiation conditions), etc.
- the thickness of the optical pressure-sensitive adhesive sheet of the present invention is not particularly limited, but in consideration of dimensional stability, strength, workability such as handling, thin layer property, etc., it is preferably in the range of 10 to 500 ⁇ m, and more preferably Preferably it is in the range of 20-300 ⁇ m, optimally in the range of 30-200 ⁇ m.
- Examples of the material constituting the base material of the present invention include glass and plastic film.
- Examples of the plastic film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cyclic olefin polymers (COP) (for example, product name "Arton” (manufactured by JSR Corporation), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate (PC), triacetyl cellulose (TAC), polysulfone, polyarylate, polyether ether ketone (PEEK), etc.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- COP cyclic olefin polymers
- Acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate (PC), triacetyl cellulose (TAC), polysulfone, polyarylate, polyether ether ketone (PEEK), etc.
- the base material of the present invention is a portion that is attached to an adherend together with the adhesive layer when the optical pressure-sensitive adhesive sheet of the present invention is attached to an adherend (image display panel, etc.).
- the "base material” does not include a release liner that is peeled off when the optical pressure-sensitive adhesive sheet of the present invention is used (applied).
- the base material of the present invention has a film-like (substrate-like) form having a first surface and a second surface.
- the base material of the present invention is not particularly limited as long as it is a member constituting the image display device of the present invention, and various optical films such as front transparent plates, touch panels, and other optical members (polarizing film, retardation film, etc.) are preferably used as the front transparent plate.
- the base material of the present invention is a front transparent plate
- the second surface becomes the outermost surface of the image display device of the present invention.
- the glass transition point (Tg) of the substrate of the present invention is not particularly limited, but is preferably 60° C. or higher.
- a structure in which the glass transition point of the substrate of the present invention is 60° C. or higher is preferable in that the mechanical properties of the image display device of the present invention are stable under the usage environment.
- the glass transition point of the base material may be 63°C or higher, or 65°C or higher.
- the upper limit of the glass transition point of the base material is not particularly limited, but in terms of simplifying the molding process of the base material, the glass transition point of the base material is preferably 350°C or lower, 250°C or lower, 200°C or lower.
- the temperature may be below 140°C, below 130°C, or below 125°C.
- the glass transition point (Tg) of the substrate of the present invention can be measured in accordance with JIS K 7121.
- the glass transition point (Tg) of the base material of the present invention can be adjusted by adjusting the type of resin constituting the base material of the present invention.
- the humidity expansion coefficient of the base material of the present invention is not particularly limited, but is preferably 5 ⁇ 10 ⁇ 5 /%RH or less.
- the structure in which the humidity expansion coefficient of the base material of the present invention is 5 ⁇ 10 -5 /%RH or less improves the dimensional stability of the base material of the present invention under humidity changes, and the image display of the present invention under the usage environment is improved. This is preferable in that it suppresses shrinkage or expansion of the device and maintains transparency without change.
- the humidity expansion coefficient of the substrate of the present invention is preferably 3 ⁇ 10 -5 /% RH or less, It may be 2 ⁇ 10 ⁇ 5 /%RH or less.
- the lower limit of the humidity expansion coefficient of the base material of the present invention is not particularly limited, and is preferably as low as possible, but may be 0.001 ⁇ 10 ⁇ 5 /%RH or more.
- the humidity expansion coefficient of the base material of the present invention can be adjusted by the type of resin constituting the base material of the present invention, the conditions at the time of manufacturing the base material (temperature, extrusion speed, etc.), and the like.
- the haze of the base material of the present invention is not particularly limited, but from the viewpoint that the image display device of the present invention exhibits excellent visibility, the haze of the base material of the present invention is more preferably 1% or less, more preferably 0.8% or less, and 0.5%. The content is more preferably below, or may be 0.4% or below.
- the lower limit of the haze of the base material of the present invention is not particularly limited, and is preferably as low as possible, but may be 0.01% or more.
- the haze of the base material of the present invention can be measured in accordance with JIS K 7136.
- the haze of the base material of the present invention can be adjusted by the type and thickness of the resin constituting the base material of the present invention, and by subjecting the surface of the base material to antireflection treatment and/or antiglare treatment.
- the reflectance of the base material of the present invention is not particularly limited, but is preferably 5% or less.
- the structure in which the reflectance of the base material of the present invention is 5% or less is preferable in that it is possible to prevent reflections caused by metal wiring, ITO wiring, etc. arranged on the substrate of the image display panel in the image display device of the present invention. It is more preferably 3% or less, and may be 1.5% or less.
- the lower limit of the reflectance of the base material of the present invention is not particularly limited, but may be 0.1% or more, or 0.3% or more.
- the reflectance of the base material of the present invention can be measured in accordance with JIS K7361-1.
- the reflectance of the base material of the present invention can be adjusted by the type and thickness of the resin constituting the base material of the present invention, and by subjecting the surface of the base material to anti-reflection treatment and/or anti-glare treatment.
- the thickness of the base material of the present invention is not particularly limited, but is preferably in the range of 10 to 500 ⁇ m, more preferably in consideration of dimensional stability, strength, workability such as handleability, and thin layer property. It is in the range of 20-300 ⁇ m, optimally in the range of 30-200 ⁇ m.
- the refractive index of the base material of the present invention is not particularly limited, but is, for example, in the range of 1.30 to 1.80, preferably in the range of 1.40 to 1.70.
- the second surface of the base material of the present invention is preferably subjected to reflective surface treatment and/or anti-glare treatment.
- the configuration in which the second surface of the base material of the present invention is subjected to reflective surface treatment and/or anti-glare treatment prevents reflections from metal wiring, ITO wiring, etc. arranged on the substrate of the image display device of the present invention. This is preferable because it can be done.
- any known anti-reflection treatment can be used without particular limitation, such as anti-reflection (AR) treatment.
- AR anti-reflection
- any known AR treatment can be applied without any particular restriction, and specifically, an optical treatment with strictly controlled thickness and refractive index may be applied to the second surface of the base material of the present invention.
- This can be carried out by forming a thin film or an antireflection layer (AR layer) in which two or more of the optical thin films described above are laminated.
- the AR layer exhibits an antireflection function by canceling out the reversed phases of incident light and reflected light using light interference effects.
- the wavelength range of visible light that exhibits the antireflection function is, for example, 380 to 780 nm, and the wavelength range with particularly high visibility is 450 to 650 nm, and the reflectance at the center wavelength of 550 nm is minimized. It is preferable to design the AR layer as follows.
- the AR layer generally includes a multilayer antireflection layer having a laminated structure of two to five optical thin layers (thin films with strictly controlled thickness and refractive index), in which components with different refractive indexes are stacked in a predetermined manner. By forming multiple layers with a thickness of become.
- each layer is generally formed by a dry method such as vacuum evaporation, sputtering, CVD, etc.
- the AR layer can also be formed using a coating solution for forming an antireflection layer.
- the coating liquid for forming an antireflection layer may contain, for example, a resin, a fluorine element-containing additive, hollow particles, solid particles, a diluent solvent, etc., and can be produced, for example, by mixing these.
- the resin examples include thermosetting resins and ionizing radiation-curable resins that are cured by ultraviolet light or light.
- thermosetting resins examples include thermosetting resins and ionizing radiation-curable resins that are cured by ultraviolet light or light.
- the resin it is also possible to use commercially available thermosetting resins, ultraviolet curable resins, and the like.
- thermosetting resin or the ultraviolet curable resin for example, a curable compound having at least one of an acrylate group and a methacrylate group that is cured by heat, light (such as ultraviolet rays), or electron beam, etc.
- a curable compound having at least one of an acrylate group and a methacrylate group that is cured by heat, light (such as ultraviolet rays), or electron beam, etc. can be used, for example, Silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, oligomers or prepolymers such as acrylates and methacrylates of polyfunctional compounds such as polyhydric alcohols, etc. can give. These may be used alone or in combination of two or more.
- a reactive diluent having at least one of an acrylate group and a methacrylate group can also be used.
- the reactive diluent can be, for example, the reactive diluent described in JP-A No. 2008-88309, and includes, for example, monofunctional acrylate, monofunctional methacrylate, polyfunctional acrylate, polyfunctional methacrylate, and the like.
- As the reactive diluent trifunctional or higher functional acrylates or trifunctional or higher functional methacrylates are preferred. This is because the hardness of the second surface of the base material of the present invention can be made excellent.
- the reactive diluent examples include butanediol glycerol ether diacrylate, isocyanuric acid acrylate, isocyanuric acid methacrylate, and the like. These may be used alone or in combination of two or more.
- the weight average molecular weight of the resin before curing may be, for example, 100 or more, 300 or more, 500 or more, 1,000 or more, or 2,000 or more, and 100,000 or less, 70,000 or less, 50 or more. ,000 or less, 30,000 or less, or 10,000 or less. If the weight average molecular weight before curing is high, the hardness decreases, but cracking tends to be less likely to occur when bent. On the other hand, if the weight average molecular weight before curing is low, the intermolecular crosslink density tends to improve and the hardness tends to increase.
- the resin preferably contains a polyfunctional acrylate (for example, pentasritol triacrylate).
- a curing agent may be added to cure the curable resin.
- the curing agent is not particularly limited, and for example, known polymerization initiators (eg, thermal polymerization initiators, photopolymerization initiators, etc.) can be used as appropriate.
- the amount of the curing agent added is not particularly limited, but for example, 0.5 parts by weight or more, 1.0 parts by weight or more, 1.5 parts by weight, based on 100 parts by weight of the resin in the coating liquid for forming an antireflection layer. It may be at least 15 parts by weight, at least 13 parts by weight, at most 10 parts by weight, at most 7 parts by weight, or at most 5 parts by weight. There may be.
- the fluorine element-containing additive is not particularly limited, but may be, for example, an organic compound or an inorganic compound containing fluorine in the molecule.
- the organic compound is not particularly limited, and examples thereof include fluorine-containing antifouling coating agents, fluorine-containing acrylic compounds, fluorine- and silicon-containing acrylic compounds, and the like. Specific examples of the organic compound include "KY-1203" (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. and "Megafac" (trade name) manufactured by DIC Corporation.
- the inorganic compound is also not particularly limited.
- the amount of the fluorine element-containing additive added is not particularly limited, but for example, the weight of the fluorine element in the solid content is, for example, relative to the weight of the entire solid content in the coating liquid for forming an antireflection layer. It may be 0.05% by weight or more, 0.1% by weight or more, 0.15% by weight or more, 0.20% by weight or more, or 0.25% by weight or more, and 20% by weight or less, 15% by weight or less , 10% by weight or less, 5% by weight or less, or 3% by weight or less. Further, for example, the weight of the fluorine element-containing additive is 0.05% by weight or more, 0.1% by weight or more, 0.
- the hollow particles are not particularly limited, but may be, for example, silica particles, acrylic particles, acrylic-styrene copolymer particles, etc.
- examples of the silica particles include products such as "Surulia 5320" and “Surulia 4320” manufactured by JGC Catalysts & Chemicals Co., Ltd.
- the weight average particle diameter of the hollow particles is not particularly limited, but may be, for example, 30 nm or more, 40 nm or more, 50 nm or more, 60 nm or more, or 70 nm or more, 150 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, Or it may be 110 nm or less.
- the shape of the hollow particles is not particularly limited, and may be, for example, approximately spherical in the shape of a bead, or irregularly shaped such as powder, but is preferably approximately spherical, and more preferably, The particles are approximately spherical particles with an aspect ratio of 1.5 or less, and most preferably spherical particles.
- the amount of the hollow particles added is not particularly limited, but for example, 30 parts by weight or more, 50 parts by weight or more, 70 parts by weight or more, 90 parts by weight based on 100 parts by weight of the resin in the coating liquid for forming an antireflection layer.
- the amount of the hollow particles added is not too small, and from the viewpoint of ensuring the mechanical properties of the anti-reflection layer, the amount of the hollow particles added is not too large. is preferred.
- the solid particles are not particularly limited, and may be, for example, silica particles, zirconium oxide particles, titanium-containing particles (for example, titanium oxide particles), or the like.
- examples of the silica particles include products such as "MEK-2140Z-AC", “MIBK-ST”, and "IPA-ST” manufactured by Nissan Chemical Industries, Ltd.
- the weight average particle diameter of the solid particles is not particularly limited, but may be, for example, 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, or 25 nm or more, and 300 nm or less, 250 nm or less, 200 nm or less, or 150 nm or less. , or 100 nm or less.
- the shape of the solid particles is not particularly limited, and may be, for example, approximately spherical in the form of beads, or irregularly shaped such as powder, but approximately spherical is preferred, and more preferably , substantially spherical particles with an aspect ratio of 1.5 or less, and most preferably spherical particles.
- the fluorine element-containing additive is likely to be unevenly distributed on the surface of the applied coating solution for forming an antireflection layer, and the antireflection layer has excellent scratch resistance. Low refractive index, good antireflection properties, etc. can be achieved.
- the amount of the solid particles added is not particularly limited, but is, for example, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, based on 100 parts by weight of the resin in the coating liquid for forming an antireflection layer. It may be at least 25 parts by weight, or at most 150 parts by weight, at most 120 parts by weight, at most 100 parts by weight, or at most 80 parts by weight.
- the diluent solvent may be, for example, a mixed solvent containing MIBK (methyl isobutyl ketone) and PMA (propylene glycol monomethyl ether acetate).
- the mixing ratio in this case is not particularly limited, but when the weight of MIBK is 100% by weight, the weight of PMA is, for example, 20% by weight or more, 50% by weight or more, 100% by weight or more, 150% by weight or more, or It may be 200% by weight or more, 400% by weight or less, 350% by weight or less, 300% by weight or less, or 250% by weight or less.
- the diluent solvent may be, for example, a mixed solvent containing TBA (tertiary butyl alcohol) in addition to MIBK and PMA.
- the mixing ratio in this case is not particularly limited, but when the weight of MIBK is 100% by weight, the weight of PMA is, for example, 10% by weight or more, 30% by weight or more, 50% by weight or more, 80% by weight or more, or It may be 100% by weight or more, 200% by weight or less, 180% by weight or less, 150% by weight or less, 130% by weight or less, or 110% by weight or less.
- the weight of TBA may be, for example, 10% by weight or more, 30% by weight or more, 50% by weight or more, 80% by weight or more, or 100% by weight or more. , 200% by weight or less, 180% by weight or less, 150% by weight or less, 130% by weight or less, or 110% by weight or less.
- the amount of the diluting solvent added is also not particularly limited, but for example, the solid content relative to the weight of the entire coating solution for forming an antireflection layer is, for example, 0.1% by weight or more, 0.3% by weight or more, or 0.3% by weight or more. It may be 5% by weight or more, 1.0% by weight or more, or 1.5% by weight or more, and 20% by weight or less, 15% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight. % or less. From the viewpoint of ensuring coating properties (wetting, leveling), it is preferable that the solid content is not too high, and from the viewpoint of preventing appearance defects caused by drying such as air drying unevenness and whitening, the solid content is preferably not too low.
- the coating liquid for forming an antireflection layer is coated on the second surface of the substrate of the present invention (the coating step).
- the coating method is not particularly limited, and for example, known coating methods such as fountain coating, die coating, spin coating, spray coating, gravure coating, roll coating, and bar coating may be used as appropriate. can.
- the coating amount of the coating liquid for forming an antireflection layer is not particularly limited, but the thickness of the antireflection layer to be formed is, for example, 0.1 ⁇ m or more, 0.3 ⁇ m or more, 0.5 ⁇ m or more, 1.0 ⁇ m. or more, or 2.0 ⁇ m or more, or 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, or 10 ⁇ m or less.
- the drying temperature is not particularly limited, and may be, for example, in the range of 30 to 200°C.
- the drying temperature may be, for example, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, or 100°C or higher, 190°C or lower, 180°C or lower, or 170°C or lower. It may be below 160°C, below 150°C, below 140°C, below 135°C, below 130°C, below 120°C, or below 110°C.
- the drying time is not particularly limited, but may be, for example, 30 seconds or more, 40 seconds or more, 50 seconds or more, or 60 seconds or more, and 150 seconds or less, 130 seconds or less, 110 seconds or less, or 90 seconds or less. It's okay.
- the coating film may be cured (curing step).
- the curing can be performed by heating, light irradiation, etc., for example.
- the light is not particularly limited, and may be, for example, ultraviolet light.
- the light source for the light irradiation is also not particularly limited, and may be, for example, a high-pressure mercury lamp.
- the irradiation amount of the energy ray source in the ultraviolet curing is preferably 50 to 500 mJ/cm 2 as a cumulative exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ/cm 2 or more, curing is likely to proceed sufficiently, and the hardness of the antireflection layer to be formed is likely to be high. Moreover, if it is 500 mJ/cm 2 or less, coloring of the formed antireflection layer can be prevented.
- any known AG treatment can be applied without particular limitation, and can be carried out, for example, by forming an anti-glare layer on the second surface of the base material of the present invention.
- an anti-glare layer any known anti-glare layer can be used without limitation, and is generally formed as a layer in which inorganic or organic particles as an anti-glare agent are dispersed in a resin.
- the anti-glare layer is not particularly limited, but is formed using an anti-glare layer-forming material containing, for example, a resin, particles, and a thixotropy-imparting agent, and the anti-glare layer is formed by aggregation of the particles and the thixotropy-imparting agent. A convex portion is formed on the surface.
- the anti-glare layer has excellent display characteristics that combine anti-glare properties and prevention of white blur, and even though the anti-glare layer is formed using particle aggregation, there are no appearance defects. It is possible to prevent the formation of protrusions on the surface of the anti-glare layer and improve the yield of products.
- the resin examples include thermosetting resins and ionizing radiation-curable resins that are cured by ultraviolet light or light.
- thermosetting resins examples include thermosetting resins and ionizing radiation-curable resins that are cured by ultraviolet light or light.
- the resin it is also possible to use commercially available thermosetting resins, ultraviolet curable resins, and the like.
- thermosetting resin or the ultraviolet curable resin for example, a curable compound having at least one of an acrylate group and a methacrylate group that is cured by heat, light (such as ultraviolet rays), or electron beam, etc.
- a curable compound having at least one of an acrylate group and a methacrylate group that is cured by heat, light (such as ultraviolet rays), or electron beam, etc. can be used, for example, Silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, oligomers or prepolymers such as acrylates and methacrylates of polyfunctional compounds such as polyhydric alcohols, etc. can give. These may be used alone or in combination of two or more.
- a reactive diluent having at least one of an acrylate group and a methacrylate group can also be used.
- the reactive diluent can be, for example, the reactive diluent described in JP-A No. 2008-88309, and includes, for example, monofunctional acrylate, monofunctional methacrylate, polyfunctional acrylate, polyfunctional methacrylate, and the like.
- As the reactive diluent trifunctional or higher functional acrylates or trifunctional or higher functional methacrylates are preferred. This is because the hardness of the anti-glare layer can be made excellent.
- Examples of the reactive diluent include butanediol glycerol ether diacrylate, isocyanuric acid acrylate, isocyanuric acid methacrylate, and the like. These may be used alone or in combination of two or more.
