WO2024019162A1 - 粘着シート及び光学積層体 - Google Patents
粘着シート及び光学積層体 Download PDFInfo
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- WO2024019162A1 WO2024019162A1 PCT/JP2023/026823 JP2023026823W WO2024019162A1 WO 2024019162 A1 WO2024019162 A1 WO 2024019162A1 JP 2023026823 W JP2023026823 W JP 2023026823W WO 2024019162 A1 WO2024019162 A1 WO 2024019162A1
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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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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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
- 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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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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
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
- H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
Definitions
- the present invention relates to an adhesive sheet and an optical laminate.
- Various image display devices typified by liquid crystal display devices and electroluminescent (EL) display devices, generally include an optical laminate that includes an optical film such as a polarizing film and an adhesive sheet.
- Adhesive sheets are usually used for bonding between optical films included in an optical laminate and for bonding an optical laminate and an image display panel.
- a typical pressure-sensitive adhesive sheet is a sheet obtained by curing a group of monomers including acrylic monomers, silicone monomers, etc. by polymerization and crosslinking.
- Patent Document 1 discloses an example of an adhesive sheet.
- Static electricity is generated in an image display device during manufacture, for example, when an optical laminate is bonded to an image display panel via an adhesive sheet, or during use, for example, when a user touches the image display device.
- This static electricity may charge the image display device and cause display defects.
- a conductive layer particularly a conductive layer containing a metal oxide such as ITO (indium tin oxide), is sometimes disposed on the surface of the image display panel.
- a pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a small amount of a carboxyl group-containing monomer in the monomer group tends to suppress corrosion of the conductive layer.
- the amount of the carboxyl group-containing monomer is small, the anchoring force between the adhesive sheet and the optical film decreases, and peeling easily occurs between the adhesive sheet and the optical film. .
- This problem occurs when the adhesive sheet is made using a photocuring method, when it is repeatedly used in a high-temperature environment, when the optical film contains a uniaxially stretched film such as a polarizer, and when the adhesive sheet has a thickness of 30 ⁇ m or less. This can occur particularly markedly.
- the present invention provides a pressure-sensitive adhesive sheet that can suppress corrosion of a conductive layer, particularly a conductive layer containing a metal oxide such as ITO, and is suitable for adjusting the anchoring force with an optical film to a large value.
- a pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a monomer group and/or a polymer of the monomer group,
- the adhesive sheet has a first surface and a second surface facing each other,
- a pressure-sensitive adhesive sheet is provided that satisfies at least one selected from the group consisting of the following requirements (1) and (2).
- the adhesive composition contains a corrosion inhibitor; Out of 100 parts by weight of the monomer group, the amount of the carboxyl group-containing monomer is 7.0 parts by weight or less, When the first surface is treated with trifluoroethanol, the elemental ratio R1 of fluorine on the first surface is 0.1 atomic % or more.
- an optical film containing at least one selected from the group consisting of a polarizing film and a retardation film an optical laminate comprising:
- an optical laminate comprising:
- a pressure-sensitive adhesive sheet that can suppress corrosion of a conductive layer, particularly a conductive layer containing a metal oxide such as ITO, and is suitable for adjusting the anchoring force with an optical film to a large value.
- FIG. 1 is a cross-sectional view schematically showing an example of a pressure-sensitive adhesive sheet of the present invention.
- FIG. 3 is a schematic diagram for explaining a method for measuring the amount of creep on a pressure-sensitive adhesive sheet.
- FIG. 3 is a schematic diagram for explaining a method for measuring the amount of creep on a pressure-sensitive adhesive sheet.
- BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram for explaining an example of a method for manufacturing a pressure-sensitive adhesive sheet of the present invention.
- BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram for explaining an example of a method for manufacturing a pressure-sensitive adhesive sheet of the present invention.
- BRIEF DESCRIPTION OF THE DRAWINGS FIG.
- FIG. 1 is a schematic diagram for explaining an example of a method for manufacturing a pressure-sensitive adhesive sheet of the present invention.
- FIG. 1 is a cross-sectional view schematically showing an example of an optical laminate of the present invention.
- FIG. 1 is a cross-sectional view schematically showing an example of an optical laminate of the present invention.
- FIG. 1 is a cross-sectional view schematically showing an example of an optical laminate of the present invention.
- the adhesive sheet according to the first aspect of the present invention is A pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a monomer group and/or a polymer of the monomer group,
- the adhesive sheet has a first surface and a second surface facing each other, At least one selected from the group consisting of the following requirements (1) and (2) is satisfied.
- the adhesive composition contains a corrosion inhibitor; Out of 100 parts by weight of the monomer group, the amount of the carboxyl group-containing monomer is 7.0 parts by weight or less, When the first surface is treated with trifluoroethanol, the elemental ratio R1 of fluorine on the first surface is 0.1 atomic % or more.
- the elemental ratio R2 of fluorine on the second surface is less than 0.1 atomic %. It is.
- the adhesive composition is photocurable.
- the content of the solvent in the adhesive composition is 5% by weight or less.
- the first surface is a surface that has been subjected to surface modification treatment.
- the surface modification treatment is corona treatment.
- the corrosion inhibitor is a silicon-containing compound having an acidic group or an acid anhydride group, or a phosphoric acid-based compound. , and at least one selected from the group consisting of phosphonic acid compounds.
- the monomer group includes a (meth)acrylic monomer.
- the adhesive sheet according to any one of the first to eighth aspects has a thickness of 50 ⁇ m or less.
- the optical laminate according to the tenth aspect of the present invention is An adhesive sheet according to any one of the first to ninth aspects, an optical film containing at least one selected from the group consisting of a polarizing film and a retardation film; Equipped with.
- the first surface of the adhesive sheet is in contact with the optical film.
- the anchoring force between the adhesive sheet and the optical film is 10.0 N/25 mm or more.
- the optical laminate according to the thirteenth aspect of the present invention is An adhesive sheet according to any one of the first to ninth aspects, a conductive layer containing a metal oxide; Equipped with.
- the second surface of the adhesive sheet is in contact with the conductive layer.
- the pressure-sensitive adhesive sheet 1 in FIG. 1 is formed from a pressure-sensitive adhesive composition containing a monomer group and/or a polymer of the monomer group.
- the adhesive sheet 1 has a first surface 1a and a second surface 1b facing each other.
- the adhesive sheet 1 is attached to an optical film via the first surface 1a, and the adhesive sheet 1 is attached to the conductive layer of an image display panel via the second surface 1b.
- the adhesive sheet 1 satisfies at least one selected from the group consisting of the following requirements (1) and (2).
- the elemental ratio R1 of fluorine on the first surface 1a is 0.1 atomic % or more.
- the adhesive composition contains a corrosion inhibitor; Out of 100 parts by weight of the monomer group, the amount of the carboxyl group-containing monomer is 7.0 parts by weight or less, When the first surface 1a of the adhesive sheet 1 is treated with trifluoroethanol, the elemental ratio R1 of fluorine on the first surface 1a is 0.1 atomic % or more.
- the amount of the carboxyl group-containing monomer in the adhesive composition is sufficiently small, and the adhesive sheet 1 (especially the second surface 1b of the adhesive sheet 1) There is a tendency that corrosion of the conductive layer can be suppressed even when the conductive layer is brought into contact with the conductive layer. Furthermore, according to the first surface 1a in which the element ratio R1 is 0.1 atomic % or more, there is a tendency that the anchoring force between the adhesive sheet 1 and the optical film can be adjusted to a large value.
- the above element ratio R1 is preferably 0.2 atomic % or more, and may be 0.3 atomic % or more, and even 0.4 atomic % or more.
- the upper limit of the element ratio R1 is, for example, 1.0 atomic % or less.
- the element ratio R1 can be specified by the following method. First, a pressure-sensitive adhesive sheet 1 cut into a size of 10 mm in length and 10 mm in width is prepared, and the pressure-sensitive adhesive sheet 1 is attached to the inner wall of a sample tube so that the first surface 1a is exposed. Trifluoroethanol (TFE) is added to this sample tube, and the vaporized TFE is brought into contact with the adhesive sheet 1. Thereby, the first surface 1a can be treated with TFE. According to the treatment with TFE, the carboxyl groups present on the first surface 1a react with TFE, and the carboxyl groups are chemically modified. The reaction between a carboxyl group and TFE is represented by the following formula. Note that the amount of TFE added to the sample tube is adjusted so that all the carboxyl groups present on the first surface 1a can react with TFE. R-COOH + CF 3 CH 2 OH ⁇ R-COOCH 2 CF 3
- the adhesive sheet 1 treated with TFE is taken out from the sample tube and set in an X-ray photoelectron spectrometer.
- a wide scan measurement is performed on the first surface 1a of the adhesive sheet 1 using an X-ray photoelectron spectrometer to perform qualitative analysis. This specifies the elements present on the first surface 1a.
- a narrow scan measurement is performed for each element present on the first surface 1a. Based on the results of the narrow scan measurement, the elemental ratio R1 of fluorine on the first surface 1a can be specified. Note that fluorine on the first surface 1a typically originates from TFE reacted with a carboxyl group. Therefore, the element ratio R1 can be used as an index of the amount of carboxyl groups present on the first surface 1a before the treatment with TFE.
