WO2022244813A1 - Optical pressure-sensitive adhesive sheet, optical laminate, and image display device - Google Patents

Optical pressure-sensitive adhesive sheet, optical laminate, and image display device Download PDF

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Publication number
WO2022244813A1
WO2022244813A1 PCT/JP2022/020709 JP2022020709W WO2022244813A1 WO 2022244813 A1 WO2022244813 A1 WO 2022244813A1 JP 2022020709 W JP2022020709 W JP 2022020709W WO 2022244813 A1 WO2022244813 A1 WO 2022244813A1
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WIPO (PCT)
Prior art keywords
sensitive adhesive
meth
pressure
group
weight
Prior art date
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PCT/JP2022/020709
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French (fr)
Japanese (ja)
Inventor
普史 形見
大輔 水野
虎太朗 雨宮
Original Assignee
日東電工株式会社
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Publication date
Priority claimed from JP2022080536A external-priority patent/JP2022179400A/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020237042735A priority Critical patent/KR20240012430A/en
Priority to CN202280036260.7A priority patent/CN117355581A/en
Publication of WO2022244813A1 publication Critical patent/WO2022244813A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02Electrically-conducting adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/02Physical, chemical or physicochemical properties
    • B32B7/023Optical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29Laminated material
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective coatings, e.g. hard coatings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to an optical pressure-sensitive adhesive sheet, an optical laminate, and an image display device. More specifically, an optical pressure-sensitive adhesive sheet having a laminated structure with a pressure-sensitive adhesive layer having excellent antistatic properties, an optical laminate in which the optical pressure-sensitive adhesive sheet and an optical member are laminated, and the optical pressure-sensitive adhesive sheet and an image display panel It relates to an image display device in which and are laminated.
  • LCDs liquid crystal displays
  • touch panels In recent years, display devices such as liquid crystal displays (LCDs) and input devices such as touch panels have been widely used in various fields.
  • adhesive sheets are used for bonding optical members.
  • transparent adhesive sheets are used for laminating optical members in various display devices such as touch panels.
  • it is widely practiced to transport optical pressure-sensitive adhesive sheets in which a pressure-sensitive adhesive layer is laminated on a polarizing film, a retardation film, a transparent cover member such as a cover glass, and other various optical members.
  • the compatibility with the adhesive layer may decrease, or the antistatic agent may precipitate on the surface of the adhesive layer, resulting in transparency such as white turbidity, especially in a hot and humid environment. and appearance defects may occur.
  • foaming, peeling, and the like may occur in a moist and hot environment, resulting in durability problems.
  • An object of the present invention is to provide an optical laminate in which a pressure-sensitive adhesive sheet for optical devices and an optical member are laminated.
  • Another object of the present invention is to provide an optical adhesive having a laminated structure in which a pressure-sensitive adhesive layer having low surface resistivity, excellent antistatic performance, which is less likely to cause defects in transparency, appearance, and durability, is laminated.
  • An object of the present invention is to provide an image display device in which an adhesive sheet for image display and an image display panel are laminated.
  • an acrylic polymer is used as a base polymer constituting a pressure-sensitive adhesive layer that the optical pressure-sensitive adhesive sheet has in a laminated structure, and as an antistatic agent,
  • an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer in the molecule defects in transparency, appearance, and durability are less likely to occur, and low surface resistivity is exhibited, resulting in excellent antistatic properties.
  • the inventors have found that a pressure-sensitive adhesive layer having performance can be formed, and completed the present invention.
  • the first aspect of the present invention has a laminated structure in which a substrate having a first surface and a second surface and an adhesive layer is laminated on the first surface of the substrate, and the adhesive layer is , an antistatic agent, and a mixture of monomer components constituting the acrylic polymer (A) or a partially polymerized product of a mixture of monomer components constituting the acrylic polymer (A).
  • a second aspect of the present invention has a laminated structure in which a substrate having a first surface and a second surface and an adhesive layer is laminated on the first surface of the substrate, and the adhesive layer is , an optical pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing an antistatic agent and an acrylic polymer (A).
  • the antistatic agent is an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in its molecule.
  • the antistatic agent is an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in its molecule.
  • the ionic compound that constitutes the antistatic agent can form a covalent bond with the acrylic polymer (A). Defects in transparency and appearance due to precipitation of the antistatic agent on the surface of the agent layer are unlikely to occur, and foaming and peeling due to the antistatic agent in a moist and hot environment are unlikely to occur, and excellent durability is also preferable. . Therefore, the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention are less likely to cause defects in transparency, appearance and durability, exhibit low surface resistivity, and have excellent antistatic performance.
  • the functional group that the antistatic agent has in the molecule includes (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, allyl group, It is preferably at least one selected from the group consisting of styryl groups, hydroxyl groups, amino groups, mercapto groups and epoxy groups. These functional groups are preferable in that they easily form a covalent bond with the acrylic polymer (A).
  • the acrylic polymer (A) does not contain or substantially does not contain a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer (A).
  • This configuration is preferable in that the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention can obtain an excellent effect of preventing corrosion of metal wiring.
  • the pressure-sensitive adhesive composition preferably contains no or substantially no organic solvent. This configuration is preferable in that defects in appearance such as citrus peel are less likely to occur.
  • the haze (according to JIS K7136) of the pressure-sensitive adhesive layer is preferably 1.0% or less.
  • the total light transmittance (according to JIS K7361-1) of the front adhesive layer is preferably 90% or more.
  • the 180° peeling adhesive force at 23°C of the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention to a glass plate is preferably 4 N/20 mm or more. This configuration is preferable in that the adhesiveness to glass and the ability to prevent floating on steps are more excellent.
  • the thickness of the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention is preferably 12-350 ⁇ m.
  • a configuration in which the thickness is equal to or greater than a certain value is preferable in that peeling at the step portion is less likely to occur.
  • a configuration in which the thickness is equal to or less than a certain value is preferable in terms of making it easier to maintain an excellent appearance during manufacturing.
  • the second surface of the base material is preferably subjected to antireflection treatment, antiglare treatment, hard coat treatment, and/or antistatic treatment.
  • the configuration in which the second surface of the base material is subjected to antireflection treatment and / or antiglare treatment prevents deterioration of visibility due to reflection of external light and reflection of images, and adjusts appearance such as glossiness. It is preferable from the viewpoint of Further, the configuration in which the second surface of the base material is hard-coated is preferable in that the surface hardness and scratch resistance are improved.
  • the configuration in which the second surface of the base material is antistatically treated suppresses static electricity from being charged to the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention, thereby preventing the optical pressure-sensitive adhesive sheet from being charged with static electricity.
  • a third aspect of the present invention provides an optical laminate in which the optical pressure-sensitive adhesive sheet of the first or second aspect of the present invention and an optical member are laminated.
  • a fourth aspect of the present invention provides an image display device in which the optical pressure-sensitive adhesive sheet of the first or second aspect of the present invention and an image display panel are laminated.
  • the optical layered body of the third aspect of the present invention and the image display device of the fourth aspect of the present invention are less likely to cause defects in transparency, appearance and durability, exhibit low surface resistivity, and are excellent in antistatic properties. Since the optical pressure-sensitive adhesive sheet of the first or second aspect of the present invention having performance is provided in a laminated structure, display defects due to static electricity are less likely to occur, which is preferable.
  • the optical pressure-sensitive adhesive sheet of the present invention is less likely to cause defects in transparency, appearance, and durability, exhibits low surface resistivity, and has excellent antistatic performance. Therefore, by using the optical pressure-sensitive adhesive sheet of the present invention for manufacturing an image display device, excellent transparency, appearance and durability can be maintained, and display defects due to static electricity can be suppressed.
  • the optical laminate and the image display device having the optical pressure-sensitive adhesive sheet of the present invention in a laminated structure can maintain excellent transparency, appearance and durability, and can suppress display defects caused by static electricity.
  • 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 one embodiment of the optical laminate of the present invention.
  • FIG. 3 is a schematic diagram (sectional view) showing an embodiment of the image display device of the present invention.
  • the optical pressure-sensitive adhesive sheet of the first aspect of the present invention has a laminated structure in which a substrate having a first surface and a second surface and an adhesive layer is laminated on the first surface of the substrate,
  • the agent layer is formed from a pressure-sensitive adhesive composition containing an antistatic agent and a mixture of monomer components constituting the acrylic polymer (A) or a partial polymer of a mixture of monomer components constituting the acrylic polymer (A). optical pressure-sensitive adhesive sheet.
  • the optical pressure-sensitive adhesive sheet of the second aspect of the present invention has a laminated structure in which a substrate having a first surface and a second surface and a pressure-sensitive adhesive layer is laminated on the first surface of the substrate,
  • the pressure-sensitive adhesive sheet for optical use wherein the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing an antistatic agent and an acrylic polymer (A).
  • the antistatic agent is an ionic compound having in its molecule a functional group capable of forming a covalent bond with the acrylic polymer (A).
  • the above-mentioned “mixture of monomer components” includes the case of being composed of a single monomer component and the case of being composed of two or more monomer components.
  • the above-mentioned “partially polymerized mixture of monomer components” means a composition in which one or more of the constituent monomer components of the above-mentioned “mixture of monomer components” is partially polymerized. do.
  • acrylic polymer (A) when simply referring to "acrylic polymer (A)", unless otherwise specified, “acrylic polymer (A)”, “mixture of monomer components constituting acrylic polymer (A)”, and “"partially polymerized mixture of monomer components constituting the acrylic polymer (A)” is also included.
  • the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention may be collectively referred to as "the optical pressure-sensitive adhesive sheet of the present invention".
  • the base material, the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive composition constituting the optical pressure-sensitive adhesive sheet of the present invention are respectively referred to as “the base material of the present invention", “the pressure-sensitive adhesive layer of the present invention”, and may be referred to as “the adhesive composition of the present invention”.
  • the antistatic agent contained in the pressure-sensitive adhesive composition of the present invention the "ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in the molecule”
  • the antistatic agent of the present invention is referred to as the "antistatic agent of the present invention”.
  • the optical layered body of the third aspect of the present invention is an optical layered body obtained by laminating the optical pressure-sensitive adhesive sheet of the present invention and an optical member.
  • the optical layered body of the third aspect of the present invention may be referred to as "the optical layered body of the present invention” in this specification.
  • the image display device of the fourth aspect of the present invention is 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 fourth aspect of the present invention may be referred to as "the image display device of the present invention” in this specification.
  • 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 pressure-sensitive adhesive sheet 10 has a laminated structure in which a substrate 1 and a pressure-sensitive adhesive layer 2 are laminated.
  • the substrate 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 substrate 1.
  • the second surface 1b of the substrate 1 is subjected to antireflection treatment, antiglare treatment, hard coat treatment, and/or antistatic treatment 3.
  • the surface (adhesive surface) of the adhesive layer 2 that is not laminated on the first surface 1 a of the substrate 1 is protected by the separator 4 .
  • FIG. 2 is a schematic diagram (cross-sectional view) showing one embodiment of the optical laminate of the present invention.
  • the optical laminate 20 has a laminate structure in which a substrate 1, an adhesive layer 2, and an optical member 5 are laminated in this order.
  • the substrate 1 has a first surface 1a and a second surface 1b, and the pressure-sensitive adhesive layer 2 is laminated on the first surface 1a of the substrate 1 .
  • the optical member 5 is laminated on the surface of the pressure-sensitive adhesive layer 2 that is not laminated on the first surface 1a of the substrate 1 .
  • the second surface 1b of the substrate 1 is subjected to antireflection treatment, antiglare treatment, hard coat treatment, and/or antistatic treatment 3.
  • FIG. 1 is a schematic diagram (cross-sectional view) showing one embodiment of the optical laminate of the present invention.
  • the optical laminate 20 has a laminate structure in which a substrate 1, an adhesive layer 2, and an optical member 5 are laminated in this order.
  • the substrate 1 has a first surface 1a and
  • FIG. 3 is a schematic diagram (sectional view) showing one embodiment of the image display device of the present invention.
  • the image display device 30 has an image display panel 6 laminated on the adhesive layer 2 of the optical adhesive sheet 10 .
  • Each configuration will be described below.
  • optical adhesive sheet The “optical” in the optical pressure-sensitive adhesive sheet of the present invention means that it is used for optical purposes, and more specifically means that it is used for manufacturing products (optical products) using optical members. do.
  • optical products include image display devices, input devices such as touch panels, and liquid crystal image display devices, self-luminous image display devices (eg, organic EL (electroluminescence) image display devices, LED image display devices, etc.). ) and the like.
  • 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 substrate of the present invention.
  • it may be a single-sided PSA sheet having an adhesive surface on only one side, or a double-sided PSA sheet having an adhesive surface on both sides.
  • the optical pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet
  • the optical pressure-sensitive adhesive sheet of the present invention may have a form in which both pressure-sensitive adhesive surfaces are provided by the pressure-sensitive adhesive layer of the present invention.
  • one pressure-sensitive adhesive surface is provided by the pressure-sensitive adhesive layer of the present invention, and the other pressure-sensitive adhesive surface is provided by a pressure-sensitive adhesive layer other than the pressure-sensitive adhesive layer of the present invention (other pressure-sensitive adhesive layer).
  • the optical pressure-sensitive adhesive sheet of the present invention constitutes the outermost surface of an optical product, a single-sided pressure-sensitive adhesive sheet is preferable, and when adherends (optical members) are bonded together, a double-sided pressure-sensitive adhesive sheet is preferable.
  • the meaning of an "adhesive tape" shall be included in an “adhesive sheet.” That is, the optical pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive tape having a tape-like shape.
  • the adhesive layer surface may be called an "adhesive surface.”
  • 180° peeling strength of the optical pressure-sensitive adhesive sheet of the present invention to a glass plate at 23°C 180° peeling adhesive force at 23°C to a glass plate) is not particularly limited, but from the viewpoint that sufficient adhesion can be obtained if the adhesive force is high, it is preferably 4 N / 20 mm or more, more preferably. is 6 N/20 mm or more, more preferably 8 N/20 mm or more, still more preferably 10 N/20 mm or more. If the optical pressure-sensitive adhesive sheet of the present invention has a 180° peeling adhesive strength to a glass plate at 23°C of a certain value or more, the adhesiveness to glass and the ability to prevent floating on steps are further improved.
  • the upper limit of the 180° peeling adhesive strength of the optical pressure-sensitive adhesive sheet of the present invention to a glass plate at 23°C is not particularly limited, but is preferably, for example, 28 N/20 mm, 27 N/20 mm, or 26 N/20 mm. Preferably, they are 25N/20mm, 24N/20mm, 23N/20mm, 22N/20mm, 21N/20mm and 20N/20mm.
  • 180° peeling strength of the optical pressure-sensitive adhesive sheet of the present invention to a glass plate at 80°C 180° peeling adhesive force at 80°C to a glass plate) is not particularly limited, but from the viewpoint that sufficient adhesion can be obtained if the adhesive force is high, it is preferably 4 N / 20 mm or more, more preferably. is 6 N/20 mm or more, more preferably 8 N/20 mm or more, still more preferably 10 N/20 mm or more. If the optical pressure-sensitive adhesive sheet of the present invention has a 180° peeling adhesive strength to a glass plate at 80°C of a certain value or more, the adhesiveness to glass and the ability to prevent floating on steps are further improved.
  • the upper limit of the 180° peeling adhesive strength at 80°C of the optical pressure-sensitive adhesive sheet of the present invention to a glass plate is not particularly limited, it is preferably 18 N/20 mm, more preferably 16 N/20 mm.
  • the 180° peeling adhesion to a glass plate at 23°C or 80°C is determined by the following method for measuring 180° peeling adhesion.
  • the glass plate is not particularly limited, for example, the product name "Soda Lime Glass #0050” (manufactured by Matsunami Glass Industry Co., Ltd.) can be mentioned.
  • non-alkali glass, chemically strengthened glass, and the like can also be used.
  • the adhesive surface of the optical pressure-sensitive adhesive sheet is adhered to the adherend, pressed with a 2-kg roller for one reciprocation, and aged in an atmosphere of 23° C. and 50% RH for 30 minutes or 240 hours. After aging, according to JIS Z 0237, the optical pressure-sensitive adhesive sheet was peeled off from the adherend under the conditions of 23° C. or 80° C., 50% RH, a tensile speed of 300 mm/min, and a peeling angle of 180°, Measure the 180° peel adhesion (N/20 mm).
  • the thickness (total thickness) of the adhesive sheet of the present invention is not particularly limited, but is preferably 12 to 350 ⁇ m, more preferably 15 to 330 ⁇ m, 18 to 325 ⁇ m, 18 to 320 ⁇ m, 20 to 300 ⁇ m, 23 to 300 ⁇ m, 25 to 275 ⁇ m. , or from 30 to 250 ⁇ m.
  • the thickness is equal to or greater than a certain value, peeling at the step portion is less likely to occur, which is preferable. Further, when the thickness is less than a certain value, it is preferable because it becomes easy to maintain an excellent appearance during production.
  • the thickness of the pressure-sensitive adhesive sheet of the present invention includes the thickness of the substrate, but does not include the thickness of the separator.
  • the haze (according to JIS K7136) of the optical pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 1.0% or less, more preferably 0.8% or less, 0.7% or less, or 0.6%. It may be below. A haze of 1.0% or less is preferable because excellent transparency and appearance can be obtained.
  • the above-mentioned haze can be measured, for example, by leaving the optical pressure-sensitive adhesive sheet in a normal state (23° C., 50% RH) for at least 24 hours, peeling off the separator, if any, and adjusting the haze on a slide glass (e.g., total light transmission).
  • haze of 92% and haze of 0.2%) can be used as a sample and measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., trade name "HM-150N").
  • the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the optical pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 90% or more, more preferably 91% or more, or 92% or more. There may be. When the total light transmittance is 90% or more, excellent transparency and excellent appearance can be obtained, which is preferable.
  • the above total light transmittance can be measured, for example, by allowing the optical pressure-sensitive adhesive sheet to stand in a normal state (23° C., 50% RH) for at least 24 hours, peeling off the separator if it has one, and using a slide glass (for example, Total light transmittance of 92%, haze of 0.2%) is used as a sample, and measured using a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HM-150N"). can be done.
  • HM-150N haze meter
  • the adhesive strength, total light transmittance and haze of the optical pressure-sensitive adhesive sheet of the present invention can be measured by the methods described in Examples below.
  • the adhesive strength, total light transmittance and haze of the optical pressure-sensitive adhesive sheet of the present invention are determined by the composition of the monomers constituting the acrylic polymer (A), the amount of the cross-linking agent, the ionic compound of the present invention, the type of other additives, and the Adjustments can be made by adjusting amounts, curing conditions, and the like.
  • Materials constituting the substrate of the present invention include glass and plastic films.
  • the plastic film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); name "Zeonor” (manufactured by Zeon Co., Ltd.), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, transparent polyimide (CPI), poly
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • Zeonor manufactured by Zeon Co., Ltd.
  • acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, transparent polyimide (CPI)
  • PMMA polymethyl methacrylate
  • TAC triacetyl cellulose
  • polysulfone polyarylate
  • polyimide polyimide
  • polyester-based resins and cyclic olefin-based polymers which are excellent in dimensional stability and resistant to shrinkage.
  • these plastic materials can be used individually or in combination of 2 or more types.
  • the substrate 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 (optical member, image display panel, etc.).
  • the "base material” does not include a separator (release liner) that is peeled off when the optical pressure-sensitive adhesive sheet of the present invention is used (attached).
  • the substrate 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 an optical member constituting the optical product, and includes various optical films such as cover members, polarizing plates, and retardation plates, and is preferably used as a cover member.
  • the second surface is, for example, the outermost surface of the optical product.
  • the glass transition point (Tg) of the base material of the present invention is not particularly limited, it is preferably 60°C or higher and 160°C or lower.
  • a configuration in which the glass transition point of the substrate of the present invention is 60° C. or higher is preferable in terms of stabilizing the mechanical properties of the image display device of the present invention under the usage environment.
  • the glass transition point of the substrate may be 63° C. or higher, or 65° C. or higher.
  • the configuration in which the glass transition point of the substrate is 160° C. or lower is preferable in that the molding process of the substrate can be simplified.
  • the glass transition point of the substrate is preferably 140° C. or lower, and may be 135° C. or lower, 130° C. or lower, or 125° C. or lower in terms of simplifying the molding process of the substrate.
  • the glass transition point (Tg) of the base material of the present invention can be measured according to JIS K 7121.
  • the glass transition point (Tg) 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 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 configuration in which the humidity expansion coefficient of the substrate of the present invention is 5 ⁇ 10 ⁇ 5 /% RH or less is preferable in terms of improving the dimensional stability of the substrate of the present invention against temperature changes and maintaining a good appearance. is.
  • the humidity expansion coefficient of the base material of the present invention is preferably 3 ⁇ 10 ⁇ 5 /% RH or less, and may be 2 ⁇ 10 ⁇ 5 /% RH or less.
  • the coefficient of humidity expansion of the base material of the present invention can be measured by the method described in Examples below.
  • 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 (temperature, extrusion speed, etc.) during the production of the base material, and the like.
  • the haze of the base material of the present invention is not particularly limited, it is preferably 5% or more.
  • the configuration in which the haze of the base material of the present invention is 5% or more is preferable in that reflection due to metal wiring, ITO wiring, or the like arranged on the substrate of the image display panel in the image display device of the present invention can be prevented. It is preferably 6% or more, and may be 7% or more.
  • the upper limit of the haze of the base material of the present invention is not particularly limited, but from the viewpoint of visibility of the image display device of the present invention, it is preferably 50% or less, and may be 40% or less or 30% or less.
  • the haze of the base material of the present invention can be measured according to JIS K 7136.
  • the haze of the substrate of the present invention can be adjusted by the type and thickness of the resin that constitutes the substrate of the present invention, and by subjecting the surface of the substrate to antireflection treatment and/or antiglare treatment.
  • the reflectance of the substrate of the present invention is not particularly limited, it is preferably 5% or less.
  • the configuration in which the reflectance of the base material of the present invention is 5% or less is preferable in that reflection due to metal wiring, ITO wiring, or the like arranged on the substrate of the image display panel in the image display device of the present invention can be prevented. It is more preferably 3% or less, and may be 1.5% or less.
  • the lower limit of the reflectance of the substrate of the present invention is not particularly limited, but may be 0.1% or more, or 0.3% or more.
  • the reflectance of the substrate of the present invention can be measured according to 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 antireflection treatment and/or antiglare treatment.
  • the thickness of the substrate of the present invention is not particularly limited, it is preferably in the range of 10 to 500 ⁇ m, more preferably in the range of 10 to 500 ⁇ m, considering dimensional stability, strength, workability such as handleability, thin layer property, and the like. It ranges from 20 to 300 ⁇ m, more preferably from 25 to 250 ⁇ m, optimally from 30 to 200 ⁇ m.
  • the refractive index of the substrate 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 substrate of the present invention is preferably subjected to reflective surface treatment and/or antiglare 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 deterioration of visibility due to reflection of external light and reflection of images, etc. This is preferable from the viewpoint of adjusting appearance. It is also preferable in that it can prevent reflection due to metal wiring, ITO wiring, and the like arranged on the substrate of the image display device of the present invention.
  • the second surface of the substrate of the present invention is subjected to a hard coat treatment.
  • the configuration in which the second surface of the substrate of the present invention is hard-coated is preferable in that the surface hardness and scratch resistance are improved.
  • any known antireflection treatment can be used without particular limitation, and examples thereof include antireflection (AR) treatment.
  • AR antireflection
  • AR antireflection
  • a known AR treatment can be applied without particular limitation. It can be carried out by forming an antireflection layer (AR layer) in which two or more layers of thin films or optical thin films are laminated.
  • the AR layer exerts an antireflection function by canceling out the reversed phases of the incident light and the reflected light using the interference effect of light.
  • the wavelength region of visible light that exhibits the antireflection function is, for example, 380 to 780 nm, and the wavelength region with particularly high luminosity is in the range of 450 to 650 nm. It is preferable to design the AR layer so that
  • the AR layer generally includes a multilayer antireflection layer having a structure in which two to five optical thin layers (thin films with strictly controlled thickness and refractive index) are laminated.