- the resin preferably includes a urethane acrylate resin, and is more preferably a copolymer of a curable urethane acrylate resin and a polyfunctional acrylate (for example, pentasritol triacrylate).
- the main functions of the particles for forming the anti-glare layer are to provide anti-glare properties by making the surface of the anti-glare layer uneven and to control the haze value of the anti-glare layer.
- the haze value of the anti-glare layer can be designed by controlling the refractive index difference between the particles and the resin.
- the particles include inorganic particles and organic particles.
- the inorganic particles are not particularly limited, and include, for example, silicon oxide particles, titanium oxide particles, aluminum oxide particles, zinc oxide particles, tin oxide particles, zirconium oxide particles, calcium carbonate particles, barium sulfate particles, talc particles, kaolin particles, Examples include calcium sulfate particles.
- the organic particles are not particularly limited, and include, for example, polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin.
- PMMA fine particles polymethyl methacrylate resin powder
- silicone resin powder silicone resin powder
- polystyrene resin powder polycarbonate resin powder
- acrylic styrene resin powder acrylic styrene resin powder
- benzoguanamine resin powder melamine resin powder
- polyolefin polyolefin
- resin powder polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder, and the like.
- One type of these inorganic particles and organic particles may be used alone, or two or more types may be used in combination.
- the weight average particle diameter (D) of the particles is preferably within the range of 2.5 to 10 ⁇ m. By setting the weight average particle diameter of the particles within the above range, for example, it is possible to have better anti-glare properties and prevent white blurring.
- the weight average particle diameter of the particles is more preferably within the range of 3 to 7 ⁇ m.
- the weight average particle diameter of the particles can be measured, for example, by the Coulter counting method. For example, using a particle size distribution measuring device (trade name: Coulter Multisizer, manufactured by Beckman Coulter) that uses the pore electrical resistance method, an electrolyte solution corresponding to the volume of the particles when the particles pass through the pores is measured. By measuring electrical resistance, the number and volume of the particles are determined, and the weight average particle diameter is calculated.
- the shape of the particles is not particularly limited, and may be, for example, approximately spherical in the form of beads, or irregularly shaped such as powder, but is preferably approximately spherical, and more preferably has an aspect ratio.
- the particles are approximately spherical particles with a ratio of 1.5 or less, and most preferably spherical particles.
- the proportion of the particles in the anti-glare layer is preferably in the range of 0.2 to 12 parts by weight, more preferably in the range of 0.5 to 12 parts by weight, even more preferably 1 part by weight, based on 100 parts by weight of the resin. ⁇ 7 parts by weight. By setting it within the above range, for example, it is possible to have better anti-glare properties and prevent white blurring.
- the anti-glare layer may contain a thixotropy agent.
- a thixotropy agent By including the thixotropy agent, the aggregation state of the particles can be easily controlled.
- the thixotropy imparting agent for forming the anti-glare layer include organic clay, oxidized polyolefin, and modified urea.
- the organic clay is a clay that has been subjected to an organic treatment in order to improve its affinity with the resin.
- the organic clay include layered organic clay.
- the organic clay may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include Lucentite SAN, Lucentite STN, Lucentite SEN, Lucentite SPN, Somasif ME-100, Somasif MAE, Somasif MTE, Somasif MEE, Somasif MPE (trade names, all manufactured by Co-op Chemical Co., Ltd.).
- the oxidized polyolefin may be prepared in-house or a commercially available product may be used.
- the commercially available products include Disparon 4200-20 (trade name, manufactured by Kusumoto Kasei Co., Ltd.) and Fluonon SA300 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).
- the modified urea is a reaction product of an isocyanate monomer or its adduct and an organic amine.
- the modified urea may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include BYK410 (manufactured by Big Chemie).
- the thixotropy imparting agent may be used alone or in combination of two or more.
- the height of the convex portion from the average roughness line of the anti-glare layer is less than 0.4 times the thickness of the anti-glare layer. More preferably, it is in the range of 0.01 times or more and less than 0.4 times, and still more preferably in the range of 0.01 times or more and less than 0.3 times. Within this range, it is possible to suitably prevent the formation of protrusions that would cause defects in appearance on the convex portion. By having convex portions with such heights, the anti-glare layer can be made less susceptible to appearance defects.
- the height from the average line can be measured, for example, by the method described in JP-A-2017-138620.
- the proportion of the thixotropy imparting agent in the anti-glare layer is preferably in the range of 0.1 to 5 parts by weight, more preferably in the range of 0.2 to 4 parts by weight, based on 100 parts by weight of the resin.
- the thickness (d) of the anti-glare layer is not particularly limited, but is preferably in the range of 3 to 12 ⁇ m.
- the thickness (d) of the anti-glare layer is preferably in the range of 3 to 12 ⁇ m.
- the thickness (d) of the anti-glare layer is preferably in the range of 3 to 12 ⁇ m.
- the weight average particle diameter (D) of the particles is preferably within the range of 2.5 to 10 ⁇ m, as described above.
- the thickness (d) of the anti-glare layer is more preferably in the range of 3 to 8 ⁇ m.
- the relationship between the thickness (d) of the anti-glare layer and the weight average particle diameter (D) of the particles is preferably within the range of 0.3 ⁇ D/d ⁇ 0.9.
- the anti-glare layer forms convex portions on the surface of the anti-glare layer by aggregation of the particles and the thixotropy imparting agent.
- the agglomerated portion forming the convex portion a plurality of the particles are present in a state of being gathered in the surface direction of the anti-glare layer.
- the convex portion has a gentle shape.
- the surface shape of the anti-glare layer can be arbitrarily designed by controlling the aggregation state of particles contained in the anti-glare layer forming material.
- the agglomeration state of the particles can be controlled by, for example, the material of the particles (for example, the chemical modification state of the particle surface, the affinity for solvents and resins, etc.), the type and combination of resins (binder) or solvents, and the like.
- the aggregation state of the particles can be controlled by the thixotropy imparting agent contained in the anti-glare layer forming material.
- the agglomeration state of the particles can be made as described above, and the convex portion can have a gentle shape.
- the base material of the present invention when the base material of the present invention is formed from a resin or the like, it is preferable to have a permeable layer at the interface between the base material of the present invention and the anti-glare layer.
- the permeable layer is formed by a resin component included in the anti-glare layer forming material permeating the base material of the present invention. It is preferable that a permeable layer is formed because it can improve the adhesion between the base material of the present invention and the anti-glare layer.
- the thickness of the permeable layer is preferably in the range of 0.2 to 3 ⁇ m, more preferably in the range of 0.5 to 2 ⁇ m.
- the permeable layer can be formed.
- the permeation layer can be confirmed and its thickness can be measured, for example, by observing a cross section of the optical pressure-sensitive adhesive sheet of the present invention using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the permeation layer be formed thicker in order to improve the adhesion of the base material to the anti-glare layer.
- the number of appearance defects having a maximum diameter of 200 ⁇ m or more is one or less per 1 m 2 of the anti-glare layer. More preferably, there is no appearance defect.
- the average inclination angle ⁇ a (°) is preferably in the range of 0.1 to 5.0, more preferably in the range of 0.3 to 4.5, and 1. It is more preferably in the range of 0 to 4.0, particularly preferably 1.6 to 4.0.
- the average inclination angle ⁇ a is a value defined by the following formula (1).
- the average inclination angle ⁇ a is a value measured by the method described in JP-A-2017-138620, for example.
- Average inclination angle ⁇ a tan-1 ⁇ a (1)
- ⁇ a is the distance between the peaks and valleys of adjacent peaks in the standard length L of the roughness curve specified in JIS B 0601 (1994 edition), as shown in the formula (2) below. This is the value obtained by dividing the total (h1+h2+h3...+hn) of the difference (height h) from the lowest point by the reference length L.
- ⁇ a is within the above range, anti-glare properties are better and white blur can be prevented.
- ⁇ 1 is the viscosity measured at a shear rate of 20 (1/s) using Rheostress 6000 manufactured by HAAKE
- ⁇ 2 is the viscosity measured at a shear rate of 200 (1/s) using Rheostress 6000 manufactured by HAAKE. This is the viscosity measured under the following conditions.
- the Ti value is less than 1.3, defects in appearance are likely to occur, and properties regarding anti-glare and white blurring deteriorate. Furthermore, when the Ti value exceeds 3.5, the particles are less likely to aggregate and become more likely to be in a dispersed state.
- the method for producing the anti-glare layer is not particularly limited and may be produced by any method, but for example, an anti-glare layer forming material (coating liquid) containing the resin, the particles, the thixotropy imparting agent, and a solvent is prepared.
- the anti-glare layer forming material (coating liquid) can be applied to the second surface of the substrate of the present invention to form a coating film, and the coating film can be cured to form an anti-glare layer.
- the solvent is not particularly limited, and various solvents can be used, and one type may be used alone or two or more types may be used in combination. There are optimal solvent types and solvent ratios depending on the composition of the resin, the types and contents of the particles and the thixotropy-imparting agent, and the like.
- the solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and 2-methoxyethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; methyl acetate, ethyl acetate.
- esters such as butyl acetate; ethers such as diisopropyl ether and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; cellosolves such as ethyl cellosolve and butyl cellosolve; aliphatic hydrocarbons such as hexane, heptane, and octane. Aromatic hydrocarbons such as benzene, toluene, xylene, etc.
- a good solvent for the polyester resin can be suitably used.
- the solvent include ethyl acetate, methyl ethyl ketone, and cyclopentanone.
- the thixotropy imparting agent can exhibit good thixotropy to the anti-glare layer forming material (coating liquid).
- organoclay toluene and xylene can be preferably used alone or in combination; for example, when using an oxidized polyolefin, methyl ethyl ketone, ethyl acetate, propylene glycol monomethyl ether can preferably be used alone. They can be used or used in combination.
- modified urea butyl acetate and methyl isobutyl ketone can be suitably used alone or in combination.
- leveling agents can be added to the anti-glare layer forming material.
- a fluorine-based or silicone-based leveling agent can be used for the purpose of preventing uneven coating (uniform coating surface).
- a leveling agent may be added as appropriate. can be selected. For example, by including the thixotropy imparting agent, the coating liquid can exhibit thixotropy, so that coating unevenness is less likely to occur. For this reason, it has the advantage that, for example, the options for the leveling agent can be expanded.
- the blending amount of the leveling agent is, for example, 5 parts by weight or less, preferably in the range of 0.01 to 5 parts by weight, based on 100 parts by weight of the resin.
- pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antifouling agents, antioxidants, etc. may be added to the anti-glare layer forming material within a range that does not impair performance. It's okay. These additives may be used alone or in combination of two or more.
- a conventionally known photopolymerization initiator as described in JP-A-2008-88309, for example, can be used.
- Examples of the method for coating the anti-glare layer forming material on the second surface of the base material of the present invention include fountain coating method, die coating method, spin coating method, spray coating method, gravure coating method, roll coating method, A coating method such as a bar coating method can be used.
- the anti-glare layer forming material is applied to form a coating film on the base material of the present invention, and the coating film is cured. It is preferable to dry the coating film prior to the curing.
- the drying may be, for example, natural drying, air drying by blowing wind, heat drying, or a combination of these methods.
- the means for curing the coating film of the anti-glare layer forming material is not particularly limited, but ultraviolet curing is preferred.
- the irradiation amount of the energy ray source is preferably 50 to 500 mJ/cm 2 as a cumulative exposure amount at an ultraviolet wavelength of 365 nm. If the irradiation amount is 50 mJ/cm 2 or more, curing will be more sufficient, and the anti-glare layer formed will also have more sufficient hardness. Moreover, if it is 500 mJ/cm 2 or less, coloring of the anti-glare layer to be formed can be prevented.
- the anti-glare layer can be formed on the second surface of the base material of the present invention.
- the anti-glare layer may be formed by a manufacturing method other than the above-mentioned method.
- the hardness of the anti-glare layer is influenced by the thickness of the layer in terms of pencil hardness, but preferably has a hardness of 2H or more.
- the anti-glare layer may have a multi-layer structure in which two or more layers are laminated.
- the above-mentioned AR layer may be placed on the anti-glare layer.
- the anti-glare layer and the anti-reflection layer may each have a multilayer structure in which two or more layers are laminated.
- an anti-contamination layer formed from a fluorine group-containing silane compound or a fluorine group-containing organic compound is added to the antireflection layer and to the anti-reflection layer. It is preferable to laminate the anti-glare layer/or on the anti-glare layer.
- the adhesion with the anti-glare layer will be further improved. Moreover, if the surface of the anti-glare layer is subjected to a surface treatment, the adhesion with the AR layer is further improved.
- the other surface of the anti-glare layer may be treated with a solvent. Further, in order to prevent curling, a transparent resin layer may be formed on the other surface of the anti-glare layer.
- the adhesive layer of the present invention may be an adhesive layer that does not have a base material (base material layer), or may be a type of adhesive layer that has a base material.
- base material layer an adhesive layer that does not have a base material (base material layer) is sometimes referred to as a "base material-less adhesive layer,” and a type of adhesive layer that has a base material is sometimes referred to as a “base material-attached adhesive layer.” It is sometimes referred to as a "layer”.
- Examples of the above-mentioned substrate-less adhesive layer include a single-layer adhesive layer consisting only of the adhesive layer of the present invention, or a single-layer adhesive layer consisting of the adhesive layer of the present invention and other adhesive layers (other than the adhesive layer of the present invention).
- an adhesive layer consisting of an adhesive layer (adhesive layer) or the like can be mentioned.
- the adhesive layer with a base material may include an adhesive layer having the adhesive layer of the present invention on both sides of the base material, or a pressure-sensitive adhesive layer having the adhesive layer of the present invention on one side of the base material and the other side. Examples include an adhesive layer having another adhesive layer on the surface side.
- base material (base material layer)" constituting the "adhesive layer with base material a plastic film similar to the base material of the present invention can be used.
- the surface resistance value of the adhesive layer of the present invention is less than 10 10 ⁇ .
- the configuration in which the adhesive layer of the present invention has a surface resistance value of less than 10 10 ⁇ means that the adhesive layer of the present invention exhibits an excellent antistatic effect and does not cause poor bonding to the image display panel of the present invention. This is preferable in that it can suppress the generation of static electricity when the adhesive sheet is peeled off from the image display panel for rework in the event of rework.
- the adhesive layer of the present invention exhibits a more excellent antistatic effect and can more efficiently suppress the generation of static electricity during rework of the image display device of the present invention.
- the surface resistance value is preferably 0.97 ⁇ 10 10 ⁇ or less, more preferably 0.96 ⁇ 10 10 ⁇ or less, and still more preferably 0.95 ⁇ 10 10 ⁇ or less.
- the lower limit of the surface resistance value of the adhesive layer of the present invention is not particularly limited, and is preferably as low as possible, but may be 10 7 ⁇ or more.
- the surface resistance value of the adhesive layer of the present invention after the following thermal shock test is preferably less than 10 10 ⁇ .
- the optical adhesive sheet of the present invention was subjected to thermal shock, with one cycle consisting of exposing it to an atmosphere of -40°C for 30 minutes, and then exposing it to an atmosphere of 80°C for 30 minutes. Apply 200 cycles using an impact tester.
- the structure in which the surface resistance value of the adhesive layer of the present invention after the above thermal shock test is less than 10 10 ⁇ indicates that the adhesive layer of the present invention has an excellent antistatic effect even in harsh environments such as thermal shock. For example, if a failure occurs such as a light emitting element not lighting up under the usage environment of the image display device, suppress the generation of static electricity when the adhesive sheet is peeled off from the image display panel for repair. This is suitable because it allows for The adhesive layer of the present invention maintains a better antistatic effect under the usage environment of the image display device, and more efficiently suppresses the generation of static electricity during rework to repair the image display device of the present invention.
- the surface resistance value of the adhesive layer of the present invention after the above thermal shock test is preferably 0.97 ⁇ 10 10 ⁇ or less, more preferably 0.96 ⁇ 10 10 ⁇ . or less, more preferably 0.95 ⁇ 10 10 ⁇ or less.
- the lower limit of the surface resistance value of the adhesive layer of the present invention after the above-mentioned thermal shock test is not particularly limited, and is preferably as low as possible, but may be 10 7 ⁇ or more.
- the absolute value of the difference in surface resistance of the adhesive layer of the present invention before and after the thermal shock test is preferably 1 log ⁇ or less.
- the difference in surface resistance of the adhesive layer of the present invention before and after the above thermal shock test is 1 log ⁇ or less, which indicates that the adhesive layer of the present invention has an excellent antistatic effect even in harsh environments such as thermal shock. For example, if a failure occurs such as a light emitting element not lighting up under the usage environment of the image display device, suppress the generation of static electricity when the adhesive sheet is peeled off from the image display panel for repair.
- the adhesive layer of the present invention maintains a better antistatic effect under the usage environment of the image display device, and more efficiently suppresses the generation of static electricity during rework to repair the image display device of the present invention.
- it is 0.7 log ⁇ or less.
- the surface resistivity of the adhesive layer of the present invention, the surface resistance values before and after the above thermal shock test, and the difference thereof are measured by surface resistance value measurement in the Examples described below.
- the surface resistivity of the adhesive layer of the present invention, the surface resistance values before and after the thermal shock test, and the difference thereof are determined by the composition of the adhesive composition (for example, the type of base polymer) for forming the adhesive layer of the present invention. It can be adjusted by adjusting the curing conditions (heating conditions, radiation irradiation conditions), molecular weight, amount used, monomer composition, type and amount of functional groups, type and amount of antistatic agent, type and amount of crosslinking agent.
- the hardness H [kPa] of the adhesive layer of the present invention measured by the nanoindentation method is preferably less than 60 kPa.
- the configuration in which the adhesive layer of the present invention has a hardness H [kPa] measured by the nanoindentation method of less than 60 kPa is applicable when an image display panel or optical member has uneven steps such as a printed layer or wiring.
- the adhesive layer of the present invention can sufficiently follow the level difference and fill it without leaving any bubbles, that is, exhibits excellent level difference absorbency, and furthermore, can prevent the above-mentioned bonding defects. , is suitable.
- the hardness H [kPa] of the adhesive layer of the present invention measured by the nanoindentation method is preferably 55 kPa or less, more preferably 50 kPa or less, and 45 kPa or less. The following may be sufficient.
- the lower limit of the hardness H [kPa] of the adhesive layer of the present invention determined by the nanoindentation method is determined by the processability such that the adhesive layer of the present invention is unlikely to protrude from the edges during storage. From the viewpoint, the pressure is preferably 1 kPa or more, and may be 5 kPa or more.
- the hardness H of the adhesive layer of the present invention measured by the nanoindentation method can be measured by the method described in Examples below.
- the hardness H of the adhesive layer of the present invention measured by the nanoindentation method is determined by the composition of the adhesive composition for forming the adhesive layer of the present invention (for example, the type, molecular weight, usage amount, and monomer composition of the base polymer). , type and amount of functional group, type and amount of antistatic agent, type and amount of crosslinking agent), curing conditions (heating conditions, radiation irradiation conditions), etc.
- the glass transition point (Tg) of the adhesive layer of the present invention is preferably ⁇ 10° C. or lower.