- the elemental ratio R2 of fluorine on the second surface 1b is, for example, less than 0.1 atomic %, unlike the elemental ratio R1. is preferred.
- the element ratio R2 is less than 0.1 atomic %, there is a tendency that corrosion of the conductive layer can be further suppressed.
- the element ratio R2 is preferably 0.08 atom% or less, more preferably 0.05 atom% or less, and even more preferably 0.03 atom%. It is as follows. However, the element ratio R2 may be the same value as the element ratio R1. In particular, when the adhesive sheet 1 contains a corrosion inhibitor, the element ratio R2 may satisfy the range described above for the element ratio R1.
- the element ratio R2 is determined by pasting the adhesive sheet 1 on the inner wall of the sample tube so that the second surface 1b is exposed, treating the second surface 1b with TFE, and performing X-ray photoelectron spectroscopy on the second surface 1b. It can be measured by the same method as for elemental ratio R1, except that elemental analysis is performed using an analyzer.
- the first surface 1a of the adhesive sheet 1 is preferably a surface that has been subjected to surface modification treatment. According to studies by the present inventors, by subjecting the first surface 1a to surface modification treatment, the above-mentioned element ratio R1 increases, and there is a tendency that the anchoring force between the pressure-sensitive adhesive sheet 1 and the optical film can be improved. On the other hand, it is preferable that the second surface 1b of the adhesive sheet 1 is not subjected to surface modification treatment. Examples of surface modification treatments include corona treatment, plasma treatment, excimer treatment, and flame treatment. The first surface 1a is preferably subjected to corona treatment as surface modification treatment.
- the surface modification treatment may be performed in an inert gas atmosphere.
- the risk of ignition of the remaining monomer can be reduced.
- the content is more preferably 6% by volume or less, and even more preferably 3% by volume or less.
- the oxygen concentration is preferably 0.01% by volume or more, and 0.1% by volume or more. More preferably, 0.5% by volume or more is particularly preferred.
- the inert gas include nitrogen and argon.
- the surface modification treatment may be carried out under normal pressure (1 atmosphere).
- the conditions for the surface modification treatment are, for example, 0.6 to 100 kJ/m 2 in terms of discharge amount.
- the lower limit of discharge amount is 1kJ/ m2 or more, 2kJ/ m2 or more, 5kJ/m2 or more, 7kJ/ m2 or more, 10kJ/ m2 or more, 13kJ/m2 or more, 15kJ/m2 or more, 20kJ/ m2 or more.
- the upper limit of the discharge amount is 70 kJ/m 2 or less, 60 kJ/m 2 or less, 50 kJ/m 2 or less, 45 kJ/m 2 or less, 40 kJ/m 2 or less, 30 kJ/m 2 or less, 20 kJ/m 2 or less, and even It may be 18 kJ/m 2 or less.
- the discharge amount may be 1 to 18 kJ/m 2 .
- the discharge amount may be 1 to 60 kJ/m 2 .
- the adhesive sheet 1 is formed from an adhesive composition.
- the adhesive composition is preferably a photocurable adhesive composition that forms the adhesive sheet 1 when irradiated with light.
- the adhesive composition may be a thermosetting adhesive composition that forms the adhesive sheet 1 by heat.
- adhesive sheets are generally manufactured by, for example, the following thermosetting method.
- a crosslinking agent and the like are added to a polymer produced by polymerizing a polymerizable monomer in an organic solvent to prepare an adhesive composition.
- This adhesive composition is applied to a base material such as a release liner, and the organic solvent is removed by heating to form a sheet.
- a pressure-sensitive adhesive sheet can be manufactured by performing heat aging as necessary to complete crosslinking. In this manufacturing process, it is necessary to burn a large amount of fuel such as LNG in order to generate the thermal energy necessary for heat removal of the solvent and heat aging.
- the organic solvent that has been removed by heating is released into the atmosphere as it is, it may have a significant negative impact on the surrounding environment.
- organic solvents are often burned in a deodorizing furnace or the like before being released.
- the organic solvent itself will also be converted into CO 2 and released into the atmosphere through combustion, resulting in a manufacturing process with extremely large CO 2 emissions. be.
- a method of producing an adhesive sheet using light tends to reduce the amount of energy and CO 2 emissions required to form the adhesive sheet compared to a thermosetting method.
- the adhesive composition contains a monomer group and/or a polymer of the monomer group.
- the monomer group includes, for example, (meth)acrylic monomers.
- the content of the (meth)acrylic component in the adhesive composition is 50% by weight or more, 60% by weight or more, 70% by weight or more, and even 80% by weight. % or more, and in this case, an acrylic pressure-sensitive adhesive sheet 1 containing a (meth)acrylic polymer and a crosslinked product thereof as main components can be formed.
- the adhesive composition is not limited to the above example.
- (meth)acrylic means acrylic and methacryl.
- (Meth)acrylate means acrylate and methacrylate. Note that the monomers included in the monomer group preferably do not contain fluorine atoms.
- An example of the (meth)acrylic monomer is a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms in the side chain.
- the number of carbon atoms in the alkyl group may be 7 or less, 6 or less, 5 or less, or even 4 or less.
- the alkyl group may be linear or branched.
- Examples of (meth)acrylic acid alkyl esters are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate.
- t-butyl (meth)acrylate isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate (lauryl (meth)acrylate), n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, pentadecyl
- the amount of (meth)acrylic acid alkyl ester is, for example, 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, It may be 85 parts by weight or more, 90 parts by weight or more, or even 95 parts by weight or more.
- the weight of the polymer is converted to the weight of each monomer before polymerization.
- the monomer group may include a carboxyl group-containing monomer.
- the carboxyl group-containing monomer may be a (meth)acrylic monomer, or in other words, the (meth)acrylic monomer may include a carboxyl group-containing monomer.
- Examples of carboxyl group-containing monomers are (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid.
- the amount of the carboxyl group-containing monomer is preferably 0.5 parts by weight or less, 0.4 parts by weight or less, 0.3 parts by weight or less, The amount may be 0.2 parts by weight or less, or even 0.1 parts by weight or less.
- the monomer group does not need to contain carboxyl group-containing monomers. If the amount of the carboxyl group-containing monomer is 0.5 parts by weight or less, corrosion of the conductive layer tends to be sufficiently inhibited even if the adhesive composition does not contain a corrosion inhibitor. .
- the amount of the carboxyl group-containing monomer may exceed 0.5 parts by weight out of 100 parts by weight of the monomer group.
- the blending amount of the carboxyl group-containing monomer is 7.0 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.5 parts by weight or less, 3.0 parts by weight or less.
- the amount may be 2.5 parts by weight or less, 2.0 parts by weight or less, 1.5 parts by weight or less, or even 1.0 parts by weight or less. It is preferable to add a large amount of the carboxyl group-containing monomer as long as corrosion can be suppressed.
- the anchoring force of the pressure-sensitive adhesive sheet 1 to the optical film tends to improve.
- the pressure-sensitive adhesive sheet 1 is produced by a photocuring method, the polymerization rate of the monomer group due to light irradiation tends to increase, which is preferable because productivity is improved.
- the monomer group may include a hydroxy group-containing monomer.
- the hydroxy group-containing monomer may be a (meth)acrylic monomer, or in other words, the (meth)acrylic monomer may include a hydroxy group-containing monomer.
- the hydroxy group-containing monomer can contribute to improving the cohesive force of the pressure-sensitive adhesive sheet.
- hydroxy group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, They are 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)-methyl acrylate.
- the hydroxy group-containing monomer is preferably 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate.
- the amount of the hydroxy group-containing monomer is, for example, 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, 7.5 parts by weight or less, 5 parts by weight or less. , 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less, or even 0.5 parts by weight or less.
- the lower limit of the blending amount may be, for example, 0.01 part by weight or more, 0.03 part by weight or more, and even 0.05 part by weight or more.
- the monomer group does not need to contain hydroxy group-containing monomers.
- the monomer group may include an ether group-containing monomer.
- the ether group-containing monomer may be a (meth)acrylic monomer, or in other words, the (meth)acrylic monomer may include an ether group-containing monomer.
- the ether group-containing monomer can contribute to improving the anchoring force between the adhesive sheet 1 and the optical film.
- the ether group-containing monomer is preferably an alkoxy group-containing monomer.
- the alkoxy group-containing monomer include an alkylene oxide adduct represented by the following chemical formula (1).
- R 1 in formula (1) is a hydrogen atom or a methyl group.
- R 2 in formula (1) is an alkyl group.
- the alkyl group may be linear or branched.
- R 2 is preferably a linear alkyl group. Examples of R 2 are methyl and ethyl groups.
- n in formula (1) is an integer of 1 to 30, preferably an integer of 1 to 12, and may be an integer of 1 to 5.
- alkylene oxide adducts shown in formula (1) include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, and methoxytriethylene glycol.
- the ether group-containing monomer is not limited to the above alkylene oxide adduct.
- the ether group-containing monomer may have a ring structure, and the ring structure may have an ether group.