  • a multilayer antireflection layer having a structure in which two to five optical thin layers (thin films with strictly controlled thickness and refractive index) are laminated.
  • the degree of freedom in the optical design of the AR layer increases, the anti-reflection effect can be further improved, and the spectral reflection characteristics can be made uniform (flat) in the visible light region. become.
  • each layer is generally formed by dry methods such as vacuum deposition, sputtering, and CVD.
  • the AR layer can also be formed using a coating solution for forming an antireflection layer.
  • the antireflection layer-forming coating liquid may contain, for example, a resin, a fluorine element-containing additive, hollow particles, solid particles, a diluent solvent, and the like, 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 possible to use a commercially available thermosetting resin, ultraviolet curable resin, or the like.
  • thermosetting resin or UV-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 (ultraviolet rays, etc.), electron beams, or the like can be used.
  • Silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiolpolyene resins, oligomers or prepolymers such as acrylates and methacrylates of polyfunctional compounds such as polyhydric alcohols. can give. These may be used individually by 1 type, and may use 2 or more types together.
  • a reactive diluent having at least one of an acrylate group and a methacrylate group can be used.
  • the reactive diluent for example, reactive diluents described in JP-A-2008-88309 can be used, and examples include monofunctional acrylates, monofunctional methacrylates, polyfunctional acrylates, polyfunctional methacrylates, and the like.
  • the reactive diluent tri- or more functional acrylates and tri- or more functional methacrylates are preferable. This is because the hardness of the second surface of the substrate of the present invention can be made excellent.
  • the reactive diluent examples include butanediol glycerol ether diacrylate, isocyanuric acid acrylate, and isocyanuric acid methacrylate. These may be used individually by 1 type, and may use 2 or more types together.
  • 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, 100,000 or less, 70,000 or less, 50 ,000 or less, 30,000 or less, or 10,000 or less. If the weight-average molecular weight before curing is high, the hardness tends to be low, but cracking tends to be less likely to occur when bent. On the other hand, when 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 (eg, pentathritol triacrylate).
  • a polyfunctional acrylate eg, pentathritol triacrylate
  • a curing agent may be added to cure the curable resin.
  • the curing agent is not particularly limited, and for example, a known polymerization initiator (eg, thermal polymerization initiator, photopolymerization initiator, etc.) can be used as appropriate.
  • the amount of the curing agent to be added is not particularly limited. 15 parts by weight or more, 13 parts by weight or less, 10 parts by weight or less, 7 parts by weight or less, or 5 parts by weight or less; 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 include, but are not limited to, 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., "Megafac” (trade name) manufactured by DIC Corporation, and the like.
  • the inorganic compound is also not particularly limited.
  • the amount of the elemental fluorine-containing additive to be added is not particularly limited.
  • 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 wt % or less, 5 wt % or less, or 3 wt % or less.
  • the weight of the fluorine element-containing additive with respect to 100 parts by weight of the resin in the antireflection layer-forming coating liquid is, for example, 0.05 wt% or more, 0.1 wt% or more, 0 .15 wt% or more, 0.20 wt% or more, or 0.25 wt% or more, and 20 wt% or less, 15 wt% or less, 10 wt% or less, 5 wt% or less, or 3 wt% It may be below.
  • the hollow particles are not particularly limited, but may be, for example, silica particles, acrylic particles, acrylic-styrene copolymer particles, or the like.
  • silica particles include trade names "Sururia 5320” and "Sururia 4320” manufactured by Nikki Shokubai & 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, Alternatively, it may be 110 nm or less.
  • the shape of the hollow particles is not particularly limited, and may be, for example, a substantially spherical shape such as a bead, or an irregular shape such as a powder. They are substantially spherical particles with an aspect ratio of 1.5 or less, most preferably spherical particles.
  • the amount of the hollow particles to be added is not particularly limited. parts by weight or more, or 100 parts by weight or more, and may be 300 parts by weight or less, 270 parts by weight or less, 250 parts by weight or less, 200 parts by weight or less, or 180 parts by weight or less.
  • the amount of the hollow particles added is preferably not too small, and from the viewpoint of ensuring the mechanical properties of the antireflection layer, the amount of the hollow particles added should not be too large. is preferred.
  • the solid particles are not particularly limited, but may be, for example, silica particles, zirconium oxide particles, titanium-containing particles (eg, titanium oxide particles), and the like.
  • examples of the silica particles include trade names "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 3300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less. , or 100 nm or less.
  • the shape of the solid particles is not particularly limited, and may be, for example, a substantially spherical bead shape, or an irregular shape such as a powder. , an aspect ratio of 1.5 or less, most preferably spherical particles.
  • the fluorine element-containing additive tends to be unevenly distributed on the surface of the coated antireflection layer-forming coating liquid, and the antireflection layer has excellent scratch resistance, A low refractive index, good antireflection properties, and the like can be realized.
  • the amount of the solid particles to be added is not particularly limited. It may be 150 parts by weight or less, 120 parts by weight or less, 100 parts by weight or less, or 80 parts by weight or less.
  • 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. It may be 200 wt% or more, 400 wt% or less, 350 wt% or less, 300 wt% or less, or 250 wt% 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. 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 MIBK is 100% by weight
  • 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 wt.% or less, 180 wt.% or less, 150 wt.% or less, 130 wt.% or less, or 110 wt.% or less.
  • the amount of the diluent solvent to be added is not particularly limited, either. 5 wt% or more, 1.0 wt% or more, or 1.5 wt% or more, and 20 wt% or less, 15 wt% or less, 10 wt% or less, 5 wt% or less, or 3 wt% % or less. From the viewpoint of ensuring coatability (wetness, leveling), it is preferable that the content of the solid content is not too high. is not too low.
  • the antireflection layer-forming coating liquid is applied onto 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 can be used as appropriate. can.
  • the coating amount of the antireflection layer-forming coating solution is not particularly limited, 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, or 1.0 ⁇ m. 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 coated antireflection layer forming coating solution is dried to form a coating film (the coating film forming step).
  • the drying temperature is not particularly limited, it may be in the range of 30 to 200°C, for example.
  • 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, 170° C. °C or lower, 160 °C or lower, 150 °C or lower, 140 °C or lower, 135 °C or lower, 130 °C or lower, 120 °C or lower, or 110 °C or lower.
  • the drying time is not particularly limited, but may be, for example, 30 seconds or longer, 40 seconds or longer, 50 seconds or longer, or 60 seconds or longer, and may be 150 seconds or shorter, 130 seconds or shorter, 110 seconds or shorter, or 90 seconds or shorter.
  • the coating film may be cured (curing step).
  • the curing can be performed, for example, by heating, light irradiation, or the like.
  • the light is not particularly limited, it 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 beam source in the ultraviolet curing is preferably 50 to 500 mJ/cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
  • the irradiation dose is 50 mJ/cm 2 or more, curing proceeds sufficiently and the hardness of the formed antireflection layer tends to increase. Also, if it is 500 mJ/cm 2 or less, coloring of the formed antireflection layer can be prevented.
  • a 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.
  • known layers can be employed without limitation, and it is generally formed as a layer in which inorganic or organic particles are dispersed as an anti-glare agent in a resin.
  • the antiglare layer may be an antiglare hard coat layer.
  • the anti-glare layer is not particularly limited. A convex portion is formed on the surface of the . With this configuration, the anti-glare layer has excellent display characteristics that achieve both anti-glare properties and prevention of white blurring, and despite the fact that the anti-glare layer is formed using aggregation of particles, there are no defects in appearance. It is possible to prevent the occurrence 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 possible to use a commercially available thermosetting resin, ultraviolet curable resin, or the like.
  • thermosetting resin or UV-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 (ultraviolet rays, etc.), electron beams, or the like can be used.
  • Silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiolpolyene resins, oligomers or prepolymers such as acrylates and methacrylates of polyfunctional compounds such as polyhydric alcohols. can give. These may be used individually by 1 type, and may use 2 or more types together.
  • a reactive diluent having at least one of an acrylate group and a methacrylate group can be used.
  • the reactive diluent for example, reactive diluents described in JP-A-2008-88309 can be used, and examples include monofunctional acrylates, monofunctional methacrylates, polyfunctional acrylates, polyfunctional methacrylates, and the like.
  • the reactive diluent tri- or more functional acrylates and tri- or more functional methacrylates are preferable. This is because the hardness of the antiglare layer can be made excellent.
  • Examples of the reactive diluent include butanediol glycerol ether diacrylate, isocyanuric acid acrylate, and isocyanuric acid methacrylate. These may be used individually by 1 type, and may use 2 or more types together.
  • the resin preferably contains a urethane acrylate resin, more preferably a copolymer of a curable urethane acrylate resin and a polyfunctional acrylate (for example, pentathritol triacrylate).
  • a urethane acrylate resin more preferably a copolymer of a curable urethane acrylate resin and a polyfunctional acrylate (for example, pentathritol triacrylate).
  • the main functions of the particles for forming the anti-glare layer are to make the surface of the formed anti-glare layer uneven to impart anti-glare properties, and to control the haze value of the anti-glare layer.
  • the haze value of the antiglare 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 examples include 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 examples include 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. Examples thereof include resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyethylene fluoride 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.
  • 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 acrylic styrene resin powder
  • melamine resin powder polyolefin
  • polyolefin examples include resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyethylene fluoride resin
  • the weight average particle size (D) of the particles is preferably within the range of 2.5 to 10 ⁇ m.
  • the weight average particle size of the particles is more preferably in the range of 3-7 ⁇ 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, Inc.) using the pore electrical resistance method, the volume of the electrolyte solution corresponding to the volume of the particles when the particles pass through the pores. By measuring the electrical resistance, the number and volume of the particles are measured, and the weight average particle diameter is calculated.
  • the shape of the particles is not particularly limited, and may be, for example, a substantially spherical bead shape, or an irregular shape such as a powder. They are substantially spherical particles with a ratio of 1.5 or less, most preferably spherical particles.
  • the proportion of the particles in the antiglare 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, still more preferably 1 part by weight, relative to 100 parts by weight of the resin. ⁇ 7 parts by weight. By setting it within the above range, for example, it is possible to achieve more excellent anti-glare properties and prevent white blurring.
  • the antiglare layer may contain a thixotropy-imparting agent.
  • a thixotropy-imparting agent By containing the thixotropy-imparting agent, the aggregation state of the particles can be easily controlled.
  • the thixotropy-imparting agent for forming the antiglare layer include organic clay, polyolefin oxide, and modified urea.
  • the organoclay is preferably an organically treated clay in order to improve the affinity with the resin.
  • organic clays include layered organic clays.
  • the organic clay may be self-prepared, or a commercially available product may be used.
  • 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 of which are 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 Disparlon 4200-20 (trade name, manufactured by Kusumoto Kasei Co., Ltd.) and Flownon 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 self-prepared, or a commercially available product may be used. Examples of the commercial product include BYK410 (manufactured by Big Chemie).
  • the thixotropy-imparting agents may be used singly or in combination of two or more.
  • the height of the convex portion from the roughness average line of the antiglare layer is preferably less than 0.4 times the thickness of the antiglare 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 projections that impair the appearance of the convex portion. Since the antiglare layer has convex portions with such heights, it is possible to make appearance defects less likely to occur.
  • 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 antiglare 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, with respect to 100 parts by weight of the resin.
  • the thickness (d) of the antiglare layer is not particularly limited, it is preferably in the range of 3 to 12 ⁇ m.
  • the optical pressure-sensitive adhesive sheet of the present invention can be prevented from curling, and the problem of reduced productivity such as poor transportability can be avoided.
  • the weight average particle size (D) of the particles is preferably within the range of 2.5 to 10 ⁇ m as described above.
  • the thickness (d) of the antiglare layer is more preferably in the range of 3-8 ⁇ m.
  • the relationship between the thickness (d) of the antiglare 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 due to aggregation of the particles and the thixotropy-imparting agent.
  • the particles are present in a state in which a plurality of the particles are aggregated in the surface direction of the antiglare layer.
  • the convex portion has a gentle shape. Since the anti-glare layer has convex portions having such a shape, it is possible to maintain the anti-glare property, prevent white blurring, and make appearance defects less likely to occur.
  • the surface shape of the antiglare layer can be arbitrarily designed by controlling the aggregation state of the particles contained in the antiglare layer forming material.
  • the aggregation state of the particles can be controlled by, for example, the material of the particles (for example, chemically modified state of the particle surface, affinity for solvent or resin, etc.), type of resin (binder) or solvent, combination, and the like.
  • the aggregation state of the particles can be controlled by the thixotropy imparting agent contained in the antiglare layer-forming material.
  • the aggregated state of the particles can be made as described above, and the convex portion can be formed into a smooth shape.
  • the substrate of the present invention when the substrate of the present invention is made of a resin or the like, it preferably has a permeation layer at the interface between the substrate of the present invention and the antiglare layer.
  • the permeation layer is formed by permeating the resin component contained in the material for forming the antiglare layer into the substrate of the present invention.
  • the formation of the permeation layer is preferable because the adhesion between the substrate of the present invention and the antiglare layer can be improved.
  • the penetration layer preferably has a thickness in the range of 0.2 to 3 ⁇ m, more preferably in the range of 0.5 to 2 ⁇ m.
  • the base material of the present invention is a polyester-based resin and the resin contained in the antiglare layer is an acrylic resin
  • the permeation layer can be formed.
  • the penetration layer can be confirmed and the thickness can be measured, for example, by observing the cross section of the optical pressure-sensitive adhesive sheet of the present invention with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the permeation layer is formed thicker in order to improve the adhesion of the base material with poor adhesion to the anti-glare layer.
  • the number of appearance defects having a maximum diameter of 200 ⁇ m or more is 1 or less per 1 m 2 of the antiglare layer. More preferably, it does not have the appearance defect.
  • the average inclination angle ⁇ a (°) is . It is preferably in the range of 1 to 5.0, more preferably in the range of 0.3 to 4.5, even more preferably in the range of 1.0 to 4.0, and 1.6 to 4.0. .0 is particularly preferred.
  • the average tilt angle ⁇ a is a value defined by the following formula (1).
  • the average tilt angle ⁇ a is, for example, a value measured by the method described in JP-A-2017-138620.
  • Average tilt angle ⁇ a tan-1 ⁇ a (1)
  • ⁇ a is, as shown in the following formula (2), in the reference length L of the roughness curve defined in JIS B 0601 (1994 edition), the distance between the top and the valley of the adjacent peaks It is a value obtained by dividing the sum (h1+h2+h3 .
  • the roughness curve is a curve obtained by removing surface waviness components longer than a predetermined wavelength from the cross-sectional curve with a phase difference compensation type high-pass filter.
  • ⁇ a is within the above range, the anti-glare property is more excellent and white blurring can be prevented.
  • ⁇ 1 is the viscosity measured at a shear rate of 20 (1/s) using HAAKE's Rheostress 6000
  • ⁇ 2 is the viscosity measured using HAAKE's Rheostress 6000 at a shear rate of 200 (1/s). Viscosity measured under conditions.
  • the Ti value is less than 1.3, defects in appearance are likely to occur, and anti-glare properties and white blur characteristics deteriorate.
  • the Ti value exceeds 3.5, the particles are less likely to agglomerate and more likely to be in a dispersed state.
  • the method for producing the anti-glare layer is not particularly limited, and it may be produced by any method. Then, the anti-glare layer-forming material (coating liquid) is applied to the second surface of the substrate of the present invention to form a coating film, and the coating film is cured to form an anti-glare layer. .
  • a transfer method using a mold, a method of imparting an uneven shape by an appropriate method such as sandblasting, embossing roll, or the like can also be used together.
  • the solvent is not particularly limited, and various solvents can be used. One type may be used alone, or two or more types may be used in combination. There is an optimum solvent type and solvent ratio depending on the composition of the resin, the types and contents of the particles and the thixotropy-imparting agent, and the like.
  • solvents 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, and xylene.
  • a good solvent for the polyester-based resin can be suitably used.
  • the solvent include ethyl acetate, methyl ethyl ketone, cyclopentanone and the like.
  • the thixotropy of the antiglare layer-forming material (coating liquid) by the thixotropy-imparting agent can be satisfactorily expressed.
  • organoclays when organoclays are used, toluene and xylene can be suitably used alone or in combination. They can be used or used in combination.
  • modified urea when modified urea is used, butyl acetate and methyl isobutyl ketone can be preferably used alone or in combination.
  • leveling agents can be added to the antiglare layer-forming material.
  • a fluorine-based or silicone-based leveling agent can be used for the purpose of preventing coating unevenness (uniformizing the coated surface).
  • a leveling agent is added as appropriate. can be selected.
  • the inclusion of the thixotropy-imparting agent makes it possible to express thixotropic properties in the coating liquid, so that unevenness in coating is less likely to occur. Therefore, for example, it has an advantage that the options for the leveling agent can be expanded.
  • the amount of the leveling agent compounded is, for example, 5 parts by weight or less, preferably in the range of 0.01 to 5 parts by weight, per 100 parts by weight of the resin.
  • Pigments, fillers, dispersants, plasticizers, UV absorbers, surfactants, antifouling agents, antioxidants and the like are added to the antiglare layer-forming material as necessary within a range that does not impair the performance. may These additives may be used singly or in combination of two or more.
  • photopolymerization initiators such as those described in JP-A-2008-88309, can be used.
  • Examples of the method for applying the anti-glare layer-forming material onto the second surface of the substrate of the present invention include a fountain coating method, a die coating method, a spin coating method, a spray coating method, a gravure coating method, a 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 substrate 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 air, heat drying, or a combination thereof.
  • the means for curing the coating film of the anti-glare layer-forming material is not particularly limited, but ultraviolet curing is preferable.
  • the irradiation amount of the energy beam source is preferably 50 to 500 mJ/cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
  • the irradiation dose is 50 mJ/cm 2 or more, the curing becomes more sufficient, and the hardness of the formed anti-glare layer becomes more sufficient. Also, if it is 500 mJ/cm 2 or less, coloring of the formed antiglare layer can be prevented.
  • the antiglare layer can be formed on the second surface of the substrate of the present invention.
  • the anti-glare layer may be formed by a manufacturing method other than the method described above.
  • the hardness of the anti-glare layer is preferably 2H or more in terms of pencil hardness, although it is also affected by the thickness of the layer.
  • the antiglare layer may have a multi-layer structure in which two or more layers are laminated.
  • the above-described AR layer (low refractive index layer) may be arranged on the antiglare layer.
  • one factor that reduces the visibility of the image is the reflection of light at the interface between the air and the anti-glare layer.
  • the AR layer reduces the surface reflection.
  • the antiglare layer and the antireflection layer may each have a multi-layer structure in which two or more layers are laminated.
  • an anti-contamination layer formed of a fluorine group-containing silane compound, a fluorine group-containing organic compound, or the like is used as the antireflection layer and the anti-reflection layer. / Or lamination on the anti-glare layer is preferred.
  • the substrate of the present invention and the antiglare layer are subjected to surface treatment.
  • the adhesion to the anti-glare layer is further improved.
  • the adhesion to the AR layer is further improved.
  • the other surface of the antiglare layer may be subjected to solvent treatment. Further, a transparent resin layer may be formed on the other surface of the antiglare layer in order to prevent curling.
  • the second surface of the base material of the present invention may be subjected to antistatic treatment.
  • the configuration in which the second surface of the base material of the present invention is subjected to electrification treatment suppresses static electricity charging of the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention. is used in an image display device, it is preferable in that display defects caused by static electricity can be suppressed.
  • a known HC treatment can be applied without particular limitation, and can be carried out, for example, by forming a hard coat layer on the second surface of the substrate of the present invention.
  • known ones can be employed without limitation.
  • a hard coat layer-forming material containing only a resin without particles and a thixotropy-imparting agent may be used. Except for this, a hard coat layer having no antiglare properties can be formed in the same manner as the above antiglare layer.
  • a known antistatic treatment can be used without particular limitation, and can be carried out, for example, by forming an antistatic layer on the second surface of the substrate of the present invention.
  • any appropriate antistatic layer can be adopted as long as it is a layer capable of exhibiting an antistatic effect, as long as it does not impair the effects of the present invention.
  • Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any suitable substrate layer. Specifically, for example, it is an antistatic layer formed by coating a substrate with a conductive coating liquid containing a conductive polymer. Specific coating methods include a roll coating method, a bar coating method, a gravure coating method, and the like.
  • any suitable conductive polymer can be adopted as the conductive polymer as long as it does not impair the effects of the present invention.
  • a conductive polymer include a conductive polymer obtained by doping a ⁇ -conjugated conductive polymer with a polyanion.
  • ⁇ -conjugated conductive polymers include linear conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene.
  • Polyanions include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyethyl acrylate sulfonic acid, polymethacrylic carboxylic acid, and the like.
  • the surface resistivity of the antistatic layer is preferably 1.0 ⁇ 10 4 ⁇ /square to 1.0 ⁇ 10 9 ⁇ /square at a temperature of 23° C. and a humidity of 50% RH, more preferably 1.0 ⁇ 10 4 ⁇ / ⁇ to 5.0 ⁇ 10 8 ⁇ / ⁇ , more preferably 5.0 ⁇ 10 4 ⁇ / ⁇ to 1.0 ⁇ 10 8 ⁇ / ⁇ , and particularly preferably 1.0 ⁇ 10 ⁇ / ⁇ . 10 5 ⁇ / ⁇ to 5.0 ⁇ 10 7 ⁇ / ⁇ . If the surface resistivity of the antistatic layer is within the above range, the effects of the present invention are more likely to be exhibited.
  • any appropriate thickness can be adopted according to the purpose as long as the effects of the present invention are not impaired.
  • Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, even more preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.
  • the antistatic layer may consist of only one layer, or may consist of two or more layers.
  • the antistatic layer may be provided alone on the second surface of the substrate of the present invention, or an antiglare layer and/or an AR layer may be provided on the antistatic layer. Alternatively, as a topcoat layer, an antistatic layer may be provided on the antiglare layer and/or the AR layer.
  • the pressure-sensitive adhesive layer of the present invention is a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
  • the pressure-sensitive adhesive composition of the present invention includes an antistatic agent, an acrylic polymer (A), a mixture of monomer components constituting the acrylic polymer (A), or a mixture of monomer components constituting the acrylic polymer (A).
  • the antistatic agent is an ionic compound having in its molecule a functional group capable of forming a covalent bond with the acrylic polymer (A).
  • the pressure-sensitive adhesive composition of the present invention may have any form, for example, emulsion type, hot melt type (hot melt type), non-solvent type (active energy ray curable type, e.g., monomer mixture, or monomer mixtures and partially polymerized products thereof) and the like.
  • the pressure-sensitive adhesive composition of the present invention is preferably non-solvent type. This is because when a pressure-sensitive adhesive layer is to be obtained using a solvent-based pressure-sensitive adhesive composition, defects in appearance such as citrus peel are likely to occur.
  • "yuzu skin” refers to a phenomenon in which unevenness occurs like the skin of "yuzu", which is a kind of citrus fruit.
  • the pressure-sensitive adhesive composition of the present invention is preferably active energy ray-curable from the viewpoint of obtaining a pressure-sensitive adhesive layer with excellent appearance.
  • the pressure-sensitive adhesive composition means a composition used for forming the pressure-sensitive adhesive layer, and includes the meaning of the composition used for forming the pressure-sensitive adhesive.
  • the organic solvent is not particularly limited as long as it is an organic compound used as a solvent.
  • examples include hydrocarbon solvents such as cyclohexane, hexane, and heptane; aromatic solvents such as toluene and xylene; ethyl acetate, methyl acetate, and the like.
  • ketone solvents such as acetone and methyl ethyl ketone; and alcohol solvents such as methanol, ethanol, butanol and isopropyl alcohol.
  • the mixed solvent containing 2 or more types of organic solvents may be sufficient as the said organic solvent.
  • substantially contains no organic solvent means that the organic solvent is not actively blended, except when the organic solvent is unavoidably mixed.
  • the content of the organic solvent in the adhesive composition is 1.0% by weight or less (preferably 0.5% by weight or less, more preferably 0.2% by weight or less) can be said to be substantially free.