- the configuration in which the adhesive layer of the present invention has a Tg of ⁇ 10° C. or less is preferable because the adhesive layer of the present invention can maintain its excellent level difference absorbability even in a low-temperature environment.
- the glass transition point of the adhesive layer of the present invention is preferably -15°C or lower, and may be -20°C or lower, in that the adhesive layer of the present invention can maintain better level difference absorption even in a low-temperature environment. .
- the lower limit of Tg of the adhesive layer of the present invention is not particularly limited, but from the viewpoint of processability, such as preventing the adhesive layer from protruding from the edges during storage of the optical adhesive sheet of the present invention, it is set at -50°C.
- the temperature is preferably -40°C or higher.
- the glass transition point (Tg) of the adhesive layer of the present invention is measured by dynamic viscoelasticity measurement in the Examples below.
- the glass transition point (Tg) of the adhesive layer of the present invention is determined by the composition of the adhesive composition for forming the adhesive layer of the present invention (for example, the type and molecular weight of the base polymer, the amount used, the monomer composition, the functional group (type and amount of antistatic agent, type and amount of crosslinking agent), curing conditions (heating conditions, radiation irradiation conditions), etc.
- the storage modulus of the adhesive layer of the present invention at 25° C. and 1 Hz is preferably less than 200 kPa.
- the configuration in which the storage modulus of the adhesive layer of the present invention at 25° C. and 1 Hz is less than 200 kPa means that the adhesive layer of the present invention sufficiently follows contraction or expansion in the usage environment of the image display device of the present invention. However, it is preferable in that lifting and peeling can be suppressed. Further, when an image display panel or an optical member has uneven steps such as a printed layer or wiring, it is suitable because it exhibits excellent step absorption properties and can prevent the above-mentioned bonding defects.
- the pressure is preferably 1 kPa or more, and may be 5 kPa or more.
- the storage modulus of the adhesive layer of the present invention at 85° C. and 1 Hz is preferably less than 100 kPa.
- the configuration in which the storage modulus of the adhesive layer of the present invention at 85° C. and 1 Hz is less than 100 kPa means that the adhesive layer of the present invention sufficiently follows contraction or expansion in the usage environment of the image display device of the present invention. However, it is preferable in that lifting and peeling can be suppressed. Further, when an image display panel or an optical member has uneven steps such as a printed layer or wiring, it is suitable because it exhibits excellent step absorption properties and can prevent the above-mentioned bonding defects.
- the pressure is preferably 1 kPa or more, and may be 5 kPa or more.
- the storage modulus of the adhesive layer of the present invention at 25° C. or 85° C. and 1 Hz is measured by dynamic viscoelasticity measurement in the Examples below.
- the storage modulus of the adhesive layer of the present invention at 25°C or 85°C and 1 Hz depends on the composition of the adhesive composition for forming the adhesive layer of the present invention (for example, the type, molecular weight, and amount of the base polymer used). , monomer composition, type and amount of functional group, type and amount of antistatic agent, type and amount of crosslinking agent), curing conditions (heating conditions, radiation irradiation conditions), etc.
- the 300% tensile residual stress value of the adhesive layer of the present invention is not particularly limited, but is preferably 25 N/cm 2 or less.
- the configuration in which the adhesive layer of the present invention has a 300% tensile residual stress value of 25 N/cm 2 or less means that the adhesive layer of the present invention can sufficiently follow the contraction or expansion in the usage environment of the image display device of the present invention. However, it is preferable in that lifting and peeling can be suppressed. Further, when an image display panel or an optical member has uneven steps such as a printed layer or wiring, it is suitable because it exhibits excellent step absorption properties and can prevent the above-mentioned bonding defects.
- the 300% tensile residual stress value of the adhesive layer of the present invention is more preferably 20 N/cm 2 or less, and 18 N/cm 2 in terms of suppressing lifting and peeling of the optical adhesive sheet of the present invention and having better step absorbability.
- the following is more preferable, and may be 15 N/cm 2 or less.
- the lower limit of the 300% tensile residual stress value of the adhesive layer of the present invention is not particularly limited, but from the viewpoint of processability, such as that the adhesive layer is unlikely to protrude from the edges during storage of the optical adhesive sheet of the present invention. Therefore, it is preferably 1 N/cm 2 or more, and may be 1.5 N/cm 2 or more.
- the 300% tensile residual stress value of the adhesive layer of the present invention is measured by measuring the 300% tensile residual stress value in the Examples described below.
- the 300% tensile residual stress value of the adhesive layer of the present invention is determined by the composition of the adhesive composition for forming the adhesive layer of the present invention (for example, the type, molecular weight, usage amount, monomer composition, functional group, etc. of the base polymer). (type and amount of antistatic agent, type and amount of crosslinking agent), curing conditions (heating conditions, radiation irradiation conditions), etc.
- the adhesive constituting the adhesive layer of the present invention is not particularly limited, but includes, for example, an acrylic adhesive, a rubber adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, and a polyamide adhesive.
- examples include adhesives, urethane adhesives, fluorine adhesives, and epoxy adhesives.
- acrylic pressure-sensitive adhesives are preferred as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer in terms of transparency, adhesiveness, weather resistance, cost, and ease of designing the pressure-sensitive adhesive. That is, the adhesive layer of the present invention is preferably an acrylic adhesive layer made of an acrylic adhesive.
- the above adhesives can be used alone or in combination of two or more.
- the acrylic adhesive layer contains an acrylic polymer as a base polymer.
- the above-mentioned acrylic polymer is a polymer containing an acrylic monomer (a monomer having a (meth)acryloyl group in the molecule) as a monomer component constituting the polymer.
- the acrylic polymer is preferably a polymer containing an alkyl (meth)acrylic acid ester as a monomer component constituting the polymer. Note that the acrylic polymers can be used alone or in combination of two or more.
- the adhesive composition forming the adhesive layer of the present invention may be in any form.
- the adhesive composition may be of an emulsion type, a solvent type (solution type), an active energy ray-curable type, a heat melt type (hot melt type), or the like.
- solvent-based and active energy ray-curable adhesive compositions are preferred from the viewpoint of productivity and the ease of obtaining an adhesive layer with excellent optical properties and appearance.
- an active energy ray-curable adhesive composition is preferred from the viewpoint of easily controlling the above-mentioned various properties of the adhesive layer (particularly, the level difference absorbability) within a predetermined range.
- the adhesive layer of the present invention is an acrylic adhesive layer containing an acrylic polymer as a base polymer, and is preferably formed from an active energy ray-curable acrylic adhesive composition. Further, the adhesive layer of the present invention is an acrylic adhesive layer containing an acrylic polymer as a base polymer, and is preferably formed from a solvent-type acrylic adhesive composition.
- the active energy rays include ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron beams, and electron beams, and ultraviolet rays, with ultraviolet rays being particularly preferred. That is, the active energy ray-curable adhesive composition is preferably an ultraviolet ray-curable adhesive composition.
- the adhesive composition (acrylic adhesive composition) forming the above-mentioned acrylic adhesive layer may be, for example, an acrylic adhesive composition containing an acrylic polymer as an essential component, or a monomer constituting the acrylic polymer.
- examples of the former include so-called solvent-type acrylic adhesive compositions.
- Examples of the latter include so-called active energy ray-curable acrylic adhesive compositions.
- the above-mentioned "monomer mixture” means a mixture containing monomer components constituting a polymer.
- the above-mentioned "partially polymerized product” may also be referred to as "prepolymer", and means a composition in which one or more of the monomer components in the monomer mixture are partially polymerized. do.
- the above acrylic polymer is a polymer composed (formed) of an acrylic monomer as an essential monomer component (monomer component).
- the acrylic polymer is preferably a polymer composed (formed) of a (meth)acrylic acid alkyl ester as an essential monomer component. That is, the acrylic polymer preferably contains (meth)acrylic acid alkyl ester as a structural unit.
- (meth)acrylic refers to "acrylic” and/or "methacrylic” (either or both of "acrylic” and “methacrylic"), and the same applies to the others.
- the said acrylic polymer is comprised from 1 type, or 2 or more types of monomer components.
- (meth)acrylic acid alkyl ester as an essential monomer component, (meth)acrylic acid alkyl ester having a linear or branched alkyl group is preferably mentioned.
- (meth)acrylic acid alkyl ester can be used individually or in combination of 2 or more types.
- the (meth)acrylic acid alkyl ester having a linear or branched alkyl group is not particularly limited, but includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, ( Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate Isopentyl acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, (meth) ) Isononyl acrylate, (meth
- the (meth)acrylic acid alkyl ester having a linear or branched alkyl group is preferably a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 4 to 18 carbon atoms. , more preferably 2-ethylhexyl acrylate (2EHA), isostearyl acrylate (ISTA), lauryl acrylate (LA), and butyl acrylate (BA).
- EHA 2-ethylhexyl acrylate
- ISA isostearyl acrylate
- LA lauryl acrylate
- BA butyl acrylate
- the above-mentioned (meth)acrylic acid alkyl esters having a linear or branched alkyl group can be used alone or in combination of two or more types.
- the proportion of the (meth)acrylic acid alkyl ester in all monomer components (100% by weight) constituting the acrylic polymer is not particularly limited, but is 50% by weight or more (for example, 50 to 100% by weight).
- the amount is preferably 53 to 100% by weight, and even more preferably 55 to 100% by weight.
- the acrylic pressure-sensitive adhesive composition may contain the alkyl (meth)acrylate ester described above.
- the acrylic adhesive composition contains an alkyl (meth)acrylate in addition to the acrylic polymer
- the content (amount) of the alkyl (meth)acrylate is based on 100 parts by weight of the acrylic polymer. On the other hand, it is preferably 10 parts by weight or more (for example, 10 to 100 parts by weight), more preferably 20 to 90 parts by weight, even more preferably 30 to 80 parts by weight.
- the acrylic polymer may contain a copolymerizable monomer together with the (meth)acrylic acid alkyl ester as a monomer component constituting the polymer. That is, the acrylic polymer may contain a copolymerizable monomer as a structural unit. Note that the copolymerizable monomers can be used alone or in combination of two or more types.
- the above-mentioned copolymerizable monomer is not particularly limited, but it can be used from the viewpoint of easily controlling the above-mentioned various properties of the pressure-sensitive adhesive layer (particularly, level difference absorbency) within a predetermined range, suppressing clouding in a high-humidity environment, and providing durability. From the viewpoint of improving properties, adhesion reliability, compatibility with various additives such as ultraviolet absorbers, and transparency, monomers having a nitrogen atom in the molecule and monomers having a hydroxyl group in the molecule are preferred. That is, the acrylic polymer preferably contains a monomer having a nitrogen atom in the molecule as a structural unit. Further, the acrylic polymer preferably contains a monomer having a hydroxyl group in the molecule as a structural unit.
- the monomer having a nitrogen atom in the molecule is a monomer (monomer) having at least one nitrogen atom in the molecule (in one molecule).
- the above-mentioned "monomer having a nitrogen atom in the molecule” may be referred to as a "nitrogen atom-containing monomer.”
- the nitrogen atom-containing monomer is not particularly limited, but preferred examples include cyclic nitrogen-containing monomers, (meth)acrylamides, and the like. Note that the nitrogen atom-containing monomers can be used alone or in combination of two or more.
- the cyclic nitrogen-containing monomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond, such as a (meth)acryloyl group or a vinyl group, and has a cyclic nitrogen structure.
- the above-mentioned cyclic nitrogen structure preferably has a nitrogen atom within the cyclic structure.
- cyclic nitrogen-containing monomer examples include N-vinyl cyclic amide (lactam vinyl monomer), vinyl monomer having a nitrogen-containing heterocycle, and the like.
- N-vinyl cyclic amide examples include N-vinyl cyclic amide represented by the following formula (1).
- R 1 represents a divalent organic group
- R 1 in the above formula (1) is a divalent organic group, preferably a divalent saturated hydrocarbon group or an unsaturated hydrocarbon group, more preferably a divalent saturated hydrocarbon group (e.g. 3 to 5 alkylene groups, etc.).
- N-vinyl cyclic amide represented by the above formula (1) examples include N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-morpholinone, and N-vinyl-2-caprolactam. , N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, and the like.
- vinyl monomer having a nitrogen-containing heterocycle examples include acrylic monomers having a nitrogen-containing heterocycle such as a morpholine ring, a piperidine ring, a pyrrolidine ring, and a piperazine ring.
- the vinyl monomer having a nitrogen-containing heterocycle is not particularly limited, but includes, for example, (meth)acryloylmorpholine, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, N-vinylpyrazine, and N-vinylmorpholine.
- acrylic monomers having a nitrogen-containing heterocycle acrylic monomers having a nitrogen-containing heterocycle are preferred, and (meth)acryloylmorpholine, (meth)acryloylpyrrolidine, and (meth)acryloylpiperidine are more preferred.
- Examples of the (meth)acrylamides include (meth)acrylamide, N-alkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, and the like.
- Examples of the N-alkyl (meth)acrylamide include N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl (meth)acrylamide, and N-octyl (meth)acrylamide. .
- N-alkyl (meth)acrylamide mentioned above also includes (meth)acrylamide having an amino group such as dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and dimethylaminopropyl (meth)acrylamide.
- N,N-dialkyl(meth)acrylamide examples include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl Examples include (meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, and N,N-di(t-butyl)(meth)acrylamide.
- the above (meth)acrylamides include, for example, various N-hydroxyalkyl (meth)acrylamides.
- N-hydroxyalkyl (meth)acrylamide examples include N-methylol (meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N- (1-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, Examples include N-(4-hydroxybutyl)(meth)acrylamide and N-methyl-N-2-hydroxyethyl(meth)acrylamide.
- the above (meth)acrylamides include, for example, various N-alkoxyalkyl (meth)acrylamides.
- the N-alkoxyalkyl (meth)acrylamide include N-methoxymethyl (meth)acrylamide and N-butoxymethyl (meth)acrylamide.
- nitrogen atom-containing monomers other than the above-mentioned cyclic nitrogen-containing monomers and the above-mentioned (meth)acrylamides include amino group-containing monomers, cyano group-containing monomers, imide group-containing monomers, isocyanate group-containing monomers, and the like.
- the amino group-containing monomer include aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate.
- the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
- the imide group-containing monomers include maleimide monomers (for example, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, etc.), itaconimide monomers (for example, N-methylitaconimide, N- ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-lauryl itaconimide, N-cyclohexy itaconimide, etc.), succinimide monomers (e.g.
- N-(meth)acryloyl oxymethylene succinimide N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyoctamethylene succinimide, etc.
- isocyanate group-containing monomer examples include 2-(meth)acryloyloxyethyl isocyanate.
- the nitrogen atom-containing monomer is preferably a cyclic nitrogen-containing monomer, and more preferably N-vinyl cyclic amide. More specifically, N-vinyl-2-pyrrolidone (NVP) is particularly preferred.
- the proportion of the nitrogen atom-containing monomer in the total monomer components (100% by weight) constituting the acrylic polymer is: Although not particularly limited, it is preferably 1% by weight or more, more preferably 3% by weight or more, and still more preferably 5% by weight or more. It is preferable that the above ratio is 1% by weight or more, since it is possible to further improve the suppression of clouding and durability in a high-humidity environment, and to obtain high adhesion reliability.
- the upper limit of the proportion of the nitrogen atom-containing monomer is determined in order to obtain an adhesive layer with appropriate flexibility, to obtain an adhesive layer with excellent transparency, and to obtain the above-mentioned various properties of the adhesive layer (especially, level difference absorption).
- the content is preferably 30% by weight or less, more preferably 25% by weight or less, and still more preferably 20% by weight or less.
- the monomer having a hydroxyl group in the molecule is a monomer having at least one hydroxyl group in the molecule (in one molecule), and is a polymer having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group.
- Preferred examples include those having a functional group and a hydroxyl group.
- the monomer having a hydroxyl group in the molecule does not include the nitrogen atom-containing monomer.
- a monomer having both a nitrogen atom and a hydroxyl group in the molecule is included in the above-mentioned "nitrogen atom-containing monomer.”
- the above-mentioned “monomer having a hydroxyl group in the molecule” may be referred to as a "hydroxyl group-containing monomer.”
- the hydroxyl group-containing monomers can be used alone or in combination of two or more.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ( Hydroxyl group-containing compounds such as 6-hydroxyhexyl meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl) (meth)acrylate Examples include meth)acrylic acid ester; vinyl alcohol; allyl alcohol.
- the hydroxyl group-containing monomer is preferably a hydroxyl group-containing (meth)acrylic ester, more preferably 2-hydroxyethyl acrylate (HEA) or 4-hydroxybutyl acrylate (4HBA).
- the proportion of the hydroxyl group-containing monomer in the total monomer components (100% by weight) constituting the acrylic polymer is particularly limited.
- the content is preferably 0.5% by weight or more, more preferably 0.8% by weight or more. , more preferably 1% by weight or more.
- the upper limit of the proportion of the hydroxyl group-containing monomer is preferably 30% by weight or less, more preferably 30% by weight or less, from the viewpoint of easily controlling the various properties (particularly, the level difference absorbency) of the adhesive layer within a predetermined range. is 25% by weight or less, more preferably 20% by weight or less.
- the acrylic pressure-sensitive adhesive composition may contain a hydroxyl group-containing monomer in addition to the acrylic polymer.
- the content (compounding amount) of the hydroxyl group-containing monomer is 1 part by weight or more per 100 parts by weight of the acrylic polymer. It is preferably 3 parts by weight or more, and even more preferably 5 parts by weight or more. It is preferable that the content is 5 parts by weight or more, since it is possible to further improve the suppression of clouding and durability in a high-humidity environment, and to obtain higher adhesion reliability.
- the upper limit of the content (compounding amount) of the above-mentioned hydroxyl group-containing monomer is determined from the viewpoint of cohesive force, adhesiveness, ease of obtaining adhesion reliability, and the above-mentioned various properties of the adhesive layer (especially step absorption). From the viewpoint of easily controlling the amount within a predetermined range, the amount is more preferably 30 parts by weight or less, more preferably 25 parts by weight or less, still more preferably 20 parts by weight or less, particularly preferably 17 parts by weight or less.
- the total proportion of the nitrogen atom-containing monomer and the hydroxyl group-containing monomer in the total monomer components (100% by weight) constituting the acrylic polymer is not particularly limited, but is effective for suppressing clouding in a high humidity environment.
- the content is preferably 5% by weight or more, more preferably 10% by weight or more, and even more preferably 15% by weight or more.
- the upper limit of the total of the above ratios is determined in order to obtain an adhesive layer with appropriate flexibility, to obtain an adhesive layer with excellent transparency, and to satisfy the above-mentioned characteristics of the adhesive layer (in particular, level difference absorbency).
- the content is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 35% by weight or less.
- Copolymerizable monomers other than nitrogen atom-containing monomers and hydroxyl group-containing monomers include carboxyl group-containing monomers.
- the carboxyl group-containing monomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond, such as a (meth)acryloyl group or a vinyl group, and also has a carboxyl group.
- Examples of carboxyl group-containing monomers include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides such as maleic anhydride and itaconic anhydride.
- Group-containing monomers are also included. Note that the carboxyl group-containing monomers can be used alone or in combination of two or more.