- the ring structure having an ether group include a tetrahydrofuran ring and a dioxane ring.
- Examples of ether group-containing monomers having a ring structure are cyclic trimethylolpropane formal (meth)acrylate and tetrahydrofurfuryl (meth)acrylate.
- the amount of the ether group-containing monomer is, for example, 1 part by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more. It may be at least 40 parts by weight, at least 50 parts by weight, at least 60 parts by weight, at least 70 parts by weight, at least 80 parts by weight, and even at least 90 parts by weight.
- the upper limit of the blending amount is, for example, 99 parts by weight or less, and may be 50 parts by weight or less depending on the case.
- the monomer group does not need to contain ether group-containing monomers.
- each of the above-mentioned monomers may be included as a polymer.
- the polymer is preferably a partial polymer.
- the partial polymer may be either a single polymer or a copolymer.
- the adhesive composition may contain a photopolymerization initiator.
- a photopolymerization initiator is a photoradical generator that generates radicals using visible light and/or ultraviolet light having a wavelength shorter than 450 nm.
- photopolymerization initiators include benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; substituted benzoin ethers such as anisole methyl ether; 2,2-diethoxyacetophenone, 2,2-dimethoxy-2- Substituted acetophenones such as phenylacetophenone; ⁇ -hydroxyalkylphenones such as 1-hydroxycyclohexyl-phenylketone; substituted alphaketols such as 2-methyl-2-hydroxypropiophenone; aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride; Photoactive oximes such as 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone
- the amount of the photopolymerization initiator in the adhesive composition is, for example, 0.02 to 10 parts by weight, and 0.05 to 5 parts by weight, based on a total of 100 parts by weight of the monomer group and its polymer. There may be.
- the adhesive composition may contain a crosslinking agent.
- a crosslinking agent is a polyfunctional monomer having two or more polymerizable functional groups in one molecule.
- the polyfunctional monomer may be a (meth)acrylic monomer.
- the polyfunctional monomer is preferably a monomer having two or more C ⁇ C bonds in one molecule.
- polyfunctional monomers examples include (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, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol diacrylate (NDDA) , 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and other polyfunctional acrylates (ester compounds of polyhydric alcohol and (meth)acrylic acid, etc.) ); allyl (meth)acrylate,
- the polyfunctional monomer is preferably a polyfunctional acrylate, more preferably trimethylolpropane tri(meth)acrylate, hexanediol di(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.
- the crosslinking agent may contain a crosslinking agent other than the above-mentioned polyfunctional monomer.
- Other crosslinking agents include isocyanate crosslinking agents.
- the adhesive composition may contain an isocyanate-based crosslinking agent as a crosslinking agent, or may contain both the above-mentioned polyfunctional monomer and isocyanate-based crosslinking agent.
- the isocyanate-based crosslinking agent can contribute to improving the anchoring force between the adhesive sheet 1 and the optical film.
- isocyanate crosslinking agent a compound having at least two isocyanate groups (isocyanate compound) can be used.
- the number of isocyanate groups contained in the isocyanate compound is preferably 3 or more.
- the upper limit of the number of isocyanate groups is not particularly limited, and is, for example, 5.
- examples of the isocyanate compound include aromatic isocyanate compounds, alicyclic isocyanate compounds, and aliphatic isocyanate compounds.
- aromatic isocyanate compounds include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and 4,4'-toluidine.
- aromatic isocyanate compounds include diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate.
- alicyclic isocyanate compounds include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated tolylene diisocyanate. , hydrogenated tetramethylxylylene diisocyanate, and the like.
- aliphatic isocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4 , 4-trimethylhexamethylene diisocyanate and the like.
- isocyanate crosslinking agent examples include multimers (dimers, trimers, pentamers, etc.) of the above isocyanate compounds, adducts obtained by adding to polyhydric alcohols such as trimethylolpropane, urea modified products, Also included are urethane prepolymers obtained by adding to biuret modified products, allophanate modified products, isocyanurate modified products, carbodiimide modified products, polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like.
- the isocyanate-based crosslinking agent preferably contains an aliphatic isocyanate compound and/or a derivative of an aliphatic isocyanate compound.
- the isocyanate-based crosslinking agent may be at least one selected from the group consisting of pentamethylene diisocyanate (PDI)-based crosslinking agents (PDI and its derivatives) and hexamethylene diisocyanate (HDI)-based crosslinking agents (HDI and its derivatives). Particularly preferred.
- PDI-based crosslinking agent include isocyanurate-modified PDI.
- Specific examples of HDI-based crosslinking agents include isocyanurate-modified HDI and biuret-modified products.
- the amount of the crosslinking agent in the adhesive composition varies depending on the molecular weight, the number of functional groups, etc., but is, for example, 5 parts by weight or less, and 3 parts by weight or less, based on the total of 100 parts by weight of the monomer group and its polymer. , 2 parts by weight or less, 1 part by weight or less, or even 0.5 parts by weight or less.
- the lower limit of the blending amount is, for example, 0.01 part by weight or more, and may even be 0.05 part by weight or more.
- the amount of the isocyanate-based crosslinking agent is, for example, 0.02 parts by weight or more with respect to 100 parts by weight of the monomer group and its polymer. , 0.05 part by weight or more, 0.1 part by weight or more, 0.5 part by weight or more, or even 1 part by weight or more.
- the adhesive composition contains an isocyanate-based crosslinking agent, adjusting the amount of the hydroxy group-containing monomer in the adhesive composition to a small value tends to further improve the anchoring force between the adhesive sheet 1 and the optical film. be.
- the pressure-sensitive adhesive sheet When an isocyanate-based crosslinking agent is added, the pressure-sensitive adhesive sheet may become hard, especially in a high-temperature environment. In such a case, the stress relaxation properties of the pressure-sensitive adhesive sheet are impaired, so that the stress of expansion and contraction of the optical film is easily transmitted to the interface between the pressure-sensitive adhesive sheet and the adherend, and peeling tends to occur easily.
- the anchoring force between the pressure-sensitive adhesive sheet and the optical film can be ensured by means other than the addition of an isocyanate-based crosslinking agent, it is desirable that the pressure-sensitive adhesive composition does not contain an isocyanate-based crosslinking agent.
- the adhesive composition may contain a corrosion inhibitor.
- a corrosion inhibitor for example, when the adhesive sheet 1 is attached to a conductive layer such as an ITO layer, the corrosion inhibitor is segregated on the surface of the conductive layer to form a coating layer that covers the surface of the conductive layer.
- This coating layer can suppress corrosive substances (for example, acid components) contained in the adhesive sheet 1 from migrating to the conductive layer.
- the coating layer also tends to improve the reworkability of the adhesive sheet 1 by reducing the adhesive force between the adhesive sheet 1 and the conductive layer.
- the corrosion inhibitor contains, for example, at least one selected from the group consisting of silicon-containing compounds, phosphoric acid compounds, and phosphonic acid compounds having acidic groups or acid anhydride groups; It is preferable to include a silicon-containing compound having a silicon-containing compound.
- silicon-containing compounds include alkoxysilane compounds and organopolysiloxane compounds.
- the acidic group is typically a carboxyl group.
- the carboxyl group may be a group generated by hydrolyzing an acid anhydride group.
- the acid anhydride group include carboxylic anhydride groups such as a succinic anhydride group, a phthalic anhydride group, and a maleic anhydride group. It is preferable that the silicon-containing compound does not have a polyether skeleton.
- the silicon-containing compound may be a silane coupling agent having an alkoxysilyl group.
- Specific examples of the alkoxy group included in the alkoxysilyl group include a methoxy group and an ethoxy group.
- alkoxysilane compound having an acid anhydride group 2-trimethoxysilylethylsuccinic anhydride, 3-trimethoxysilylpropylsuccinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-12-967C") , 3-triethoxysilylpropylsuccinic anhydride, 3-methyldiethoxysilylpropylsuccinic anhydride, 1-carboxy-3-triethoxysilylpropylsuccinic anhydride, and the like.
- organopolysiloxane compound having an acid anhydride group examples include an acid anhydride group-containing oligomeric silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. (trade name "X-24-9591F").
- Examples of phosphoric acid compounds include phosphoric acid itself, phosphoric esters, and salts thereof.
- the phosphoric acid ester may be a phosphoric acid monoester or a phosphoric diester.
- Phosphoric acid esters have, for example, a structure in which a hydrocarbon group having 1 to 18 carbon atoms is introduced into phosphoric acid.
- Examples of phosphonic acid compounds include phosphonic acid itself, alkylphosphonic acids, and salts thereof.
- the alkyl group contained in the alkylphosphonic acid has, for example, 1 to 18 carbon atoms.
- the amount of the corrosion inhibitor in the adhesive composition is, for example, 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, based on a total of 100 parts by weight of the monomer group and its polymer.
- the amount may be at least 0.2 parts by weight, or even at least 0.4 parts by weight.
- the upper limit of the blending amount may be, for example, 10 parts by weight or less, 5 parts by weight or less, and even 1 part by weight or less.
- the adhesive composition may not contain a corrosion inhibitor.
- the adhesive composition may contain additives other than those mentioned above.