  • the base polymer contained in the adhesive composition of the present invention is acrylic polymer (A). That is, the pressure-sensitive adhesive composition of the present invention is an acrylic pressure-sensitive adhesive composition containing an acrylic polymer as a base polymer. Acrylic polymers are preferred because of their transparency, weather resistance, adhesion reliability, and ease of functional design of the pressure-sensitive adhesive layer due to the wide variety of monomers available.
  • the pressure-sensitive adhesive composition of the present invention is preferably an acrylic pressure-sensitive adhesive composition containing the below-described acrylic polymer (A) as a base polymer.
  • acrylic polymer (A) can be used individually or in combination of 2 or more types.
  • the content of the acrylic polymer (A) in the pressure-sensitive adhesive layer of the present invention is not particularly limited, but may be 75% by weight or more (for example, 75 to 99.9%). 9% by weight), more preferably 85% by weight or more (for example, 85 to 99.9% by weight).
  • the adhesive composition of the present invention preferably does not contain or substantially does not contain acidic group-containing monomers (eg, carboxyl group-containing monomers, sulfo group-containing monomers, phosphoric acid group-containing monomers, etc.). This configuration is preferable in that an excellent effect of preventing corrosion of metal wiring can be obtained.
  • the content of the acidic group-containing monomer is preferably 0.05% by weight or less (for example, 0 to 0.05% by weight), more preferably 0.01% by weight, based on the total amount of the adhesive composition of the present invention. % or less (eg, 0 to 0.01% by weight), more preferably 0.001% by weight or less (eg, 0 to 0.001% by weight), it can be said to be substantially free.
  • the pressure-sensitive adhesive composition of the present invention preferably does not contain, or substantially does not contain, an acidic group-containing monomer such as a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer contained as the base polymer. More preferably, the pressure-sensitive adhesive composition of the present invention does not contain or substantially does not contain a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer (A). Therefore, the pressure-sensitive adhesive composition of the present invention can obtain an excellent anti-corrosion effect.
  • the meaning of the carboxyl group-containing monomer, the meaning of "not containing substantially", the monomer having an acidic group other than the carboxyl group, etc. are the same as in the case of the monomer component constituting the acrylic polymer (A).
  • the content of the carboxyl group-containing monomer is preferably 0.05% by weight or less (for example, 0 to 0.05% by weight), more preferably 0.01% by weight, based on the total amount of the pressure-sensitive adhesive composition of the present invention. % or less (eg, 0 to 0.01% by weight), more preferably 0.001% by weight or less (eg, 0 to 0.001% by weight), it can be said to be substantially free.
  • the adhesive layer of the present invention (the adhesive layer formed from the adhesive composition of the present invention) has excellent antistatic performance. Therefore, display defects due to static electricity can be suppressed when an image display device and an optical member are attached to each other via the pressure-sensitive adhesive layer of the present invention.
  • the pressure-sensitive adhesive layer of the present invention is suitably used for manufacturing image display devices.
  • the surface resistivity (according to JIS K 6271) of the pressure-sensitive adhesive layer of the present invention is preferably 1.0 ⁇ from the viewpoint of excellent antistatic performance. 10 10 ⁇ / ⁇ or less, more preferably 0.5 ⁇ 10 10 ⁇ / ⁇ or less, still more preferably 1.0 ⁇ 10 9 ⁇ / ⁇ or less, and 0.5 ⁇ 10 9 ⁇ / ⁇ or less or less, or 1.0 ⁇ 10 8 ⁇ / ⁇ or less.
  • the lower limit of the surface resistivity of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but may be 1.0 ⁇ 10 5 ⁇ / ⁇ or more, or 0.5 ⁇ 10 5 ⁇ / ⁇ or more.
  • the pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) can suppress the bleed-out of the anticonductive agent and maintain the transparency of the appearance even in a moist and hot environment, and has excellent It can stably impart antistatic performance. For this reason, display defects due to static electricity can be suppressed while maintaining transparency even in a moist and hot environment after bonding the image display device and the optical member via the pressure-sensitive adhesive layer of the present invention.
  • the pressure-sensitive adhesive layer of the present invention is suitably used for manufacturing image display devices.
  • the pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) was placed in an environment of 60°C and 95% RH for 240 hours and then taken out, and then placed in an environment of 23°C and 50% RH. After controlling the temperature and humidity for 24 hours, the surface resistivity of the adhesive layer surface after a moist heat test in an atmosphere of 23 ° C and 50% RH suppresses the bleeding out of the anti-conductive agent even in a moist heat environment. 5.0 ⁇ 10 10 ⁇ / ⁇ is preferable from the viewpoint of stably imparting excellent antistatic performance by ensuring the stability of the resistance value before and after the wet heat test while maintaining the transparency of the appearance.
  • the lower limit of the surface resistivity of the pressure-sensitive adhesive layer of the present invention after the humidification test is not particularly limited, but is 1.0 ⁇ 10 5 ⁇ / ⁇ or more, or 0.5 ⁇ 10 5 ⁇ / ⁇ or more. good too.
  • the ratio of the surface resistivity of the adhesive layer surface before and after the wet heat test suppresses the bleeding out of the anti-conductive agent even in the wet heat environment, and the appearance While maintaining the transparency of, by ensuring the stability of the resistance value before and after the wet heat test, from the viewpoint of being able to impart the stability of excellent antistatic performance, preferably 90 or less, more preferably 50 or less. Yes, more preferably 30 or less, 20 or less, or 10 or less.
  • the surface resistivity of the pressure-sensitive adhesive layer of the present invention and the surface resistivity after the humidification test can be measured by the method described in Examples below.
  • the surface resistivity of the pressure-sensitive adhesive layer of the present invention and the surface resistivity after a humidification test are determined by the monomer composition constituting the acrylic polymer (A), the amount of the cross-linking agent, the ionic compound of the present invention, the type of other additives, and the like. Adjustments can be made by adjusting amounts, curing conditions, and the like.
  • the pressure-sensitive adhesive layer of the present invention (The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is transparent or has transparency. Therefore, the visibility and appearance through the pressure-sensitive adhesive layer of the present invention are excellent. Thus, the pressure-sensitive adhesive layer of the present invention is suitable for optical applications.
  • the haze (according to JIS K7136) of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 1.0% or less, more preferably It may be 0.8% or less, 0.7% or less, or 0.6% or less. A haze of 1.0% or less is preferable because excellent transparency and appearance can be obtained.
  • the haze is, for example, an adhesive layer (thickness: 100 ⁇ m), which is allowed to stand in a normal state (23° C., 50% RH) for at least 24 hours, and then slide glass (for example, total light transmittance of 92%, Haze of 0.2%) can be used as a sample and measured using a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HM-150N").
  • HM-150N haze meter
  • the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the adhesive layer of the present invention is not particularly limited, but is preferably 90% or more, more preferably 91% or more, or 92% or more. may When the total light transmittance is 90% or more, excellent transparency and excellent appearance can be obtained, which is preferable.
  • the above total light transmittance is, for example, an adhesive layer (thickness: 100 ⁇ m), which is allowed to stand in a normal state (23 ° C., 50% RH) for at least 24 hours, and then peeled off if it has a separator.
  • a slide glass for example, total light transmittance of 92%, haze of 0.2%) is used as a sample, and a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HM-150N” ) can be measured using
  • the total light transmittance and haze of the pressure-sensitive adhesive layer of the present invention can be measured by the methods described in Examples below.
  • the total light transmittance and haze of the pressure-sensitive adhesive layer of the present invention are determined by the monomer composition constituting the acrylic polymer (A), the amount of the cross-linking agent, the ionic compound of the present invention, the type and amount of other additives, curing conditions, etc. can be adjusted by adjusting
  • the gel fraction (proportion of solvent-insoluble components) of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 40 to 95%, more preferably 50 to 92%, more preferably 55 to 90%.
  • the gel fraction is 40% or more, the cohesive force of the pressure-sensitive adhesive layer is improved, causing foaming and peeling at the interface with the adherend in a high-temperature environment, dents during handling, and edges during processing. Contamination of the part is suppressed, and excellent anti-foaming peeling property is easily obtained, which is preferable.
  • the gel fraction is 95% or less, appropriate flexibility can be obtained, and the adhesiveness and step followability are further improved, which is preferable.
  • the gel fraction (ratio of solvent-insoluble components) is, for example, a value calculated by the following "Method for measuring gel fraction".
  • Adhesive layer About 0.1 g was collected from the adhesive sheet, wrapped in a porous tetrafluoroethylene sheet (trade name “NTF1122”, manufactured by Nitto Denko Co., Ltd.) with an average pore size of 0.2 ⁇ m, and tied with a kite string. The weight at that time is measured, and the weight is taken as the weight before immersion. The weight before immersion is the total weight of the adhesive layer (the adhesive layer collected above), the tetrafluoroethylene sheet, and the kite string. Also, the total weight of the tetrafluoroethylene sheet and the kite string is measured, and this weight is taken as the weight of the package.
  • the gel fraction can be controlled by, for example, the monomer composition of the acrylic polymer (A), the weight average molecular weight, the amount of cross-linking agent used (added amount), and the like.
  • the storage modulus of the pressure-sensitive adhesive layer (especially the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) at 25° C. and 1 Hz is not particularly limited, but is preferably 3 ⁇ 10 4 Pa or more. .
  • the configuration in which the pressure-sensitive adhesive layer of the present invention has a storage elastic modulus of 3 ⁇ 10 4 Pa or more at 25° C. and 1 Hz is preferable in that dents are less likely to occur during handling.
  • the storage elastic modulus of the pressure-sensitive adhesive layer of the present invention at 25° C. and 1 Hz is more preferably 5 ⁇ 10 4 Pa or more, more preferably 1 ⁇ 10 5 Pa or more, in that dents on the pressure-sensitive adhesive layer of the present invention can be suppressed.
  • the upper limit of the storage elastic modulus at 25° C. and 1 Hz of the pressure-sensitive adhesive layer of the present invention is not particularly limited, it is preferably 5 ⁇ 10 6 Pa or less, and 1 ⁇ It may be 10 6 Pa or less.
  • the storage elastic modulus of the optical pressure-sensitive adhesive sheet of the present invention at 25°C and 1 Hz can be measured by dynamic viscoelasticity measurement, and specifically by the method described in Examples below.
  • the storage elastic modulus of the optical pressure-sensitive adhesive sheet of the present invention at 25° C. and 1 Hz is determined by the composition of the monomers constituting the acrylic polymer (A), the amount of the cross-linking agent, the ionic compound of the present invention, the type of other additives, and the like. Adjustments can be made by adjusting amounts, curing conditions, and the like.
  • the pressure-sensitive adhesive layer (in particular, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is not particularly limited, but is preferably 5 to 250 ⁇ m, more preferably 7 to 240 ⁇ m, 10 to 230 ⁇ m, 12 to 220 ⁇ m, It may be 15-210 ⁇ m, 20-200 ⁇ m, 23-175 ⁇ m, or 25-150 ⁇ m.
  • the thickness is at least a certain value, the followability to unevenness and adhesion reliability are improved, which is preferable.
  • the thickness is a certain value or less, it is particularly excellent in handleability and manufacturability, which is preferable.
  • the method for producing the pressure-sensitive adhesive layer of the present invention is not particularly limited.
  • it can be produced by preparing the pressure-sensitive adhesive composition (precursor composition) of the present invention and, if necessary, performing irradiation with active energy rays, heat drying, and the like.
  • a mixture of monomer components or a partial polymer thereof, the antistatic agent of the present invention ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in the molecule
  • it may be produced by adding additives and the like and mixing.
  • the pressure-sensitive adhesive composition of the present invention contains at least the ionic compound of the present invention (an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in the molecule) as an antistatic agent as an essential component. contains.
  • the ionic compound of the present invention is a functional group capable of forming a covalent bond with the acrylic polymer (A) (hereinafter, sometimes referred to as "functional group (A)" in the present specification). It is an ionic compound having a constituent cation part and/or an anion part (either or both).
  • the ionic compound of the present invention is liquid (liquid) at any temperature within the range of 0 to 150° C., and is preferably a non-volatile molten salt having transparency (ionic liquid).
  • the ionic compound of this invention can be used individually or in combination of 2 or more types.
  • the acrylic polymer (A) reacts with the functional group (A) of the ionic compound of the present invention to form a covalent bond.
  • the ionic compound is incorporated into the molecule of the acrylic polymer (A), so even if a large amount of the ionic compound of the present invention is blended, the compatibility in the pressure-sensitive adhesive layer of the present invention is impaired. It becomes easier to maintain transparency.
  • bleeding out of the antistatic component can be suppressed even under harsh conditions such as moist and hot environments, precipitation, foaming, and peeling on the surface of the adhesive layer are suppressed, and durability such as appearance and adhesion reliability is improved.
  • the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention containing the ionic compound of the present invention can satisfy excellent antistatic properties, transparency, resistance to moist heat, and low staining properties, and is useful. .
  • the cation moiety of the ionic compound of the present invention can be used without particular limitation, and includes quaternary ammonium cations, imidazolium cations, pyridinium cations, piperinidinium cations, pyrrolidinium cations, quaternary phosphonium cations, tri Alkylsulfonium cations, pyrrole cations, pyrazolium cations, guanidinium cations, and the like, among which quaternary ammonium cations, imidazolium cations, pyridinium cations, piperinidinium cations, pyrrolidinium cations, quaternary Phosphonium cations and trialkylsulfonium cations are more preferably used.
  • the anions include SCN ⁇ , BF 4 ⁇ , PF 6 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 - , CF3SO3- , ( FSO2 ) 2N- , ( CF3SO2 ) 2N- , ( CF3SO2 ) 3C- , AsF6- , SbF6- , NbF6- , TaF6 - , F ( HF) n- , ( CN ) 2N- , C4F9SO3- , ( C2F5SO2 ) 2N- , C3F7COO- , ( CF3SO2 ) ( CF3CO )N- , B ( CN) 4- , C ( CN) 3- , N ( CN ) 2- , CH3OSO3- , C2H5OSO3
  • the functional group (A) (functional group capable of forming a covalent bond with the acrylic polymer (A)) possessed by the ionic compound of the present invention includes, for example, a (meth)acryloyloxy group, a (meth)acryloylamino group, and a vinyl group. , allyl group, styryl group, hydroxyl group, amino group, mercapto group, epoxy group and the like. Among them, a (meth)acryloyloxy group, a (meth)acryloylamino group and a hydroxyl group are preferred, and a (meth)acryloyloxy group copolymerizable with the acrylic polymer (A) is particularly preferred.
  • (meth)acryloyl represents either one or both of “acryloyl” and “methacryloyl”, and the same applies to others.
  • the amino group also includes --NH 2 and --NHR (R is an alkyl group having 1 to 6 carbon atoms).
  • the number of functional groups (A) possessed by the ionic compound of the present invention is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. .
  • the number of functional groups (A) is two or more, two or more functional groups (A) may be the same or different.
  • the ionic compound of the present invention can also function as a cross-linking agent for cross-linking two or more acrylic polymers (A).
  • the ionic compound of the present invention can be used without any particular limitation, it is preferably an ionic compound represented by the following general formula (A).
  • X + is a cation moiety.
  • Y ⁇ is an anion.
  • Z 1 and Z 2 are the same or different and each represents a single bond or an alkylene group having 1 to 16 carbon atoms.
  • a 1 and A 2 are the same or different and are functional groups capable of forming a covalent bond with the acrylic polymer (A).
  • n 1 is 0 or 1
  • n 2 is 0 or 1, provided that n 1 +n 2 is 1 or 2;
  • the cation moiety (X + ) constituting the ionic compound represented by the general formula (A) includes a quaternary ammonium group, an imidazolium group, a pyridinium group, a piperinidinium group, a pyrrolidinium group, a pyrrole group and a quaternary phosphonium group. , a trialkylsulfonium group, a pyrazolium group, a guanidinium group, and the like.
  • a quaternary ammonium group is particularly excellent in transparency and is a preferred embodiment for electronic and optical applications.
  • quaternary ammonium groups are suitable because they are less likely to inhibit general radical polymerization reactions during ultraviolet (UV) curing and are presumed to have high curability.
  • n 1 +n 2 is 1, trimethylammonium group, triethylammonium group, tripropylammonium group, methyldiethylammonium group, ethyldimethylammonium group, methyldipropylammonium group, dimethylbenzyl ammonium group, diethylbenzylammonium group, methyldibenzylammonium group, ethyldibenzylammonium group, dimethyloctadecylammonium group, dimethyloleyl ammonium group, etc.; This is a preferred embodiment because the materials are readily available.
  • n 1 +n 2 is 2, dimethylammonium group, diethylammonium group, dipropylammonium group, methylethylammonium group, methylpropylammonium group, methylbenzylammonium group, ethylbenzylammonium group group, methyloctadecylammonium group, ethyloctadecylammonium group, methyloleyl ammonium group, ethyl oleyl ammonium group, etc.
  • dimethyl ammonium group and methyl oleyl ammonium group are particularly preferable in terms of easy availability of inexpensive industrial materials. It becomes a mode.
  • the anions include SCN ⁇ , BF 4 ⁇ , PF 6 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF3COO- , CH3SO3- , CF3SO3- , ( FSO2 ) 2N- , ( CF3SO2 ) 2N- , ( CF3SO2 ) 3C- , AsF6- , SbF 6- , NbF6- , TaF6- , F ( HF) n- , ( CN ) 2N- , C4F9SO3- , ( C2F5SO2 ) 2N- , C3F7COO - , ( CF3SO2 ) ( CF3CO )N- , B(CN) 4- , C ( CN) 3- , N ( CN ) 2- , CH3OSO3-
  • Z 1 and Z 2 constituting the ionic compound represented by the general formula (A) are single bonds or alkylene groups having 1 to 16 carbon atoms.
  • the alkylene group having 1 to 16 carbon atoms is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms. Specific examples include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, etc., and an ethylene group and a trimethylene group are preferable.
  • Z 1 and Z 2 may be the same or different.
  • a 1 and A 2 constituting the ionic compound represented by the general formula (A) are functional groups capable of forming a covalent bond with the acrylic polymer (A), specifically, a (meth)acryloyloxy group , (meth)acryloylamino group, vinyl group, allyl group, styryl group, hydroxyl group, amino group, mercapto group, epoxy group and the like.
  • a (meth)acryloyloxy group, a (meth)acryloylamino group and a hydroxyl group are preferred, and a (meth)acryloyloxy group copolymerizable with the acrylic polymer (A) is particularly preferred.
  • a 1 and A 2 may be the same or different.
  • X + is a quaternary ammonium group
  • n 1 is 1
  • n 2 is 0,
  • a 1 is a vinyl group
  • Specific examples of embodiments that are oxy groups or (meth)acryloylamino groups include N,N,N-trialkyl-N-vinylammonium tetrafluoroborate, N,N,N-trialkyl-N-vinylammonium tri Fluoroacetate, N,N,N-trialkyl-N-vinylammonium heptafluorobutyrate, N,N,N-trialkyl-N-vinylammonium trifluoromethanesulfonate, N,N,N-trialkyl-N-vinyl ammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-vinylammonium bis(trifluoromethanesulfonate, N,N,
  • N-trialkyl-N-(meth)acryloylaminoalkylammonium cation-containing ionic compounds are preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
  • X + is a quaternary ammonium group
  • n 1 is 1
  • n 2 is 0,
  • a 1 is a (meth)acryloyloxy group.
  • Preferred specific examples of certain embodiments include (meth)acryloyloxypropyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxypropyldimethylbenzylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxyethyltrimethylammonium Bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxyethyldimethylbenzylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxyethyltrimethylammonium bis(fluorosulfonyl)imide, (meth)acryloyloxypropyltrimethylam
  • X + is a quaternary ammonium group
  • n 1 is 1
  • n 2 is 0,
  • a 1 is a (meth)acryloylamino group.
  • Preferred specific examples of certain embodiments include (meth)acryloylaminopropyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloylaminopropyldimethylbenzylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloylaminopropyltrimethylammonium Bis(fluorosulfonyl)imide, (meth)acryloylaminopropyldimethylbenzylammonium bis(fluorosulfonyl)imide, (meth)acryloylaminopropyltrimethylammonium trifluoromethanesulfonic acid, (meth)acryloylaminopropyld
  • X + is an imidazolium group
  • n 1 is 1
  • n 2 is 0 or 1
  • a 1 and A 2 are vinyl groups.
  • Specific examples of embodiments include 1-alkyl-3-vinylimidazolium tetrafluoroborate, 1-alkyl-3-vinylimidazolium trifluoroacetate, 1-alkyl-3-vinylimidazolium heptafluorobutyrate, 1-alkyl -3-vinylimidazolium trifluoromethanesulfonate, 1-alkyl-3-vinylimidazolium perfluorobutanesulfonate, 1-alkyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-vinylimidazolium bis (Pentafluoroethanesulfonyl)imide, 1-alkyl-3-vinylimidazolium bis (Pent
  • 1,3-divinylimidazolium cation-containing ionic compounds 1-vinylimidazolium bis(fluorosulfonyl)imide, 1-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-vinylimidazolium dicyanamide, 1-vinyl imidazoli and ionic compounds containing 1-vinylimidazolium cations such as umthiocyanate.
  • X + is an imidazolium group
  • n 1 is 1
  • n 2 is 0 or 1
  • a 1 and A 2 are (meth)acryloyl
  • Specific examples of embodiments that are oxy groups include 1-alkyl-3-(meth)acryloyloxyalkylimidazolium tetrafluoroborate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium trifluoroacetate, 1-alkyl -3-(meth)acryloyloxyalkylimidazolium heptafluorobutyrate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium perfluorobutane Sulfonate, 1-alkyl-3-(meth)acryloyloxyalkylimida
  • 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium cation-containing ionic compound 2-alkyl-1,3-di (Meth) acryloyloxyalkylimidazolium bis(fluorosulfonyl)imide, 2-alkyl-1,3-di(meth)acryloyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1,3-di( 2-alkyl-1,3-di(meth)acryloyloxyalkylimidazolium cation-containing ions such as meth)acryloyloxyalkylimidazolium dicyanamide, 2-alkyl-1,3-di(meth)acryloyloxyimidazolium thiocyanate 1-(meth)acryloyloxyalkylimidazolium bis(fluorosulfonyl)imide, 1-(meth)acryl
  • X + is an imidazolium group
  • n 1 is 1
  • n 2 is 0 or 1
  • a 1 and A 2 are (meth)acryloyl
  • amino groups include 1-alkyl-3-(meth)acryloylaminoalkylimidazolium tetrafluoroborate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium trifluoroacetate, 1-alkyl -3-(meth)acryloylaminoalkylimidazolium heptafluorobutyrate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium perfluorobutane Sulfonate, 1-alkyl-3-(meth)acryloylaminoalkylimid
  • 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium cation-containing ionic compounds 2-alkyl-1,3-di (Meth) acryloylaminoalkylimidazolium bis(fluorosulfonyl)imide, 2-alkyl-1,3-di(meth)acryloylaminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1,3-di( 2-alkyl-1,3-di(meth)acryloylaminoalkylimidazolium cation-containing ions such as meth)acryloylaminoalkylimidazolium dicyanamide, 2-alkyl-1,3-di(meth)acryloylaminoimidazolium thiocyanate 1-(meth)acryloylaminoalkylimidazolium bis(fluorosulfonyl)imide,
  • X + is a pyridinium group, n 1 is 1, n 2 is 0,
  • a 1 is a vinyl group, a (meth)acryloyloxy group, or (meth)acryloylamino group, 1-vinylpyridinium bis(fluorosulfonyl)imide, 1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 1-vinylpyridinium dicyanamide, 1-vinyl 1-vinylpyridinium cation-containing ionic compounds such as pyridinium thiocyanate; 1-(meth)acryloyloxyalkylpyridinium cation-containing ionic compounds such as (meth)acryloyloxyalkylpyridinium dicyanamide, 1-(meth)acryloyloxyalkylpyridinium thiocyanate; 1-(meth)acryloylaminoalkylpyridinium
  • (Meth)acryloylaminoalkylpyridinium cation-containing ionic compounds 2-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1- 2-alkyl-1-vinylpyridinium cation-containing ionic compounds such as vinylpyridinium dicyanamide, 2-alkyl-1-vinylpyridinium thiocyanate; 2-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl) imide, 2-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 2-alkyl-1-(meth)
  • Alkylpyridinium cation-containing ionic compounds 4-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 4-alkyl-1-vinylpyridinium dicyanamide , 4-alkyl-1-vinylpyridinium thiocyanate 4-alkyl-1-vinylpyridinium cation-containing ionic compounds such as; 4-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium bis 4-alkyl-1-(meth), such as (trifluoromethanesulfonyl)imide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 4-alkyl-1
  • Acryloyloxyalkylpyridinium cation-containing ionic compounds 4-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide , 4-alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 4-alkyl-1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc.