- the proportion of the carboxyl group-containing monomer in the total monomer components (100% by weight) constituting the acrylic polymer is:
- the content is preferably 0.5% by weight or more, more preferably 0.8% by weight or more, and even more preferably 1% by weight or more.
- the upper limit of the proportion of the carboxyl group-containing monomer is preferably 30% by weight or less, and more preferably It is preferably 25% by weight or less, more preferably 20% by weight or less.
- Copolymerizable monomers other than nitrogen atom-containing monomers and hydroxyl group-containing monomers further include alicyclic structure-containing monomers.
- the alicyclic structure-containing monomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond, such as a (meth)acryloyl group or a vinyl group, and has an alicyclic structure.
- alkyl (meth)acrylates having a cycloalkyl group are included in the alicyclic structure-containing monomers. Note that the alicyclic structure-containing monomers can be used alone or in combination of two or more.
- the alicyclic structure in the alicyclic structure-containing monomer is a cyclic hydrocarbon structure, and preferably has 5 or more carbon atoms, more preferably 6 to 24 carbon atoms, even more preferably 6 to 15 carbon atoms, and 6 to 10 are particularly preferred.
- Examples of the alicyclic structure-containing monomer include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, Isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, HPMPA represented by the following formula (2), TMA-2 represented by the following formula (3), HCPA represented by the following formula (4), etc.
- Examples include (meth)acrylic monomers.
- the bonding position between the cyclohexyl ring connected by a line and the structural formula in parentheses is not particularly limited. Among these, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate are preferred.
- the proportion of the alicyclic structure-containing monomer in the total monomer components (100% by weight) constituting the acrylic polymer is preferably 10% by weight or more from the viewpoint of improving durability and obtaining high adhesive reliability.
- the upper limit of the proportion of the alicyclic structure-containing monomer is set so that an adhesive layer with appropriate flexibility can be obtained, and the above-mentioned various properties of the adhesive layer (in particular, level difference absorbency) can be easily controlled within a predetermined range. From this point of view, the content is preferably 50% by weight or less, more preferably 40% by weight or less, even more preferably 30% by weight or less.
- examples of copolymerizable monomers include polyfunctional monomers.
- examples of the polyfunctional monomer include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, Examples include allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Note that the polyfunctional monomers can be used alone or in
- the proportion of the polyfunctional monomer in the total monomer components (100% by weight) constituting the acrylic polymer is: Although not particularly limited, from the viewpoint of easily controlling the above-mentioned various properties of the adhesive layer (in particular, level difference absorbency) within a predetermined range, 0.5% by weight or less (for example, more than 0% by weight and 0.5% by weight) % or less), and more preferably 0.2 weight % or less (for example, more than 0 weight % and 0.2 weight % or less).
- the above polyfunctional monomer may be blended into the acrylic pressure-sensitive adhesive composition in addition to the above acrylic polymer.
- the acrylic adhesive composition contains a polyfunctional monomer in addition to the acrylic polymer
- the content (compounding amount) of the polyfunctional monomer is determined based on 100 parts by weight of the acrylic polymer in the adhesive layer. From the viewpoint of easily controlling the above-mentioned various properties (especially step absorbability) within a predetermined range, it is preferably 0.5 parts by weight or less (for example, more than 0 parts by weight and less than 0.5 parts by weight), more preferably is 0.2 parts by weight or less (for example, more than 0 parts by weight and not more than 0.2 parts by weight).
- examples of the copolymerizable monomer include (meth)acrylic acid alkoxyalkyl ester.
- the above (meth)acrylic acid alkoxyalkyl ester is not particularly limited, but includes, for example, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, ( Examples include 3-methoxypropyl meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 4-ethoxybutyl (meth)acrylate.
- the (meth)acrylic acid alkoxyalkyl ester is preferably an acrylic acid alkoxyalkyl ester, and more preferably 2-methoxyethyl acrylate (MEA). Note that the above (meth)acrylic acid alkoxyalkyl esters can be used alone or in combination of two or more types.
- the ratio of the (meth)acrylic acid alkyl ester to the (meth)acrylic acid alkoxyalkyl ester is as follows: Although not particularly limited, [former:latter] (weight ratio) is preferably more than 100:0 and less than 25:75, more preferably more than 100:0 and less than 50:50.
- examples of the copolymerizable monomer include epoxy group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, (meth)acrylic acid esters having aromatic hydrocarbon groups, vinyl esters, aromatic Examples include group vinyl compounds, olefins or dienes, vinyl ethers, vinyl chloride, and the like.
- examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and the like.
- examples of the sulfonic acid group-containing monomer include sodium vinyl sulfonate.
- examples of the phosphoric acid group-containing monomer include 2-hydroxyethyl acryloyl phosphate.
- Examples of the (meth)acrylic ester having an aromatic hydrocarbon group include phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate.
- Examples of the vinyl esters include vinyl acetate and vinyl propionate.
- Examples of the aromatic vinyl compound include styrene and vinyltoluene.
- Examples of the olefins or dienes include ethylene, propylene, butadiene, isoprene, and isobutylene.
- Examples of the vinyl ethers include vinyl alkyl ethers.
- the content of the base polymer (especially acrylic polymer) in the adhesive layer of the present invention is not particularly limited, but is 50% by weight or more (for example, 50% by weight or more based on 100% by weight of the total weight of the adhesive layer of the present invention). to 100% by weight), more preferably 80% by weight or more (for example, 80 to 100% by weight), still more preferably 90% by weight or more (for example, 90 to 100% by weight).
- the weight average molecular weight (Mw) of the acrylic polymer is 100,000 to 5,000,000, preferably 500,000 to 4,000,000, more preferably 750,000 to 3,000,000.
- a configuration in which the weight average molecular weight of the acrylic polymer is 100,000 or more is preferable in terms of improved adhesive strength and improved foam peeling resistance.
- a structure in which the weight average molecular weight of the acrylic polymer is 5,000,000 or less is preferable since it is easy to increase the adhesive strength and the foaming peeling resistance is improved.
- the weight average molecular weight (Mw) of the acrylic polymer can be determined in terms of polystyrene using the GPC method. For example, measurement can be performed using a high-speed GPC device "HPLC-8120GPC" manufactured by Tosoh Corporation under the following conditions. Column: TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000 Solvent: Tetrahydrofuran Flow rate: 0.6ml/min
- the glass transition temperature (Tg) of the acrylic polymer is not particularly limited, but is preferably -70 to -10°C, more preferably -65 to -15°C, and even more preferably -60 to -20°C. It is preferable that the glass transition temperature of the acrylic polymer is ⁇ 70° C. or higher, since the cohesive force is improved and the foaming peeling resistance is easily improved. Further, the configuration in which the glass transition temperature of the acrylic polymer is -10°C or lower allows the stress relaxation properties of the adhesive layer to be maintained even in a low-temperature environment, and the image display device of the present invention shrinks or expands under the usage environment. This is preferable because the pressure-sensitive adhesive layer can sufficiently follow the conditions, suppress lifting and peeling, and ensure sufficient adhesion to the adherend.
- Tg is the glass transition temperature of the acrylic polymer (unit: K)
- Tg i is the glass transition temperature (unit: K) when monomer i forms a homopolymer
- Tg of the homopolymer of monomers constituting the acrylic polymer the following values can be adopted.
- Tg of a homopolymer of a monomer not described above the value described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be adopted. Further, as the Tg of a homopolymer of a monomer that is not described in the above literature, a value obtained by the above-mentioned measuring method (peak top temperature of tan ⁇ by viscoelasticity test) can be adopted.
- the base polymer, such as the above-mentioned acrylic polymer, contained in the adhesive layer of the present invention is obtained by polymerizing monomer components.
- This polymerization method is not particularly limited, and includes, for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a polymerization method using active energy ray irradiation (active energy ray polymerization method), and the like.
- solution polymerization method and active energy ray polymerization method are preferred, and active energy ray polymerization method is more preferred.
- various common solvents may be used during the polymerization of the above monomer components.
- the solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane. alicyclic hydrocarbons; organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
- a solvent can be used individually or in combination of 2 or more types.
- a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) may be used depending on the type of polymerization reaction.
- a polymerization initiator can be used individually or in combination of 2 or more types.
- the thermal polymerization initiator is not particularly limited, but includes, for example, an azo polymerization initiator, a peroxide polymerization initiator (e.g., dibenzoyl peroxide, tert-butyl permaleate, etc.), a redox polymerization initiator, etc. can be mentioned.
- the azo polymerization initiator disclosed in JP-A No. 2002-69411 is preferred.
- the azo polymerization initiator include 2,2'-azobisisobutyronitrile (hereinafter sometimes referred to as "AIBN”) and 2,2'-azobis-2-methylbutyronitrile (hereinafter referred to as "AIBN"). (sometimes referred to as "AMBN”), dimethyl 2,2'-azobis(2-methylpropionate), and 4,4'-azobis-4-cyanovaleric acid.
- AIBN 2,2'-azobisisobutyronitrile
- AIBN 2,2'-azobis-2-methylbutyronitrile
- AMBN di
- the amount of the azo polymerization initiator used is not particularly limited, but for example, 100 parts by weight of all monomer components constituting the acrylic polymer. It is preferably 0.05 part by weight or more, more preferably 0.1 part by weight or more, and preferably 0.5 part by weight or less, more preferably 0.3 part by weight. It is as follows.
- the above photopolymerization initiators are not particularly limited, but include, for example, benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photopolymerization initiators.
- photopolymerization initiators include active oxime photopolymerization initiators, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, thioxanthone photopolymerization initiators, and the like.
- acylphosphine oxide photopolymerization initiators examples include acylphosphine oxide photopolymerization initiators and titanocene photopolymerization initiators.
- benzoin ether photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, Examples include anisole methyl ether.
- Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-(t-butyl ) dichloroacetophenone, etc.
- Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like. It will be done.
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
- Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(O-ethoxycarbonyl)-oxime.
- Examples of the benzoin-based photopolymerization initiator include benzoin.
- Examples of the benzyl-based photopolymerization initiator include benzyl.
- Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and ⁇ -hydroxycyclohexylphenyl ketone.
- Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal.
- Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
- Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like. .
- titanocene photopolymerization initiator examples include bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl). ) titanium, etc.
- a photoinitiator can be used individually or in combination of 2 or more types.
- the amount of the photopolymerization initiator used is not particularly limited, but for example, for 100 parts by weight of all monomer components constituting the acrylic polymer.
- the amount is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and preferably 3 parts by weight or less, and more preferably 1.5 parts by weight or less.
- the adhesive layer of the present invention contains a liquid antistatic agent.
- the antistatic agent imparts antistatic properties to the adhesive layer of the present invention, and the adhesive sheet is peeled off from the image display panel for rework in the event of poor adhesion to the image display panel. This is preferable in that it can suppress the generation of static electricity.
- the configuration in which the antistatic agent is in liquid form can impart an excellent antistatic effect to the adhesive layer of the present invention without impairing the adhesive properties of the adhesive layer of the present invention. This is preferred because it improves the adhesion between the pressure-sensitive adhesive layer and the base material of the present invention and provides excellent thermal shock resistance.
- the above-mentioned liquid antistatic agent is not particularly limited as long as it is a liquid antistatic agent at room temperature (for example, 25°C), and examples thereof include ionic liquids, alkali metal salts, and ionic group-containing silicones. . Since it is possible to impart an excellent antistatic effect to the adhesive layer of the present invention without impairing the adhesive properties of the adhesive layer of the present invention, the adhesive layer of the present invention and the base material of the present invention can be Ionic liquids are preferred because they improve adhesion and provide excellent thermal shock resistance. Note that the liquid antistatic agent can be used alone or in combination of two or more.
- the ionic liquid is a molten salt (ionic compound) that is liquid at room temperature (25° C.). Ionic liquids can be easily added to, dispersed or dissolved in the adhesive layer of the present invention, have easy molecular movement, and are thought to provide excellent antistatic ability without impairing adhesive properties.
- ionic liquid one consisting of an organic cation component represented by the following formulas (A) to (E) and an anion component is preferably used.
- An ionic liquid containing these cations provides an adhesive layer with even better antistatic ability.
- R a in the formula (A) represents a divalent hydrocarbon group having 4 to 20 carbon atoms, and a portion of the hydrocarbon group is a hetero atom (e.g., oxygen atom, nitrogen atom, sulfur atom, etc.). , the same), and R b and R c are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and some of the hydrocarbon groups may be hetero It may also be a functional group substituted with an atom. However, when the nitrogen atom (N) contains a double bond, R c is absent.
- R d in the formula (B) represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and may be a functional group in which a portion of the hydrocarbon group is substituted with a hetero atom
- R e , R f , and R g are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and may be a functional group in which a portion of the hydrocarbon group is substituted with a hetero atom.
- R h in the formula (C) represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and may be a functional group in which a portion of the hydrocarbon group is substituted with a hetero atom
- R i , R j and R k are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and may be a functional group in which a portion of the hydrocarbon group is substituted with a hetero atom.
- Z in the formula (D) represents a nitrogen, sulfur, or phosphorus atom
- R l , R m , R n , and R o are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. , a portion of the hydrocarbon group may be a functional group substituted with a hetero atom. However, when Z is a sulfur atom, R o is not present.
- R P in the formula (E) represents a hydrocarbon group having 1 to 18 carbon atoms, and may be a functional group in which a portion of the hydrocarbon group is substituted with a hetero atom.
- Examples of the cation represented by formula (A) include pyridinium cations, piperidinium cations, pyrrolidinium cations, cations having a pyrroline skeleton, cations having a pyrrole skeleton, and morpholinium cations.
- cation represented by formula (A) include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl- 4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation , 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-Methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation,
- Examples of the cation represented by formula (B) include imidazolium cation, tetrahydropyrimidinium cation, and dihydropyrimidinium cation.
- cation represented by formula (B) include 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-butyl- 3-Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium Cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium Cation, 1-hexyl-2,3-dimethylimidazolium cation, 1-(2-me
- Examples of the cation represented by formula (C) include pyrazolium cations and pyrazolinium cations.
- cation represented by formula (C) include 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-2 , 3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation, 1-ethyl-2,3 , 5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, and 1-butyl-2,3,5-trimethylpyrazolinium cation.
- Examples of the cation represented by formula (D) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a cation in which a portion of the alkyl group is substituted with an alkenyl group, an alkoxyl group, or an epoxy group. You can give things such as
- cation represented by formula (D) include, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium cation.
- tributylethylammonium cation trimethyldecylammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, Hexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium c
- asymmetric cations such as triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, and trimethyldecylphosphonium cation Tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N,N -dimethyl-N-ethyl-N-
- Examples of the cation represented by formula (E) include sulfonium cations. Further, specific examples of R P in the formula (E) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, Examples include octadecyl group.
- the anionic component is not particularly limited as long as it satisfies the ability to form an ionic liquid, such as Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF.
- an anion represented by the following formula (F) can also be used.
- an anion component containing a fluorine atom is particularly preferably used because an ionic liquid with a low melting point can be obtained.
- the ionic liquid preferably contains an anion component having 10 or less fluorine atoms.
- the configuration in which the ionic liquid contains an anion component having 10 or less fluorine atoms is due to the improved compatibility of the ionic liquid with the adhesive layer of the present invention and separation of the ionic liquid from the adhesive layer. This is preferable because it can suppress the increase in haze and improve the visibility of the image display device.
- the number of fluorine atoms contained in the anion component of the ionic liquid is preferably 8 or less. Preferably, six pieces are more preferable.
- the lower limit of the number of fluorine atoms contained in the anion component of the ionic liquid is preferably 4 or more from the viewpoint of obtaining an ionic liquid with a low melting point.
- ionic liquid used in the present invention include appropriately selected combinations of the above-mentioned cationic components and anionic components, such as 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, and 1-butylpyridinium hexafluorophosphate.
- the content of the liquid antistatic agent in the adhesive layer (particularly the acrylic adhesive layer) of the present invention is not particularly limited, but may be used for rework in the event of poor bonding to the image display panel.
- the amount is preferably 0.5 parts by weight or more, more preferably 0.5 parts by weight or more based on 100 parts by weight of the base polymer, from the viewpoint of efficiently suppressing the generation of static electricity when peeling the adhesive sheet from the image display panel. is 1 part by weight or more, more preferably 1.5 parts by weight or more.
- the upper limit of the content of the liquid antistatic agent is not particularly limited, but from the viewpoint of visibility of the image display device, it is preferably 20 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the base polymer. is 15 parts by weight or less.
- the acrylic pressure-sensitive adhesive composition preferably contains, together with the acrylic polymer, an acrylic oligomer having a weight average molecular weight of 1,000 to 30,000. Containing an acrylic oligomer improves the adhesion to the adherend at the interface of the optical pressure-sensitive adhesive sheet of the present invention, making it easier to obtain strong adhesion and excellent foaming and peeling resistance. Become. In this specification, "acrylic oligomer having a weight average molecular weight of 1,000 to 30,000" may be simply referred to as "acrylic oligomer.”
- the acrylic oligomer include acrylic polymers composed of (meth)acrylic esters having a cyclic structure in the molecule as an essential monomer component; More preferred examples include acrylic polymers composed of (meth)acrylic acid alkyl esters having linear or branched alkyl groups as an essential monomer component. That is, the above-mentioned acrylic oligomer is preferably an acrylic polymer containing (meth)acrylic acid ester having a cyclic structure in the molecule as a monomer unit; More preferred examples include acrylic polymers containing esters and (meth)acrylic acid alkyl esters having a linear or branched alkyl group.
- the cyclic structure (ring) of the (meth)acrylic ester (hereinafter sometimes referred to as "ring-containing (meth)acrylic ester") having a cyclic structure within the molecule (within one molecule) is an aromatic ring. , non-aromatic ring, and is not particularly limited.
- the aromatic ring include aromatic carbocycles [for example, monocyclic carbocycles such as benzene ring, fused carbocycles such as naphthalene ring, etc.], various aromatic heterocycles, and the like.
- non-aromatic rings examples include non-aromatic aliphatic rings (non-aromatic alicyclic rings) [for example, cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring]. ; Cycloalkene rings such as cyclohexene rings], non-aromatic bridged rings [e.g., bicyclic hydrocarbon rings in pinane, pinene, bornane, norbornane, norbornene, etc.; tricyclic or more aliphatic hydrocarbons in adamantane, etc. rings (bridged hydrocarbon rings), non-aromatic heterocycles [for example, epoxy rings, oxolane rings, oxetane rings, etc.].
- non-aromatic aliphatic rings non-aromatic aliphatic rings
- non-aromatic aliphatic rings for example, cyclo
- Examples of the tricyclic or more aliphatic hydrocarbon ring include a dicyclopentanyl group represented by the following formula (5a), and a dicyclopentanyl group represented by the following formula (5b).
- Examples include a dicyclopentenyl group represented by the following formula (5c), an adamantyl group represented by the following formula (5d), a tricyclopentanyl group represented by the following formula (5e), etc. .
- examples of the ring-containing (meth)acrylic esters include (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate.
- Acrylic acid cycloalkyl ester having a bicyclic aliphatic hydrocarbon ring such as isobornyl (meth)acrylate; dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth) Tricyclic or more aliphatic groups such as acrylate, tricyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, etc.