- additives are chain transfer agents, silane coupling agents other than corrosion inhibitors, viscosity modifiers, tackifiers, plasticizers, softeners, anti-aging agents, fillers, colorants, antioxidants, and surfactants. agent, antistatic agent and ultraviolet absorber.
- the content of the solvent in the adhesive composition is, for example, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, and even 0.5% by weight or less. Good too.
- the adhesive composition may be substantially free of solvent. "Substantially free of solvent” means that the content of solvents derived from additives etc. is, for example, 0.1% by weight or less, preferably 0.05% by weight or less, more preferably 0.01% by weight or less. The intention is to allow it.
- the viscosity of the adhesive composition is preferably 5 to 150 poise.
- a pressure-sensitive adhesive composition having a viscosity within the above range is particularly suitable for forming the coating layer described below.
- the polymerization rate of the monomer group in the adhesive sheet 1 is preferably 90% or more.
- the polymerization rate may be 95% or more, 98% or more, or even 99% or more.
- the gel fraction of the adhesive sheet 1 is, for example, 50% or more, and may be 75% or more, 80% or more, or even 85% or more.
- the creep amount of the adhesive sheet 1 is, for example, 500 ⁇ m or less, and may be 300 ⁇ m or less, 180 ⁇ m or less, 160 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, or even 50 ⁇ m or less.
- the lower limit of the creep amount may be, for example, 5 ⁇ m or more, 10 ⁇ m or more, or even 20 ⁇ m or more.
- the amount of creep of the adhesive sheet 1 can be evaluated as follows (see FIGS. 2A and 2B).
- a test piece 52 is obtained by cutting a laminate of the adhesive sheet 1 and the support film 51 to be evaluated into a strip of 10 mm x 50 mm.
- the support film 51 is disposed for the purpose of suppressing deformation of the load-applied portion of the pressure-sensitive adhesive sheet 1 during a test, and thereby measuring the amount of creep with higher accuracy.
- a resin film such as a polyethylene terephthalate (PET) film can be used.
- PET polyethylene terephthalate
- the support film 51 may be an optical film or a laminate including an optical film.
- the thickness of the support film 51 may be such that it does not deform itself under the above load, and is, for example, 20 to 200 ⁇ m.
- the test piece 52 is attached to the surface of the stainless steel test plate 53 using the adhesive sheet 1 at a joint surface measuring 10 mm in length and 10 mm in width.
- FIG. 2B is a cross section BB in FIG. 2A.
- the test piece 52 is attached to the test plate 53 so that air bubbles are not mixed between the test plate 53 and the adhesive sheet 1.
- the test plate 53 and the adhesive sheet 1 are placed in an autoclave at 50° C. and 5 atm (absolute pressure) for 15 minutes to homogenize the bond between the test plate 53 and the adhesive sheet 1.
- test plate 53 and the test piece 52 are held vertically with the test plate 53 facing upward and left in an atmosphere of 25°C for at least 5 minutes.
- a weight with a mass of 500 g is fixed at the center of the lower end, and a load 54 of 500 gf is applied vertically downward.
- the amount of creep (deviation amount) of the adhesive sheet 1 with respect to the test plate 53 at the time point 3600 seconds after the start of applying the load 54 is measured as the amount of fall of the weight.
- a laser displacement meter can be used to measure the amount of weight fall.
- the thickness of the adhesive sheet 1 is, for example, 500 ⁇ m or less, and may be 250 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, 30 ⁇ m or less, 25 ⁇ m or less, or even 20 ⁇ m or less.
- the lower limit of the thickness of the adhesive sheet 1 is, for example, 2 ⁇ m or more, and may be 5 ⁇ m or more.
- the method for manufacturing the adhesive sheet 1 is not particularly limited.
- the adhesive sheet 1 can be manufactured by the following method. First, as shown in FIGS. 3A and 3B, a first laminate 15 including a base sheet 21, a coating layer 22 containing an adhesive composition, and a release liner 23 in this order is produced.
- the adhesive sheet 1 can be formed from the coating layer 22 by irradiating the first laminate 15 with the light 14 (FIG. 3C).
- the first laminate 15 is typically irradiated with the light 14 from the base sheet 21 side (FIG. 3A). At this time, the light 14 passes through the base sheet 21, reaches the coating layer 22, and cures the coating layer 22. However, the irradiation with the light 14 may be performed from the release liner 23 side, or from both sides of the release liner 23 and the base sheet 21 (FIG. 3B).
- the adhesive sheet 1 formed from the coating layer 22 is sandwiched between the base sheet 21 and the release liner 23 and constitutes a part of the second laminate 16 until the release liner 23 is peeled off.
- the base material of the release liner 23 is a resin film.
- resins that can be included in the liner base material are polyesters such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfones, polycarbonates, polyamides, polyimides, polyolefins, (meth)acrylic resins, polyvinyl chloride, polyvinylidene chloride. , polystyrene, polyvinyl alcohol, polyarylate, and polyphenylene sulfide.
- the resin is preferably a polyester such as polyethylene terephthalate.
- the release liner 23 may have a light 14 transmittance, or may have a light 14 transmittance comparable to that of the base sheet 21.
- the thickness of the release liner 23 is, for example, 10 to 200 ⁇ m, and may be 25 to 150 ⁇ m.
- the release liner 23 may include layers other than the liner base material.
- the release liner 23 may include a release layer.
- the release liner 23 includes, for example, a liner base material and a release layer formed on one surface of the liner base material. This release liner 23 can be used so that the release layer is on the coating layer 22 side.
- the release layer is typically a cured layer of a release agent composition containing a release agent.
- Various mold release agents can be used as the mold release agent, such as a silicone mold release agent, a fluorine mold release agent, a long chain alkyl mold release agent, a fatty acid amide mold release agent, and silica powder.
- the release liner 23 may include a cured layer of a release agent composition containing a silicone release agent as a main component (hereinafter referred to as "silicone release layer").
- the silicone release layer is particularly suitable for achieving both adhesion and releasability to the pressure-sensitive adhesive sheet 1.
- the main component means the component with the largest content rate.
- the silicone mold release agent is, for example, various types of curable silicone materials such as addition reaction type, condensation reaction type, ultraviolet curable type, electron beam curable type, and solvent-free type, with addition reaction curable silicone materials being preferred.
- the addition reaction-curable silicone material is particularly suitable for forming a release layer that has both adhesion and releasability to the pressure-sensitive adhesive sheet 1.
- the curable silicone material may be a silicone-modified resin in which reactive silicone is introduced into an organic resin such as urethane, epoxy, or alkyd resin by graft polymerization or the like.
- An example of an addition reaction-curable silicone material is a polyorganosiloxane having a vinyl group or an alkenyl group in the molecule.
- the addition reaction curable silicone material does not need to have a hydrosilyl group.
- alkenyl groups are 3-butenyl, 4-pentenyl, 5-hexenyl, 6-heptenyl, 7-octenyl, 8-nonenyl, 9-decenyl, 10-undecenyl, and 11-dodecenyl. It is the basis.
- polyorganosiloxanes examples include polyalkylalkylsiloxanes such as polydimethylsiloxane, polydiethylsiloxane, and polymethylethylsiloxane, polyalkylarylsiloxanes, and a plurality of Si atom-containing monomers such as poly(dimethylsiloxane-diethylsiloxane). It is a copolymer.
- the polyorganosiloxane is preferably polydimethylsiloxane.
- a mold release agent composition containing a silicone mold release agent as a main component usually contains a crosslinking agent.
- crosslinking agents are polyorganosiloxanes containing hydrosilyl groups.
- the crosslinking agent may have two or more hydrosilyl groups in one molecule.
- the silicone mold release agent composition may contain a curing catalyst.
- a curing catalyst is a platinum-based catalyst.
- platinum-based catalysts are chloroplatinic acid, olefin complexes of platinum, and olefin complexes of chloroplatinic acid.
- the amount of the platinum-based catalyst used is, for example, 10 to 1000 ppm (by weight, in terms of platinum) based on the total solid content of the composition.
- the silicone mold release agent composition may contain additives.
- additives are release control agents and adhesion promoters.
- release control agents are unreacted silicone resins, and more specific examples are organosiloxanes such as octamethylcyclotetrasiloxane, and MQ resins.
- the total amount of the peel control agent and adhesion improver used is, for example, 1 to 30% by weight based on the total solid content of the composition.
- Further examples of additives are fillers, antistatic agents, antioxidants, UV absorbers, plasticizers and colorants.
- the amount of further additives used is, for example, up to 10% by weight in total, based on the total solids content of the composition.
- the silicone mold release agent composition may contain an organic solvent.
- organic solvents include hydrocarbon solvents such as cyclohexane, n-hexane, and n-heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate; ketone solvents such as acetone and methyl ethyl ketone.
- Solvent Alcohol solvent such as methanol, ethanol, butanol. Two or more types of organic solvents may be included. The amount of organic solvent used is preferably 80 to 99.9% by weight of the silicone mold release agent composition.
- the release layer can be formed, for example, by heating and drying a coating film containing a release agent composition formed on a liner base material.
- Application of the release agent composition includes roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, and die coating.