  • the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
  • X + is a piperinidinium group, n 1 is 1, n 2 is 0,
  • a 1 is a vinyl group, a (meth)acryloyloxy group, or a (meth)acryloylamino group, 1-alkyl-1-vinylalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-vinylalkylpiperidinium bis(trifluoromethanesulfonyl ) 1-alkyl-1-vinylalkylpiperidinium cation-containing ionic compounds such as imides, 1-alkyl-1-vinylalkylpiperidinium dicyanamides, 1-alkyl-1-vinylalkylpiperidinium thiocyanates; -alkyl-1-(meth)acryloyloxyalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloyloxyalkylpiperid
  • X + is a pyrrolidinium group, n 1 is 1, n 2 is 0,
  • a 1 is a vinyl group, a (meth)acryloyloxy group, or a (meth)acryloylamino group, 1-alkyl-1-vinylalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-vinylalkylpyrrolidinium bis(trifluoromethanesulfonyl ) 1-alkyl-1-vinylalkylpyrrolidinium cation-containing ionic compounds such as imides, 1-alkyl-1-vinylalkylpyrrolidinium dicyanamides, 1-alkyl-1-vinylalkylpyrrolidinium thiocyanates; 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-vinylalkylpyrroli
  • Ionic compounds 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1 -1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium such as alkyl-1-(meth)acryloylaminoalkylpyrrolidinium dicyanamide, 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium thiocyanate Examples include ionic compounds containing nium cations.
  • the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
  • X + is a trialkylsulfonium group, n 1 is 1, n 2 is 0,
  • a 1 is a vinyl group, (meth)acryloyloxy or (meth)acryloylamino group, dialkyl(vinyl)sulfonium bis(fluorosulfonyl)imide, dialkyl(vinyl)sulfonium bis(trifluoromethanesulfonyl)imide, dialkyl(vinyl)sulfonium dicyanide
  • Dialkyl (vinyl) sulfonium cation-containing ionic compounds such as amides, dialkyl (vinyl) sulfonium thiocyanates; Dialkyl ((meth)acryloyloxyalkyl)sulfonium cation-containing ionic compounds such as (trifluoromethanesulfonyl)imide, dialkyl ((meth)acryl
  • X + is a quaternary phosphonium group
  • n 1 is 1
  • n 2 is 0,
  • a 1 is a vinyl group
  • Specific examples of embodiments that are an oxy group or a (meth)acryloylamino group include trialkyl(vinyl)phosphonium bis(fluorosulfonyl)imide, trialkyl(vinyl)phosphonium bis(trifluoromethanesulfonyl)imide, trialkyl(vinyl ) phosphonium dicyanamide, trialkyl (vinyl) phosphonium thiocyanate, trialkyl (vinyl) phosphonium cation-containing ionic compounds; trialkyl ((meth) acryloyloxyalkyl) phosphonium bis (fluorosulfonyl) imide, trialkyl (( trialkyl ((meth)acryloyloxyalkyl)phosphon
  • Acryloyloxyalkyl)phosphonium cation-containing ionic compounds trialkyl((meth)acryloylaminoalkyl)phosphonium bis(fluorosulfonyl)imide, trialkyl((meth)acryloylaminoalkyl)phosphonium bis(trifluoromethanesulfonyl)imide, trialkyl trialkyl((meth)acryloylaminoalkyl)phosphonium cation-containing ionic compounds such as ((meth)acryloylaminoalkyl)phosphonium dicyanamide and trialkyl((meth)acryloylaminoalkyl)phosphonium thiocyanate;
  • the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
  • X + is a quaternary ammonium group
  • n 1 is 1
  • n 2 is 1
  • a 1 and A 2 are hydroxyl groups.
  • Specific examples include bis(2-hydroxyethyl)-methyl-octylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-decylammonium bis(trifluoromethanesulfonyl)imide, bis(2- Hydroxyethyl)-methyl-dodecylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-tetradecylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-hexadecylammonium Bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-hex
  • ionic compounds represented by the above general formula (A) specific examples of embodiments in which X + is a pyridinium group, n 1 is 1, n 2 is 0, and A 1 is a hydroxyl group include: and N-hydroxyethylpyridinium bis(trifluoromethasulfonyl)imide.
  • ionic compounds represented by the above general formula (A) as a specific example of an aspect in which X + is an imidazolium group, n 1 is 1, n 2 is 0, and A 1 is a hydroxyl group, , 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and the like.
  • X + is an imidazolium group or a quaternary ammonium group
  • n 1 is 1
  • n 2 is 0,
  • a 1 and A 2 is an amino group, 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-aminopropyl-3-methylimidazolium dicyanoamide, 1-aminopropyl-3- Methylimidazolium tetrafluoroborate, 1-aminohexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-aminohexyl-3-methylimidazolium dicyanoamide, 1-aminohexyl-3-methylimidazolium tetrafluoro borate, trimethylaminohexylammonium bis(trifluoromethanesulfonyl)imide, trimethylaminohexylammonium bis(tri
  • the content of the ionic compound of the present invention is not particularly limited, but from the viewpoint of imparting sufficient antistatic performance to the pressure-sensitive adhesive layer of the present invention, it is preferably 0 per 100 parts by weight of the acrylic polymer (A). 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, 0.5 parts by weight or more, or 0.5 parts by weight or more, 1.0 parts by weight or more, 2.0 It may be included in parts by weight or more, 3.0 parts by weight or more, 4.0 parts by weight or more, or 5.0 parts by weight or more.
  • the content of the ionic compound of the present invention is not particularly limited, the acrylic polymer (A) 100 It may be contained in an amount of preferably 50 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less.
  • the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is an acrylic pressure-sensitive adhesive layer containing the acrylic polymer (A) as a main component.
  • the specific content of the acrylic polymer (A) is not particularly limited, it is 75% by weight or more (for example, 75 to 99.9% by weight) relative to the total amount of the pressure-sensitive adhesive layer of the present invention (total weight, 100% by weight). ), more preferably 85% by weight or more (for example, 85 to 99.9% by weight).
  • the adhesive composition for forming the adhesive layer containing the acrylic polymer (A) as a main component is not particularly limited, but for example, a composition containing the acrylic polymer (A) as an essential component; an acrylic polymer ( Examples thereof include a mixture of monomer components constituting A) (sometimes referred to as a "monomer mixture") or a composition containing a partial polymer thereof as an essential component.
  • examples of the former include so-called water-dispersible compositions (emulsion-type compositions), and examples of the latter include so-called active energy ray-curable compositions.
  • the said adhesive composition may contain the other additive agent as needed.
  • the above “monomer mixture” includes cases where it is composed of a single monomer component and cases where it is composed of two or more monomer components.
  • the acrylic polymer (A) is a polymer (polymer) containing an acrylic monomer (acrylic monomer) as an essential monomer unit (monomer unit, monomer structural unit).
  • the acrylic polymer (A) is a polymer containing structural units derived from acrylic monomers as structural units.
  • the acrylic polymer (A) is a polymer constituted (formed) with an acrylic monomer as an essential monomer component.
  • "(meth)acryl” means either one or both of "acryl” and “methacryl", and the same applies to others.
  • the weight average molecular weight of the acrylic polymer (A) is not particularly limited, it is preferably from 100,000 to 5,000,000.
  • the acrylic polymer (A) is a (meth)acrylic acid alkyl ester having a linear or branched alkyl group as an essential monomer unit (hereinafter sometimes simply referred to as "(meth)acrylic acid alkyl ester"). ) is preferred.
  • Examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate ((meth) ) n-butyl acrylate), isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth) hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) ) Dec
  • the (meth)acrylic acid alkyl ester is preferably a (meth)acrylic acid alkyl ester having an alkyl group with a carbon number of 1 to 18 from the viewpoint of obtaining strong adhesiveness and adjusting residual stress.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • EHA 2-ethylhexyl acrylate
  • ISO isostearyl acrylate
  • the content (percentage) of the (meth)acrylic acid alkyl ester in the total monomer units of the acrylic polymer (A) is not particularly limited, but the adhesion reliability , Especially in terms of adhesion reliability at low temperatures, the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) is preferably 30 to 95 parts by weight, more preferably 35 to 90 parts by weight, More preferably 40 to 85 parts by weight.
  • the acrylic polymer (A) may contain a copolymerizable monomer (copolymerizable monomer) in addition to the (meth)acrylic acid alkyl ester as a monomer unit.
  • the acrylic polymer (A) may contain a copolymerizable monomer as a constituent monomer component.
  • the copolymerizable monomers may be used alone or in combination of two or more.
  • a hydroxyl group-containing monomer is preferably mentioned.
  • the acrylic polymer (A) contains a hydroxyl group-containing monomer as a monomer unit, it becomes easy to polymerize the constituent monomer components, and it becomes easy to obtain good cohesive strength. For this reason, it becomes easy to obtain strong adhesiveness, and it becomes easy to obtain excellent anti-foaming peeling property by increasing the gel fraction. Furthermore, it becomes easy to suppress whitening of the adhesive sheet that may occur in a high-humidity environment.
  • the hydroxyl group can also serve as a reaction point with the functional group (A) of the ionic compound of the present invention.
  • the content (proportion) of the hydroxyl group-containing monomer relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) is not particularly limited.
  • the amount of the hydroxyl group-containing monomer is at least a certain amount, the whitening of the pressure-sensitive adhesive sheet, which may occur in a high-humidity environment, can be further suppressed, and the transparency such as resistance to humid clouding can be ensured.
  • the lower limit of the content of the hydroxyl group-containing monomer is preferably 1 part by weight or more, more preferably 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more.
  • the upper limit of the content of the hydroxyl group-containing monomer is preferably 40 parts by weight or less, and 35 parts by weight, from the viewpoint of cohesive strength, adhesiveness, and ease of obtaining adhesion reliability such as resistance to foaming and peeling. It is more preferably 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, or 31 parts by weight or less, and even more preferably 30 parts by weight or less.
  • a nitrogen atom-containing monomer is preferably mentioned.
  • the acrylic polymer (A) contains a nitrogen atom-containing monomer as a monomer unit, it becomes easy to obtain an appropriate cohesive force. For this reason, the 180° (degree) peeling adhesive force to the glass plate and the 180° peeling adhesive force to the acrylic plate are increased, making it easier to obtain strong adhesiveness, and increasing the gel fraction to achieve excellent adhesion. It becomes easy to obtain anti-foaming peeling property. Furthermore, it becomes easy to obtain appropriate flexibility in the pressure-sensitive adhesive layer, adjust the 300% tensile residual stress within a specific range, and easily obtain excellent stress relaxation properties and excellent conformability to unevenness.
  • the content (proportion) of the nitrogen atom-containing monomer relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) is not particularly limited, but is preferably 5 parts by weight or more.
  • the lower limit of the content of the nitrogen atom-containing monomer is 7 parts by weight with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) from the viewpoint of cohesive strength, adhesiveness, and resistance to foaming and peeling. It is preferably 8 parts by weight or more, more preferably 9 parts by weight or more, or even more preferably 10 parts by weight or more.
  • the upper limit of the content of the nitrogen atom-containing monomer is 40 parts by weight from the point that it becomes easier to obtain appropriate flexibility in the pressure-sensitive adhesive layer, and it becomes easier to obtain excellent stress relaxation and excellent step conformability. It is preferably 35 parts by weight or less, more preferably 30 parts by weight or less.
  • the above acrylic polymer (A) can be obtained by polymerizing the above monomer units (monomer components) by a known or commonly used polymerization method.
  • the polymerization method of the acrylic polymer (A) include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method).
  • the solution polymerization method and the active energy ray polymerization method are preferable, and the active energy ray polymerization method is more preferable, from the viewpoints of the transparency, water resistance, cost, etc. of the pressure-sensitive adhesive layer.
  • Examples of the active energy ray irradiated during the active energy ray polymerization (photopolymerization) include ionizing radiation such as ⁇ -ray, ⁇ -ray, ⁇ -ray, neutron beam, and electron beam, and ultraviolet rays, particularly ultraviolet rays. is preferred.
  • the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the photopolymerization initiator can be activated to cause the reaction of the monomer components.
  • solvents may be used in the polymerization of the acrylic polymer (A).
  • examples of such solvents 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; Alicyclic hydrocarbons such as cyclohexane; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • a solvent may 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 may be used individually or in combination of 2 or more types.
  • the photopolymerization initiator is not particularly limited. Active oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like can be mentioned.
  • a photoinitiator may be used individually or in combination of 2 or more types.
  • benzoin ether-based 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, anisole methyl ether and the like.
  • acetophenone-based photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4-(t-butyl ) and dichloroacetophenone.
  • Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like. 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.
  • benzophenone-based photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone, and the like.
  • ketal-based photopolymerization initiator examples include benzyl dimethyl ketal.
  • thioxanthone-based photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
  • the amount of the photopolymerization initiator to be used is not particularly limited. 001 to 1 part by weight, more preferably 0.01 to 0.50 part by weight.
  • the thermal polymerization initiator is not particularly limited, but for example, an azo polymerization initiator, a peroxide polymerization initiator (e.g., dibenzoyl peroxide, tert-butyl permaleate, etc.), a redox polymerization initiator agents and the like.
  • an azo polymerization initiator e.g., dibenzoyl peroxide, tert-butyl permaleate, etc.
  • a redox polymerization initiator agents e.g., dibenzoyl peroxide, tert-butyl permaleate, etc.
  • the azo polymerization initiator disclosed in JP-A-2002-69411 is preferable.
  • azo polymerization initiator examples include 2,2'-azobisisobutyronitrile (hereinafter sometimes referred to as "AIBN”), 2,2'-azobis-2-methylbutyronitrile (hereinafter, “AMBN”), 2,2′-azobis(2-methylpropionate)dimethyl, 4,4′-azobis-4-cyanovaleric acid and the like.
  • AIBN 2,2'-azobisisobutyronitrile
  • AMBN 2,2'-azobis-2-methylbutyronitrile
  • 2,2′-azobis(2-methylpropionate)dimethyl 2,4′-azobis-4-cyanovaleric acid and the like.
  • the amount of the thermal polymerization initiator used is not particularly limited.
  • all monomer units of the acrylic polymer (A) (the total amount of monomer components constituting the acrylic polymer (A)) It is preferably 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight, per 100 parts by weight.
  • the pressure-sensitive adhesive layer does not substantially contain a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer (A).
  • the phrase "substantially does not contain” means that it is not actively blended except when it is unavoidably mixed.
  • a carboxyl group-containing monomer means a monomer having at least one carboxyl group in the molecule. From the viewpoint of obtaining a more excellent anti-corrosion effect, specifically, the content of the carboxyl group-containing monomer is 0.00% relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A).
  • 05 parts by weight or less e.g., 0 to 0.05 parts by weight
  • more preferably 0.01 parts by weight or less e.g., 0 to 0.01 parts by weight
  • still more preferably 0.001 parts by weight or less e.g., , 0 to 0.001 parts by weight
  • carboxyl group-containing monomer examples include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • Acid anhydride group-containing monomers such as maleic acid and itaconic anhydride are also intended to be included.
  • the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer
  • the pressure-sensitive adhesive layer contains a carboxyl group as a monomer component constituting the acrylic polymer (A).
  • monomers having acidic groups other than carboxyl groups are also substantially contained as monomer components constituting the acrylic polymer (A). preferably not. That is, the acrylic polymer (A) preferably contains substantially no carboxyl group-containing monomers and other monomers having acidic groups as constituent monomer components.
  • the total amount of the carboxyl group-containing monomers and other monomers having an acidic group as the monomer components constituting the acrylic polymer (A) is the total amount of the monomer components constituting the acrylic polymer (A) (100 parts by weight ), preferably 0.05 parts by weight or less (e.g., 0 to 0.05 parts by weight), more preferably 0.01 parts by weight or less (e.g., 0 to 0.01 parts by weight), more preferably 0 It can be said that the content of 0.001 part by weight or less (for example, 0 to 0.001 part by weight) is substantially absent.
  • the pressure-sensitive adhesive layer does not contain an acidic group-containing monomer as a monomer component constituting a polymer other than the acrylic polymer (A) (for example, an acrylic polymer (B) described later). Or it is preferable not to contain substantially. For example, it is preferred that substantially no carboxyl group-containing monomer is contained.
  • the meaning of "not containing substantially", the preferred degree, and the monomer having an acidic group other than a carboxyl group are the same as in the case of the monomer component constituting the acrylic polymer (A). .
  • the pressure-sensitive adhesive layer does not contain, or substantially does not contain, a basic group-containing monomer as a monomer component constituting the base polymer.
  • a basic group-containing monomer is added as a monomer component constituting a polymer other than the acrylic polymer (A). It is preferable that it does not substantially contain, and even if it is not a monomer component constituting various polymers, it is preferable that the pressure-sensitive adhesive layer does not substantially contain a basic group-containing monomer. is the same as for In addition, the same applies to the meaning of "substantially free of", the preferred degree, and the like.
  • a hydroxyl group-containing monomer means a monomer having at least one hydroxyl group in the molecule. Also, a monomer having at least one hydroxyl group in the molecule and at least one carboxyl group in the molecule is a carboxyl group-containing monomer and is not a hydroxyl group-containing monomer.
  • the hydroxyl group-containing monomer is not particularly limited, but specific examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 3-hydroxypropyl meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, (meth)acrylic acid hydroxyl group-containing (meth)acrylic acid esters such as hydroxyllauryl and (meth)acrylic acid (4-hydroxymethylcyclohexyl); vinyl alcohol, allyl alcohol and the like.
  • the hydroxyl group-containing monomer is preferably a hydroxyl group-containing (meth)acrylic acid ester, more preferably 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl (meth)acrylate (HPA), acrylic acid 4 - hydroxybutyl (4HBA).
  • HOA 2-hydroxyethyl acrylate
  • HPA 2-hydroxypropyl (meth)acrylate
  • 4HBA acrylic acid 4 - hydroxybutyl
  • the hydroxyl group-containing monomers may be used alone or in combination of two or more.
  • a nitrogen atom-containing monomer means a monomer having at least one nitrogen atom in its molecule (in one molecule).
  • the hydroxyl group-containing monomer does not include the nitrogen atom-containing monomer. That is, in this specification, a monomer having a hydroxyl group and a nitrogen atom in its molecule is included in the nitrogen atom-containing monomer.
  • a monomer having at least one nitrogen atom in the molecule and at least one carboxyl group in the molecule is a carboxyl group-containing monomer and is not a nitrogen atom-containing monomer.
  • N-vinyl cyclic amides, (meth)acrylamides, and the like are preferable as the nitrogen atom-containing monomer.
  • the nitrogen atom-containing monomers may be used alone or in combination of two or more.
  • N-vinyl cyclic amide an N-vinyl cyclic amide represented by the following formula (1) is preferable.
  • 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., carbon number 3 to 5 alkylene groups, etc.).
  • N-vinyl-2-pyrrolidone N-vinyl-2-pyrrolidone
  • N-vinyl-2-piperidone N-vinyl -2-caprolactam
  • N-vinyl-3-morpholinone N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione and the like
  • N-vinyl-2- pyrrolidone N-vinyl-2-caprolactam
  • N-vinyl-2-pyrrolidone N-vinyl-2-pyrrolidone
  • N-vinyl-2-caprolactam more preferably N-vinyl-2-pyrrolidone.
  • Examples of the (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, and N,N-dialkyl(meth)acrylamide.
  • Examples of the N-alkyl(meth)acrylamide include N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-octylacrylamide and the like.
  • N-alkyl(meth)acrylamides also include (meth)acrylamides having an amino group such as dimethylaminoethyl(meth)acrylamide, diethylaminoethyl(meth)acrylamide, and dimethylaminopropyl(meth)acrylamide.
  • N,N-dialkyl(meth)acrylamides examples include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl (Meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide and the like.
  • the (meth)acrylamides also 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, N-(4-hydroxybutyl)(meth)acrylamide, N-methyl-N-2-hydroxyethyl(meth)acrylamide and the like.
  • the (meth)acrylamides also include, for example, various N-alkoxyalkyl(meth)acrylamides.
  • Examples of the N-alkoxyalkyl(meth)acrylamides include N-methoxymethyl(meth)acrylamide and N-butoxymethyl(meth)acrylamide.
  • Nitrogen atom-containing monomers other than the N-vinyl cyclic amides and the (meth)acrylamides include, for example, aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylamino (meth)acrylate propyl, amino group-containing monomers such as t-butylaminoethyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; (meth)acryloylmorpholine, N-vinylpiperazine, N-vinylpyrrole, N-vinyl imidazole, N-vinylpyrazine, N-vinylmorpholine, N-vinylpyrazole, vinylpyridine, vinylpyrimidine, vinyloxazole, vinylisoxazole, vinylthiazole, vinylisothiazole, vinylpyridazine, (meth)acryloylpyrrolidone, (
  • 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.
  • an alkyl (meth)acrylate having a cycloalkyl group is included in the alicyclic structure-containing monomer.
  • an alicyclic structure containing monomer can be used individually or in combination of 2 or more types.
  • the alicyclic structure in the alicyclic structure-containing monomer is a cyclic hydrocarbon structure, preferably having 5 or more carbon atoms, more preferably 6 to 24 carbon atoms, further 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. (Meth)acrylic monomers.
  • formula (4) there is no particular limitation on the bonding position between the cyclohexyl ring connected by a line and the structural formula in parentheses. Among these, isobornyl (meth)acrylate is preferred.
  • the acrylic polymer contains the alicyclic structure-containing monomer as a monomer component constituting the polymer
  • the proportion of the monomer is not particularly limited, it is preferably 10% by weight or more from the viewpoint of improving durability and obtaining high adhesion reliability.
  • the upper limit of the ratio of the alicyclic structure-containing monomer is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 30% by weight or less, from the viewpoint of obtaining a pressure-sensitive adhesive layer having appropriate flexibility. is.
  • copolymerizable monomers in the acrylic polymer (A) include, in addition to the above nitrogen atom-containing monomers and hydroxyl group-containing monomers, (meth)acrylic acid alkoxyalkyl esters [for example, 2-methoxyethyl (meth)acrylate , 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate , 4-ethoxybutyl (meth)acrylate, etc.]; epoxy group-containing monomers [e.g., glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, etc.]; sulfonic acid group-containing monomers [e.g., sodium vinyl sulfonate, etc.
  • (meth)acrylic acid alkoxyalkyl esters for
  • phosphoric acid group-containing monomer (meth) acrylic acid ester having an aromatic hydrocarbon group [e.g., phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, etc.]; vinyl ester analogues [e.g., vinyl acetate, vinyl propionate, etc.]; aromatic vinyl compounds [e.g., styrene, vinyltoluene, etc.]; olefins or dienes [e.g., ethylene, propylene, butadiene, isoprene, isobutylene, etc.]; vinyl ethers [e.g. For example, vinyl alkyl ether, etc.]; vinyl chloride, etc. may be mentioned.
  • aromatic hydrocarbon group e.g., phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, etc
  • the copolymerizable monomers in the acrylic polymer (A) also include polyfunctional monomers.
  • a polyfunctional monomer acts as a cross-linking component.
  • 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, Allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, ure
  • the content (proportion) of the polyfunctional monomer in all monomer units of the acrylic polymer (A) is not particularly limited, but with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A), It is preferably 0.5 parts by weight or less (for example, 0 to 0.5 parts by weight), more preferably 0 to 0.35 parts by weight, still more preferably 0 to 0.3 parts by weight.