- adamantyl (meth)acrylate 2-methyl-2-adamantyl (meth)acrylate
- 2-ethyl-2-adamantyl (meth)acrylate etc.
- (meth)acrylic acid esters having a hydrocarbon ring examples include (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; (meth)acrylic acid aryloxyalkyl esters such as phenoxyethyl (meth)acrylate; Examples include (meth)acrylic esters having an aromatic ring, such as arylalkyl (meth)acrylic esters such as benzyl acrylate.
- the ring-containing (meth)acrylic ester is particularly preferably a non-aromatic ring-containing (meth)acrylic ester, more preferably cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHMA), or acrylic ester.
- a non-aromatic ring-containing (meth)acrylic ester more preferably cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHMA), or acrylic ester.
- these include dicyclopentanyl acid (DCPA) and dicyclopentanyl methacrylate (DCPMA), and more preferably dicyclopentanyl acrylate (DCPA) and dicyclopentanyl methacrylate (DCPMA).
- DCPA dicyclopentanyl acid
- DCPMA dicyclopentanyl methacrylate
- DCPMA dicyclopentanyl methacrylate
- the ring-containing (meth)acrylic esters may be used alone
- (meth)acrylic esters having three or more aliphatic hydrocarbon rings are used. This is particularly preferable in that polymerization inhibition is less likely to occur.
- a dicyclopentanyl group represented by the above formula (5a), an adamantyl group represented by the above formula (5c), and a tricyclopentanyl group represented by the above formula (5d) which do not have an unsaturated bond.
- the content (ratio) of the ring-containing (meth)acrylic acid ester in all monomer units of the acrylic oligomer is not particularly limited, but the total amount of monomer components constituting the acrylic oligomer (100 parts by weight), preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight. It is preferable that the content of the ring-containing (meth)acrylic ester is 10 parts by weight or more, since the foaming peeling resistance is likely to be improved. Moreover, when the content is 90 parts by weight or less, the adhesive layer has appropriate flexibility, and the adhesive strength, level difference absorbency, etc. are easily improved, which is preferable.
- examples of the (meth)acrylic acid alkyl ester having a linear or branched alkyl group as a monomer unit of an acrylic oligomer include methyl (meth)acrylate, ethyl (meth)acrylate, and ) propyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate , isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid Nonyl, isononyl (meth)acrylate, decyl (me)acryl
- (meth)acrylic acid alkyl esters 1 to 20 (meth)acrylic acid alkyl esters, and the like.
- methyl methacrylate (MMA) is preferred because it has good compatibility with acrylic polymers.
- the above (meth)acrylic acid alkyl esters may be used alone or in combination of two or more types.
- the content (ratio) of the (meth)acrylic acid alkyl ester having the linear or branched alkyl group in the total monomer units of the acrylic oligomer is not particularly limited. In terms of foam peeling resistance, it is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, even more preferably 20 to 60 parts by weight, based on the total amount of monomer components (100 parts by weight) constituting the acrylic oligomer. Parts by weight. When the content is 10 parts by weight or more, the adhesion to adherends made of acrylic resin or polycarbonate is particularly likely to be improved, which is preferable.
- the monomer units of the acrylic oligomer can be copolymerized with these monomers.
- monomers (copolymerizable monomers) may be included.
- the content (ratio) of the copolymerizable monomer in all monomer units of the acrylic oligomer is not particularly limited, but The amount is preferably 49.9 parts by weight or less (for example, 0 to 49.9 parts by weight), more preferably 30 parts by weight or less.
- the copolymerizable monomers may be used alone or in combination of two or more types.
- Examples of the above-mentioned copolymerizable monomer as a monomer unit of the acrylic oligomer include (meth)acrylic acid alkoxyalkyl ester [for example, (meth)acrylic acid 2-methoxy Ethyl, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxy (meth)acrylate butyl, 4-ethoxybutyl (meth)acrylate, etc.]; Hydroxyl group-containing monomers [e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.]; - Hydroxyalkyl (meth)acrylates such as hydroxybutyl
- an acrylic oligomer is an acrylic polymer containing a (meth)acrylic acid ester having a cyclic structure in the molecule as a monomer unit and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group. It is preferable that Among these, an acrylic polymer containing a ring-containing (meth)acrylic acid ester and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group as a monomer unit is preferable.
- the total amount of monomer components constituting the acrylic oligomer (100)
- the amount of the ring-containing (meth)acrylic ester is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight.
- the content of the (meth)acrylic acid alkyl ester having a linear or branched alkyl group is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, even more preferably The amount is 20 to 60 parts by weight.
- the monomer units include (1) at least one selected from the group consisting of dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate; Examples include acrylic polymers containing one type of monomer and (2) methyl methacrylate.
- the acrylic oligomer having the above particularly preferred specific structure (1) content of dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate in all monomer units of the acrylic oligomer The amount (total amount if two or more types are included) is 30 to 70 parts by weight based on the total amount (100 parts by weight) of the monomer components constituting the acrylic oligomer. (2) The content of methyl methacrylate is The amount is preferably 30 to 70 parts by weight.
- the acrylic oligomer is not limited to the specific configuration described above.
- the acrylic oligomer can be obtained by polymerizing the above monomer components using a known or commonly used polymerization method.
- the polymerization method for the acrylic oligomer include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method using active energy ray irradiation (active energy ray polymerization method).
- active energy ray polymerization method active energy ray polymerization method
- bulk polymerization methods and solution polymerization methods are preferred, and solution polymerization methods are more preferred.
- solvents When polymerizing the acrylic oligomer, various common solvents may be used.
- the solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane. alicyclic hydrocarbons; organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone. Note that such solvents may be used alone or in combination of two or more.
- a known or commonly used polymerization initiator for example, a thermal polymerization initiator, a photopolymerization initiator, etc.
- a polymerization initiator may be used individually or in combination of 2 or more types.
- thermal polymerization initiator examples include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile (AMBN), and 2,2'-azobis(2- dimethyl (methyl propionate), 4,4'-azobis-4-cyanovalerianic acid, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4- Azo initiators such as dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis(2,4,4-trimethylpentane); benzoyl peroxide, t-butyl Hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1- Examples include peroxide-based initiators such as
- the amount of the thermal polymerization initiator used is not particularly limited, but for example, 0.1 to 15 parts by weight per 100 parts by weight of all monomer units of the acrylic oligomer (total amount of monomer components constituting the acrylic oligomer). It is.
- the photopolymerization initiator is not particularly limited, but includes, for example, the same photopolymerization initiator as the photopolymerization initiator used in the polymerization of the acrylic polymer listed above.
- the amount of the photopolymerization initiator used is not particularly limited and is appropriately selected.
- a chain transfer agent may be used to adjust the molecular weight (specifically, to adjust the weight average molecular weight to 1,000 to 30,000).
- the chain transfer agent include 2-mercaptoethanol, ⁇ -thioglycerol, 2,3-dimercapto-1-propanol, octylmercaptan, t-nonylmercaptan, dodecylmercaptan (laurylmercaptan), t-dodecylmercaptan, glycidyl Mercaptan, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooc
- ⁇ -thioglycerol and methyl thioglycolate are preferred, and ⁇ -thioglycerol is particularly preferred, from the viewpoint of suppressing whitening of the optical pressure-sensitive adhesive sheet of the present invention due to humidification.
- a chain transfer agent may be used individually or in combination of 2 or more types.
- the content (amount used) of the chain transfer agent is not particularly limited, but is 0.1 to 20 parts by weight based on 100 parts by weight of all monomer units of the acrylic oligomer (total amount of monomer components constituting the acrylic oligomer).
- the amount is preferably 0.2 to 15 parts by weight, and even more preferably 0.3 to 10 parts by weight.
- the weight average molecular weight (Mw) of the acrylic oligomer is 1,000 to 30,000, preferably 1,000 to 20,000, more preferably 1,500 to 10,000, and even more preferably 2,000 to 8,000. Since the weight average molecular weight of the acrylic oligomer is 1000 or more, adhesive strength and retention properties are improved, and foaming peeling resistance is improved. On the other hand, since the weight average molecular weight of the acrylic oligomer is 30,000 or less, it is easy to increase the adhesive strength and the foaming peeling resistance is improved.
- the weight average molecular weight (Mw) of the acrylic oligomer can be determined in terms of polystyrene using the GPC method. For example, measurement can be performed using a high-speed GPC device "HPLC-8120GPC" manufactured by Tosoh Corporation under the following conditions. Column: TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000 Solvent: Tetrahydrofuran Flow rate: 0.6ml/min
- the glass transition temperature (Tg) of the acrylic oligomer is not particularly limited, but is preferably 20 to 300°C, more preferably 30 to 300°C, even more preferably 40 to 300°C. It is preferable that the glass transition temperature of the acrylic oligomer is 20° C. or higher because the foaming peeling resistance is likely to be improved. In addition, when the glass transition temperature of the acrylic oligomer is 300°C or lower, the adhesive layer has appropriate flexibility, which makes it easier to obtain good adhesive strength and good level difference absorption, and provides excellent adhesion reliability. This is preferable because it is easier to obtain.
- the glass transition temperature (Tg) of the acrylic oligomer is the glass transition temperature (theoretical value) expressed by the FOX formula.
- Tg of the homopolymer of monomers constituting the acrylic oligomer the values listed in Table 1 below can be adopted.
- Tg of a homopolymer of a monomer not listed in Table 1 the numerical value described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be adopted.
- a value obtained by the above-mentioned measuring method (the peak top temperature of tan ⁇ by a viscoelasticity test) can be adopted.
- the content of the acrylic oligomer is not particularly limited, but is 1 to 30 parts by weight based on 100 parts by weight of the acrylic polymer. It is preferably 2 to 20 parts by weight, and even more preferably 2 to 10 parts by weight. That is, the content of the acrylic oligomer in the pressure-sensitive adhesive composition is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of all monomer units of the acrylic polymer. Parts by weight, more preferably 2 to 10 parts by weight.
- the content of the acrylic oligomer in the acrylic pressure-sensitive adhesive composition is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the monomer mixture.
- the amount is more preferably 2 to 10 parts by weight.
- the content of the acrylic oligomer is 1 part by weight or more, excellent adhesiveness and excellent foaming peeling resistance are easily obtained, which is preferable. Further, it is preferable that the content of the acrylic oligomer is 30 parts by weight or less, since excellent transparency and adhesion reliability can be easily obtained.
- the content of the acrylic oligomer is preferably 10 parts by weight or less, more preferably 8 parts by weight or less.
- an acrylic oligomer and an additive are added to a mixture of monomer components constituting an acrylic polymer or a partial polymer of a mixture of monomer components constituting an acrylic polymer (a monomer mixture forming an acrylic polymer or a partial polymer thereof). etc. are added as necessary and mixed.
- the adhesive layer of the present invention is not particularly limited, but preferably contains an ultraviolet absorber (UVA). It is preferable that the adhesive layer of the present invention contains an ultraviolet absorber because damage to the image display panel caused by ultraviolet rays can be suppressed. Note that the ultraviolet absorbers can be used alone or in combination of two or more.
- UVA ultraviolet absorber
- UV absorbers are not particularly limited, but include, for example, benzotriazole-based UV absorbers, hydroxyphenyltriazine-based UV absorbers, benzophenone-based UV absorbers, salicylic acid ester-based UV absorbers, cyanoacrylate-based UV absorbers, and Examples include benzophenone ultraviolet absorbers.
- benzotriazole-based ultraviolet absorbers examples include 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (trade name "TINUVIN PS", manufactured by BASF), benzene Ester compound of propanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and straight chain alkyl) (trade name "TINUVIN 384”) -2'', manufactured by BASF), octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[ Mixture of 3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2yl)phenyl]propionate (trade name "TINUVIN 109", manufactured by BASF), 2-
- hydroxyphenyltriazine-based ultraviolet absorbers examples include 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5 - Reaction product of hydroxyphenyl and [(C10-C16 (mainly C12-C13) alkyloxy)methyl]oxirane (trade name "TINUVIN 400", manufactured by BASF), 2-[4,6-bis(2, 4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol), 2-(2,4-dihydroxyphenyl)-4, Reaction product of 6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester (trade name "TINUVIN 405", manufactured by BASF), 2,4 -bis(2-hydroxy-4-butoxyphenyl)
- benzophenone ultraviolet absorbers (benzophenone compounds) and oxybenzophenone ultraviolet absorbers (oxybenzophenone compounds)
- examples of benzophenone ultraviolet absorbers (benzophenone compounds) and oxybenzophenone ultraviolet absorbers (oxybenzophenone compounds) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4- Methoxybenzophenone-5-sulfonic acid (anhydride and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'- Dihydroxy-4-methoxybenzophenone (trade name "KEMISORB 111", manufactured by Chemipro Kasei Co., Ltd.), 2,2',4,4'-tetrahydroxybenzophenone (trade name "SEESORB 106", manufactured by Cipro Kasei Co., Ltd.) , 2,2'-dihydroxy-4
- salicylic acid ester ultraviolet absorbers examples include phenyl 2-acryloyloxybenzoate, phenyl 2-acryloyloxy-3-methylbenzoate, phenyl 2-acryloyloxy-4-methylbenzoate, and phenyl 2-acryloyloxybenzoate.
- cyanoacrylate ultraviolet absorber examples include alkyl 2-cyanoacrylate, cycloalkyl 2-cyanoacrylate, alkoxyalkyl 2-cyanoacrylate, alkenyl 2-cyanoacrylate, alkynyl 2-cyanoacrylate, and the like. Can be mentioned.
- the above-mentioned ultraviolet absorber has high ultraviolet absorption, improves corrosion resistance (especially UV resistance), has excellent optical properties, and is easy to obtain an adhesive layer with high transparency.
- at least one type of UV absorber selected from the group consisting of benzotriazole-based UV absorbers, benzophenone-based UV absorbers, and hydroxyphenyltriazine-based UV absorbers is preferred; More preferred are triazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers.
- Particularly preferred are benzotriazole ultraviolet absorbers in which a group having 6 or more carbon atoms and a phenyl group having a hydroxyl group as a substituent are bonded to the nitrogen atom constituting the benzotriazole ring.
- the above-mentioned ultraviolet absorber preferably has an absorbance A of 0.5 or less as determined below in order to obtain higher ultraviolet absorbency and further improve corrosion resistance (particularly UV resistance).
- Absorbance A Absorbance measured by applying light with a wavelength of 400 nm to a 0.08% toluene solution of the ultraviolet absorber.
- the content of the ultraviolet absorber in the adhesive layer of the present invention is not particularly limited, but corrosion resistance (especially , UV resistance), it is preferably 0.01 part by weight or more, more preferably 0.05 part by weight or more, and still more preferably 0.01 part by weight or more, based on 100 parts by weight of the base polymer. It is 1 part by weight or more.
- the upper limit of the content of the ultraviolet absorber is set at the point where the yellowing phenomenon of the adhesive due to the addition of the ultraviolet absorber is suppressed, and excellent optical properties, high transparency, and excellent appearance characteristics are obtained. Therefore, it is preferably 10 parts by weight or less, more preferably 9 parts by weight or less, and even more preferably 8 parts by weight or less, based on 100 parts by weight of the base polymer.
- the adhesive layer of the present invention may contain a light stabilizer.
- a light stabilizer When the adhesive layer of the present invention contains a light stabilizer, it is particularly preferable to contain the light stabilizer together with the ultraviolet absorber. Since the light stabilizer can capture radicals generated by photo-oxidation, it can improve the resistance of the adhesive layer to light (particularly ultraviolet light).
- a light stabilizer can be used individually or in combination of 2 or more types.
- the above-mentioned light stabilizers are not particularly limited, but include, for example, phenolic light stabilizers (phenol compounds), phosphorus light stabilizers (phosphorus compounds), thioether light stabilizers (thioether compounds), and amine light stabilizers (thioether compounds).
- phenol compounds phenol compounds
- phosphorus light stabilizers phosphorus compounds
- thioether light stabilizers thioether compounds
- amine light stabilizers thioether compounds
- examples include stabilizers (amine compounds) (particularly hindered amine light stabilizers (hindered amine compounds)).
- phenolic light stabilizer examples include 2,6-di-tertiary butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tertiary butylphenol, 2, 6-di-tert-butyl-4-ethylphenol, butylated hydroxyanisole, n-octadecyl 3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate, distearyl (4-hydroxy- 3-methyl-5-tert-butyl)benzyl malonate, tocopherol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), tertiary butylphenol), 4,4'-methylenebis(2,6-di-tertiary butylphenol), 4,4'-butylidenebis(6-tertiary butyl-m-cresol), 4,4'
- Examples of phosphorus-based light stabilizers include trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris[2-tert-butyl-4-( 3-tertiary butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl) monophenyl phosphite, di(tridecyl) penta Erythritol diphosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tertiary butylphenyl) pentaerythritol diphosphit
- thioether light stabilizers examples include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl; polyol ⁇ such as tetrakis[methylene(3-dodecylthio)propionate]methane; -Alkylmercaptopropionic acid ester compounds and the like.
- amine light stabilizer for example, a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol (trade name "TINUVIN 622", BASF ), a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and N,N',N'',N''-tetrakis-(4, 6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine and (trade name "TINUVIN 119", manufactured by BASF), dibutylamine/1,3-triazine/N,N'-bis(2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidy
- the content of the light stabilizer in the adhesive layer of the present invention is not particularly limited, but the content of the light stabilizer is not particularly limited.
- the amount is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, based on 100 parts by weight of the base polymer.
- the upper limit of the above content should be 5 parts by weight or less based on 100 parts by weight of the base polymer, from the viewpoint of preventing coloring by the light stabilizer itself, making it easy to obtain high transparency, and from the viewpoint of optical properties. is preferable, and more preferably 3 parts by weight or less.
- a crosslinking agent may be used in forming the adhesive layer of the present invention.
- the gel fraction can be controlled by crosslinking the acrylic polymer in the acrylic adhesive layer.
- a crosslinking agent can be used individually or in combination of 2 or more types.
- crosslinking agents mentioned above are not particularly limited, but include, for example, isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, and metal chelate crosslinking agents.
- examples include crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, and amine crosslinking agents.
- isocyanate-based crosslinking agents and epoxy-based crosslinking agents are preferred, and isocyanate-based crosslinking agents are more preferred.
- isocyanate crosslinking agent polyfunctional isocyanate compound
- examples of the isocyanate crosslinking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate; , cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and other alicyclic polyisocyanates; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and aromatic polyisocyanates such as xylylene diisocyanate.
- lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diiso
- examples of the isocyanate-based crosslinking agent include trimethylolpropane/tolylene diisocyanate adduct (product name "Coronate L", manufactured by Nippon Polyurethane Industries, Ltd.), trimethylolpropane/hexamethylene diisocyanate adduct (product name Commercially available products such as “Coronate HL” (manufactured by Nippon Polyurethane Industries, Ltd.) and trimethylolpropane/xylylene diisocyanate adduct (trade name "Takenate D-110N", manufactured by Mitsui Chemicals, Ltd.) can also be mentioned.