- Various coating methods such as can be applied. For example, hot air drying can be used for heating and drying.
- the heating temperature and time vary depending on the heat resistance of the liner base material, but are usually about 80 to 150°C and about 10 seconds to 10 minutes. If necessary, irradiation with active energy rays such as ultraviolet rays may be used in combination.
- the thickness of the release layer is, for example, 10 to 300 nm.
- the upper limit of the thickness may be 200 nm or less, 150 nm or less, 120 nm or less, 110 nm or less, 100 nm or less, less than 100 nm, 90 nm or less, 80 nm or less, 70 nm or less, less than 70 nm, or even 65 nm or less.
- the lower limit of the thickness may be 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, or even 50 nm or more.
- the release liner 23 may be sheet-shaped or elongated.
- An example of the base sheet 21 is a resin film.
- Examples of resins included in the base sheet 21 are the same as examples of resins that can be included in the liner base material.
- the base sheet 21 has excellent transparency for the light 14.
- the thickness of the base sheet 21 is, for example, 10 to 200 ⁇ m, and may be 25 to 150 ⁇ m.
- the base sheet 21 may include a release layer on the surface facing the coating layer 22.
- Examples of the release layer that the base sheet 21 can include and its manufacturing method are the same as the examples of the release layer that the release liner 23 can include and its manufacturing method.
- Both the release liner 23 and the base sheet 21 may be provided with a release layer.
- both mold release layers may be formed from mold release agent compositions containing the same mold release agent as a main component. Further, the thicknesses of both release layers may be different, and for example, the release layer included in the base sheet 21 may be thicker.
- a sheet can usually be selected that has a greater peeling force with the adhesive sheet 1 than the release liner 23.
- the base sheet 21 may be sheet-shaped or elongated.
- the first laminate 15 is constructed by, for example, forming a coating layer 22 on a base sheet 21 (or a release liner 23), and disposing a release liner 23 (or a base sheet 21) on the formed coating layer 22. It can be formed by Further, the first laminate 15 is formed by pouring and applying the adhesive composition into the space between the base sheet 21 and the release liner 23 which are held at a predetermined interval so that their main surfaces face each other. You can.
- the coating layer 22 can be formed using a roll coat, a kiss roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, a dip roll coat, a bar coat, a knife coat, an air knife coat, a curtain coat, a lip coat, a die coat, etc.
- Various application methods can be applied.
- the thickness of the coating layer 22 can be adjusted depending on the desired thickness of the adhesive sheet 1, and is, for example, 5 to 500 ⁇ m, 5 to 250 ⁇ m, 5 to 150 ⁇ m, 5 to 100 ⁇ m, 5 to 50 ⁇ m, 5 to 30 ⁇ m, It may be 5 to 25 ⁇ m, or even 5 to 20 ⁇ m.
- the light 14 irradiated onto the first laminate 15 is, for example, visible light or ultraviolet light having a wavelength shorter than 450 nm.
- the light 14 may include light with a wavelength in the same region as the absorption wavelength of the photopolymerization initiator included in the adhesive composition.
- the light 14 may be irradiated by cutting short wavelength light with a wavelength of 300 nm or less using a filter or the like, and cutting off the short wavelength light is suitable for suppressing deterioration of the base sheet 21 due to the light 14.
- the light source of the light 14 is, for example, a light irradiation device including an ultraviolet irradiation lamp.
- ultraviolet irradiation lamps examples include ultraviolet LEDs, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, extra-high-pressure mercury lamps, metal halide lamps, xenon lamps, microwave-excited mercury lamps, black light lamps, chemical lamps, germicidal lamps, and low-pressure discharge mercury lamps. , an excimer laser. Two or more ultraviolet irradiation lamps may be combined.
- Irradiation of the light 14 may be continuous or intermittent.
- the illuminance of the light 14 is, for example, 1 to 20 mW/cm 2 .
- the irradiation time of the light 14 is, for example, 5 minutes to 5 hours.
- the cumulative amount of light 14 to the first laminate 15 is, for example, 100 to 5000 mJ/cm 2 .
- the release liner 23 may be peeled off from the second laminate 16 to expose the surface (for example, the surface 1a) of the adhesive sheet 1, and the surface may be subjected to surface modification treatment.
- FIG. 4 An example of the optical laminate of this embodiment is shown in FIG.
- the optical laminate 10 in FIG. 4 includes the adhesive sheet 1 described above and at least one optical film 2 selected from the group consisting of a polarizing film and a retardation film. It is preferable that the adhesive sheet 1 is in direct contact with the optical film 2. In the example of FIG. 4, the first surface 1a of the adhesive sheet 1 is in contact with the optical film 2.
- the optical laminate 10 may have a structure in which the base sheet used in producing the adhesive sheet 1 is laminated on the adhesive sheet 1.
- the optical laminate 10 can be used as an optical film with an adhesive sheet.
- Optical film 2 has a surface 2 a facing adhesive sheet 1 .
- the surface 2a is in contact with the first surface 1a of the adhesive sheet 1.
- the surface 2a of the optical film 2 may be subjected to a surface modification treatment. According to the surface 2a subjected to the surface modification treatment, there is a tendency that the anchoring force between the adhesive sheet 1 and the optical film 2 can be improved. Examples of the surface modification treatment include those described above for the adhesive sheet 1.
- the surface 2a is preferably subjected to corona treatment as surface modification treatment.
- conditions such as the amount of discharge can be adjusted as appropriate within the range described above for the adhesive sheet 1, for example.
- the optical film 2 includes at least one selected from the group consisting of a polarizing film and a retardation film.
- the optical film 2 may be a laminated film including a polarizing film and/or a retardation film.
- the optical film 2 may include a glass film.
- the optical film 2 is not limited to the above example.
- the polarizing film includes a polarizer.
- a polarizing film typically includes a polarizer and a protective film (transparent protective film).
- the protective film is placed, for example, in contact with the main surface (the surface with the widest area) of the polarizer.
- a polarizer may be placed between two protective films.
- the protective film may be placed on at least one surface of the polarizer.
- the polarizer is not particularly limited, and examples include hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, partially saponified ethylene/vinyl acetate copolymer films, iodine, and dichroism. Examples include those obtained by adsorbing dichroic substances such as dyes and uniaxially stretched; polyene-based oriented films such as dehydrated polyvinyl alcohol and dehydrochloric acid treated polyvinyl chloride.
- a polarizer typically consists of a polyvinyl alcohol film (polyvinyl alcohol films include partially saponified ethylene/vinyl acetate copolymer films) and a dichroic substance such as iodine.
- the thickness of the polarizer is not particularly limited, and may be, for example, 80 ⁇ m or less, 50 ⁇ m or less, 30 ⁇ m or less, 25 ⁇ m or less, or even 20 ⁇ m or less.
- the lower limit of the thickness of the polarizer is not particularly limited, and may be, for example, 1 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, or even 15 ⁇ m or more.
- a thin polarizer (for example, 20 ⁇ m or less in thickness) has suppressed dimensional changes and can contribute to improving the durability of the optical laminate, especially the durability under high temperatures.
- thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc.
- thermoplastic resins include cellulose resins such as triacetylcellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, and cyclic resins.
- examples include polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
- the material of the protective film may be a thermosetting resin or an ultraviolet curing resin such as (meth)acrylic, urethane, acrylic urethane, epoxy, or silicone.
- the materials of the two protective films may be the same or different.
- a protective film made of a thermoplastic resin is attached to one main surface of a polarizer via an adhesive
- a protective film made of a thermosetting resin or an ultraviolet curable resin is attached to the other main surface of the polarizer.
- a protective film made of molded resin may be attached.
- the protective film may contain one or more types of arbitrary additives. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color inhibitors, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like.
- films containing (meth)acrylic resin tend to have low adhesive strength with adhesive sheets.
- the surface of the protective film containing (meth)acrylic resin corresponds to the surface 2a of the optical film 2 because the adhesive sheet 1 satisfies the above requirements (1) or (2).
- the anchoring force between the adhesive sheet 1 and the optical film 2 can be adjusted to a sufficiently high value.
- the thickness of the protective film can be determined as appropriate, but is generally about 10 to 200 ⁇ m from the viewpoint of strength, workability such as handleability, thin film property, etc.
- a polarizer and a protective film are usually attached to each other via a water-based adhesive or the like.
- water-based adhesives include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latex, water-based polyurethanes, and water-based polyesters.
- adhesives other than the above adhesives include ultraviolet curable adhesives and electron beam curable adhesives.
- Electron beam-curable adhesives for polarizing plates exhibit suitable adhesion to various types of protective films.
- the adhesive may include a metal compound filler.
- a retardation film or the like can also be formed on the polarizer instead of the protective film. It is also possible to provide another protective film, a retardation film, etc. on the protective film.
- a hard coat layer may be provided on the surface opposite to the surface bonded to the polarizer, and treatments for the purpose of anti-reflection, anti-sticking, diffusion, anti-glare, etc. can also be applied. .
- the polarizing film may be a circularly polarizing film.
- the retardation film one obtained by stretching a polymer film or one obtained by aligning and fixing a liquid crystal material can be used.
- the retardation film has, for example, birefringence in the plane and/or in the thickness direction.