  • the content of the polyfunctional monomer is 0.5 parts by weight or less, the pressure-sensitive adhesive layer has appropriate cohesive strength, and the pressure-sensitive adhesive strength and step absorbability are easily improved, which is preferable.
  • the polyfunctional monomer when using a cross-linking agent, may not be used, but the content of the multi-functional monomer when the cross-linking agent is not used is preferably 0.001 to 0.5 parts by weight. , more preferably 0.001 to 0.35 parts by weight, more preferably 0.002 to 0.3 parts by weight.
  • Acrylic polymer (B) When the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) contains an acrylic polymer (A) as a base polymer, the pressure-sensitive adhesive layer, together with the acrylic polymer (A), It preferably contains an acrylic polymer (B) having a weight average molecular weight of 1,000 to 30,000. When the acrylic polymer (B) is contained, the adhesion to the adherend at the interface of the pressure-sensitive adhesive sheet is improved, so that it becomes easy to obtain strong adhesion and excellent resistance to foaming and peeling. In this specification, "acrylic polymer (B) having a weight average molecular weight of 1000 to 30000" may be simply referred to as "acrylic polymer (B)".
  • an acrylic polymer composed of a (meth)acrylic ester having a cyclic structure in the molecule as an essential monomer component is preferably mentioned, and a (meth) having a cyclic structure in the molecule.
  • An acrylic polymer composed of an acrylic acid ester and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group as essential monomer components is more preferable.
  • the acrylic polymer (B) preferably includes an acrylic polymer containing a (meth)acrylic acid ester having a cyclic structure in the molecule as a monomer unit, and has a cyclic structure in the molecule as a monomer unit (meth) )
  • Acrylic polymers containing acrylic acid esters and (meth)acrylic acid alkyl esters having linear or branched alkyl groups are more preferred.
  • the cyclic structure (ring) of the (meth)acrylic acid ester having a cyclic structure in the molecule (in one molecule) is an aromatic ring , a non-aromatic ring, and is not particularly limited.
  • the aromatic ring include aromatic carbocyclic rings [eg, monocyclic carbocyclic rings such as benzene ring, condensed carbocyclic rings such as naphthalene ring, etc.], various aromatic heterocyclic rings, and the like.
  • non-aromatic ring examples include non-aromatic aliphatic rings (non-aromatic alicyclic rings) [e.g., cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring cycloalkene rings such as cyclohexene rings], non-aromatic bridging rings [e.g., bicyclic hydrocarbon rings in pinane, pinene, bornane, norbornane, norbornene, etc.; tricyclic or higher aliphatic hydrocarbons in adamantane, etc. ring (bridged hydrocarbon ring), etc.], non-aromatic heterocyclic ring [eg, epoxy ring, oxolane ring, oxetane ring, etc.], and the like.
  • non-aromatic aliphatic rings e.g., cycloalkane
  • tricyclic or higher aliphatic hydrocarbon ring examples include, for example, a dicyclopentanyl group represented by the following formula (5a), and a dicyclopentanyl group represented by the following formula (5b).
  • an adamantyl group represented by the following formula (5d) an adamantyl group represented by the following formula (5d)
  • a tricyclopentenyl group represented by the following formula (5e) examples include, for example, a dicyclopentanyl group represented by the following formula (5a), and a dicyclopentanyl group represented by the following formula (5b).
  • an adamantyl group represented by the following formula (5d) an adamantyl group represented by the following formula (5d)
  • examples of the ring-containing (meth)acrylic acid ester include (meth)acrylic esters such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate.
  • Acrylic acid cycloalkyl ester (meth)acrylic acid ester having a bicyclic aliphatic hydrocarbon ring such as isobornyl (meth)acrylate; dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth) Tricyclic or higher aliphatics such as acrylates, tricyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate (Meth)acrylic acid esters having a hydrocarbon ring; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate, (meth)acrylic acid aryloxyalkyl esters such as phenoxyethyl (meth)acrylate, (meth)acrylic acid esters Examples thereof include (meth)acrylic acid esters having an aromatic ring, such as (
  • the ring-containing (meth)acrylic acid ester is particularly preferably a non-aromatic ring-containing (meth)acrylic acid ester, more preferably cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHMA), acrylic Dicyclopentanyl acid (DCPA) and dicyclopentanyl methacrylate (DCPMA), more preferably dicyclopentanyl acrylate (DCPA) and dicyclopentanyl methacrylate (DCPMA).
  • ring-containing (meth)acrylic acid esters may be used alone or in combination of two or more.
  • non-aromatic ring-containing (meth)acrylic acid esters a (meth)acrylic acid ester having a tricyclic or higher aliphatic hydrocarbon ring (particularly, a tricyclic or higher bridging hydrocarbon ring) is used. This is particularly preferable in that polymerization inhibition is less likely to occur.
  • a dicyclopentanyl group having no unsaturated bond 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) When using a (meth) acrylic acid ester having, it is possible to further increase the resistance to foaming and peeling, and furthermore, the adhesion to low-polar adherends such as polyethylene and polypropylene can be significantly improved. .
  • the content (percentage) of the ring-containing (meth)acrylic acid ester in the total monomer units of the acrylic polymer (B) is not particularly limited, but the acrylic polymer It is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting (B).
  • the content of the ring-containing (meth)acrylic acid ester is 10 parts by weight or more, the resistance to foaming and peeling is easily improved, which is preferable.
  • the content is 90 parts by weight or less, the pressure-sensitive adhesive layer has appropriate flexibility, and the pressure-sensitive adhesive strength, step absorbability, etc. are likely to be improved, which is preferable.
  • Examples of the (meth)acrylic acid alkyl ester having a linear or branched alkyl group as the monomer unit of the acrylic polymer (B) include methyl (meth)acrylate and ethyl (meth)acrylate. , propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, (meth)acrylate Pentyl acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, (meth) ) nonyl acrylate, isononyl (meth
  • Examples thereof include (meth)acrylic acid alkyl esters having 1 to 20 carbon atoms.
  • methyl methacrylate (MMA) is preferable because it has good compatibility with the acrylic polymer (A).
  • said (meth)acrylic-acid alkylester may be used individually or in combination of 2 or more types.
  • Content (percentage) of (meth)acrylic acid alkyl ester having a linear or branched alkyl group in all monomer units of acrylic polymer (B) is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (B) in terms of resistance to foaming and peeling. parts by weight, more preferably 20 to 60 parts by weight. When the content is 10 parts by weight or more, the adhesive strength to an adherend made of acrylic resin or polycarbonate tends to be improved, which is preferable.
  • the monomer unit of the acrylic polymer (B) in addition to the ring-containing (meth)acrylic acid ester and the (meth)acrylic acid alkyl ester having a linear or branched alkyl group, these monomers and A polymerizable monomer (copolymerizable monomer) may be included.
  • the content (proportion) of the copolymerizable monomer in the total monomer units of the acrylic polymer (B) is not particularly limited, but the acrylic polymer (B ) is preferably 49.9 parts by weight or less (eg, 0 to 49.9 parts by weight), more preferably 30 parts by weight or less, relative to the total amount (100 parts by weight) of the monomer components constituting Also, the copolymerizable monomers may be used alone or in combination of two or more.
  • Examples of the copolymerizable monomer (the copolymerizable monomer constituting the acrylic polymer (B)) as monomer units of the acrylic polymer (B) include (meth)acrylic acid alkoxyalkyl esters [for example, (meth) ) 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, (meth) ) 4-methoxybutyl acrylate, 4-ethoxybutyl (meth)acrylate, etc.]; hydroxyl group (hydroxyl group)-containing monomers [e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth
  • the acrylic polymer (B) includes, as monomer units, a (meth)acrylic acid ester having a cyclic structure in the molecule and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group.
  • Acrylic polymers are preferred.
  • an acrylic polymer containing, as monomer units, a ring-containing (meth)acrylic acid ester and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group is preferred.
  • a monomer component constituting the acrylic polymer (B) The amount of the ring-containing (meth)acrylic acid ester relative to the total amount (100 parts by weight) 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, and even more preferably 20 to 60 parts by weight.
  • the monomer unit is (1) selected from the group consisting of dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate. and (2) an acrylic polymer containing methyl methacrylate.
  • dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and the content of cyclohexyl methacrylate is 30 to 70 parts by weight with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (B), 2)
  • the content of methyl methacrylate is preferably 30 to 70 parts by weight.
  • the acrylic polymer (B) is not limited to the above specific configuration.
  • the acrylic polymer (B) can be obtained by polymerizing the above monomer components by a known or commonly used polymerization method.
  • the polymerization method of the acrylic polymer (B) include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method).
  • the bulk polymerization method and the solution polymerization method are preferable, and the solution polymerization method is more preferable.
  • Various common solvents may be used in the polymerization of the acrylic polymer (B).
  • 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, methylcyclohexane and the like. alicyclic hydrocarbons; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • such a solvent may be used individually or in combination of 2 or more types.
  • 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 initiators examples include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile (AMBN), 2,2'-azobis(2- methylpropionate) dimethyl, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4- dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4,4-trimethylpentane) and other azo initiators; 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 bis(
  • the amount of the thermal polymerization initiator to be used is not particularly limited. .1 to 15 parts by weight.
  • 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 (A) mentioned above.
  • the amount of the photopolymerization initiator to be used is not particularly limited, and is appropriately selected.
  • a chain transfer agent may be used in the polymerization of the acrylic polymer (B) to adjust the molecular weight (specifically, to adjust the weight average molecular weight to 1000 to 30000).
  • the chain transfer agent include 2-mercaptoethanol, ⁇ -thioglycerol, 2,3-dimercapto-1-propanol, octyl mercaptan, t-nonyl mercaptan, dodecyl mercaptan (lauryl mercaptan), t-dodecyl mercaptan, glycidyl mercaptan, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate
  • ⁇ -thioglycerol and methyl thioglycolate are preferred, and ⁇ -thioglycerol is particularly preferred, from the viewpoint of suppressing whitening of the adhesive sheet 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 per 100 parts by weight of all monomer units of the acrylic polymer (B) (the total amount of the monomer components constituting the acrylic polymer (B)). .1 to 20 parts by weight is preferred, more preferably 0.2 to 15 parts by weight, and still more preferably 0.3 to 10 parts by weight.
  • the weight average molecular weight (Mw) of the acrylic polymer (B) is 1,000 to 30,000, preferably 1,000 to 20,000, more preferably 1,500 to 10,000, and still more preferably 2,000 to 8,000. Since the acrylic polymer (B) has a weight-average molecular weight of 1000 or more, the adhesive strength and holding properties are improved, and the resistance to foaming and peeling is improved. On the other hand, since the acrylic polymer (B) has a weight-average molecular weight of 30,000 or less, the adhesive strength is easily increased, and the resistance to foaming and peeling is improved.
  • the weight-average molecular weight (Mw) of the acrylic polymer (B) can be determined by the GPC method in terms of polystyrene. For example, it can be measured under the following conditions using a high-speed GPC apparatus "HPLC-8120GPC" manufactured by Tosoh Corporation. Column: TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000 Solvent: Tetrahydrofuran Flow rate: 0.6 ml/min
  • the glass transition temperature (Tg) of the acrylic polymer (B) is not particularly limited, it is preferably 20 to 300°C, more preferably 30 to 300°C, and even more preferably 40 to 300°C.
  • the glass transition temperature of the acrylic polymer (B) is 20° C. or higher, the resistance to foaming and peeling is likely to be improved, which is preferable.
  • the glass transition temperature of the acrylic polymer (B) is 300° C. or less, the pressure-sensitive adhesive layer has appropriate flexibility, and it becomes easy to obtain good adhesive strength and good step absorbability, resulting in excellent adhesion. This is preferable because it makes it easier to obtain reliability.
  • Tg is the glass transition temperature (unit: K) of the acrylic polymer (B)
  • Tg is the glass transition temperature (unit: K) when the monomer i forms a homopolymer
  • Table 1 As the Tg of the homopolymer of the monomers constituting the acrylic polymer (B), the values shown in Table 1 below can be adopted.
  • Tg of homopolymers of monomers not listed in Table 1 values described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be used. Furthermore, as the Tg of a homopolymer of a monomer not described in the above literature, the value obtained by the above-described measuring method (tan ⁇ peak top temperature by viscoelasticity test) can be employed.
  • the content of the acrylic polymer (B) when the pressure-sensitive adhesive layer contains the acrylic polymers (A) and (B) is not particularly limited. It is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, still more preferably 2 to 10 parts by weight. That is, the content of the acrylic polymer (B) in the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 30 parts by weight with respect to 100 parts by weight of all monomer units of the acrylic polymer (A), and more It is preferably 2 to 20 parts by weight, more preferably 2 to 10 parts by weight.
  • the content of the acrylic polymer (B) in the adhesive layer is not particularly limited. , more preferably 2 to 10 parts by weight.
  • the content of the acrylic polymer (B) is 1 part by weight or more, excellent adhesiveness and excellent resistance to foaming and peeling can be easily obtained, which is preferable. Moreover, when the content of the acrylic polymer (B) is 30 parts by weight or less, excellent transparency and adhesion reliability can be easily obtained, which is preferable.
  • the method for producing the pressure-sensitive adhesive layer containing the acrylic polymers (A) and (B) is not particularly limited.
  • a mixture of monomer components constituting the acrylic polymer (A) or a partial polymer of a mixture of monomer components constituting the acrylic polymer (A) (a monomer mixture forming the acrylic polymer (A) or a partial polymer thereof ), the acrylic polymer (B), additives and the like are added as necessary and mixed.
  • the pressure-sensitive adhesive layer of the present invention may optionally contain an antistatic agent other than the ionic compound of the present invention (herein, may be referred to as "other antistatic agent").
  • antistatic agent include materials capable of imparting antistatic properties, such as ionic compounds, ionic surfactants, conductive polymers, and conductive fine particles.
  • ionic compounds are preferred from the viewpoint of compatibility with the acrylic polymer (A) and transparency of the pressure-sensitive adhesive layer.
  • an inorganic cation anion salt and/or an organic cation anion salt can be preferably used, and it is particularly preferable to use an inorganic cation anion salt.
  • An ionic compound containing an inorganic cation (inorganic cation anion salt) is more preferable than an organic cation anion salt because it can suppress a decrease in adhesiveness (anchor force) of the pressure-sensitive adhesive layer when used.
  • the term "inorganic cation anion salt" as used in the present invention generally indicates an alkali metal salt formed from an alkali metal cation and an anion, and the alkali metal salt includes an organic salt and an inorganic salt of an alkali metal. can be used.
  • organic cation anion salt as used in the present invention means an organic salt, the cation portion of which is composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance.
  • Organic cation anion salts are also referred to as ionic liquids and ionic solids.
  • the anion component constituting the ionic compound it is preferable to use a fluorine-containing anion from the viewpoint of antistatic function.
  • alkali metal ions that make up the cation portion of the alkali metal salt include ions of lithium, sodium, and potassium. Among these alkali metal ions, lithium ions are preferred.
  • the anion portion of the alkali metal salt may be composed of an organic substance or may be composed of an inorganic substance.
  • the anion moiety constituting the organic salt include CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 3 C ⁇ , C 4 F 9 SO 3 - , C3F7COO- , ( CF3SO2 ) ( CF3CO ) N- , -O3S ( CF2 ) 3SO3- , PF6- , CO32- , or the following general formula ( 1) to (4), (1): (C n F 2n+1 SO 2 ) 2 N ⁇ (where n is an integer of 1 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N ⁇ (where m is an integer of 1 to 10), (3): - O 3 S(CF 2 ) l SO 3 - (where l is an integer of
  • an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained.
  • the anion moiety constituting the inorganic salt include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , NbF 6 ⁇ , TaF 6 ⁇ , (CN) 2 N ⁇ , etc. are used.
  • fluorine-containing imide anions are preferable, and among these, bis(trifluoromethanesulfonyl)imide anions and bis(fluorosulfonyl)imide anions are preferable.
  • a bis(fluorosulfonyl)imide anion is preferable because it can impart excellent antistatic properties even when added in a relatively small amount, maintains adhesive properties, and is advantageous for durability in a humidified or heated environment.
  • alkali metal organic salts include sodium acetate, sodium alginate, sodium ligninsulfonate , sodium toluenesulfonate, LiCF3SO3 , Li ( CF3SO2 )2N, Li ( CF3SO2 ).
  • Li (CF 3 SO 2 )2N Li ( C2F5SO2 )2N , Li ( C4F9SO2 ) 2N , Li ( CF3SO2 ) 3C , KO3S ( CF2 ) 3SO3K , LiO 3 S(CF 2 ) 3 SO 3 K, among others, LiCF 3 SO 3 , Li(FSO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, etc.
  • Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N , Li(C 4 F 9 SO 2 ) 2 N and the like are preferred, and bis(trifluoromethanesulfonyl)imidelithium and bis(fluorosulfonyl)imidelithium are particularly preferred.
  • Inorganic salts of alkali metals include lithium perchlorate and lithium iodide.
  • An organic cation anion salt is composed of a cation component and an anion component, and the cation component is composed of an organic substance.
  • cationic components include pyridinium cations, piperidinium cations, pyrrolidinium cations, cations having a pyrroline skeleton, cations having a pyrrole skeleton, imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, Examples include pyrazolium cations, pyrazolinium cations, tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and the like.
  • anion components include Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , ClO 4 - , NO 3 - , CH 3 COO - , CF 3 COO - , CH3SO3- , CF3SO3- , ( CF3SO2 ) 3C- , AsF6- , SbF6- , NbF6- , TaF6- , ( CN) 2N- , C4F 9 SO 3 ⁇ , C 3 F 7 COO ⁇ , ((CF 3 SO 2 )(CF 3 CO) N ⁇ , —O 3 S(CF 2 ) 3 SO 3 ⁇ , and compounds represented by the following general formulas (1) to (4) ), (1): (C n F 2n+1 SO 2 ) 2 N ⁇ (where n is an integer of 1 to 10), ( 2 ): CF2 ( Cm
  • anions containing a fluorine atom are particularly preferred because they yield ionic compounds with good ion dissociation properties.
  • fluorine-containing imide anions are preferable, and among these, bis(trifluoromethanesulfonyl)imide anions and bis(fluorosulfonyl)imide anions are preferable.
  • a bis(fluorosulfonyl)imide anion is preferable because it can impart excellent antistatic properties even when added in a relatively small amount, maintains adhesive properties, and is advantageous for durability in a humidified or heated environment.
  • the ionic compounds include inorganic compounds such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate. salt. These ionic compounds can be used alone or in combination.
  • ionic surfactants examples include cationic surfactants (e.g., quaternary ammonium salt type, phosphonium salt type, sulfonium salt type, etc.) and anionic surfactants (carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphite type, etc.). , Zwitterionic (sulfobetaine type, alkylbetaine type, alkylimidazolium betaine type, etc.) or nonionic (polyhydric alcohol derivative, ⁇ -cyclodextrin inclusion compound, sorbitan fatty acid monoester/diester, polyalkylene oxide derivative, amine oxide, etc.).
  • cationic surfactants e.g., quaternary ammonium salt type, phosphonium salt type, sulfonium salt type, etc.
  • anionic surfactants carboxylic acid type, sulfonate type, sulfate type,
  • Examples of conductive polymers include polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoxaline-based polymers. Among these, polyaniline, polythiophene, and the like are preferably used. Polythiophene is particularly preferred.
  • Examples of conductive fine particles include metal oxides such as tin oxide, antimony oxide, indium oxide, and zinc oxide. Among these, the tin oxide type is preferable. Tin oxides include, in addition to tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide-tin oxide composite, titanium oxide- Composites of tin oxide and the like can be mentioned.
  • the fine particles have an average particle size of about 1 to 100 nm, preferably 2 to 50 nm.
  • antistatic agents other than the above acetylene black, ketjen black, natural graphite, artificial graphite, titanium black, cationic type (quaternary ammonium salt, etc.), amphoteric ion type (betaine compound, etc.), anionic type (sulfonic acid salts, etc.), homopolymers of monomers having nonionic (glycerin, etc.) ion-conductive groups or copolymers of the above monomers with other monomers, acrylates or methacrylates having a quaternary ammonium base Polymers having ionic conductivity such as polymers having sites of origin; and permanent antistatic agents of the type in which hydrophilic polymers such as polyethylene methacrylate copolymers are alloyed with acrylic resins or the like.
  • the content is not particularly limited, but the transparency, appearance, and durability such as contact reliability of the pressure-sensitive adhesive layer of the present invention are ensured. From the point of view, it is preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, 0.4 parts by weight or less, 0.3 parts by weight or less, or 0.3 part by weight or less with respect to 100 parts by weight of the acrylic polymer (A). 2 parts by weight or less.
  • the lower limit of the content is not particularly limited. Alternatively, it may be 0.05 parts by weight or more.
  • a cross-linking agent In the pressure-sensitive adhesive layer, if necessary, a cross-linking agent, a cross-linking accelerator, a silane coupling agent, a tackifying resin (rosin derivative, polyterpene resin, petroleum resin, oil-soluble phenol, etc.), an anti-aging agent, a filler, Known additives such as colorants (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, rust inhibitors, etc., within the range that does not impair the characteristics of the present invention. may be included in In addition, such an additive may be used individually or in combination of 2 or more types.
  • the base polymer is cross-linked to increase the gel fraction, making it easier to improve the resistance to foaming and peeling.
  • the acrylic polymer especially the acrylic polymer (A)
  • the acrylic polymer (A)) can be crosslinked to easily increase the control of the gel fraction.
  • the acrylic polymer (A) and the ionic compound of the present invention can form a covalent bond via a cross-linking agent.
  • cross-linking agent examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal Examples include salt-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and amine-based cross-linking agents.
  • the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer containing an acrylic polymer (A) as a base polymer
  • isocyanate-based cross-linking agents and epoxy-based cross-linking agents are preferable and more preferable from the viewpoint of improving resistance to foaming and peeling.
  • a crosslinking agent may be used individually or in combination of 2 or more types.
  • isocyanate-based crosslinking agent examples 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 , xylylene diisocyanate and other aromatic polyisocyanates.
  • lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate
  • cyclopentylene diisocyanate cycl
  • isocyanate-based cross-linking agent examples include trimethylolpropane/tolylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”], trimethylolpropane/hexamethylene diisocyanate adduct [Nippon Polyurethane Kogyo Co., Ltd., trade name “Coronate HL”], trimethylolpropane/xylylene diisocyanate adduct [Mitsui Chemicals Co., Ltd., trade name “Takenate D-110N”].
  • epoxy-based cross-linking agent examples include N,N,N',N'-tetraglycidyl-m-xylenediamine, 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 content of the cross-linking agent in the pressure-sensitive adhesive layer is not particularly limited. 5 parts by weight. When the content of the cross-linking agent is 0.001 parts by weight or more, the resistance to foaming and peeling is easily improved, which is preferable. On the other hand, when the content of the cross-linking agent is 10 parts by weight or less, the pressure-sensitive adhesive layer has appropriate flexibility and the pressure-sensitive adhesive strength is easily improved, which is preferable.
  • the pressure-sensitive adhesive layer contains a silane coupling agent, excellent adhesion to glass (in particular, excellent adhesion reliability to glass at high temperature and high humidity) can be easily obtained, which is preferable.
  • the silane coupling agent include, but are not limited to, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N-phenyl-aminopropyltrimethoxysilane. etc. Among them, ⁇ -glycidoxypropyltrimethoxysilane is preferred.
  • silane coupling agent examples include commercially available products such as the product name "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a silane coupling agent may be used individually or in combination of 2 or more types.
  • the content of the silane coupling agent in the adhesive layer is not particularly limited, but for example, when the adhesive layer is an adhesive layer containing an acrylic polymer (A) as a base polymer, the adhesion reliability to glass From the viewpoint of improving properties, it is preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight, per 100 parts by weight of the acrylic polymer (A).
  • the form of the reaction in which the acrylic polymer (A) and the functional group (A) of the ionic compound of the present invention form a covalent bond is not particularly limited as long as the covalent bond can be formed.