- epoxy crosslinking agent examples include N,N,N',N'-tetraglycidyl-m-xylene diamine, diglycidylaniline, 1,3-bis(N,N-diglycidyl (aminomethyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether , glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether,
- the amount of the crosslinking agent used is not particularly limited, but from the viewpoint of obtaining sufficient adhesion reliability, it is 0.000 parts by weight based on 100 parts by weight of the base polymer. It is preferably at least 0.001 part by weight, more preferably at least 0.01 part by weight.
- the upper limit of the amount used is determined in order to obtain appropriate flexibility in the adhesive layer and improve adhesive strength, and to control the above-mentioned properties of the adhesive layer (in particular, level difference absorption) within a predetermined range. From the viewpoint of simplicity, the amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the base polymer.
- the adhesive layer (especially the acrylic adhesive layer) of the present invention contains a silane coupling agent in order to improve the adhesive reliability under humid conditions, especially to improve the adhesive reliability to glass. You can. Note that the silane coupling agents can be used alone or in combination of two or more. When the pressure-sensitive adhesive layer contains a silane coupling agent, the adhesiveness under humid conditions, especially the adhesiveness to glass, can be improved.
- silane coupling agent is not particularly limited, but examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N-phenyl-aminopropyltrimethoxysilane, Examples include methoxysilane.
- examples of the silane coupling agent include commercially available products such as the trade name "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, ⁇ -glycidoxypropyltrimethoxysilane is preferred as the silane coupling agent.
- the content of the silane coupling agent in the adhesive layer of the present invention is not particularly limited, but the content of the silane coupling agent as described above is not particularly limited. It is preferably 0.01 part by weight or more, more preferably 0.02 part by weight or more, based on 100 parts by weight of the base polymer. Further, the upper limit of the content of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.5 part by weight or less, based on 100 parts by weight of the base polymer.
- the adhesive layer of the present invention may contain a colorant.
- the colorants can be used alone or in combination of two or more.
- the pressure-sensitive adhesive layer contains a coloring agent since it is possible to prevent reflections caused by metal wiring, ITO wiring, etc. disposed on the substrate of the image display device of the present invention.
- the colorant may be a dye or a pigment as long as it can be dissolved or dispersed in the adhesive layer of the present invention.
- Dyes are preferred because they can achieve low haze even when added in small amounts, and are easy to distribute uniformly without settling unlike pigments.
- Pigments are also preferred because they provide high color development even when added in small amounts. If a pigment is used as a coloring agent, it is preferably one with low or no electrical conductivity. Moreover, when using a dye, it is preferable to use it together with the above-mentioned light stabilizer.
- the colorant is not limited to those that are transparent to ultraviolet rays (wavelength 330 to 400 nm) or those that are absorbent to ultraviolet rays, as long as they absorb visible light (wavelength 400 to 700 nm). Although any material can be used, those that absorb visible light and are transparent to ultraviolet light are preferred. That is, the colorant preferably has a maximum value of transmittance in the wavelength range of 330 to 400 nm that is larger than a maximum value of transmittance in the wavelength range of 400 to 700 nm. Further, it is preferable that the colorant has an average transmittance in the wavelength range of 330 to 400 nm that is larger than that in the wavelength range of 400 to 700 nm.
- the transmittance of the colorant is determined by using an appropriate solvent or dispersion medium (an organic solvent with low absorption in the wavelength range of 330 to 700 nm) such as tetrahydrofuran (THF) so that the transmittance at a wavelength of 400 nm is about 50 to 60%. Measure using a diluted solution or dispersion.
- an appropriate solvent or dispersion medium an organic solvent with low absorption in the wavelength range of 330 to 700 nm
- THF tetrahydrofuran
- Carbon black and titanium black which are commonly used as black colorants, absorb more ultraviolet light than visible light (their ultraviolet transmittance is lower than their visible light transmittance). Therefore, when a colorant such as carbon black is added to an active energy ray-curable acrylic adhesive composition, most of the ultraviolet rays irradiated for photocuring are absorbed by the colorant, and the amount of light absorbed by the photopolymerization initiator is small and takes time to photocure (integrated amount of irradiation light increases). Furthermore, when the adhesive layer is thick, less ultraviolet rays reach the surface opposite to the light irradiation surface, so even if light irradiation is performed for a long time, photocuring tends to be insufficient. On the other hand, by using a colorant that has a higher transmittance for ultraviolet light than visible light, curing inhibition caused by the colorant can be suppressed.
- ultraviolet-transparent black pigments examples include “9050BLACK” and “UVBK-0001” manufactured by Tokushiki.
- examples of the ultraviolet absorbing black dye include “VALIFAST BLACK 3810” and “NUBIAN Black PA-2802” manufactured by Orient Chemical Industry Co., Ltd.
- Examples of ultraviolet absorbing black pigments include carbon black and titanium black.
- the content of the colorant in the adhesive layer of the present invention is, for example, about 0.01 to 20 parts by weight based on 100 parts by weight of the base polymer, and depends on the type of colorant, the color tone of the adhesive layer, and the light intensity. What is necessary is just to set it suitably according to transmittance
- the colorant may be added to the composition as a solution or dispersion dissolved or dispersed in a suitable solvent.
- the adhesive layer of the present invention may further contain a crosslinking accelerator, a tackifier resin (rosin derivative, polyterpene resin, petroleum resin, oil-soluble
- the haze of the adhesive layer of the present invention is not particularly limited, but from the viewpoint of appearance characteristics, transparency, and optical properties, it is preferably 1% or less, more preferably 0.8% or less, and even more preferably 0.5%. % or less.
- the haze of an adhesive layer can be measured according to JISK7136 using a haze meter, for example.
- the visible light transmittance of the adhesive layer of the present invention is not particularly limited, but from the viewpoint of appearance characteristics, transparency, and optical properties, it is preferably 90% or more, more preferably 90.5% or more, and even more preferably It is 91% or more.
- the visible light transmittance of the adhesive layer can be measured according to JIS K 7361-1 using, for example, a haze meter. Note that the above visible light transmittance is the transmittance of light (visible light) with a wavelength of 400 to 780 nm.
- the thickness of the adhesive layer of the present invention is not particularly limited, but from the viewpoint of obtaining sufficient adhesion reliability, it is preferably 12 ⁇ m or more, preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, particularly preferably 25 ⁇ m or more. . It is preferable that the thickness is 12 ⁇ m or more because the adhesive layer can sufficiently follow the contraction or expansion in the usage environment of the image display device of the present invention, suppressing lifting and peeling, and having excellent level difference absorbability. Moreover, from the point of optical properties, the above-mentioned thickness is preferably 500 ⁇ m or less, preferably 300 ⁇ m or less, and more preferably 200 ⁇ m or less.
- optical pressure-sensitive adhesive sheet of the present invention can be prepared by laminating the pressure-sensitive adhesive layer of the present invention on the first surface of the base material of the present invention.
- the method for laminating the adhesive layer of the present invention on the first surface of the base material of the present invention is not particularly limited.
- a release liner is further attached to the surface of the coating film, and the adhesive composition is irradiated with active energy rays while being sandwiched between two release liners to remove oxygen. It is preferable to prevent polymerization inhibition caused by.
- Another method for laminating the adhesive layer of the present invention on the first surface of the substrate of the present invention is, for example, applying (coating) the above-mentioned adhesive composition onto the first surface of the substrate of the present invention. , by drying and curing the obtained adhesive composition layer, or by applying (coating) the above-mentioned adhesive composition on the first surface of the substrate of the present invention, and applying an active layer to the obtained adhesive composition layer. It can also be cured by irradiating energy rays. Moreover, if necessary, it may be further dried by heating.
- a release liner is attached to the surface of the coating film, and the active energy rays are irradiated with the adhesive composition sandwiched between the base material of the present invention and the release liner. It is preferable to prevent inhibition of polymerization by oxygen.
- the sheet-like coating film Before irradiation with active energy rays, the sheet-like coating film may be heated for the purpose of removing the solvent, etc. When removing the solvent and the like by heating, it is preferable to remove the solvent before attaching the release liner.
- the active energy rays include ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron beams, and electron beams, and ultraviolet rays, with ultraviolet rays being particularly preferred.
- the irradiation energy, irradiation time, irradiation method, etc. of the active energy rays are not particularly limited.
- the above-mentioned pressure-sensitive adhesive composition can be produced by a known or commonly used method.
- a solvent-based acrylic pressure-sensitive adhesive composition can be prepared by mixing a liquid antistatic agent and, if necessary, additives (such as an ultraviolet absorber) into a solution containing the acrylic polymer.
- additives such as an ultraviolet absorber
- an active energy ray-curable acrylic pressure-sensitive adhesive composition includes a mixture of the acrylic monomers or a partial polymer thereof, a liquid antistatic agent, and, if necessary, additives (such as an ultraviolet absorber). ) can be prepared by mixing.
- a known coating method may be used to apply (coating) the above-mentioned pressure-sensitive adhesive composition.
- coaters such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater may be used.
- the active energy ray-curable adhesive composition when forming an adhesive layer using an active energy ray-curable adhesive composition, it is preferable that the active energy ray-curable adhesive composition contains a photopolymerization initiator.
- the active energy ray-curable pressure-sensitive adhesive composition contains an ultraviolet absorber, it is preferable to include at least a photopolymerization initiator having light absorption characteristics in a wide wavelength range. For example, it is preferable to include at least a photopolymerization initiator that has absorption characteristics not only for ultraviolet light but also for visible light.
- the adhesive composition contains a photoinitiator that has light-absorbing properties over a wide wavelength range, the adhesive composition will have high photocurability. This is because it is easier to obtain.
- the optical pressure-sensitive adhesive sheet of the present invention may have an antistatic layer on the surface or between arbitrary layers. Since the optical adhesive sheet of the present invention has an antistatic layer, generation of static electricity is suppressed when the adhesive sheet is peeled off from the image display panel for rework in the event of poor adhesion to the image display panel. This is preferable in that it can be done.
- the antistatic layer is preferably formed between the base material of the present invention and the adhesive layer of the present invention.
- the antistatic layer is not particularly limited, but is, for example, an antistatic layer formed by coating a release liner with a conductive coating liquid containing a conductive polymer. Specifically, for example, it is an antistatic layer formed by coating the first surface of the base material of the present invention with a conductive coating liquid containing a conductive polymer. Specific coating methods include roll coating, bar coating, and gravure coating.
- Examples of the conductive polymer include a conductive polymer in which a ⁇ -conjugated conductive polymer is doped with a polyanion.
- Examples of the ⁇ -conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene.
- Examples of the polyanion include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyethyl acrylate sulfonic acid, and polymethacrylic carboxylic acid.
- the thickness of the antistatic layer is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm.
- the antistatic layer may have only one layer, or may have two or more layers.
- the surface of the pressure-sensitive adhesive layer of the present invention may be protected by a release liner until use.
- the release liner is used as a protective material for the adhesive layer, and is peeled off when the optical adhesive sheet of the present invention is applied to an adherend.
- a conventional release paper or the like can be used, and specifically, in addition to a base material having a release treatment layer formed by a release agent on at least one surface, fluorine-based polymers (such as polytetrafluorocarbon ethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.), and non-polar
- a low adhesive base material made of a polymer for example, an olefin resin such as polyethylene or polypropylene
- a release liner in which a release treatment layer is formed on at least one surface of a release liner base material can be suitably used.
- base materials for release liners include polyester films (polyethylene terephthalate films, etc.), olefin resin films (polyethylene films, polypropylene films, etc.), polyvinyl chloride films, polyimide films, polyamide films (nylon films), and rayon films.
- plastic base films synthetic resin films
- synthetic resin films such as (composite of two to three layers).
- the release agent constituting the release layer is not particularly limited, and for example, a silicone release agent, a fluorine release agent, a long chain alkyl release agent, or the like can be used.
- the release agent can be used alone or in combination of two or more.
- the thickness of the release liner is not particularly limited, and may be appropriately selected from the range of 5 to 100 ⁇ m.
- an antistatic layer may be formed on at least one surface of the release liner base material in order to prevent damage to adherends such as image display panels.
- the antistatic layer may be formed on one side (release treated side or untreated side) of the release liner, or may be formed on both sides (release treated side and untreated side) of the release liner.
- the antistatic layer is not particularly limited, but is, for example, an antistatic layer formed by coating a release liner with a conductive coating liquid containing a conductive polymer. Specifically, for example, it is an antistatic layer formed by coating a release liner (release treated surface and/or untreated surface) with a conductive coating liquid containing a conductive polymer. Specific coating methods include roll coating, bar coating, and gravure coating.
- the same conductive polymer as the conductive polymer constituting the antistatic layer constituting the optical pressure-sensitive adhesive sheet of the present invention described above can be used.
- the thickness of the antistatic layer is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm.
- the antistatic layer may have only one layer, or may have two or more layers.
- the second surface of the base material of the present invention may be protected by a surface protection film.
- the surface protection film is used as a protective material for the second surface of the base material of the present invention during manufacturing and transportation of the optical pressure-sensitive adhesive sheet of the present invention and the image display device of the present invention.
- Materials for forming the surface protection film include ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene, polyamide resins, polycarbonate resins, and copolymers thereof. Examples include resin. Ester resins (especially polyethylene terephthalate resins) are preferred.
- the thickness of the surface protection film is typically 20 ⁇ m to 250 ⁇ m, preferably 30 ⁇ m to 150 ⁇ m.
- the surface protection film is releasably bonded to the second surface of the base material of the present invention via any suitable adhesive.
- a surface protection film on which an adhesive layer is formed is formed, and this is bonded to the second surface of the substrate of the invention of the optical adhesive sheet of the invention.
- the adhesive used for laminating the surface protection film has a base resin such as acrylic resin, styrene resin, or silicone resin, and the base resin is selected from isocyanate compounds, epoxy compounds, aziridine compounds, etc. Examples include adhesive compositions containing a crosslinking agent, a silane coupling agent, and the like.
- the thickness of the adhesive layer is usually 1 ⁇ m to 60 ⁇ m, preferably 3 ⁇ m to 30 ⁇ m.
- the adhesive layer is too thin, problems such as decreased adhesiveness and easy inclusion of air bubbles may occur, while if it is too thick, problems such as the adhesive extruding may occur.
- acrylic adhesives are preferably used.
- the image display device of the present invention has a laminated structure in which the optical pressure-sensitive adhesive sheet of the present invention and an image display panel are laminated.
- an image display panel 4 is laminated on the adhesive layer 1 of the optical adhesive sheet 10B.
- the adhesive sheet of the present invention Since the image display device of the present invention has the optical adhesive sheet of the present invention in the laminated structure, the adhesive sheet is peeled off from the image display panel in order to rework when a bonding failure to the image display panel occurs. This is preferable in that it is possible to suppress the generation of static electricity and to suppress damage to the image display panel. Furthermore, since it is possible to impart an excellent antistatic effect to the adhesive layer of the present invention without impairing the adhesive properties of the adhesive layer of the present invention, the adhesive layer of the present invention and the base material of the present invention can be It is also suitable because it improves adhesion and provides excellent thermal shock resistance.
- the adhesive layer of the present invention maintains excellent antistatic effects even in harsh environments such as thermal shock, and can be repaired in the event of a malfunction such as a light emitting element not lighting up under the usage environment of an image display device.
- This is preferable in that it can suppress the generation of static electricity when the adhesive sheet is peeled off from the image display panel.
- the adhesive layer of the present invention sufficiently follows the contraction or expansion of the image display device, and is less likely to lift or peel off.
- the adhesive layer of the present invention can sufficiently follow the level difference and fill it without leaving any air bubbles. Excellent in
- the image display panel is not particularly limited, but includes, for example, a liquid crystal image display panel, a self-luminous image display panel (for example, an organic EL (electroluminescence) image display panel, an LED image display panel), and the like.
- a liquid crystal image display panel for example, a liquid crystal image display panel, a self-luminous image display panel (for example, an organic EL (electroluminescence) image display panel, an LED image display panel), and the like.
- the image display panel is formed by alternately arranging RGB elements, and in order to improve contrast, it is preferable that a black matrix (BM) be filled between the RGB elements.
- BM black matrix
- the image display device of the present invention may include an optical member other than the optical pressure-sensitive adhesive sheet of the present invention and the image display panel on the surface or between arbitrary layers.
- the optical member include, but are not particularly limited to, a polarizing plate, a retardation plate, an antireflection film, a viewing angle adjustment film, an optical compensation film, and the like.
- the above-mentioned optical members also include members (design films, decorative films, surface protection plates, etc.) that play the role of decoration and protection while maintaining the visibility of the image display device and input device.
- the image display device of the present invention can be manufactured by bonding the image display panel and the adhesive layer of the optical adhesive sheet of the present invention.
- the image display panel and the optical adhesive sheet of the present invention can be attached by laminating them under heat and/or pressure. After lamination under heating and/or pressure, curing may be performed by irradiating active energy rays. Irradiation with active energy rays can be performed in the same manner as in the formation of the adhesive layer of the present invention.
- the tiling display of the present invention is formed by arranging a plurality of image display devices of the present invention.
- the tiling display 30 is formed by arranging nine image display devices 20 (the stacked structure is not shown) in a 3 ⁇ 3 arrangement on a support substrate 31 in the form of tiles. They are in contact with each other with a gap 32.
- a glass plate or a plastic film similar to the base material of the present invention can be used.
- the image display device of the present invention is suppressed from shrinking or expanding under the usage environment, gaps and overlaps are less likely to occur between the plurality of image display devices in the tiling display of the present invention, gaps are less noticeable, and good performance is achieved. Appearance is maintained. Furthermore, there is little shrinkage or expansion, and transparency can be maintained without change. Further, the adhesive layer of the present invention can sufficiently follow the contraction or expansion of the image display device, and can prevent problems caused by lifting or peeling.
- the metal wiring arranged on the substrate of the image display device of the present invention is preferable in that it can prevent reflections caused by ITO wiring and the like.
- the gap between the image display devices of the present invention is preferable in that it becomes difficult to visually recognize the gap.
- the tiling display of the present invention may include members other than the image display device of the present invention and the support substrate.
- Such members include, but are not limited to, backlights, touch sensors, and the like.
- the tiling display of the present invention can be manufactured by arranging a plurality of image display devices of the present invention on the support substrate without gaps, and fixing them by sealing the outermost surface with glass or the like.
- acrylic adhesive composition 1 The (meth)acrylic polymer solution 1 (30% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of this solution (solid content 100 parts by mass) was added with an epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd.). 0.075 parts by mass (solid content 0.075 parts by mass) ), 3 parts by mass (actual amount: 3 parts by mass) of a liquid antistatic agent (manufactured by Nippon Carlit Co., Ltd., trade name "CIL312", 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide) were added. Thereafter, mixing and stirring were performed to prepare acrylic adhesive composition 1 (acrylic adhesive solution).
- the acrylic adhesive composition 1 was applied to the surface of a 75 ⁇ m thick polyethylene terephthalate film (PET film, transparent base material, release liner) treated with a silicone release agent, air-dried for 3 minutes, and then heated at 145°C. was heated for 90 seconds to form an adhesive layer 1 with a thickness of 50 ⁇ m.