- the retardation film includes a retardation film for antireflection (see JP-A-2012-133303 [0221], [0222], and [0228]) and a retardation film for viewing angle compensation (see JP-A 2012-133303 [0221], [0222], and [0228]). 0225], [0226]), an obliquely oriented retardation film for viewing angle compensation (see JP-A-2012-133303 [0227]), and the like.
- the specific structure of the retardation film for example, retardation value, arrangement angle, three-dimensional birefringence, single layer or multilayer, etc., is not particularly limited, and any known retardation film can be used.
- the thickness of the retardation film is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 1 to 9 ⁇ m, particularly preferably 3 to 8 ⁇ m.
- the retardation film may include, for example, a quarter-wave plate and/or a half-wave plate in which a liquid crystal material is oriented and fixed.
- the anchoring force F between the adhesive sheet 1 and the optical film 2 tends to be large.
- the anchoring force F is, for example, 10.0 N/25 mm or more, 11.0 N/25 mm or more, 12.0 N/25 mm or more, 13.0 N/25 mm or more, 14.0 N/25 mm or more, 15.0 N/25 mm or more, It may be 16.0 N/25 mm or more, or even 17.0 N/25 mm or more. It is preferable that the anchoring force F is greater than 16.0 N/25 mm.
- the upper limit of the anchoring force F is not particularly limited, and may be, for example, 50 N/25 mm or less, and may be 30 N/25 mm or less.
- the anchoring force F between the adhesive sheet 1 and the optical film 2 can be measured by the following method.
- the optical laminate 10 to be evaluated is cut out into a piece having a width of 25 mm and a length of 150 mm to form a test piece.
- the entire surface of the optical film 2 included in the test piece was superimposed on a stainless steel test plate via double-sided tape, and a 2 kg roller was moved back and forth once to press them together.
- the adhesive sheet 1 included in the test piece is superimposed on the evaluation sheet, and a 2 kg roller is moved back and forth once to press them together.
- the evaluation sheet has a size of 30 mm width x 150 mm length, and is not particularly limited as long as it does not peel off from the adhesive sheet 1 during the test.
- an ITO film 125 Tetraite OES (manufactured by Oike Kogyo Co., Ltd.), etc.
- the adhesive sheet 1 was peeled off from the optical film 2 at a peeling angle of 180° and a pulling speed of 300 mm/min while holding the evaluation sheet.
- the value is specified as the anchoring force F between the adhesive sheet 1 and the optical film 2. Note that the above test is conducted in an atmosphere at 23°C.
- the optical laminate 10 has a ratio R 250 /R i of a surface resistance value R 250 ( ⁇ / ⁇ ) determined by the following test 2 to a surface resistance value R i ( ⁇ / ⁇ ) determined by the following test 1. is preferably 3.0 or less.
- the ratio R 250 /R i can be used as an index of how easily the ITO layer is corroded by the adhesive sheet 1.
- Test 1 The adhesive sheet 1 of the optical laminate 10 (specifically, the second surface 1b of the adhesive sheet 1) is attached to an alkali-free glass ITO layer on which an amorphous ITO layer is formed.
- the adhesive sheet 1 is placed in an autoclave at 50° C. and 5 atmospheres (absolute pressure) for 15 minutes to homogenize the bond between the ITO layer and the adhesive sheet 1, and to bring the adhesive sheet 1 into close contact with the ITO layer.
- the surface resistance value R i ( ⁇ / ⁇ ) of the ITO layer is measured.
- Test 2 By the same method as Test 1, the bond between the ITO layer and the adhesive sheet 1 is homogenized in an autoclave, and an evaluation sample is obtained. This evaluation sample is treated at 65° C. and 95% RH for 250 hours under atmospheric pressure. The surface resistance value R 250 ( ⁇ / ⁇ ) of the ITO layer is measured in the evaluation sample after the treatment.
- the ITO layer can be produced by sputtering.
- the Sn ratio of ITO contained in the ITO layer is, for example, 3% by weight.
- the ratio R 250 /R i is preferably 3 or less, and may be 2.5 or less, 2 or less, 1.5 or less, or even 1.3 or less.
- the ratio R 250 /R i is, for example, greater than 1.0.
- the optical laminate 11 in FIG. 5 has a laminate structure in which an adhesive sheet 1A, an optical film 2A, an adhesive sheet 1B, and an optical film 2B are laminated in this order.
- the optical laminate 11 may have a structure in which the base sheet used in producing the adhesive sheet 1A is laminated on the adhesive sheet 1A.
- the optical film 2A is a retardation film
- the optical film 2B is a polarizing film.
- the adhesive sheet 1B functions as an interlayer adhesive between the optical films 2A and 2B.
- the adhesive sheet 1B may be one using a known adhesive.
- optical laminates 10 and 11 of this embodiment can be distributed and stored, for example, as a roll of a band-shaped optical laminate or as a sheet-shaped optical laminate.
- the optical laminate 12 in FIG. 6 includes the adhesive sheet 1 described above and a conductive layer 3 containing a metal oxide. It is preferable that the adhesive sheet 1 is in direct contact with the conductive layer 3. In the example of FIG. 6, the second surface 1b of the adhesive sheet 1 is in contact with the conductive layer 3.
- the optical laminate 12 further includes, for example, an optical film 2 and a substrate 4.
- the optical laminate 12 has a laminate structure in which an optical film 2, an adhesive sheet 1, a conductive layer 3, and a substrate 4 are laminated in this order.
- a specific example of the substrate 4 is a glass substrate.
- the metal oxide contained in the conductive layer 3 is, for example, a composite oxide.
- the composite oxide include indium zinc composite oxide (IZO), indium gallium zinc composite oxide (IGZO), indium gallium composite oxide (IGO), indium tin composite oxide (ITO), and antimony tin composite oxide. (ATO), etc.
- the optical laminate of this embodiment is typically used in an image display device.
- the image display device may be an organic EL display or a liquid crystal display. However, the image display device is not limited to the above example.
- the image display device may be an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED), or the like.
- EL electroluminescence
- PD plasma display
- FED field emission display
- the image display device can be used for household appliances, in-vehicle applications, public information displays (PID), and the like.
- Release liner B which has a release layer (thickness: 120 nm) on one side, was prepared by the same method as release liner A, except that the thickness of the release agent composition applied to the liner base material was changed.
- adhesive compositions C1 to C4 Next, monomer syrup, crosslinking agent, and corrosion inhibitor were mixed to obtain adhesive compositions C1 to C4 so as to have the compositions shown in Table 2 below.
- NDDA 1,9-nonanediol diacrylate
- 9591F Oligomeric silane coupling agent containing acid anhydride group (manufactured by Shin-Etsu Chemical Co., Ltd., X-24-9591F)
- Adhesive composition C1 was applied to the surface of the release layer of release liner A using an applicator to form a coating layer (thickness: 20 ⁇ m).
- the above-described release liner B was placed on the formed coating layer to obtain a first laminate.
- Release liner B was arranged so that the release layer was in contact with the coating layer.
- ultraviolet light black light source
- a second laminate consisting of liner A, adhesive sheet (thickness: 20 ⁇ m), and release liner B was formed.
- the release liner B was peeled off from the second laminate, and the exposed surface (first surface) of the adhesive sheet was subjected to corona treatment at a discharge amount of 61 W/m 2 ⁇ min. Thereby, the adhesive sheet of Example 1 was obtained.
- Example 2 A pressure-sensitive adhesive sheet of Example 2 was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition C2 was used.
- Example 3 Adhesive sheets of Examples 3 and 4 were obtained in the same manner as in Example 2, except that the discharge amount of the corona treatment was changed as shown in Table 3.
- Comparative example 1 A pressure-sensitive adhesive sheet of Comparative Example 1 was obtained in the same manner as in Example 2, except that no corona treatment was performed.
- Comparative example 2 A pressure-sensitive adhesive sheet of Comparative Example 2 was obtained by the same method as Comparative Example 1 except that pressure-sensitive adhesive composition C3 was used.
- Example 5 A pressure-sensitive adhesive sheet of Example 5 was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition C4 was used.
- a polarizing film was prepared by the following method. First, a polyvinyl alcohol film having a thickness of 80 ⁇ m was stretched up to 3 times the length between rolls having different speed ratios while being dyed for 1 minute in an iodine solution having a concentration of 0.3% at a temperature of 30°C. Next, the film was stretched while being immersed for 0.5 minutes in an aqueous solution containing boric acid at a concentration of 4% and potassium iodide at a concentration of 10% at a temperature of 60°C until the total stretching ratio became 6 times.
- a polarizer with a thickness of 28 ⁇ m was obtained by immersing it in an aqueous solution containing potassium iodide at a concentration of 1.5% and washing it for 10 seconds at a temperature of 30°C, and then drying it at 50°C for 4 minutes.
- Ta A 30 ⁇ m thick transparent protective film made of a modified acrylic polymer having a lactone ring structure was attached to one side of the polarizer using a polyvinyl alcohol adhesive.
- a 47 ⁇ m thick transparent protective film made of a triacetyl cellulose film (manufactured by Konica Minolta, product name "KC4UY”) with a hard coat layer (HC) is attached using a polyvinyl alcohol adhesive.