  • the functional group (A) may be incorporated as a monomer unit of the acrylic polymer (A), or the acrylic polymer (A) reacts with the functional group in the side chain to form a covalent bond. It may be in the form of forming.
  • the acrylic polymer (A) and the functional group (A) of the ionic compound of the present invention may react via the above-mentioned cross-linking agent to form a covalent bond.
  • the functional group (A) of the ionic compound of the present invention is a copolymerizable functional group such as (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, allyl group, styryl group, When it is contained in the mixture of monomer components constituting the acrylic polymer (A), it is incorporated as a monomer unit in the process of polymerizing the acrylic polymer (A) to form a covalent bond.
  • the functional group (A) of the ionic compound of the present invention is a copolymerizable functional group such as (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, allyl group, styryl group, etc.
  • a copolymerizable functional group such as (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, allyl group, styryl group, etc.
  • the functional group (A) of the ionic compound of the present invention is a hydroxyl group, an amino group, a mercapto group, etc.
  • the acrylic polymer (A) has an isocyanate group, a thioisocyanate group, an epoxy group, etc. in the side chain.
  • the functional group (A) is an epoxy group or the like
  • the acrylic polymer (A) has a hydroxyl group, an amino group, a mercapto group, or the like in the side chain.
  • it has a functional group capable of reacting with the functional group (A) of, it reacts with the functional group (A) to form a covalent bond.
  • the functional group (A) of the ionic compound of the present invention is a hydroxyl group, an amino group, a mercapto group, etc.
  • the acrylic polymer (A) has a hydroxyl group, an amino group, a mercapto group, etc. in the side chain.
  • the above-mentioned cross-linking agent is blended, and the functional group (A) and the side chain functional group of the acrylic polymer (A) react with the isocyanate group, thioisocyanate group, epoxy group, etc. of the cross-linking agent, and through the cross-linking agent can form a covalent bond.
  • the optical pressure-sensitive adhesive sheet of the present invention includes other layers, for example, a base material other than the base material of the present invention, as long as the effects of the present invention are not impaired. , a pressure-sensitive adhesive layer other than the pressure-sensitive adhesive layer of the present invention, an intermediate layer, an undercoat layer (anchor layer), a separator, a surface protective film, and the like on the surface or between any layers.
  • an undercoat layer may be provided between the first surface of the base material of the present invention and the pressure-sensitive adhesive layer of the present invention.
  • the thickness of the anchor layer is 0.01 to 0.5 ⁇ m, preferably 0.01 to 0.4 ⁇ m, more preferably 0.02 to 0.3 ⁇ m, from the viewpoint of adhesion with the pressure-sensitive adhesive layer. It is preferable to have
  • a binder component can be added for the purpose of improving the film-forming property and adhesion to the base material of the present invention.
  • binders include oxazoline group-containing polymers, polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polyvinylpyrrolidone, polystyrene resins, polyethylene glycol, pentaerythritol and the like. Polyurethane-based resins, polyester-based resins, and acrylic-based resins are particularly preferred. One or more of these binders can be used as appropriate depending on the application.
  • the anchor layer may have conductivity (antistatic property).
  • the antistatic function is excellent compared to the case where the adhesive layer alone imparts antistatic properties, and the amount of antistatic agent used in the adhesive layer can be suppressed to a small amount, and this is a preferable embodiment from the viewpoint of durability and appearance defects such as precipitation and segregation of the antistatic agent and cloudiness under a humidified environment.
  • the surface resistance thereof is preferably 1.0 ⁇ 10 8 to 1.0 ⁇ 10 10 ⁇ / ⁇ , more preferably 1.0 ⁇ 10 8 to 8.0 ⁇ 10 ⁇ / ⁇ . 9 ⁇ / ⁇ is more preferable, and 2.0 ⁇ 10 8 to 6.0 ⁇ 10 9 ⁇ / ⁇ is even more preferable.
  • the antistatic properties can be imparted by including a conductive polymer in the binder component.
  • the conductive polymer is preferably used from the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect when heated and when humidified.
  • conductive polymers such as polyaniline and polythiophene are preferably used.
  • An organic solvent-soluble, water-soluble, or water-dispersible conductive polymer can be appropriately used, but a water-soluble conductive polymer or a water-dispersible conductive polymer is preferably used.
  • a water-soluble conductive polymer or a water-dispersible conductive polymer can be prepared as an aqueous solution or an aqueous dispersion when forming an antistatic layer, and the coating solution does not need to use a non-aqueous organic solvent, and the organic This is because deterioration of the optical film substrate due to the solvent can be suppressed.
  • the aqueous solution or aqueous dispersion can contain an aqueous solvent in addition to water.
  • the water-soluble conductive polymer or water-dispersible conductive polymer such as polyaniline and polythiophene preferably has a hydrophilic functional group in the molecule.
  • Hydrophilic functional groups include, for example, a sulfone group, an amino group, an amide group, an imino group, a quaternary ammonium base, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfate group, a phosphate group, or salts thereof. etc.
  • Having a hydrophilic functional group in the molecule makes it easier to dissolve in water or easier to disperse in water in the form of fine particles, making it possible to easily prepare the water-soluble conductive polymer or water-dispersible conductive polymer.
  • polystyrene sulfonic acid is usually used together.
  • the anchor layer can be formed, for example, by coating the first surface of the substrate of the present invention with a conductive coating liquid obtained by blending a conductive polymer with the above binder component, if necessary.
  • a conductive coating liquid obtained by blending a conductive polymer with the above binder component, if necessary.
  • Specific coating methods include a roll coating method, a bar coating method, a gravure coating method, and the like.
  • the surface of the pressure-sensitive adhesive layer of the present invention may be protected by a separator until use.
  • the separator is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when the optical pressure-sensitive adhesive sheet of the present invention is attached to an adherend. Note that the separator does not necessarily have to be provided.
  • a conventional release paper or the like can be used.
  • a fluorine-based polymer e.g., polytetrafluoroethylene
  • polychlorotrifluoroethylene polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.
  • a low-adhesive base material made of for example, olefin resin such as polyethylene, polypropylene, etc.
  • olefin resin such as polyethylene, polypropylene, etc.
  • a separator in which a release treatment layer is formed on at least one surface of a separator substrate can be suitably used.
  • Base materials for such separators include polyester film (polyethylene terephthalate film, etc.), olefin resin film (polyethylene film, polypropylene film, etc.), polyvinyl chloride film, polyimide film, polyamide film (nylon film), rayon film, etc.
  • plastic base film synthetic resin film
  • paper wooden paper, Japanese paper, kraft paper, glassine paper, synthetic paper, top coat paper, etc.
  • these are multi-layered by lamination or co-extrusion. (composite of 2 to 3 layers) and the like.
  • the release treatment agent that constitutes the release treatment layer is not particularly limited, but for example, a silicone-based release treatment agent, a fluorine-based release treatment agent, a long-chain alkyl-based release treatment agent, or the like can be used.
  • the release agents can be used alone or in combination of two or more.
  • the thickness of the separator is not particularly limited, and may be appropriately selected from the range of 5 to 100 ⁇ m.
  • the above separator may have an antistatic layer formed on at least one surface of the separator substrate in order to prevent damage to an adherend such as an image display panel.
  • the antistatic layer may be formed on one surface of the separator (release-treated surface or untreated surface) or may be formed on both surfaces of the separator (release-treated surface and untreated surface).
  • the antistatic layer is not particularly limited, but is, for example, an antistatic layer formed by coating a separator with a conductive coating liquid containing a conductive polymer. Specifically, for example, it is an antistatic layer formed by coating a separator (release-treated surface and/or untreated surface) with a conductive coating liquid containing a conductive polymer. Specific coating methods include a roll coating method, a bar coating method, a gravure coating method, and the like.
  • the same conductive polymer that constitutes the antistatic agent that may be contained in the optical pressure-sensitive adhesive sheet of the present invention 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 consist of only one layer, or may consist of two or more layers.
  • 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 substrate of the present invention.
  • the method for laminating the pressure-sensitive adhesive layer of the present invention on the first surface of the base material of the present invention is not particularly limited.
  • By drying and curing the adhesive composition layer, or by applying (coating) the adhesive composition on the separator and curing the obtained adhesive composition layer by irradiating it with an active energy ray, on the separator It can be carried out by molding into a sheet-like pressure-sensitive adhesive layer, and bonding the pressure-sensitive adhesive layer on the first surface of the substrate of the present invention. Moreover, you may heat-dry further as needed.
  • a separator When curing by irradiation with active energy rays, a separator is further attached to the surface of the coating film, and the adhesive composition is sandwiched between two separators and irradiated with active energy rays to polymerize with oxygen. It is preferred to prevent inhibition.
  • Another method for laminating the pressure-sensitive 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 pressure-sensitive adhesive composition onto the first surface of the substrate of the present invention. , drying and curing the obtained pressure-sensitive adhesive composition layer, or applying (coating) the above-mentioned pressure-sensitive adhesive composition on the first surface of the substrate of the present invention, and applying an active agent to the obtained pressure-sensitive adhesive composition layer. It can also be cured by irradiation with energy rays. Moreover, you may heat-dry further as needed.
  • a separator is attached to the surface of the coating film, and the adhesive composition is irradiated with active energy rays while being sandwiched between the base material of the present invention and the separator. It is preferable to prevent polymerization inhibition by oxygen.
  • the sheet-like coating film may be heated for the purpose of removing the solvent, etc., before the active energy ray irradiation. If the solvent or the like is removed by heating, it is preferably carried out before attaching the separator.
  • 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 of the active energy ray, the irradiation time, the irradiation method, etc. are not particularly limited.
  • the above 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 additives, if necessary, with a solution containing the acrylic polymer (A) and the ionic compound of the present invention.
  • an active energy ray-curable acrylic pressure-sensitive adhesive composition can be prepared by mixing the mixture of the acrylic monomer (A) or a partial polymer thereof and the ionic compound of the present invention with additives, if necessary. can be produced by
  • a known coating method may be used for applying (coating) the pressure-sensitive adhesive composition.
  • coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, comma coaters, and direct coaters may be used.
  • the active energy ray-curable adhesive composition when the adhesive layer is formed from an active energy ray-curable adhesive composition, the active energy ray-curable adhesive composition preferably contains a photopolymerization initiator.
  • the active energy ray-curable pressure-sensitive adhesive composition contains an ultraviolet absorber, it preferably contains at least a photopolymerization initiator having light absorption properties in a wide wavelength range as a photopolymerization initiator.
  • it preferably contains at least a photopolymerization initiator that absorbs not only ultraviolet light but also visible light.
  • the adhesive composition contains a photopolymerization initiator that has light absorption characteristics in a wide wavelength range, high photocurability will be achieved in the adhesive composition. This is because it becomes easier to obtain.
  • the optical pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention), it has excellent antistatic performance. Therefore, display defects due to static electricity are less likely to occur when used for lamination with an optical member or an image display device. In addition, since bleeding out of the antistatic component can be suppressed even under harsh conditions such as a moist and hot environment, precipitation, foaming, and peeling on the surface of the adhesive layer are suppressed, and appearance and adhesion reliability are improved. Poor durability is less likely to occur. Therefore, the optical pressure-sensitive adhesive sheet of the present invention satisfies excellent antistatic properties, transparency, moist heat resistance, and low staining properties, and is useful for the production of image display devices.
  • the optical pressure-sensitive adhesive sheet of the present invention is excellent in adhesiveness, resistance to foaming and peeling, and stress relaxation, as well as step followability and adhesion reliability, especially at high temperatures. Moreover, it is excellent in external appearance. Therefore, the optical pressure-sensitive adhesive sheet of the present invention is useful for adherends that tend to foam at the interface at high temperatures.
  • adherends that tend to foam at the interface at high temperatures.
  • PMMA polymethyl methacrylate
  • PC Polycarbonate
  • the pressure-sensitive adhesive sheet of the present invention is excellent in resistance to foaming and peeling, it is also useful for plastic adherends containing such resins.
  • the optical pressure-sensitive adhesive sheet of the present invention is useful not only for adherends with a small coefficient of linear expansion, but also for adherends with a large coefficient of linear expansion.
  • the adherend having a small coefficient of linear expansion is not particularly limited. material (PET film, coefficient of linear expansion: 1.5 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 5 /° C.).
  • the adherend having a large coefficient of linear expansion is not particularly limited, but examples thereof include resin substrates having a large coefficient of linear expansion.
  • the optical pressure-sensitive adhesive sheet of the present invention is useful for lamination with adherends made of various materials, and is particularly useful for lamination with glass adherends and plastic adherends.
  • the plastic adherend may be an optical film such as a plastic film having an ITO (indium tin oxide) layer on its surface.
  • the optical pressure-sensitive adhesive sheet of the present invention is useful not only for adherends with smooth surfaces, but also for adherends with uneven surfaces.
  • the optical pressure-sensitive adhesive sheet of the present invention even if at least one of the glass adherend and the resin substrate having a large coefficient of linear expansion has steps on the surface, the glass adherend and the linear expansion coefficient It is useful for bonding with a resin base material having a large modulus.
  • the optical pressure-sensitive adhesive sheet of the present invention is preferably used for manufacturing portable electronic devices.
  • portable electronic devices include mobile phones, PHS, smartphones, tablets (tablet computers), mobile computers (mobile PCs), personal digital assistants (PDA), electronic notebooks, portable televisions, portable radios, and the like. type broadcast receivers, portable game machines, portable audio players, portable DVD players, cameras such as digital cameras, and camcorder type video cameras.
  • the optical laminate of the present invention has a laminate structure in which the optical pressure-sensitive adhesive sheet of the present invention and an optical member are laminated.
  • the optical layered body 20 has an optical member 5 laminated on the pressure-sensitive adhesive layer 2 of the optical pressure-sensitive adhesive sheet 10 . Since the optical layered body of the present invention has the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention), it has excellent antistatic performance. Therefore, static electricity is less likely to occur when used to bond another optical member.
  • the optical laminate of the present invention can satisfy excellent antistatic properties, transparency, moist heat resistance, and low staining properties.
  • An optical member refers to a member having optical properties (e.g., polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, optical rotation, visibility, etc.).
  • the substrate constituting the optical member is not particularly limited.
  • transparent conductive films for example, plastic films having an ITO layer on the surface (preferably ITO films such as PET-ITO, polycarbonate, cycloolefin polymer, etc.), design films, decorative films, surface protection plates, prisms , lenses, color filters, transparent substrates (glass sensors, glass display panels (LCD, etc.), glass substrates such as glass plates with transparent electrodes, etc.), and substrates on which these are laminated (these are collectively referred to as " may be referred to as "functional film”) and the like.
  • these films may have a metal nanowire layer, a conductive polymer layer, or the like. Further, these films may be mesh-printed with thin metal wires.
  • plate and film include forms such as plate-like, film-like, and sheet-like, respectively.
  • polarizing film includes “polarizing plate” and “polarizing sheet”.
  • film shall include film sensors and the like.
  • Examples of the display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), electronic paper, and the like. Moreover, a touch panel etc. are mentioned as said input device.
  • the substrate constituting the optical member is not particularly limited. etc.).
  • the "optical member" in the present invention includes members (design films, decorative films, surface protective films, etc.) that play a role of decoration and protection while maintaining the visibility of display devices and input devices. shall be taken.
  • the optical member is preferably transparent.
  • the total light transmittance (according to JIS K7361-1) of the optical member in the visible light wavelength region is not particularly limited, but is preferably 85% or more, more preferably 88% or more.
  • the haze (according to JIS K7136) of the optical member is not particularly limited, but is preferably 1.0% or less, more preferably 0.8% or less.
  • transparent substrates include PET films and non-oriented films such as the trade name "Arton" and the trade name "Zeonor".
  • the thickness of the optical member is not particularly limited, it is preferably 12 to 500 ⁇ m, for example.
  • the optical member may have either a single-layer structure or a multilayer structure.
  • the surface of the optical member may be appropriately subjected to a known and commonly used surface treatment such as physical treatment such as corona discharge treatment and plasma treatment, and chemical treatment such as undercoating treatment.
  • the optical laminate of the present invention can be produced by laminating the optical member and the pressure-sensitive adhesive layer of the optical pressure-sensitive adhesive sheet of the present invention.
  • the optical member and the optical pressure-sensitive adhesive sheet of the present invention can be attached by laminating them under heat and/or pressure. Curing may be performed by irradiating active energy rays after lamination under heat and/or pressure. Irradiation with active energy rays can be performed in the same manner as in the formation of the pressure-sensitive adhesive layer of the present invention.
  • the image display device of the present invention has a laminate structure in which the optical pressure-sensitive adhesive sheet of the present invention and an image display panel are laminated.
  • the image display device 30 has an image display panel 6 laminated on the adhesive layer 1 of the optical adhesive sheet 10 . Since the image display device of the present invention has the optical pressure-sensitive adhesive sheet of the present invention having excellent antistatic performance in the laminated structure, display defects due to static electricity are less likely to occur. In addition, since it is possible to suppress bleeding out of the antistatic component even under harsh conditions such as a moist and hot environment, precipitation, foaming, and peeling on the surface of the adhesive layer are suppressed, and appearance and adhesion reliability are improved. Poor durability is less likely to occur. Therefore, the image display device of the present invention can satisfy excellent antistatic properties, transparency, moist heat resistance, and low staining properties.
  • the pressure-sensitive 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. Furthermore, when the image display panel has uneven steps due to wiring or the like, the pressure-sensitive adhesive layer of the present invention can sufficiently follow the steps and can be filled without leaving air bubbles.
  • the image display panel is not particularly limited, but includes, for example, a liquid crystal image display panel, a self-luminous image display panel (eg, an organic EL (electroluminescence) image display panel, an LED image display panel), and the like.
  • a liquid crystal image display panel e.g., a liquid crystal image display panel, a self-luminous image display panel (eg, 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 the contrast, it is preferable that the spaces between the RGB elements be filled with a black matrix (BM).
  • 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 any layers.
  • the optical member include, but are not particularly limited to, a polarizing plate, a retardation plate, an antireflection film, a viewing angle adjusting film, and an optical compensation film.
  • the optical member includes members (design film, decorative film, surface protection plate, etc.) that play a role of decoration and protection while maintaining the visibility of the image display device and the input device.
  • the image display device of the present invention can be manufactured by laminating the image display panel and the pressure-sensitive adhesive layer of the optical pressure-sensitive adhesive sheet of the present invention.
  • the image display panel and the optical pressure-sensitive adhesive sheet of the present invention can be attached by laminating them under heat and/or pressure. Curing may be performed by irradiating active energy rays after lamination under heat and/or pressure. Irradiation with active energy rays can be performed in the same manner as in the formation of the pressure-sensitive adhesive layer of the present invention.
  • Production example 1 preparation of antiglare film 1 [Preparation of coating solution for forming antiglare layer 1]
  • the resin contained in the antiglare layer forming material 40 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Oligo UA-53H-80BK”)
  • a diluted solution of a composition for an optical adjustment layer containing 57.5 parts by weight of a functional acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat #300"
  • zirconia particles zirconia particles
  • an ultraviolet curable resin (“OPSTAR Z7540 ”, manufactured by JSR)
  • 2.5 parts by weight of silicone particles Momentive Performance Materials Japan LLC, trade name “Tospearl 130ND”
  • 2.8 parts by weight of organic clay as a thixotropy-imparting agent.
  • the organoclay was diluted with toluene so that the solid content was 6% by weight. This mixture was added to a toluene/cyclopentanone (CPN) mixed solvent ( (weight ratio: 64/36) to prepare an antiglare layer-forming material (coating liquid) using an ultrasonic disperser.
  • CPN toluene/cyclopentanone
  • a transparent plastic film substrate (PET film, manufactured by Toray Industries, Inc., trade name “38U413”, thickness: 38 ⁇ m) was prepared.
  • the antiglare layer-forming material (coating solution) was applied to one side of the transparent plastic film substrate using a wire bar to form a coating film (coating step).
  • the coating film was dried by heating at 95° C. for 1 minute (drying step).
  • the coating film was cured by irradiating ultraviolet light with an accumulated light amount of 300 mJ/cm 2 with a high-pressure mercury lamp to form an antiglare layer having a thickness of 6.5 ⁇ m.
  • a laminate of the light transmissive substrate and the antiglare layer 1 was obtained.
  • a mixed solvent of MIBK (methyl isobutyl ketone) and PMA (propylene glycol monomethyl ether acetate) mixed at a weight ratio of 70:30 was added as a dilution solvent so that the total solid content was 1.5% by weight. and stirred to prepare a coating solution for forming an antireflection layer.
  • the antireflection layer-forming coating liquid was applied to the antiglare layer surface of the laminate of the light transmissive substrate and the antiglare layer 1 with a wire bar (coating step). The applied coating liquid was heated at 80° C. for 1 minute and dried to form a coating film (drying step).
  • the coating film was cured by irradiating ultraviolet light with an accumulated light amount of 300 mJ/cm 2 from a high-pressure mercury lamp (curing step). Thereby, the coating film was cured to form an antireflection layer having a thickness of 0.1 ⁇ m (antireflection layer forming step).
  • Antiglare film 1 of Production Example 1 was produced as described above.
  • Production Example 2 Production of PSA Sheet A As a monomer mixture, 58 parts by weight of butyl acrylate (BA), 23 parts by weight of 4-hydroxybutyl acrylate (4HBA), 7 parts by weight of 2-hydroxyethyl acrylate (HEA), and 12 parts by weight of cyclohexyl acrylate (CHA), 0.05 parts by weight of a photopolymerization initiator (trade name "Omnirad 184", manufactured by IGM Resins B.V.), and a photopolymerization initiator (trade name Name "Omnirad 651", manufactured by IGM Resins B.V.) After blending 0.05 parts by weight, the viscosity (measurement conditions: BH viscometer No.
  • BA butyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • HOA 2-hydroxyethyl acrylate
  • CHA cyclohexyl acrylate
  • a photopolymerization initiator trade name "Omnirad
  • a prepolymer composition in which a part of the monomer component was polymerized was obtained by irradiating with ultraviolet rays until the temperature reached 100%.
  • 0.025 parts by weight of dipentaerythritol hexaacrylate (DPHA) and a quaternary ammonium salt (2-acryloyloxyethyl)trimethylammonium having an acroyl group as a reactive functional group are added to 100 parts by weight of the prepolymer composition.
  • a pressure-sensitive adhesive sheet G was formed in the same manner as the pressure-sensitive adhesive sheet A, except that 15 parts by weight of was added.
  • one separator is peeled off from the pressure-sensitive adhesive sheets obtained in Production Examples 2-6 and Comparative Production Examples 1-2, and the double-sided pressure-sensitive adhesive sheet is applied to a slide glass (manufactured by Matsunami Glass Industry Co., Ltd., "White polishing No. .1”, thickness 0.8 to 1.0 mm, total light transmittance 92%, haze 0.2%), and a test having a layer configuration of separator / double-sided adhesive sheet (adhesive layer) / slide glass A piece was made. Put in an atmosphere of 85 ° C. and 85% RH for 240 hours, take out to room temperature, adjust temperature and humidity for 24 hours in an environment of 23 ° C.
  • Adhesive layer/slide glass layer structure was measured using a haze meter (apparatus name "HM-150N", manufactured by Murakami Color Laboratory Co., Ltd.) and evaluated according to the following evaluation criteria. The measurement results are shown in Table 2. (Evaluation criteria) ⁇ : Haze of 1.0 or less, particularly good ⁇ : Haze of more than 1.0 to 2.0 or less, good ⁇ : Haze of more than 2.0, practically problematic level
  • Example 1 Preparation of Optical Adhesive Sheet A
  • One release film was peeled off from the adhesive sheet A obtained in Production Example 2 above, and the exposed adhesive surface was coated with the antiglare film 1 shown in Production Example 1.
  • Optical adhesive sheet A consisting of antiglare film 1/adhesive layer/release film was obtained by attaching to the non-antiglare layer surface of .
  • Example 2 Preparation of optical adhesive sheet B The adhesive surface exposed by peeling one release film from the adhesive sheet C obtained in Production Example 4 above was coated with an antireflection film (TAC film; Dai Nippon Printing ( Co., Ltd.; product name “DSG-17V1”; substrate thickness: 60 ⁇ m; total thickness: 70 ⁇ m). An adhesive sheet B was obtained.