- PET film polyethylene terephthalate film
- the non-glare layer side of an anti-glare film manufactured by DNP Corporation, trade name "DSG23", PET film
- DSG23 anti-glare layer formed on one side
- This laminate was photocured by irradiating ultraviolet rays from a black light whose position was adjusted so that the irradiation intensity on the irradiation surface directly under the lamp was 5 mW/cm 2 from the cover sheet side, and a 50 ⁇ m thick adhesive layer was formed. I got 3.
- Adhesive sheet 3 An anti-glare film (manufactured by DNP Corporation, product name "DSG23") in which an anti-glare layer was formed on one side of the adhesive surface exposed by peeling one release liner from the adhesive layer 3 obtained above, The non-antiglare layer surfaces of the PET film) were bonded together to obtain an adhesive sheet 3 consisting of an antiglare film/adhesive layer 3/release liner.
- Example 4 Except that 3 parts by mass of 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. under the trade name "IL220", was used as a liquid antistatic agent. In the same manner as in Example 3, a pressure-sensitive adhesive sheet 4 consisting of an anti-glare film/adhesive layer 4/release liner was obtained.
- IL220 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide
- Example 5 Example 3 except that 3 parts by mass of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, manufactured by Nippon Carlit Co., Ltd. under the trade name "CIL612", was used as the liquid antistatic agent. In the same manner, an adhesive sheet 5 consisting of an anti-glare film/adhesive layer 5/release liner was obtained.
- Example 6 Same as Example 1 except that 2 parts by mass of 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, manufactured by Nippon Carlit Co., Ltd., trade name "CIL312", was used as a liquid antistatic agent.
- CIL312 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, manufactured by Nippon Carlit Co., Ltd., trade name "CIL312”
- a pressure-sensitive adhesive sheet 6 consisting of an anti-glare film/adhesive layer 6/release liner was obtained.
- Example 7 Same as Example 1 except that 5 parts by mass of 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, manufactured by Nippon Carlit Co., Ltd., trade name "CIL312", was used as a liquid antistatic agent. Thus, a pressure-sensitive adhesive sheet 7 consisting of an anti-glare film/adhesive layer 7/release liner was obtained.
- Example 8 Same as Example 1 except that 10 parts by mass of 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, manufactured by Nippon Carlit Co., Ltd., trade name "CIL312", was used as a liquid antistatic agent.
- CIL312 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, manufactured by Nippon Carlit Co., Ltd., trade name "CIL312”
- a pressure-sensitive adhesive sheet 8 consisting of an anti-glare film/adhesive layer 8/release liner was obtained.
- Example 1 except that 0.1 part by mass of 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, manufactured by Nippon Carlit Co., Ltd. under the trade name "CIL312", was used as a liquid antistatic agent.
- a pressure-sensitive adhesive sheet 9 consisting of an anti-glare film/adhesive layer 9/release liner was obtained.
- ⁇ Comparative example 2> The antistatic agent was prepared in the same manner as in Example 1, except that 3 parts by mass of lithium bis(trifluoromethanesulfonyl)imide, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. under the trade name "LiTFSI", was used as the solid antistatic agent.
- An adhesive sheet 10 consisting of a glare film/adhesive layer 10/release liner was obtained.
- the hardness H is calculated by the following formula (1) from the applied load (maximum load P max ) when the indenter is pushed to the above-mentioned indentation depth and the contact area (contact projected area Ac) between the indenter and the sample at that time. did.
- b * after the thermal shock test after subjecting the test piece prepared as above to the above thermal shock test, it was left in an environment at a temperature of 23°C and a relative humidity of 50% for more than 2 hours, and then measured using a simple spectrophotometer. (Product name: "DOT-3C", manufactured by Murakami Color Research Institute Co., Ltd.). The difference in b * after the thermal shock test ( ⁇ b * ) was obtained by subtracting the b * before the thermal shock test from the b * after the thermal shock test.
- Adhesive force to acrylic plate and peeling charge amount [Method for measuring adhesive force to acrylic plate]
- an acrylic plate manufactured by Mitsubishi Rayon Co., Ltd., trade name "Acrylite", thickness: 1 mm
- the adhesive sheet obtained in each Example and Comparative Example was cut into a size of 25 mm in width and 100 mm in length, and the adhesive surface thereof was pressed onto the above-mentioned acrylic plate at a pressure of 0.25 MPa and a speed of 0.3 m/min. .
- the adhesive sheet obtained in each example and comparative example was cut into a size of 25 mm in width and 80 mm in length, and after peeling off the release liner, an acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., product name: Light", thickness: 1 mm, width: 25 mm, length: 70 mm), and one end of the adhesive sheet protruded 10 mm from the edge of the acrylic plate, and was crimped using a hand roller. After this sample was left in an environment of 23° C. and 50% RH for one day, it was set on a sample fixing table with a height of 20 mm.
- the end of the adhesive sheet that protruded by 10 mm from the acrylic plate was fixed to an automatic winder and peeled off at a peeling angle of 150° and a peeling speed of 5 m/min.
- the potential on the surface of the adherend (acrylic plate) generated at this time was measured using a potential measuring device (manufactured by Kasuga Denki, model "KSD-0103") fixed at a height of 100 mm from the center of the acrylic plate. , and the peeling voltage was measured. The measurement was performed in an environment of 23° C. and 50% RH.
- the adhesive layer contains a liquid antistatic agent,
- the adhesive layer has a surface resistance value of less than 10 ⁇
- An optical pressure-sensitive adhesive sheet having a haze of 1% or less after the following thermal shock test. ⁇ Thermal Shock Test The optical adhesive sheet was subjected to a thermal shock test in which one cycle consisted of exposing it to an atmosphere of -40°C for 30 minutes, and then exposing it to an atmosphere of 80°C for 30 minutes. Give 200 cycles using a machine.
- Appendix 8 An image display device in which the optical adhesive sheet according to any one of Appendices 1 to 7 and an image display panel are laminated.
- Appendix 9 A tiling display in which a plurality of image display devices according to Appendix 8 are arranged side by side.
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Abstract
Description
・熱衝撃試験
本発明の光学用粘着シートに対し、-40℃の雰囲気下に30分曝露し、続いて、80℃の雰囲気下に30分曝露することを1サイクルとした熱衝撃を、熱衝撃試験機を用いて200サイクル分与える。
|Log10B-Log10A|
A:熱衝撃試験前の表面抵抗値
B:熱衝撃試験後の表面抵抗値
本発明の画像表示装置は、本発明の光学用粘着シートを積層構造中に有するため、画像表示パネルへの貼り合わせ不良が生じた場合にリワークするために、粘着シートを画像表示パネルから剥離する際の静電気の発生を抑制することができる点で、好適である。また、熱衝撃により、粘着シートと画像表示パネルとの界面に空隙が生じたり、粘着シートのヘイズが上昇して、画像表示装置の視認性が経時的に低下することを防止できる点で、好適である。
図1において、光学用粘着シート10Aは、基材1と、粘着剤層2とが積層された積層構造を有する。基材1は、第1面1aおよび第2面1bを有し、基材1の第1面1aに粘着剤層2が積層されている。
以下、各構成について説明する。
本発明の光学用粘着シートにおける「光学」とは、光学用途に用いられることを意味し、より具体的には、光学部材が用いられた製品(光学製品)の製造などに用いられることを意味する。光学製品としては、例えば、画像表示装置、タッチパネルなどの入力装置などが挙げられるが、液晶画像表示装置、自発光型画像表示装置(例えば、有機EL(エレクトロルミネッセンス)画像表示装置、LED画像表示装置)などの製造に好適に使用することができる。特に、本発明の光学用粘着シートは、自発光型画像表示装置の製造に適する。
・熱衝撃試験
本発明の光学用粘着シートに対し、-40℃の雰囲気下に30分曝露し、続いて、80℃の雰囲気下に30分曝露することを1サイクルとした熱衝撃を、熱衝撃試験機を用いて200サイクル分与える。
本発明の基材を構成する素材としては、ガラスやプラスチックフィルム等があげられる。前記プラスチックフィルムとしては、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)等のポリエステル系樹脂、環状オレフィン系ポリマー(COP)(例えば、商品名「アートン」(JSR(株)製)、商品名「ゼオノア」(日本ゼオン(株)製)等)、ポリメチルメタクリレート(PMMA)等のアクリル系樹脂、ポリカーボネート(PC)、トリアセチルセルロース(TAC)、ポリサルフォン、ポリアリレート、ポリエーテルエーテルケトン(PEEK)、ポリイミド(PI)、透明ポリイミド(CPI)、ポリ塩化ビニル、ポリ酢酸ビニル、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体などのプラスチック材料が挙げられ、寸法安定性に優れ、収縮しにくいポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)等のポリエステル系樹脂、環状オレフィン系ポリマー(COP)、ポリカーボネート(PC)、ポリエーテルエーテルケトン(PEEK)、透明ポリイミド(CPI)が好ましい。なお、これらのプラスチック材料は、単独で又は2種以上を組み合わせて用いることができる。本発明の基材は、本発明の光学用粘着シートを被着体(画像表示パネル等)に貼付する際に、粘着剤層とともに被着体に貼付される部分である。本発明の光学用粘着シートの使用時(貼付時)に剥離されるはく離ライナーは「基材」には含まない。
本発明の基材の湿度膨張係数の下限値は、特に限定はなく、低いほど好ましいが、0.001×10-5/%RH以上であってもよい。
本発明の基材の湿度膨張係数は、本発明の基材を構成する樹脂の種類や基材製造時の条件(温度、押出速度など)などにより調整することができる。
平均傾斜角θa=tan-1Δa (1)
Δa=(h1+h2+h3・・・+hn)/L (2)
Ti値=β1/β2
ここで、β1はHAAKE社製レオストレス6000を用いてずり速度20(1/s)の条件で測定される粘度、β2はHAAKE社製レオストレス6000を用いてずり速度200(1/s)の条件で測定される粘度である。
本発明の粘着剤層は、基材(基材層)を有しない粘着剤層であってもよいし、基材を有するタイプの粘着剤層であってもよい。なお、本明細書において、基材(基材層)を有しない粘着剤層を「基材レス粘着剤層」と称する場合があり、基材を有するタイプの粘着剤層を「基材付き粘着剤層」と称する場合がある。上記基材レス粘着剤層としては、例えば、本発明の粘着剤層のみからなる単層の粘着剤層や、本発明の粘着剤層とその他の粘着剤層(本発明の粘着剤層以外の粘着剤層)からなる粘着剤層等が挙げられる。また、上記基材付き粘着剤層としては、基材の両面側に本発明の粘着剤層を有する粘着剤層や、基材の一方の面側に本発明の粘着剤層を有し、他方の面側にその他の粘着剤層を有する粘着剤層などが挙げられる。「基材付き粘着剤層」を構成する「基材(基材層)」としては、本発明の基材と同様のプラスチックフィルムを使用することができる。
・熱衝撃試験
本発明の光学用粘着シートに対し、-40℃の雰囲気下に30分曝露し、続いて、80℃の雰囲気下に30分曝露することを1サイクルとした熱衝撃を、熱衝撃試験機を用いて200サイクル分与える。
|Log10B-Log10A|
A:熱衝撃試験前の表面抵抗値
B:熱衝撃試験後の表面抵抗値
カラム:TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000
溶媒:テトラヒドロフラン
流速:0.6ml/分
1/Tg = W1/Tg1+W2/Tg2+・・・+Wn/Tgn
上記式中、Tgはアクリル系ポリマーのガラス転移温度(単位:K)、Tgiはモノマーiがホモポリマーを形成した際のガラス転移温度(単位:K)、Wiはモノマーiのモノマー成分全量中の重量分率を表す(i=1、2、・・・・n)。
上記アクリル系ポリマーを構成するモノマーのホモポリマーのTgとしては、下記の値を採用できる。
2-エチルヘキシルアクリレート -70℃
n-ヘキシルアクリレート -65℃
n-オクチルアクリレート -65℃
イソノニルアクリレート -60℃
n-ノニルアクリレート -58℃
n-ブチルアクリレート -55℃
エチルアクリレート -20℃
ラウリルアクリレート 0℃
2-エチルヘキシルメタクリレート -10℃
メチルアクリレート 8℃
n-ブチルメタクリレート 20℃
メチルメタクリレート 105℃
アクリル酸 106℃
メタクリル酸 228℃
酢酸ビニル 32℃
スチレン 100℃
前記イオン液体は、フッ素原子の数が10個以下のアニオン成分を含むことが好ましい。前記イオン液体が、フッ素原子の数が10個以下のアニオン成分を含むという構成は、前記イオン液体の本発明の粘着剤層に対する相溶性が向上し、イオン液体が粘着剤層から分離することによるヘイズの上昇を抑制し、画像表示装置の視認性が向上できる点で、好ましい。前記イオン液体の本発明の粘着剤層に対する相溶性が向上し、粘着剤層のヘイズの上昇を抑制する観点から、前記イオン液体のアニオン成分に含まれるフッ素原子の数は、8個以下がより好ましく、6個がさらに好ましい。前記イオン液体のアニオン成分に含まれるフッ素原子の数の下限値は、低融点のイオン液体が得られる点から、4個以上が好ましい。
チル)アンモニウムテトラフルオロボレート、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウムトリフルオロメタンスルホネート、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-Nメチル-N-(2-メトキシエチル)アンモニウムビス(ペンタフルオロエタンスルホニル)イミド、グリシジルトリメチルアンモニウムトリフルオロメタンスルホネート、グリシジルトリメチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、グリシジルトリメチルアンモニウムビス(ペンタフルオロエタンスルホニル)イミド、テトラオクチルホスホニウムトリフルオロメタンスルホネート、テトラオクチルホスホニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-プロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ブチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-へキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ノニルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N,N-ジプロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ブチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-ブチル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-ブチル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-ペンチル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N,N-ジヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリメチルヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-プロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-プロピル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリエチルプロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリエチルペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリエチルヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N-メチル-N-エチルアンモニウムビス(トリフルオロメダンスルホニル)イミド、N,N-ジプロピル-N-メチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N-ブチル-N-へキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N,N-ジヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジブチル-N-メチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジブチル-N-メチル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリオクチルメチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N-メチル-N-エチル-N-プロピル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、1-ブチルピリジニウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、1-ブチル-3-メチルピリジニウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、1-エチル-3-メチルイミダゾリウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、N-エチル-N-メチルモルフォリニウムチオシアネート、4-エチル-4-メチルモルフォリニウムメチルカーボネートなどがあげられる。前記イオン液体は、単独で使用してもよく、または2種以上を混合して使用してもよい。