- a polarizing film was produced by heating and drying it for 5 minutes in an oven set at 70°C.
- the surface of the polarizing film on the side of the transparent protective film made of a modified acrylic polymer was subjected to corona treatment at a discharge amount of 61 W/m 2 ⁇ min.
- the above polarizing film was placed on the first surface of the adhesive sheet (the surface that was in contact with release liner B in the second laminate) to produce an optical laminate.
- the polarizing film was placed so that the surface of the transparent protective film made of a modified acrylic polymer was in contact with the adhesive sheet.
- the anchoring force F between the adhesive sheet and the polarizing film was measured by the method described above.
- product name "No. 531" manufactured by Nitto Denko Corporation was used.
- stainless steel test plate a SUS304 plate (width 40 mm x length 120 mm) was used.
- an ITO film 125 Tetraite OES, manufactured by Oike Kogyo
- Autograph SHIMAZU AG-I 10KN was used.
- the Sn ratio of ITO contained in the ITO layer was 3% by weight.
- the glass with an ITO layer was cut into pieces of 25 mm in length and 25 mm in width.
- the optical laminate was cut into a size of 15 mm in length and 15 mm in width, and was bonded to the center of the ITO layer of the ITO layered glass.
- the surface resistance values R i and R 250 were measured using HL5500PC manufactured by Accent Optical Technologies.
- the pressure-sensitive adhesive sheets of Examples 1 to 4 that satisfy the above-mentioned requirement (1) and the pressure-sensitive adhesive sheet of Example 5 that satisfies requirement (2) have a lower ratio R 250 /R than the comparative example.
- the value of i was small, and corrosion of the ITO layer was suppressed.
- the adhesive sheet of the example had a large anchoring force F with the optical film (polarizing film).
- the pressure-sensitive adhesive sheet of the present invention can be used, for example, in optical laminates and image display devices.
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Abstract
Description
単量体群及び/又は前記単量体群の重合物を含む粘着剤組成物から形成された粘着シートであって、
前記粘着シートは、互いに対向する第1表面及び第2表面を有し、
下記要件(1)及び(2)からなる群より選ばれる少なくとも1つを満たす、粘着シートを提供する。
(1)前記単量体群100重量部のうち、カルボキシル基含有単量体の配合量が0.5重量部以下であり、
前記第1表面をトリフルオロエタノールで処理した場合に、前記第1表面におけるフッ素の元素比率R1が0.1原子%以上である。
(2)前記粘着剤組成物が腐食防止剤を含み、
前記単量体群100重量部のうち、カルボキシル基含有単量体の配合量が7.0重量部以下であり、
前記第1表面をトリフルオロエタノールで処理した場合に、前記第1表面におけるフッ素の元素比率R1が0.1原子%以上である。
上記の粘着シートと、
偏光フィルム及び位相差フィルムからなる群より選ばれる少なくとも1つを含む光学フィルムと、
を備えた、光学積層体を提供する。
上記の粘着シートと、
金属酸化物を含む導電層と、
を備えた、光学積層体を提供する。
単量体群及び/又は前記単量体群の重合物を含む粘着剤組成物から形成された粘着シートであって、
前記粘着シートは、互いに対向する第1表面及び第2表面を有し、
下記要件(1)及び(2)からなる群より選ばれる少なくとも1つを満たす。
(1)前記単量体群100重量部のうち、カルボキシル基含有単量体の配合量が0.5重量部以下であり、
前記第1表面をトリフルオロエタノールで処理した場合に、前記第1表面におけるフッ素の元素比率R1が0.1原子%以上である。
(2)前記粘着剤組成物が腐食防止剤を含み、
前記単量体群100重量部のうち、カルボキシル基含有単量体の配合量が7.0重量部以下であり、
前記第1表面をトリフルオロエタノールで処理した場合に、前記第1表面におけるフッ素の元素比率R1が0.1原子%以上である。
第1~第9態様のいずれか1つにかかる粘着シートと、
偏光フィルム及び位相差フィルムからなる群より選ばれる少なくとも1つを含む光学フィルムと、
を備える。
第1~第9態様のいずれか1つにかかる粘着シートと、
金属酸化物を含む導電層と、
を備える。
本実施形態の粘着シートの一例を図1に示す。図1の粘着シート1は、単量体群及び/又は当該単量体群の重合物を含む粘着剤組成物から形成されている。粘着シート1は、互いに対向する第1表面1a及び第2表面1bを有する。一例として、第1表面1aを介して粘着シート1が光学フィルムに貼り付けられ、第2表面1bを介して粘着シート1が画像表示パネルの導電層に貼り付けられる。
(1)単量体群100重量部のうち、カルボキシル基含有単量体の配合量が0.5重量部以下であり、
粘着シート1の第1表面1aをトリフルオロエタノールで処理した場合に、第1表面1aにおけるフッ素の元素比率R1が0.1原子%以上である。
(2)粘着剤組成物が腐食防止剤を含み、
単量体群100重量部のうち、カルボキシル基含有単量体の配合量が7.0重量部以下であり、
粘着シート1の第1表面1aをトリフルオロエタノールで処理した場合に、第1表面1aにおけるフッ素の元素比率R1が0.1原子%以上である。
R-COOH + CF3CH2OH → R-COOCH2CF3
上述のとおり、粘着シート1は、粘着剤組成物から形成されている。粘着剤組成物は、光が照射されることによって粘着シート1を形成する光硬化性の粘着剤組成物であることが好ましい。ただし、粘着剤組成物は、熱によって粘着シート1を形成する熱硬化性の粘着剤組成物であってもよい。
粘着シート1における単量体群の重合率は、好ましくは90%以上である。重合率は、95%以上、98%以上、さらには99%以上であってもよい。
粘着シート1の製造方法は、特に限定されない。一例として、粘着剤組成物が光硬化性である場合、粘着シート1は、次の方法によって製造できる。まず、図3Aや図3Bに示すように、基材シート21、粘着剤組成物を含む塗布層22、及びはく離ライナー23をこの順に含む第1の積層体15を作製する。第1の積層体15に光14を照射することによって塗布層22から粘着シート1を形成することができる(図3C)。
本実施形態の光学積層体の一例を図4に示す。図4の光学積層体10は、上記の粘着シート1と、偏光フィルム及び位相差フィルムからなる群より選ばれる少なくとも1つの光学フィルム2とを含む。粘着シート1は、光学フィルム2と直接接していることが好ましい。図4の例では、粘着シート1の第1表面1aが光学フィルム2と接している。光学積層体10は、粘着シート1の作製時に用いた基材シートが粘着シート1に積層された構造を有していてもよい。光学積層体10は、粘着シート付き光学フィルムとして使用できる。
光学フィルム2は、粘着シート1に対向する表面2aを有する。例えば、表面2aが粘着シート1の第1表面1aと接している。光学フィルム2の表面2aには、表面改質処理が施されていてもよい。表面改質処理が施された表面2aによれば、粘着シート1と光学フィルム2との投錨力を向上できる傾向がある。表面改質処理としては、粘着シート1について上述したものが挙げられる。
上述のとおり、本実施形態では、粘着シート1が要件(1)又は(2)を満たすため、粘着シート1と光学フィルム2との投錨力Fが大きい傾向がある。投錨力Fは、例えば10.0N/25mm以上であり、11.0N/25mm以上、12.0N/25mm以上、13.0N/25mm以上、14.0N/25mm以上、15.0N/25mm以上、16.0N/25mm以上、さらには17.0N/25mm以上であってもよい。投錨力Fは、16.0N/25mmより大きいことが好ましい。投錨力Fがこの程度に大きい場合、粘着シート1と光学フィルム2との間での剥がれを十分に抑制することができる。投錨力Fの上限は、特に限定されず、例えば50N/25mm以下であり、30N/25mm以下であってもよい。