  • TAC film Dai Nippon Printing ( Co., Ltd.; product name “DSG-17V1”; substrate thickness: 60 ⁇ m; total thickness: 70 ⁇ m.
  • An optical pressure-sensitive adhesive sheet having a laminated structure in which a substrate having a first surface and a second surface and an adhesive layer is laminated on the first surface of the substrate, A pressure-sensitive adhesive composition in which the pressure-sensitive adhesive layer contains an antistatic agent and a mixture of monomer components constituting the acrylic polymer (A) or a partial polymer of a mixture of monomer components constituting the acrylic polymer (A). formed by The optical pressure-sensitive adhesive sheet, wherein the antistatic agent is an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in its molecule.
  • An optical pressure-sensitive adhesive sheet having a laminated structure in which a substrate having a first surface and a second surface and a pressure-sensitive adhesive layer is laminated on the first surface of the substrate,
  • the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing an antistatic agent and an acrylic polymer (A),
  • the optical pressure-sensitive adhesive sheet, wherein the antistatic agent is an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in its molecule.
  • the functional group is at least selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, an allyl group, a styryl group, a hydroxyl group, an amino group, a mercapto group, and an epoxy group.
  • Appendix 4 The optical adhesive sheet according to any one of Appendices 1 to 3, wherein the acrylic polymer (A) does not contain or substantially does not contain a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer (A).
  • [Appendix 8] The optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 7, which has a 180° peeling adhesive force to a glass plate at 23° C. of 4 N/20 mm or more.
  • Appendix 9 The optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 8, which has a thickness of 12 to 350 ⁇ m.
  • Appendix 10 The optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 9, wherein the second surface of the substrate is subjected to antireflection treatment, antiglare treatment, hard coat treatment and/or antistatic treatment.
  • [Appendix 11] An optical laminate obtained by laminating the optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 10 and an optical member.
  • Appendix 12 An image display device in which the optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 10 and an image display panel are laminated.
  • the optical pressure-sensitive adhesive sheet of the present invention is less likely to cause defects in transparency, appearance, and durability, exhibits a low surface resistivity, and has excellent antistatic performance, so it is suitable for manufacturing image display devices.

Abstract

A purpose of the present invention is to provide: an optical pressure-sensitive adhesive sheet that has a layered structure including a pressure-sensitive adhesive layer which is less apt to have failures regarding transparency, appearance, or durability, exhibits a low surface resistivity, and has excellent antistatic performance; and an optical laminate. This optical pressure-sensitive adhesive sheet has a layered structure comprising: a substrate 1 having a first surface 1a and a second surface 1b; and a pressure-sensitive adhesive layer 2 superposed on the first surface 1a of the substrate 1. The pressure-sensitive adhesive layer 2 is formed from a pressure-sensitive adhesive composition comprising: an antistatic agent; and an acrylic polymer (A), a mixture of monomers for constituting the acrylic polymer (A), or a partial polymer of a mixture of monomers for constituting the acrylic polymer (A). The antistatic agent is characterized by being an ionic compound having, in the molecule, a functional group capable of forming a covalent bond with the acrylic polymer (A).

Description

光学用粘着シート、光学積層体、及び画像表示装置Optical pressure-sensitive adhesive sheet, optical laminate, and image display device
 本発明は、光学用粘着シート、光学積層体、及び画像表示装置に関する。より詳細には、帯電防止性に優れる粘着剤層を積層構造に有する光学用粘着シート、該光学用粘着シートと光学部材とが積層された光学積層体、及び該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に関する。 The present invention relates to an optical pressure-sensitive adhesive sheet, an optical laminate, and an image display device. More specifically, an optical pressure-sensitive adhesive sheet having a laminated structure with a pressure-sensitive adhesive layer having excellent antistatic properties, an optical laminate in which the optical pressure-sensitive adhesive sheet and an optical member are laminated, and the optical pressure-sensitive adhesive sheet and an image display panel It relates to an image display device in which and are laminated.
 近年、様々な分野で、液晶ディスプレイ(LCD)等の表示装置や、タッチパネル等の入力装置が広く用いられている。これらの表示装置や入力装置の製造等においては、光学部材を貼り合わせる用途に粘着シートが使用されている。例えば、タッチパネル等の各種表示装置における光学部材の貼り合わせには、透明な粘着シートが使用されている。近年、生産効率の向上のため、偏光フィルム、位相差フィルム、カバーガラス等の透明カバー部材、その他種々の光学部材に粘着剤層を積層させた光学用粘着シートとして移送することが広く行われている。 In recent years, display devices such as liquid crystal displays (LCDs) and input devices such as touch panels have been widely used in various fields. In manufacturing such display devices and input devices, adhesive sheets are used for bonding optical members. For example, transparent adhesive sheets are used for laminating optical members in various display devices such as touch panels. In recent years, in order to improve production efficiency, it is widely practiced to transport optical pressure-sensitive adhesive sheets in which a pressure-sensitive adhesive layer is laminated on a polarizing film, a retardation film, a transparent cover member such as a cover glass, and other various optical members. there is
 これらの表示装置や入力装置の製造において、上記の光学用粘着シートを表示装置に貼り付ける際には、粘着剤層を保護している剥離シートが剥がされるが、その際に粘着剤層に静電気が発生する。発生した静電気は、表示装置の表示セルの配向性などに影響を与え、表示不良を起こす原因となる。このような静電気の発生を抑制する手段として、粘着剤層の表面抵抗率を低減するために帯電防止剤が配合されている(例えば、特許文献1~3)。 In the manufacture of these display devices and input devices, when the optical pressure-sensitive adhesive sheet is attached to the display device, the release sheet protecting the pressure-sensitive adhesive layer is peeled off. occurs. The generated static electricity affects the orientation of the display cells of the display device and causes display defects. As means for suppressing the generation of such static electricity, an antistatic agent is added to reduce the surface resistivity of the pressure-sensitive adhesive layer (eg, Patent Documents 1 to 3).
特開2020-187365号公報JP 2020-187365 A 特開2019-56115号公報JP 2019-56115 A WO2018/008712号公報WO2018/008712
 近年、高画質化により、高密度化された表示セルを有する表示装置が受ける静電気の影響が大きくなっており、静電気を効率的に除去するため、粘着シートの表面抵抗率をさらに低減すること(例えば、1010Ω/□程度)が求められている。また、表示装置の薄型化、軽量化の要請から、粘着シートの薄型化も要求されており、表面抵抗率が低い薄型の粘着シートを実現するために多量の帯電防止剤を配合することが求められている。 In recent years, due to higher image quality, the influence of static electricity on display devices having high-density display cells has increased. For example, about 10 10 Ω/□) is required. In addition, due to the demand for thinner and lighter display devices, thinner pressure-sensitive adhesive sheets are also required. It is
 しかしながら、粘着剤層に多量の帯電防止剤を配合すると、粘着剤層との相溶性が低下したり、粘着剤層表面で帯電防止剤が析出して、特に湿熱環境下で白濁などの透明性や外観に不良が生じることがある。また、湿熱環境下で発泡や剥がれなどが発生して、耐久性に問題が生じる場合がある。 However, if a large amount of antistatic agent is blended into the adhesive layer, the compatibility with the adhesive layer may decrease, or the antistatic agent may precipitate on the surface of the adhesive layer, resulting in transparency such as white turbidity, especially in a hot and humid environment. and appearance defects may occur. In addition, foaming, peeling, and the like may occur in a moist and hot environment, resulting in durability problems.
 従って、本発明の目的は、透明性、外観、耐久性に不良が生じにくく、且つ低い表面抵抗率を示し、優れた帯電防止性能を有する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を提供することである。
 また、本発明の他の目的は、透明性、外観、耐久性に不良が生じにくく、且つ低い表面抵抗率を示し、優れた帯電防止性能を有する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と、光学部材とが積層された光学積層体を提供することである。
 また、本発明の他の目的は、透明性、外観、耐久性に不良が生じにくく、且つ低い表面抵抗率を示し、優れた帯電防止性能を有する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と、画像表示パネルとが積層された画像表示装置を提供することである。
Accordingly, an object of the present invention is to provide an optical pressure-sensitive adhesive having a laminated structure in which pressure-sensitive adhesive layers having low surface resistivity, excellent antistatic performance, and excellent antistatic performance are unlikely to cause defects in transparency, appearance, and durability. It is to provide a sheet.
Another object of the present invention is to provide an optical adhesive having a laminated structure in which a pressure-sensitive adhesive layer having low surface resistivity, excellent antistatic performance, which is less likely to cause defects in transparency, appearance, and durability, is laminated. An object of the present invention is to provide an optical laminate in which a pressure-sensitive adhesive sheet for optical devices and an optical member are laminated.
Another object of the present invention is to provide an optical adhesive having a laminated structure in which a pressure-sensitive adhesive layer having low surface resistivity, excellent antistatic performance, which is less likely to cause defects in transparency, appearance, and durability, is laminated. An object of the present invention is to provide an image display device in which an adhesive sheet for image display and an image display panel are laminated.
 そこで、本発明者等が、上記課題を解決するために鋭意検討した結果、光学用粘着シートが積層構造に有する粘着剤層を構成するベースポリマーとしてアクリル系ポリマーを用い、且つ帯電防止剤として、前記アクリル系ポリマーと共有結合を形成できる官能基を分子内に有するイオン性化合物を用いることにより、透明性、外観、耐久性に不良が生じにくく、且つ低い表面抵抗率を示し、優れた帯電防止性能を有する粘着剤層を形成できることを見出し、本発明を完成させた。 Therefore, as a result of intensive studies by the present inventors in order to solve the above problems, an acrylic polymer is used as a base polymer constituting a pressure-sensitive adhesive layer that the optical pressure-sensitive adhesive sheet has in a laminated structure, and as an antistatic agent, By using an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer in the molecule, defects in transparency, appearance, and durability are less likely to occur, and low surface resistivity is exhibited, resulting in excellent antistatic properties. The inventors have found that a pressure-sensitive adhesive layer having performance can be formed, and completed the present invention.
 すなわち、本発明の第1の側面は、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し、前記粘着剤層が、帯電防止剤と、アクリル系ポリマー(A)を構成するモノマー成分の混合物又はアクリル系ポリマー(A)を構成するモノマー成分の混合物の部分重合物とを含有する粘着剤組成物により形成される光学用粘着シートを提供する。
 また、本発明の第2の側面は、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し、前記粘着剤層が、帯電防止剤とアクリル系ポリマー(A)とを含有する粘着剤組成物により形成される光学用粘着シートを提供する。
 本発明の第1及び第2の側面の光学用粘着シートにおいて、前記帯電防止剤は、前記アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物である。
That is, the first aspect of the present invention has a laminated structure in which a substrate having a first surface and a second surface and an adhesive layer is laminated on the first surface of the substrate, and the adhesive layer is , an antistatic agent, and a mixture of monomer components constituting the acrylic polymer (A) or a partially polymerized product of a mixture of monomer components constituting the acrylic polymer (A). We provide adhesive sheets for
Further, a second aspect of the present invention has a laminated structure in which a substrate having a first surface and a second surface and an adhesive layer is laminated on the first surface of the substrate, and the adhesive layer is , an optical pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing an antistatic agent and an acrylic polymer (A).
In the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention, the antistatic agent is an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in its molecule.
 本発明の第1及び第2の側面の光学用粘着シートにおいて、前記帯電防止剤は、前記アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物であるという構成は、帯電防止剤を構成するイオン性化合物がアクリル系ポリマー(A)と共有結合を形成し得るため、帯電防止剤を多く配合しても、粘着剤層との相溶性が低下したり、粘着剤層表面で帯電防止剤が析出することによる透明性や外観の不良が生じにくく、また、湿熱環境下で帯電防止剤に起因する発泡や剥がれなどが発生しにくく、耐久性に優れる点でも好ましい。従って、本発明の第1及び第2の側面の光学用粘着シートは、透明性、外観、耐久性に不良が生じにくく、且つ低い表面抵抗率を示し、優れた帯電防止性能を有する。 In the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention, the antistatic agent is an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in its molecule. , the ionic compound that constitutes the antistatic agent can form a covalent bond with the acrylic polymer (A). Defects in transparency and appearance due to precipitation of the antistatic agent on the surface of the agent layer are unlikely to occur, and foaming and peeling due to the antistatic agent in a moist and hot environment are unlikely to occur, and excellent durability is also preferable. . Therefore, the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention are less likely to cause defects in transparency, appearance and durability, exhibit low surface resistivity, and have excellent antistatic performance.
 本発明の第1及び第2の側面の光学用粘着シートにおいて、前記帯電防止剤が分子内に有する官能基は、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミノ基、ビニル基、アリル基、スチリル基、水酸基、アミノ基、メルカプト基、エポキシ基からなる群から選ばれる少なくとも1種であることが好ましい。これらの官能基は、前記アクリル系ポリマー(A)との共有結合を形成しやすい点で好ましい。 In the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention, the functional group that the antistatic agent has in the molecule includes (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, allyl group, It is preferably at least one selected from the group consisting of styryl groups, hydroxyl groups, amino groups, mercapto groups and epoxy groups. These functional groups are preferable in that they easily form a covalent bond with the acrylic polymer (A).
 本発明の第1及び第2の側面の光学用粘着シートにおいて、前記アクリル系ポリマー(A)が構成するモノマー成分としてカルボキシル基含有モノマーを含有せず又は実質的に含有しないことが好ましい。この構成は、本発明の第1及び第2の側面の光学用粘着シートが、優れた金属配線の腐食防止効果を得ることができる点で好ましい。 In the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention, it is preferable that the acrylic polymer (A) does not contain or substantially does not contain a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer (A). This configuration is preferable in that the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention can obtain an excellent effect of preventing corrosion of metal wiring.
 本発明の第1及び第2の側面の光学用粘着シートにおいて、前記粘着剤組成物は、有機溶剤を含有しない又は実質的に含有しないことが好ましい。この構成は、ゆず肌等の外観の不具合が発生しにくい点で、好ましい。 In the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention, the pressure-sensitive adhesive composition preferably contains no or substantially no organic solvent. This configuration is preferable in that defects in appearance such as citrus peel are less likely to occur.
 本発明の第1及び第2の側面の光学用粘着シートにおいて、前記粘着剤層のヘイズ(JIS K7136に準じる)は1.0%以下であることが好ましい。また、前鬼粘着剤層の全光線透過率(JIS K7361-1に準じる)は90%以上であることが好ましい。これらの構成は、優れた透明性や優れた外観が得られる点で好ましい。 In the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention, the haze (according to JIS K7136) of the pressure-sensitive adhesive layer is preferably 1.0% or less. In addition, the total light transmittance (according to JIS K7361-1) of the front adhesive layer is preferably 90% or more. These configurations are preferable in terms of obtaining excellent transparency and excellent appearance.
 本発明の第1及び第2の側面の光学用粘着シートのガラス板に対する23℃での180°引き剥がし接着力は4N/20mm以上であることが好ましい。この構成は、ガラスへの接着性、段差における浮きの抑止性に一層優れる点で好ましい。 The 180° peeling adhesive force at 23°C of the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention to a glass plate is preferably 4 N/20 mm or more. This configuration is preferable in that the adhesiveness to glass and the ability to prevent floating on steps are more excellent.
 本発明の第1及び第2の側面の光学用粘着シートの厚みは12~350μmであることが好ましい。厚みが一定以上であるという構成は、段差部位での剥がれが生じにくくなる点で、好ましい。また、厚みが一定以下であるという構成は、製造時に優れた外観を保持しやすくなる点で、好ましい。 The thickness of the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention is preferably 12-350 μm. A configuration in which the thickness is equal to or greater than a certain value is preferable in that peeling at the step portion is less likely to occur. In addition, a configuration in which the thickness is equal to or less than a certain value is preferable in terms of making it easier to maintain an excellent appearance during manufacturing.
 本発明の第1及び第2の側面の光学用粘着シートにおいて、前記基材の第2面は、反射防止処理、アンチグレア処理、ハードコート処理、及び/又は帯電防止処理されていることが好ましい。前記基材の第2面が反射防止処理及び/又はアンチグレア処理されているという構成は、外光の反射や像の映り込み等による視認性の低下を防止する、光沢度などの見栄えを調整するといった観点で好ましい。また、前記基材の第2面がハードコート処理されているという構成は、表面硬度、耐擦傷性が向上する点で好ましい。また、前記基材の第2面が帯電防止処理されているという構成は、本発明の第1及び第2の側面の光学用粘着シートに静電気が帯電するのを抑制し、光学用粘着シートを画像表示装置に用いた場合に、静電気に起因する表示不良を抑制できる点で好ましい。 In the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention, the second surface of the base material is preferably subjected to antireflection treatment, antiglare treatment, hard coat treatment, and/or antistatic treatment. The configuration in which the second surface of the base material is subjected to antireflection treatment and / or antiglare treatment prevents deterioration of visibility due to reflection of external light and reflection of images, and adjusts appearance such as glossiness. It is preferable from the viewpoint of Further, the configuration in which the second surface of the base material is hard-coated is preferable in that the surface hardness and scratch resistance are improved. In addition, the configuration in which the second surface of the base material is antistatically treated suppresses static electricity from being charged to the optical pressure-sensitive adhesive sheet of the first and second aspects of the present invention, thereby preventing the optical pressure-sensitive adhesive sheet from being charged with static electricity. When used in an image display device, it is preferable in that display defects caused by static electricity can be suppressed.
 本発明の第3の側面は、本発明の第1又は第2の側面の光学用粘着シートと、光学部材とが積層された光学積層体を提供する。また、本発明の第4の側面は、本発明の第1又は第2の側面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を提供する。本発明の第3の側面の光学積層体及び本発明の第4の側面の画像表示装置は、透明性、外観、耐久性に不良が生じにくく、且つ低い表面抵抗率を示し、優れた帯電防止性能を有する本発明の第1又は第2の側面の光学用粘着シートを積層構造に有するため、静電気による表示不良が生じにくく、好ましい。 A third aspect of the present invention provides an optical laminate in which the optical pressure-sensitive adhesive sheet of the first or second aspect of the present invention and an optical member are laminated. A fourth aspect of the present invention provides an image display device in which the optical pressure-sensitive adhesive sheet of the first or second aspect of the present invention and an image display panel are laminated. The optical layered body of the third aspect of the present invention and the image display device of the fourth aspect of the present invention are less likely to cause defects in transparency, appearance and durability, exhibit low surface resistivity, and are excellent in antistatic properties. Since the optical pressure-sensitive adhesive sheet of the first or second aspect of the present invention having performance is provided in a laminated structure, display defects due to static electricity are less likely to occur, which is preferable.
 本発明の光学用粘着シートは、透明性、外観、耐久性に不良が生じにくく、且つ低い表面抵抗率を示し、優れた帯電防止性能を有する。このため、本発明の光学用粘着シートを画像表示装置の製造に用いることにより、優れた透明性、外観、耐久性が維持された上、静電気による表示不良を抑制することができる。また、本発明の光学用粘着シートを積層構造に有する光学積層体、画像表示装置は、優れた透明性、外観、耐久性が維持された上、静電気による表示不良を抑制することができる。 The optical pressure-sensitive adhesive sheet of the present invention is less likely to cause defects in transparency, appearance, and durability, exhibits low surface resistivity, and has excellent antistatic performance. Therefore, by using the optical pressure-sensitive adhesive sheet of the present invention for manufacturing an image display device, excellent transparency, appearance and durability can be maintained, and display defects due to static electricity can be suppressed. In addition, the optical laminate and the image display device having the optical pressure-sensitive adhesive sheet of the present invention in a laminated structure can maintain excellent transparency, appearance and durability, and can suppress display defects caused by static electricity.
図1は、本発明の光学用粘着シートの一実施形態を示す模式図(断面図)である。FIG. 1 is a schematic diagram (cross-sectional view) showing one embodiment of the optical pressure-sensitive adhesive sheet of the present invention. 図2は、本発明の光学積層体の一実施形態を示す模式図(断面図)である。FIG. 2 is a schematic diagram (cross-sectional view) showing one embodiment of the optical laminate of the present invention. 図3は、本発明の画像表示装置の一実施形態を示す模式図(断面図)である。FIG. 3 is a schematic diagram (sectional view) showing an embodiment of the image display device of the present invention.
 本発明の第1の側面の光学用粘着シートは、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し、前記粘着剤層が、帯電防止剤と、アクリル系ポリマー(A)を構成するモノマー成分の混合物又はアクリル系ポリマー(A)を構成するモノマー成分の混合物の部分重合物とを含有する粘着剤組成物により形成される光学用粘着シートである。
 また、本発明の第2の側面の光学用粘着シートは、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し、前記粘着剤層が、帯電防止剤とアクリル系ポリマー(A)とを含有する粘着剤組成物により形成される光学用粘着シートである。
 本発明の第1及び第2の側面光学用粘着シートにおいて、前記帯電防止剤は、前記アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物である。
The optical pressure-sensitive adhesive sheet of the first aspect of the present invention has a laminated structure in which a substrate having a first surface and a second surface and an adhesive layer is laminated on the first surface of the substrate, The agent layer is formed from a pressure-sensitive adhesive composition containing an antistatic agent and a mixture of monomer components constituting the acrylic polymer (A) or a partial polymer of a mixture of monomer components constituting the acrylic polymer (A). optical pressure-sensitive adhesive sheet.
Further, the optical pressure-sensitive adhesive sheet of the second aspect of the present invention has a laminated structure in which a substrate having a first surface and a second surface and a pressure-sensitive adhesive layer is laminated on the first surface of the substrate, The pressure-sensitive adhesive sheet for optical use, wherein the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing an antistatic agent and an acrylic polymer (A).
In the first and second side optical pressure-sensitive adhesive sheets of the present invention, the antistatic agent is an ionic compound having in its molecule a functional group capable of forming a covalent bond with the acrylic polymer (A).
 なお、本明細書において、上記の「モノマー成分の混合物」は、単一モノマー成分で構成される場合と2以上のモノマー成分で構成される場合を含むものとする。また、上記の「モノマー成分の混合物の部分重合物」とは、上記の「モノマー成分の混合物」の構成モノマー成分のうち1又は2以上のモノマー成分が部分的に重合している組成物を意味する。
 本明細書において、単に「アクリル系ポリマー(A)」というときは、特に言及しない限り、「アクリル系ポリマー(A)」、「アクリル系ポリマー(A)を構成するモノマー成分の混合物」、及び「アクリル系ポリマー(A)を構成するモノマー成分の混合物の部分重合物」をも包含するものとする。
In addition, in this specification, the above-mentioned "mixture of monomer components" includes the case of being composed of a single monomer component and the case of being composed of two or more monomer components. In addition, the above-mentioned "partially polymerized mixture of monomer components" means a composition in which one or more of the constituent monomer components of the above-mentioned "mixture of monomer components" is partially polymerized. do.
In this specification, when simply referring to "acrylic polymer (A)", unless otherwise specified, "acrylic polymer (A)", "mixture of monomer components constituting acrylic polymer (A)", and ""partially polymerized mixture of monomer components constituting the acrylic polymer (A)" is also included.
 本発明の第1及び第2の側面の光学用粘着シートを、本明細書において、まとめて「本発明の光学用粘着シート」と称する場合がある。また、本発明の光学用粘着シートを構成する前記基材、粘着剤層、粘着剤組成物を、本明細書において、それぞれ、「本発明の基材」、「本発明の粘着剤層」、及び「本発明の粘着剤組成物」と称する場合がある。また、本発明の粘着剤組成物が含有する帯電防止剤である「アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物」を「本発明の帯電防止剤」又は「本発明のイオン性化合物」を称する場合がある。 In this specification, the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention may be collectively referred to as "the optical pressure-sensitive adhesive sheet of the present invention". In the present specification, the base material, the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive composition constituting the optical pressure-sensitive adhesive sheet of the present invention are respectively referred to as "the base material of the present invention", "the pressure-sensitive adhesive layer of the present invention", and may be referred to as "the adhesive composition of the present invention". In addition, the antistatic agent contained in the pressure-sensitive adhesive composition of the present invention, the "ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in the molecule", is referred to as the "antistatic agent of the present invention". Alternatively, it may be referred to as "the ionic compound of the present invention".