カラム:TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000
溶媒:テトラヒドロフラン
流速:0.6ml/分
上記アクリル系オリゴマーを構成するモノマーのホモポリマーのTgとしては、下記の表1記載の値を採用できる。また、表1に記載のないモノマーのホモポリマーのTgとしては、「Polymer Handbook」(第3版、John Wiley & Sons,Inc、1989年)に記載の数値を採用できる。さらに、上記文献にも記載されていないモノマーのホモポリマーのTgとしては、上述の測定方法により得られる値(粘弾性試験によるtanδのピークトップ温度)を採用できる。
吸光度A:前記紫外線吸収剤の0.08%トルエン溶液に対して、波長400nmの光を当て、測定される吸光度
本発明の光学用粘着シートは、本発明の基材の第1面上に、本発明の粘着剤層を積層させることより調製することができる。
活性エネルギー線の照射により硬化を行う際は、塗膜の表面にさらにはく離ライナーを付設して、粘着剤組成物を2枚のはく離ライナー間に挟持した状態で活性エネルギー線を照射して、酸素による重合阻害を防止することが好ましい。
活性エネルギー線の照射により硬化を行う際は、塗膜の表面にはく離ライナーを付設して、粘着剤組成物を本発明の基材とはく離ライナーの間に挟持した状態で活性エネルギー線を照射して、酸素による重合阻害を防止することが好ましい。
本発明の光学用粘着シートにおいて、表面又は任意の層間に帯電防止層を有していてもよい。本発明の光学用粘着シートが帯電防止層を有することにより、画像表示パネルへの貼り合わせ不良が生じた場合にリワークするために、粘着シートを画像表示パネルから剥離する際の静電気の発生を抑制することができる点で、好適である。前記帯電防止層は、本発明の基材と本発明の粘着剤層の間に形成されることが好ましい。
本発明の光学用粘着シートにおいて、本発明の粘着剤層の表面(本発明の粘着剤層の粘着面)は、使用時までははく離ライナーにより保護されていてもよい。はく離ライナーは粘着剤層の保護材として用いられるものであり、本発明の光学用粘着シートを被着体に貼付する際に剥がされる。
本発明の光学用粘着シートにおいて、本発明の基材の第2面は、表面保護フィルムにより保護されていてもよい。前記表面保護フィルムは、本発明の光学用粘着シート、本発明の画像表示装置の製造時や搬送時に本発明の基材の第2面の保護材として用いられるものである。
本発明の画像表示装置は、本発明の光学用粘着シートと、画像表示パネルとが積層された積層構造を有する。図3において、画像表示装置20は、光学用粘着シート10Bの粘着剤層1において、画像表示パネル4が積層されている。
本発明のタイリングディスプレイは、本発明の画像表示装置を複数枚並べて形成されるものである。図4において、タイリングディスプレイ30は、9枚の画像表示装置20(積層構造は図示略)を3×3の配列で、支持基板31上にタイル状に並べて形成されており、画像表示装置20同士は隙間32で接している。前記支持基板としては、本発明の基材と同様のガラス板やプラスチックフィルムを使用することができる。
〔(メタ)アクリル系ポリマー溶液1の調製〕
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、ブチルアクリレート(BA)95質量部、アクリル酸(AA)5質量部、重合開始剤として2,2'-アゾビスイソブチロニトリル(AIBN)0.2質量部、酢酸エチル234質量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を65℃付近に保って6時間重合反応を行い、(メタ)アクリル系ポリマー溶液1(30質量%)を調製した。前記(メタ)アクリル系ポリマーの重量平均分子量(Mw)は60万、分子量分布(Mw/Mn)は4.0、ガラス転移温度(Tg)は、-47℃であった。
前記(メタ)アクリル系ポリマー溶液1(30質量%)を酢酸エチルで20質量%に希釈し、この溶液500質量部(固形分100質量部)に、エポキシ系架橋剤(三菱ガス化学(株)製、商品名「テトラッド-C」、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、エポキシ当量:110、官能基数:4)0.075質量部(固形分0.075質量部)、液状の帯電防止剤(日本カーリット(株)製、商品名「CIL312」、1-ブチル-3-メチルピリジニウムビス(トリフルオロメタンスルホニル)イミド)3質量部(実質量3質量部)を添加した後、混合攪拌を行い、アクリル系粘着剤組成物1(アクリル系粘着剤溶液)を調製した。
前記アクリル系粘着剤組成物1を、シリコーン系剥離剤で処理された厚さ75μmのポリエチレンテレフタレートフィルム(PETフィルム、透明基材、はく離ライナー)の表面に塗布し、3分風乾させた後145℃で90秒加熱し、厚さ50μmの粘着剤層1を形成した。次いで、前記粘着剤層1の表面に、片面に防眩層が形成された防眩性フィルム(DNP株式会社製、商品名「DSG23」、PETフィルム)の非防眩層面を貼り合わせ、防眩性フィルム/粘着剤層1/はく離ライナーからなる粘着シート1を得た。
〔アクリル系粘着剤組成物2の調製〕
(メタ)アクリル系ポリマー溶液2(綜研化学(株)製、商品名「SKダイン2137KH」、ブチルアクリレート(BA)99質量部と4-ヒドロキシブチルアクリレート(HBA)1質量部の共重合体、18質量%)の556質量部(固形分100質量部)に、イソシアネート系架橋剤(三井化学(株)製、商品名「タケネートD110N」、トリメチロールプロパンキシリレンジイソシアネート)0.27質量部(固形分0.2質量部)、過酸化物系架橋剤(日本油脂(株)製、商品名「ナイパーBMT」、ベンゾイルパーオキサイド)0.75重量部(固形分0.3質量部)、液状の帯電防止剤(三菱マテリアル電子化成(株)製、商品名「MTOATFSI」、トリオクチルメチルアンモニウムビス(トリフルオロメタンスルホニル)イミド)3重量部(実質量3質量部)を添加した後、混合攪拌を行い、アクリル系粘着剤組成物2を調製した。
〔粘着シート2の作製〕
前記アクリル系粘着剤組成物2を使用したこと以外は、実施例1と同様にして、防眩性フィルム/粘着剤層1/はく離ライナーからなる粘着シート1を得た。
〔アクリル系粘着剤組成物3の調製〕
プレポリマー形成用モノマー成分として、ブチルアクリレート(BA)67質量部、シクロヘキシルアクリレート(大阪有機化学工業社製、商品名「ビスコート#155」)14質量部、および4-ヒドロキシブチルアクリレート(4HBA)19質量部、ならびに光重合開始剤(BASF製、商品名「Omnirad184」)0.09質量部、光重合開始剤(BASF製、商品名「Omnirad651」)0.09質量部を配合し、紫外線を照射して重合を行い、プレポリマー組成物を得た。上記のプレポリマー組成物100重量部に、液状の帯電防止剤(三菱マテリアル電子化成(株)製、商品名「MTOATFSI」、トリオクチルメチルアンモニウムビス(トリフルオロメタンスルホニル)イミド)3質量部を添加した後、これらを均一に混合して、アクリル系粘着剤組成物3を調製した。
表面にシリコーン系離型層が設けられた厚み75μmのポリエチレンテレフタレート(PET)フィルム(三菱ケミカル製「ダイアホイルMRF75」)を基材(兼重はく離ライナー)として、基材の離型層上に上記のアクリル系粘着剤組成物3を厚み50μmになるように塗布して塗布層を形成した。この塗布層上に、カバーシート(兼軽はく離ライナー)として片面がシリコーン剥離処理された厚み75μmのPETフィルム(三菱ケミカル製「ダイアホイルMRE75」)の離型層を貼り合わせた。この積層体に、カバーシート側から、ランプ直下の照射面における照射強度が5mW/cm2になるように位置調節したブラックライトにより、紫外線を照射して光硬化を行い、厚み50μmの粘着剤層3を得た。
上記で得られた粘着剤層3から一方のはく離ライナーを剥離して露出させた粘着面に、片面に防眩層が形成された防眩性フィルム(DNP株式会社製、商品名「DSG23」、PETフィルム)の非防眩層面を貼り合わせ、防眩性フィルム/粘着剤層3/はく離ライナーからなる粘着シート3を得た。
液状の帯電防止剤として、第一工業製薬(株)製、商品名「IL220」、1-メチル-1-プロピルピロリジニウムビス(トリフルオロメタンスルホニル)イミドを3質量部使用したこと以外は、実施例3と同様にして、防眩性フィルム/粘着剤層4/はく離ライナーからなる粘着シート4を得た。
液状の帯電防止剤として、日本カーリット(株)製、商品名「CIL612」、1-エチル-3-メチルイミダゾリウムビス(トリフルオロメタンスルホニル)イミドを3質量部使用したこと以外は、実施例3と同様にして、防眩性フィルム/粘着剤層5/はく離ライナーからなる粘着シート5を得た。
液状の帯電防止剤として、日本カーリット(株)製、商品名「CIL312」、1-ブチル-3-メチルピリジニウムビス(トリフルオロメタンスルホニル)イミドを2質量部使用したこと以外は、実施例1と同様にして、防眩性フィルム/粘着剤層6/はく離ライナーからなる粘着シート6を得た。
液状の帯電防止剤として、日本カーリット(株)製、商品名「CIL312」、1-ブチル-3-メチルピリジニウムビス(トリフルオロメタンスルホニル)イミドを5質量部使用したこと以外は、実施例1と同様にして、防眩性フィルム/粘着剤層7/はく離ライナーからなる粘着シート7を得た。
液状の帯電防止剤として、日本カーリット(株)製、商品名「CIL312」、1-ブチル-3-メチルピリジニウムビス(トリフルオロメタンスルホニル)イミドを10質量部使用したこと以外は、実施例1と同様にして、防眩性フィルム/粘着剤層8/はく離ライナーからなる粘着シート8を得た。
液状の帯電防止剤として、日本カーリット(株)製、商品名「CIL312」、1-ブチル-3-メチルピリジニウムビス(トリフルオロメタンスルホニル)イミドを0.1質量部使用したこと以外は、実施例1と同様にして、防眩性フィルム/粘着剤層9/はく離ライナーからなる粘着シート9を得た。
固体状の帯電防止剤として、三菱マテリアル電子化成(株)製、商品名「LiTFSI」、リチウムビス(トリフルオロメタンスルホニル)イミドを3質量部使用したこと以外は、実施例1と同様にして、防眩性フィルム/粘着剤層10/はく離ライナーからなる粘着シート10を得た。
液状の帯電防止剤として、三菱マテリアル電子化成(株)製、商品名「EMIN441」、1-エチル-3-メチルイミダゾリウムビス(ノナフルオロブチルスルホニル)イミドを3質量部使用したこと以外は、実施例3と同様にして、防眩性フィルム/粘着剤層11/はく離ライナーからなる粘着シート11を得た。
上記の実施例及び比較例で得られた粘着シートを用いて、以下の評価を行った。評価方法を以下に示す。結果を表2に示す。
上記の実施例及び比較例で得られた粘着シートから剥離ライナーを剥離し、温度23℃、相対湿度50%の環境下で、抵抗率計(TREK製「Model 152-1」)を用い、粘着剤表面に、プローブ(TREK製「Model 152P-2P」)を接触させ、印加電圧100V、電圧印加時間10秒の条件で、表面抵抗値を測定した。
下記の熱衝撃試験から粘着シートを取り出した後、温度23℃、相対湿度50%の環境下に2時間以上放置し、抵抗率計(TREK製「Model 152-1」)を用い、剥離ライナーを剥離した粘着剤表面に、プローブ(TREK製「Model 152P-2P」)を接触させ、印加電圧100V、電圧印加時間10秒の条件で、表面抵抗値を測定した。
・熱衝撃試験
実施例及び比較例で得られた粘着シートに対し、-40℃の雰囲気下に30分曝露し、続いて、80℃の雰囲気下に30分曝露することを1サイクルとした熱衝撃を、熱衝撃試験機を用いて200サイクル分与えた。
熱衝撃試験前後の粘着剤層の表面抵抗値の差の絶対値を次式に従い、算出した。
|Log10B-Log10A|
A:熱衝撃試験前の表面抵抗値
B:熱衝撃試験後の表面抵抗値
実施例及び比較例の粘着剤層について、1cm角程度に切り出したものを、支持体(松浪硝子工業株式会社製、スライドガラス)に固定して、ナノインデンテーション測定用試料とし、以下の条件でナノインデンテーション測定を行い、負荷荷重-変位曲線を取得した。
・ナノインデンテーション測定条件
装置 :Hysitron Inc.社製のTriboindenter
使用圧子:Berkovich(三角錐)
測定方法:単一押し込み測定
測定温度:室温
押し込み深さ:100nm
各実施例および比較例で得られた粘着剤層からはく離ライナーを剥離し、複数の粘着剤層を積層して、厚さ約2mmの試験サンプルを作製した。この試験サンプルを直径7.9mmの円盤状に打ち抜き、パラレルプレートに挟み込み、Rheometric Scientific社製「Advanced Rheometric Expansion System(ARES)」を用いて、以下の条件により、動的粘弾性測定を行い、測定結果から、25℃及び85℃における貯蔵弾性率G'を読み取った。また、tanδが極大となる温度を粘着剤層のガラス転移温度とした。
(測定条件)
変形モード:ねじり
測定周波数:1Hz
測定温度:-70℃~150℃
各実施例および比較例で得られた粘着剤層を40mm×40mmのサイズにカットし、片方の面のはく離ライナーを剥がした後、粘着剤面同士が貼り合わせられるように1回折り畳み、片面のはく離ライナーを再度剥がして再び粘着剤面同士を貼り合わせて、約10mm×40mmのサイズ、厚さが約400μmである粘着剤層サンプルを作製した。チャック間距離を20mmに設定した引張試験機に上記粘着剤層サンプルをセットし、引張速度200mm/分で60mm(300%)引っ張った(引張後のチャック間距離は80mm)。60mm引っ張った位置で300秒間固定保持し、その後の応力値を測定し、下記式より「300%引張残存応力値」を算出した。
300%引張残存応力値(N/cm2)=300秒間固定保持後の応力値(N)/(4×粘着シート厚さ(mm)/10)
各実施例および各比較例で得られた粘着シートを、ヘイズ測定装置(村上色彩研究所製HR-100)を用いて、室温(23℃)にて測定した。繰り返し回数3回測定し、その平均値を測定値とした。
各実施例および各比較例で得られた粘着シートを、上記の熱衝撃試験に付した後、ヘイズ測定装置(村上色彩研究所製HR-100)を用いて、室温(23℃)にて測定した。繰り返し回数3回測定し、その平均値を測定値とした。
熱衝撃試験前後のヘイズの差(熱衝撃試験後のヘイズ-熱衝撃試験前のヘイズ)を算出した。
各実施例および各比較例で得られた粘着シートを、ヘイズ測定装置(村上色彩研究所製HR-100)を用いて、室温(23℃)にて測定した。繰り返し回数3回測定し、その平均値を測定値とした。
各実施例および比較例で得られた粘着シートをスライドガラス(商品名「MICRO SLIDE GLASS」、白研磨、NO.2、厚み:1.0~1.2mm、松浪硝子株式会社製)に貼り付け、試験片とした。なお、粘着シートを貼り付ける際には、ハンドローラーを用い、表面に指紋等の汚れがつかないようにし、異物や気泡を噛み込まないようにした。
上記試験片のL*値、b*値及びa*値を、簡易型分光色差計(商品名「DOT-3C」、株式会社村上色彩技術研究所製)を用いて測定した。なお、測定は、試験片の粘着シート面に光を当てて行った。
L*値、b*値及びa*値は、JIS Z 8781-4(2013年)に準じて行った。
熱衝撃試験後のb*に関しては、上記の通り作製した試験片を上記熱衝撃試験に付した後、温度23℃、相対湿度50%の環境下に2時間以上放置し、簡易型分光色差計(商品名「DOT-3C」、株式会社村上色彩技術研究所製)を用いて測定した。熱衝撃試験後のb*から、熱衝撃試験前のb*を引いたものを、熱衝撃試験後のb*の差(Δb*)とした。
〔対アクリル板粘着力の測定方法〕
被着体として、幅70mm、長さ100mmのアクリル板(三菱レイヨン社製、商品名「アクリライト」、厚み:1mm)を用意した。各実施例および比較例で得られた粘着シートを幅25mm、長さ100mmのサイズにカットし、その粘着面を上記アクリル板に、0.25MPaの圧力、0.3m/minの速度で圧着した。これを23℃、50%RHの環境下に30分間貼付して放置した後、同環境下で万能引張試験機を用いて剥離速度300mm/min、剥離角度180°の条件で上記アクリル板から粘着シートを剥離し、このときの粘着力[N/25mm]を測定した。
各実施例および比較例で得られた粘着シートを幅25mm、長さ80mmのサイズにカットし、はく離ライナーを剥離した後、あらかじめ除電しておいたアクリル板(三菱レイヨン社製、商品名「アクリライト」、厚み:1mm、幅:25mm、長さ:70mm)に貼り合わせ、粘着シートの片方の端部がアクリル板の端から10mmはみ出すようにして、ハンドローラーにて圧着した。
このサンプルを23℃・50%RHの環境下に1日放置した後、高さ20mmのサンプル固定台の位置にセットした。アクリル板から10mmはみ出した粘着シートの端部を自動巻取り機に固定し、剥離角度150°、剥離速度5m/minとなるように剥離した。このときに発生する被着体(アクリル板)表面の電位を、アクリル板の中央から高さ100mmの位置に固定してある電位測定器(春日電機社製、型式「KSD-0103」)にて、剥離帯電圧を測定した。測定は、23℃、50%RHの環境下で行った。
各実施例および比較例で得られた粘着シートについて、いわゆる印刷ガラスを用いて密着性(段差吸収性)を調べた。用いた印刷ガラスの表面には、ガラス表面に対して15μmの印刷段差を生じさせる印刷層がパターン形成されおり、このような印刷ガラスの印刷パターン形成面に対し、ハンドローラーを使用して、室温にて粘着シートを貼り合せた。そして、印刷ガラスに貼り合わされた粘着シートにおいて、ガラス表面の印刷パターンの縁端(印刷段差の部分)に沿って幅1mm以上の浮きを生じなかった場合を、密着性は良好(○)と評価し、そのような幅1mm以上の浮きを生じた場合を、密着性は不良(×)と評価した。
上記密着性の評価と同様に、印刷ガラスに粘着シートをハンドローラーで貼り合わせて試験片を作製した。作製した試験片を上記の熱衝撃試験に付した後、温度23℃、相対湿度50%の環境下に2時間以上放置し、印刷段差部分に空隙があるか目視にて確認した。印刷ガラスに貼り合わされた粘着シートにおいて、ガラス表面の印刷パターンの縁端(印刷段差の部分)に沿って幅1mm以上の浮きを生じなかった場合を、密着性は良好(○)と評価し、そのような幅1mm以上の浮きを生じた場合を、密着性は不良(×)と評価した。
〔付記1〕第1面および第2面を有する基材と、前記基材の第1面に粘着剤層が積層された積層構造を有する光学用粘着シートであって、
前記粘着剤層は、液状の帯電防止剤を含有し、
前記粘着剤層の表面抵抗値は、1010Ω未満であり、
下記の熱衝撃試験後のヘイズは、1%以下であることを特徴とする光学用粘着シート。
・熱衝撃試験
前記光学用粘着シートに対し、-40℃の雰囲気下に30分曝露し、続いて、80℃の雰囲気下に30分曝露することを1サイクルとした熱衝撃を、熱衝撃試験機を用いて200サイクル分与える。
〔付記2〕前記帯電防止剤は、イオン液体である、付記1に記載の光学用粘着シート。
〔付記3〕前記イオン液体は、フッ素原子の数が10個以下のアニオン部を含む、付記2に記載の光学用粘着シート。
〔付記4〕前記熱衝撃試験前後の前記光学用粘着シートのヘイズの差(熱衝撃試験後の光学用粘着シートのヘイズ-熱衝撃試験前の光学用粘着シートのヘイズ)が、2%以下である、付記1~3のいずれか1つに記載の光学用粘着シート。
〔付記5〕前記熱衝撃試験前後の前記粘着剤層の下記式で示される表面抵抗値の差の絶対値は、1logΩ以下である、付記1~4のいずれか1つに記載の光学用粘着シート。
|Log10B-Log10A|
A:熱衝撃試験前の表面抵抗値
B:熱衝撃試験後の表面抵抗値
〔付記6〕前記基材の第2面は、反射防止処理及び/又はアンチグレア処理されている、付記1~5のいずれか1つに記載の光学用粘着シート。
〔付記7〕前記粘着剤層がアクリル系ポリマーを含むアクリル系粘着剤層である、付記1~6のいずれか1つに記載の光学用粘着シート。
〔付記8〕付記1~7いずれか1つに記載の光学用粘着シートと、画像表示パネルとが積層された画像表示装置。
〔付記9〕付記8に記載の画像表示装置を複数枚並べたタイリングディスプレイ。
1 基材
1a 基材の第1面
1b 基材の第2面
2 粘着剤層
3 反射防止処理及び/又はアンチグレア処理
20 画像表示装置
4 画像表示パネル
30 タイリングディスプレイ
31 支持基板
Claims (9)
- 第1面および第2面を有する基材と、前記基材の第1面に粘着剤層が積層された積層構造を有する光学用粘着シートであって、
前記粘着剤層は、液状の帯電防止剤を含有し、
前記粘着剤層の表面抵抗値は、1010Ω未満であり、
下記の熱衝撃試験後のヘイズは、1%以下であることを特徴とする光学用粘着シート。
・熱衝撃試験
前記光学用粘着シートに対し、-40℃の雰囲気下に30分曝露し、続いて、80℃の雰囲気下に30分曝露することを1サイクルとした熱衝撃を、熱衝撃試験機を用いて200サイクル分与える。 - 前記帯電防止剤は、イオン液体である、請求項1に記載の光学用粘着シート。
- 前記イオン液体は、フッ素原子の数が10個以下のアニオン部を含む、請求項2に記載の光学用粘着シート。
- 前記熱衝撃試験前後の前記光学用粘着シートのヘイズの差(熱衝撃試験後の光学用粘着シートのヘイズ-熱衝撃試験前の光学用粘着シートのヘイズ)が、2%以下である、請求項1~3のいずれか1項に記載の光学用粘着シート。
- 前記熱衝撃試験前後の前記粘着剤層の下記式で示される表面抵抗値の差の絶対値は、1logΩ以下である、請求項1~4のいずれか1項に記載の光学用粘着シート。
|Log10B-Log10A|
A:熱衝撃試験前の表面抵抗値
B:熱衝撃試験後の表面抵抗値 - 前記基材の第2面は、反射防止処理及び/又はアンチグレア処理されている、請求項1~5のいずれか1項に記載の光学用粘着シート。
- 前記粘着剤層がアクリル系ポリマーを含むアクリル系粘着剤層である、請求項1~6のいずれか1項に記載の光学用粘着シート。
- 請求項1~7いずれか1項に記載の光学用粘着シートと、画像表示パネルとが積層された画像表示装置。
- 請求項8に記載の画像表示装置を複数枚並べたタイリングディスプレイ。
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| JP2016166317A (ja) * | 2015-03-03 | 2016-09-15 | リンテック株式会社 | 粘着性組成物、粘着剤、粘着シートおよび粘着剤層付き光学フィルム |
| JP2016028289A (ja) * | 2015-09-18 | 2016-02-25 | 日東電工株式会社 | 粘着型偏光板および画像表示装置 |
| JP2017155243A (ja) * | 2017-04-19 | 2017-09-07 | 日東電工株式会社 | 粘着剤組成物、及び粘着シート |
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| Publication number | Publication date |
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| JP2023146370A (ja) | 2023-10-12 |
| TW202348763A (zh) | 2023-12-16 |
| CN118946644A (zh) | 2024-11-12 |
| KR20240166558A (ko) | 2024-11-26 |
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