試験1:表面に非晶性のITO層が形成された無アルカリガラスのITO層に、光学積層体10の粘着シート1(詳細には、粘着シート1の第2表面1b)を貼り付ける。50℃及び5気圧(絶対圧)のオートクレーブ内に15分収容してITO層と粘着シート1との接合を均質化させ、粘着シート1をITO層に密着させる。得られた評価サンプルにおいて、ITO層の表面抵抗値Ri(Ω/□)を測定する。
試験2:試験1と同じ方法によって、オートクレーブ内でITO層と粘着シート1との接合を均質化させ、評価サンプルを得る。この評価サンプルについて、大気圧下、65℃95%RHで250時間処理を行う。処理後の評価サンプルにおいて、ITO層の表面抵抗値R250(Ω/□)を測定する。
導電層3に含まれる金属酸化物は、例えば複合酸化物である。複合酸化物としては、例えば、インジウム亜鉛複合酸化物(IZO)、インジウムガリウム亜鉛複合酸化物(IGZO)、インジウムガリウム複合酸化物(IGO)、インジウムスズ複合酸化物(ITO)、アンチモンスズ複合酸化物(ATO)などが挙げられる。
付加反応硬化型シリコーン(ヘキセニル基含有ポリオルガノシロキサンを含むLTC761、30重量%トルエン溶液、東レ・ダウコーニング製)30重量部、剥離コントロール剤(未反応性シリコーン樹脂を含むBY24-850、東レ・ダウコーニング製)0.9重量部、及び硬化触媒(白金触媒を含むSRX212、東レ・ダウコーニング製)2重量部、及び希釈溶媒としてトルエン/ヘキサン混合溶媒(体積比1:1)を混合して、シリコーン系離型剤組成物を得た。離型剤組成物におけるシリコーン固形分の濃度は、1.0重量%であった。次に、ライナー基材(ポリエステルフィルムであるルミラーXD500P、厚さ75μm)の片面に離型剤組成物をワイヤーバーにより塗布し、130℃で1分間加熱して、離型層(厚さ60nm)を片面に備えるはく離ライナーAを作製した。
ライナー基材に塗布する離型剤組成物の厚さを変更した以外は、はく離ライナーAと同じ方法によって、離型層(厚さ120nm)を片面に備えるはく離ライナーBを作製した。
n-ブチルアクリレート(BA)99重量部、4-ヒドロキシブチルアクリレート(HBA)1重量部、及びアクリル酸(AA)0.2重量部と、光重合開始剤として1-ヒドロキシシクロヘキシル-フェニルケトン(Omnirad184、IGM Resins B.V.社製)0.05重量部、及び2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(Omnirad651、IGM Resins B.V.社製)0.05重量部とを4つロフラスコに投入し、窒素雰囲気下で紫外線を照射することによって、部分的に光重合したモノマーシロップA1を得た。紫外線の照射は、フラスコ内の液体の粘度(計測条件:BH粘度計No.5ローター、10rpm、測定温度30℃)が約20Pa・sになるまで実施した。
使用するモノマーを表1のように変更したことを除き、モノマーシロップA1と同じ方法によって、モノマーシロップA2~A4を調製した。
BA:n-ブチルアクリレート
HBA:4-ヒドロキシブチルアクリレート
AA:アクリル酸
次に、以下の表2に示す組成となるように、モノマーシロップ、架橋剤及び腐食防止剤を混合して、粘着剤組成物C1~C4を得た。
NDDA:1,9-ノナンジオールジアクリレート
9591F:酸無水物基含有オリゴマー型シランカップリング剤(信越化学工業社製、X-24-9591F)
はく離ライナーAの離型層の面に、粘着剤組成物C1をアプリケーターにより塗布し、塗布層(厚さ20μm)を形成した。次に、形成した塗布層の上に、上述のはく離ライナーBを配置して第1の積層体を得た。はく離ライナーBは、離型層が塗布層に接するように配置した。次に、第1の積層体におけるはく離ライナーAの側から、照度2.5mW/cm2、照射時間640秒の条件で紫外線(Black light光源)を照射し、塗布層を光硬化させて、はく離ライナーA、粘着シート(厚さ20μm)及びはく離ライナーBにより構成される第2の積層体を形成した。
粘着剤組成物C2を用いたことを除き、実施例1と同じ方法によって、実施例2の粘着シートを得た。
コロナ処理の放電量を表3のように変更したことを除き、実施例2と同じ方法によって、実施例3及び4の粘着シートを得た。
コロナ処理を行わなかったことを除き、実施例2と同じ方法によって、比較例1の粘着シートを得た。
粘着剤組成物C3を用いたことを除き、比較例1と同じ方法によって、比較例2の粘着シートを得た。
粘着剤組成物C4を用いたことを除き、実施例1と同じ方法によって、実施例5の粘着シートを得た。
実施例及び比較例の粘着シートの第1表面(第2の積層体において、はく離ライナーBと接していた表面)について、上述した方法によって、トリフルオロエタノールで処理し、フッ素の元素比率R1を測定した。なお、X線光電子分光分析装置を用いたナロースキャン測定は、C、N、O、F、Si元素について行った。X線光電子分光分析装置による測定条件は、以下のとおりであった。
(測定条件)
装置:アルバック・ファイ社製Quantera SXM
X線源:モノクロAlKα
X Ray setting:100μmφ[15kV,25W]
光電子取出し角:試料表面に対して45°
結合エネルギーの補正:C1sスペクトルのC-C結合由来のピークを285.0eVに補正
帯電中和条件:電子中和銃とArイオン銃(中和モード)の併用
実施例及び比較例の粘着シートについて、偏光フィルムとの投錨力Fを測定した。偏光フィルムは、次の方法によって準備した。まず、厚さ80μmのポリビニルアルコールフィルムを、速度比の異なるロール間において、温度30℃、濃度0.3%のヨウ素溶液中で1分間染色しながら、3倍まで延伸した。次に、濃度4%でホウ酸を含み、かつ濃度10%でヨウ化カリウムを含む、温度60℃の水溶液中に0.5分間浸漬しながら、総合延伸倍率が6倍になるまで延伸した。次に、濃度1.5%でヨウ化カリウムを含む、温度30℃の水溶液中に10秒間浸漬させて洗浄した後、50℃で4分間乾燥を行うことによって、厚さ28μmの偏光子を得た。当該偏光子の片面に、ラクトン環構造を有する変性アクリル系ポリマーからなる厚さ30μmの透明保護フィルムをポリビニルアルコール系接着剤により貼り合せた。さらに、偏光子の他方の面に、トリアセチルセルロースフィルム(コニカミノルタ製、商品名「KC4UY」)にハードコート層(HC)を形成した厚さ47μmの透明保護フィルムをポリビニルアルコール系接着剤により貼り合せた。70℃に設定されたオーブン内で5分間加熱乾燥させることによって偏光フィルムを作製した。さらに、変性アクリル系ポリマーからなる透明保護フィルム側の偏光フィルムの表面に対して、放電量61W/m2・minでコロナ処理を行った。
まず、上記の投錨力Fの測定方法と同じ方法によって、光学積層体を作製した。得られた光学積層体を用いて、上述の試験1及び2を行い、表面抵抗値Ri(Ω/□)に対する表面抵抗値R250(Ω/□)の比R250/Riを特定した。試験1及び2において、ITO層は、厚さ0.7mmの無アルカリガラス(コーニング社製、商品名「EG-XG」)にITOをスパッタ成膜することによって作製した。ITO層に含まれるITOのSn比率(Sn原子の重量/(Sn原子の重量+In原子の重量))は3重量%であった。ITO層付きガラスは、縦25mm×横25mmに切断して用いた。光学積層体は、縦15mm×横15mmに切断して、ITO層付きガラスのITO層の中央部に貼り合わせた。表面抵抗値Ri及びR250は、Accent Optical Technologies社製のHL5500PCを用いて測定した。
Claims (14)
- 単量体群及び/又は前記単量体群の重合物を含む粘着剤組成物から形成された粘着シートであって、
前記粘着シートは、互いに対向する第1表面及び第2表面を有し、
下記要件(1)及び(2)からなる群より選ばれる少なくとも1つを満たす、粘着シート。
(1)前記単量体群100重量部のうち、カルボキシル基含有単量体の配合量が0.5重量部以下であり、
前記第1表面をトリフルオロエタノールで処理した場合に、前記第1表面におけるフッ素の元素比率R1が0.1原子%以上である。
(2)前記粘着剤組成物が腐食防止剤を含み、
前記単量体群100重量部のうち、カルボキシル基含有単量体の配合量が7.0重量部以下であり、
前記第1表面をトリフルオロエタノールで処理した場合に、前記第1表面におけるフッ素の元素比率R1が0.1原子%以上である。 - 前記第2表面をトリフルオロエタノールで処理した場合に、前記第2表面におけるフッ素の元素比率R2が0.1原子%未満である、請求項1に記載の粘着シート。
- 前記粘着剤組成物は、光硬化性である、請求項1に記載の粘着シート。
- 前記粘着剤組成物における溶剤の含有率が5重量%以下である、請求項1に記載の粘着シート。
- 前記第1表面は、表面改質処理が施された面である、請求項1に記載の粘着シート。
- 前記表面改質処理がコロナ処理である、請求項5に記載の粘着シート。
- 前記腐食防止剤は、酸性基又は酸無水物基を有するケイ素含有化合物、リン酸系化合物、及びホスホン酸系化合物からなる群より選ばれる少なくとも1つを含む、請求項1に記載の粘着シート。
- 前記単量体群は、(メタ)アクリル系単量体を含む、請求項1に記載の粘着シート。
- 厚さが50μm以下である、請求項1に記載の粘着シート。
- 請求項1~9のいずれか1項に記載の粘着シートと、
偏光フィルム及び位相差フィルムからなる群より選ばれる少なくとも1つを含む光学フィルムと、
を備えた、光学積層体。 - 前記粘着シートの前記第1表面が前記光学フィルムと接している、請求項10に記載の光学積層体。
- 前記粘着シートと前記光学フィルムとの投錨力が10.0N/25mm以上である、請求項10に記載の光学積層体。
- 請求項1~9のいずれか1項に記載の粘着シートと、
金属酸化物を含む導電層と、
を備えた、光学積層体。 - 前記粘着シートの前記第2表面が前記導電層と接している、請求項13に記載の光学積層体。
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