 また、本発明の第3の側面の光学積層体は、本発明の光学用粘着シートと、光学部材とが積層された光学積層体である。本発明の第3の側面の光学積層体を、本明細書において、「本発明の光学積層体」と称する場合がある。
 さらに、本発明の第4の側面の画像表示装置は、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画像表示装置である。本発明の第4の側面の画像表示装置を、本明細書において、「本発明の画像表示装置」と称する場合がある。
Further, the optical layered body of the third aspect of the present invention is an optical layered body obtained by laminating the optical pressure-sensitive adhesive sheet of the present invention and an optical member. The optical layered body of the third aspect of the present invention may be referred to as "the optical layered body of the present invention" in this specification.
Furthermore, the image display device of the fourth aspect of the present invention is 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 fourth aspect of the present invention may be referred to as "the image display device of the present invention" in this specification.
 以下、本発明の光学用粘着シートの実施形態を図に関連して説明するが、本発明はこれに限定されるものではなく、例示に過ぎない。 Hereinafter, embodiments of the optical pressure-sensitive adhesive sheet of the present invention will be described with reference to the drawings, but the present invention is not limited thereto and is merely an example.
 図1は、本発明の光学用粘着シートの一実施態様を示す模式図(断面図)である。
 図1において、光学用粘着シート10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。基材1の第2面1bは、反射防止処理、アンチグレア処理、ハードコート処理、及び/又は帯電防止処理3が施されている。粘着剤層2の基材1の第1面1aに積層されていない面(粘着面)は、セパレータ4により保護されている。
FIG. 1 is a schematic diagram (cross-sectional view) showing one embodiment of the optical pressure-sensitive adhesive sheet of the present invention.
In FIG. 1, an optical pressure-sensitive adhesive sheet 10 has a laminated structure in which a substrate 1 and a pressure-sensitive adhesive layer 2 are laminated. The substrate 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 substrate 1. As shown in FIG. The second surface 1b of the substrate 1 is subjected to antireflection treatment, antiglare treatment, hard coat treatment, and/or antistatic treatment 3. FIG. The surface (adhesive surface) of the adhesive layer 2 that is not laminated on the first surface 1 a of the substrate 1 is protected by the separator 4 .
 図2は、本発明の光学積層体の一実施態様を示す模式図(断面図)である。
 図2において、光学積層体20は、基材1と、粘着剤層2と、光学部材5とが、この順に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。粘着剤層2の基材1の第1面1aに積層されていない面は、光学部材5が積層されている。基材1の第2面1bは、反射防止処理、アンチグレア処理、ハードコート処理、及び/又は帯電防止処理3が施されている。
FIG. 2 is a schematic diagram (cross-sectional view) showing one embodiment of the optical laminate of the present invention.
In FIG. 2, the optical laminate 20 has a laminate structure in which a substrate 1, an adhesive layer 2, and an optical member 5 are laminated in this order. The substrate 1 has a first surface 1a and a second surface 1b, and the pressure-sensitive adhesive layer 2 is laminated on the first surface 1a of the substrate 1 . The optical member 5 is laminated on the surface of the pressure-sensitive adhesive layer 2 that is not laminated on the first surface 1a of the substrate 1 . The second surface 1b of the substrate 1 is subjected to antireflection treatment, antiglare treatment, hard coat treatment, and/or antistatic treatment 3. FIG.
 図3は、本発明の画像表示装置の一実施態様を示す模式図(断面図)である。図3において、画像表示装置30は、光学用粘着シート10の粘着剤層2において、画像表示パネル6が積層されている。
 以下、各構成について説明する。
FIG. 3 is a schematic diagram (sectional view) showing one embodiment of the image display device of the present invention. In FIG. 3, the image display device 30 has an image display panel 6 laminated on the adhesive layer 2 of the optical adhesive sheet 10 .
Each configuration will be described below.
[1.光学用粘着シート]
 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。
[1. Optical adhesive sheet]
The “optical” in the optical pressure-sensitive adhesive sheet of the present invention means that it is used for optical purposes, and more specifically means that it is used for manufacturing products (optical products) using optical members. do. Examples of optical products include image display devices, input devices such as touch panels, and liquid crystal image display devices, self-luminous image display devices (eg, organic EL (electroluminescence) image display devices, LED image display devices, etc.). ) and the like.
 本発明の光学用粘着シートは、本発明の基材の第1面に本発明の粘着剤層が積層されている限り、その形態は特に限定されない。例えば、片面のみが粘着面である片面粘着シートであってもよいし、両面が粘着面である両面粘着シートであってもよい。また、本発明の光学用粘着シートが両面粘着シートである場合、本発明の光学用粘着シートは、両方の粘着面が本発明の粘着剤層により提供される形態を有していてもよいし、一方の粘着面が本発明の粘着剤層により提供され、他方の粘着面が本発明の粘着剤層以外の粘着剤層(その他の粘着剤層)により提供される形態を有していてもよい。本発明の光学用粘着シートが光学製品の最表面を構成する場合は片面粘着シートが好ましく、被着体(光学部材)同士を貼り合わせる場合は、両面粘着シートが好ましい。なお、「粘着シート」には、「粘着テープ」の意味を含むものとする。すなわち、本発明の光学用粘着シートは、テープ状の形態を有する粘着テープであってもよい。また、本明細書においては、粘着剤層表面を「粘着面」と称する場合がある。 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 substrate of the present invention. For example, it may be a single-sided PSA sheet having an adhesive surface on only one side, or a double-sided PSA sheet having an adhesive surface on both sides. When the optical pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet, the optical pressure-sensitive adhesive sheet of the present invention may have a form in which both pressure-sensitive adhesive surfaces are provided by the pressure-sensitive adhesive layer of the present invention. , one pressure-sensitive adhesive surface is provided by the pressure-sensitive adhesive layer of the present invention, and the other pressure-sensitive adhesive surface is provided by a pressure-sensitive adhesive layer other than the pressure-sensitive adhesive layer of the present invention (other pressure-sensitive adhesive layer). good. When the optical pressure-sensitive adhesive sheet of the present invention constitutes the outermost surface of an optical product, a single-sided pressure-sensitive adhesive sheet is preferable, and when adherends (optical members) are bonded together, a double-sided pressure-sensitive adhesive sheet is preferable. In addition, the meaning of an "adhesive tape" shall be included in an "adhesive sheet." That is, the optical pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive tape having a tape-like shape. Moreover, in this specification, the adhesive layer surface may be called an "adhesive surface."
[1-1.光学用粘着シートの各種物性]
 本発明の光学用粘着シートのガラス板に対する23℃での180°引き剥がし接着力(特に、上記粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)により提供される粘着面のガラス板に対する23℃での180°引き剥がし接着力)は、特に限定されないが、接着力が高ければ、十分な密着が得られるという観点から、4N/20mm以上であることが好ましく、より好ましくは6N/20mm以上、さらに好ましくは8N/20mm以上、さらにより好ましくは10N/20mm以上である。本発明の光学用粘着シートの、ガラス板に対する23℃での180°引き剥がし接着力が一定の値以上であれば、ガラスへの接着性、段差における浮きの抑止性に一層優れる。なお、本発明の光学用粘着シートのガラス板に対する23℃での180°引き剥がし接着力の上限値は、特に限定されないが、例えば、28N/20mm、27N/20mm、26N/20mmが好ましく、より好ましくは、25N/20mm、24N/20mm、23N/20mm、22N/20mm、21N/20mm、20N/20mmである。
[1-1. Various Physical Properties of Optical Adhesive Sheets]
180° peeling strength of the optical pressure-sensitive adhesive sheet of the present invention to a glass plate at 23°C 180° peeling adhesive force at 23°C to a glass plate) is not particularly limited, but from the viewpoint that sufficient adhesion can be obtained if the adhesive force is high, it is preferably 4 N / 20 mm or more, more preferably. is 6 N/20 mm or more, more preferably 8 N/20 mm or more, still more preferably 10 N/20 mm or more. If the optical pressure-sensitive adhesive sheet of the present invention has a 180° peeling adhesive strength to a glass plate at 23°C of a certain value or more, the adhesiveness to glass and the ability to prevent floating on steps are further improved. The upper limit of the 180° peeling adhesive strength of the optical pressure-sensitive adhesive sheet of the present invention to a glass plate at 23°C is not particularly limited, but is preferably, for example, 28 N/20 mm, 27 N/20 mm, or 26 N/20 mm. Preferably, they are 25N/20mm, 24N/20mm, 23N/20mm, 22N/20mm, 21N/20mm and 20N/20mm.
 本発明の光学用粘着シートのガラス板に対する80℃での180°引き剥がし接着力(特に、上記粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)により提供される粘着面のガラス板に対する80℃での180°引き剥がし接着力)は、特に限定されないが、接着力が高ければ、十分な密着が得られるという観点から、4N/20mm以上であることが好ましく、より好ましくは6N/20mm以上、さらに好ましくは8N/20mm以上、さらにより好ましくは10N/20mm以上である。本発明の光学用粘着シートの、ガラス板に対する80℃での180°引き剥がし接着力が一定の値以上であれば、ガラスへの接着性、段差における浮きの抑止性に一層優れる。なお、本発明の光学用粘着シートのガラス板に対する80℃での180°引き剥がし接着力の上限値は、特に限定されないが、例えば、18N/20mmが好ましく、より好ましくは16N/20mmである。ガラス板に対する23℃又は80℃での180°引き剥がし接着力は、下記の180°引き剥がし接着力の測定方法により求められる。 180° peeling strength of the optical pressure-sensitive adhesive sheet of the present invention to a glass plate at 80°C 180° peeling adhesive force at 80°C to a glass plate) is not particularly limited, but from the viewpoint that sufficient adhesion can be obtained if the adhesive force is high, it is preferably 4 N / 20 mm or more, more preferably. is 6 N/20 mm or more, more preferably 8 N/20 mm or more, still more preferably 10 N/20 mm or more. If the optical pressure-sensitive adhesive sheet of the present invention has a 180° peeling adhesive strength to a glass plate at 80°C of a certain value or more, the adhesiveness to glass and the ability to prevent floating on steps are further improved. Although the upper limit of the 180° peeling adhesive strength at 80°C of the optical pressure-sensitive adhesive sheet of the present invention to a glass plate is not particularly limited, it is preferably 18 N/20 mm, more preferably 16 N/20 mm. The 180° peeling adhesion to a glass plate at 23°C or 80°C is determined by the following method for measuring 180° peeling adhesion.
 上記ガラス板としては、特に限定されないが、例えば、商品名「ソーダライムガラス ♯0050」(松浪硝子工業株式会社製)が挙げられる。また、無アルカリガラスや化学強化ガラス等も挙げられる。 Although the glass plate is not particularly limited, for example, the product name "Soda Lime Glass #0050" (manufactured by Matsunami Glass Industry Co., Ltd.) can be mentioned. In addition, non-alkali glass, chemically strengthened glass, and the like can also be used.
(A-1.180°引き剥がし接着力の測定方法)
 光学用粘着シートの粘着面を被着体に貼り合わせ、2kgローラー、1往復の圧着条件で圧着し、23℃、50%RHの雰囲気下で30分間又は240時間エージングする。エージング後、JIS Z 0237に準拠して、23℃又は80℃、50%RHの雰囲気下、引張速度300mm/分、剥離角度180°の条件で、被着体から光学用粘着シートを引きはがし、180°引き剥がし接着力(N/20mm)を測定する。
(A-1. 180° peeling adhesive force measurement method)
The adhesive surface of the optical pressure-sensitive adhesive sheet is adhered to the adherend, pressed with a 2-kg roller for one reciprocation, and aged in an atmosphere of 23° C. and 50% RH for 30 minutes or 240 hours. After aging, according to JIS Z 0237, the optical pressure-sensitive adhesive sheet was peeled off from the adherend under the conditions of 23° C. or 80° C., 50% RH, a tensile speed of 300 mm/min, and a peeling angle of 180°, Measure the 180° peel adhesion (N/20 mm).
(B.厚み)
 本発明の粘着シートの厚み(総厚み)は、特に限定されないが、12~350μmが好ましく、より好ましくは15~330μm、18~325μm、18~320μm、20~300μm、23~300μm、25~275μm、又は30~250μmであってもよい。厚みが一定以上であると、段差部位での剥がれが生じにくくなり、好ましい。また、厚みが一定以下であると、製造時に優れた外観を保持しやすくなり、好ましい。なお、本発明の粘着シートの厚みには、基材付き粘着シートの場合は基材の厚さは含まれるが、セパレータの厚みは含めないものとする。
(B. Thickness)
The thickness (total thickness) of the adhesive sheet of the present invention is not particularly limited, but is preferably 12 to 350 μm, more preferably 15 to 330 μm, 18 to 325 μm, 18 to 320 μm, 20 to 300 μm, 23 to 300 μm, 25 to 275 μm. , or from 30 to 250 μm. When the thickness is equal to or greater than a certain value, peeling at the step portion is less likely to occur, which is preferable. Further, when the thickness is less than a certain value, it is preferable because it becomes easy to maintain an excellent appearance during production. In the case of a pressure-sensitive adhesive sheet with a substrate, the thickness of the pressure-sensitive adhesive sheet of the present invention includes the thickness of the substrate, but does not include the thickness of the separator.
(C.ヘイズ)
 本発明の光学用粘着シートのヘイズ(JIS K7136に準じる)は、特に限定されないが、1.0%以下が好ましく、より好ましくは0.8%以下、0.7%以下、又は0.6%以下であってもよい。ヘイズが1.0%以下であると、優れた透明性や優れた外観が得られ、好ましい。なお、上記ヘイズは、例えば、光学用粘着シートを常態(23℃、50%RH)に少なくとも24時間静置した後、セパレータを有する場合にはこれを剥離し、スライドガラス(例えば、全光線透過率92%、ヘイズ0.2%のもの)に貼り合わせたものを試料とし、ヘイズメーター(株式会社村上色彩技術研究所製、商品名「HM-150N」)を用いて測定することができる。
(C. Hayes)
The haze (according to JIS K7136) of the optical pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 1.0% or less, more preferably 0.8% or less, 0.7% or less, or 0.6%. It may be below. A haze of 1.0% or less is preferable because excellent transparency and appearance can be obtained. Incidentally, the above-mentioned haze can be measured, for example, by leaving the optical pressure-sensitive adhesive sheet in a normal state (23° C., 50% RH) for at least 24 hours, peeling off the separator, if any, and adjusting the haze on a slide glass (e.g., total light transmission). haze of 92% and haze of 0.2%) can be used as a sample and measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., trade name "HM-150N").
(D.全光線透過率)
 本発明の光学用粘着シートの可視光波長領域における全光線透過率(JIS K7361-1に準じる)は、特に限定されないが、90%以上が好ましく、より好ましくは91%以上、又は92%以上であってもよい。全光線透過率が90%以上であると、優れた透明性や優れた外観が得られ、好ましい。なお、上記全光線透過率は、例えば、光学用粘着シートを常態(23℃、50%RH)に少なくとも24時間静置した後、セパレータを有する場合にはこれを剥離し、スライドガラス(例えば、全光線透過率92%、ヘイズ0.2%のもの)に貼り合わせたものを試料とし、ヘイズメーター(株式会社村上色彩技術研究所製、商品名「HM-150N」)を用いて測定することができる。
(D. Total light transmittance)
The total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the optical pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 90% or more, more preferably 91% or more, or 92% or more. There may be. When the total light transmittance is 90% or more, excellent transparency and excellent appearance can be obtained, which is preferable. The above total light transmittance can be measured, for example, by allowing the optical pressure-sensitive adhesive sheet to stand in a normal state (23° C., 50% RH) for at least 24 hours, peeling off the separator if it has one, and using a slide glass (for example, Total light transmittance of 92%, haze of 0.2%) is used as a sample, and measured using a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HM-150N"). can be done.
 本発明の光学用粘着シートの上記接着力、全光線透過率及びヘイズは、後掲の実施例に記載の方法により、測定できる。本発明の光学用粘着シートの上記接着力、全光線透過率及びヘイズは、アクリル系ポリマー(A)を構成するモノマー組成、架橋剤の量、本発明のイオン性化合物、その他添加剤の種類や量、硬化条件などを調整することによって、調整することができる。 The adhesive strength, total light transmittance and haze of the optical pressure-sensitive adhesive sheet of the present invention can be measured by the methods described in Examples below. The adhesive strength, total light transmittance and haze of the optical pressure-sensitive adhesive sheet of the present invention are determined by the composition of the monomers constituting the acrylic polymer (A), the amount of the cross-linking agent, the ionic compound of the present invention, the type of other additives, and the Adjustments can be made by adjusting amounts, curing conditions, and the like.
<基材>
 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」(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、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、ポリイミド、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ステル系樹脂、環状オレフィン系ポリマー(COP)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(光学部材、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)に剥離されるセパレータ(剥離ライナー)は「基材」には含まない。
<Base material>
Materials constituting the substrate of the present invention include glass and plastic films. Examples of the plastic film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); name "Zeonor" (manufactured by Zeon Co., Ltd.), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, transparent polyimide (CPI), poly Examples thereof include plastic materials such as vinyl chloride, polyvinyl acetate, polyethylene, polypropylene, and ethylene-propylene copolymers. Preferred are polyester-based resins and cyclic olefin-based polymers (COP), which are excellent in dimensional stability and resistant to shrinkage. In addition, these plastic materials can be used individually or in combination of 2 or more types. The substrate 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 (optical member, image display panel, etc.). The "base material" does not include a separator (release liner) that is peeled off when the optical pressure-sensitive adhesive sheet of the present invention is used (attached).
 本発明の基材は、第1面と第2面を有するフィルム状(基板状)の形態を有するものである。本発明の基材は、前記光学製品を構成する光学部材であれば、特に限定されず、カバー部材、偏光板、位相差板などの各種光学フィルムが挙げられ、好ましくはカバー部材として用いられる。本発明の基材がカバー部材である場合には、第2面が、例えば、上記光学製品の最表面となる。 The substrate 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 an optical member constituting the optical product, and includes various optical films such as cover members, polarizing plates, and retardation plates, and is preferably used as a cover member. When the substrate of the present invention is a cover member, the second surface is, for example, the outermost surface of the optical product.
 本発明の基材のガラス転移点(Tg)は、特に限定されないが、60℃以上160℃以下であることが好ましい。本発明の基材のガラス転移点が60℃以上であるという構成は、使用環境下での本発明の画像表示装置の機械的物性が安定する点で好ましい。本発明の画像表示装置の機械的物性の安定性の観点から前記基材のガラス転移点は63℃以上、又は65℃以上であってもよい。また、前記基材のガラス転移点が160℃以下であるという構成は、基材の成形プロセスが簡便化できる点で好ましい。基材の成形プロセスが簡便化できる点で、前記基材のガラス転移点は140℃以下以下が好ましく、135℃以下、130℃、又は125℃以下であってもよい。 Although the glass transition point (Tg) of the base material of the present invention is not particularly limited, it is preferably 60°C or higher and 160°C or lower. A configuration in which the glass transition point of the substrate of the present invention is 60° C. or higher is preferable in terms of stabilizing the mechanical properties of the image display device of the present invention under the usage environment. From the viewpoint of the stability of the mechanical properties of the image display device of the present invention, the glass transition point of the substrate may be 63° C. or higher, or 65° C. or higher. Moreover, the configuration in which the glass transition point of the substrate is 160° C. or lower is preferable in that the molding process of the substrate can be simplified. The glass transition point of the substrate is preferably 140° C. or lower, and may be 135° C. or lower, 130° C. or lower, or 125° C. or lower in terms of simplifying the molding process of the substrate.
 本発明の基材のガラス転移点(Tg)は、JIS K 7121に準拠して測定することができる。本発明の基材のガラス転移点(Tg)は、本発明の基材を構成する樹脂の種類などにより調整することができる。 The glass transition point (Tg) of the base material of the present invention can be measured according to JIS K 7121. The glass transition point (Tg) of the base material of the present invention can be adjusted by the type of resin constituting the base material of the present invention.
 本発明の基材の湿度膨張係数は、特に限定されないが、5×10-5/%RH以下であることが好ましい。本発明の基材の湿度膨張係数が5×10-5/%RH以下であるという構成は、本発明の基材の温度変化における寸法安定性が向上し、良好な外観を維持する点で好適である。本発明の基材の寸法安定性の点から、本発明の基材の湿度膨張係数は3×10-5/%RH以下が好ましく、2×10-5/%RH以下であってもよい。 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 configuration in which the humidity expansion coefficient of the substrate of the present invention is 5×10 −5 /% RH or less is preferable in terms of improving the dimensional stability of the substrate of the present invention against temperature changes and maintaining a good appearance. is. From the viewpoint of dimensional stability of the base material of the present invention, the humidity expansion coefficient of the base material of the present invention is preferably 3×10 −5 /% RH or less, and may be 2×10 −5 /% RH or less.
 本発明の基材の湿度膨張係数は、具体的には、後掲の実施例に記載の方法で測定することができる。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。 Specifically, the coefficient of humidity expansion of the base material of the present invention can be measured by the method described in Examples below. 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 (temperature, extrusion speed, etc.) during the production of the base material, and the like.
 本発明の基材のヘイズは、特に限定されないが、5%以上が好ましい。本発明の基材のヘイズが5%以上であるという構成は、本発明の画像表示装置における画像表示パネルの基板上に配置された金属配線やITO配線などによる反射を防止できる点で好ましく、より好ましくは6%以上であり、7%以上であってもよい。本発明の基材のヘイズの上限は、特に限定されないが、本発明の画像表示装置の視認性の観点から、50%以下が好ましく、40%以下、又は30%以下であってもよい。 Although the haze of the base material of the present invention is not particularly limited, it is preferably 5% or more. The configuration in which the haze of the base material of the present invention is 5% or more is preferable in that reflection due to metal wiring, ITO wiring, or the like arranged on the substrate of the image display panel in the image display device of the present invention can be prevented. It is preferably 6% or more, and may be 7% or more. The upper limit of the haze of the base material of the present invention is not particularly limited, but from the viewpoint of visibility of the image display device of the present invention, it is preferably 50% or less, and may be 40% or less or 30% or less.
 本発明の基材のヘイズは、JIS K 7136に準拠して測定することができる。本発明の基材のヘイズは、本発明の基材を構成する樹脂の種類や厚さ、基材表面に反射防止処理及び/又はアンチグレア処理を施すことなどにより調整することができる。 The haze of the base material of the present invention can be measured according to JIS K 7136. The haze of the substrate of the present invention can be adjusted by the type and thickness of the resin that constitutes the substrate of the present invention, and by subjecting the surface of the substrate to antireflection treatment and/or antiglare treatment.
 本発明の基材の反射率は、特に限定されないが、5%以下が好ましい。本発明の基材の反射率が5%以下であるという構成は、本発明の画像表示装置における画像表示パネルの基板上に配置された金属配線やITO配線などによる反射を防止できる点で好ましく、より好ましくは3%以下であり、1.5%以下であってもよい。本発明の基材の反射率の下限は、特に限定されないが、0.1%以上、又は0.3%以上であってもよい。 Although the reflectance of the substrate of the present invention is not particularly limited, it is preferably 5% or less. The configuration in which the reflectance of the base material of the present invention is 5% or less is preferable in that reflection due to metal wiring, ITO wiring, or the like arranged on the substrate of the image display panel in the image display device of the present invention can be prevented. It is more preferably 3% or less, and may be 1.5% or less. The lower limit of the reflectance of the substrate of the present invention is not particularly limited, but may be 0.1% or more, or 0.3% or more.
 本発明の基材の反射率は、JIS K7361-1に準拠して測定することができる。本発明の基材の反射率は、本発明の基材を構成する樹脂の種類や厚さ、基材表面に反射防止処理及び/又はアンチグレア処理を施すことなどにより調整することができる。 The reflectance of the substrate of the present invention can be measured according to 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 antireflection treatment and/or antiglare treatment.
 本発明の基材の厚みは、特に制限されないが、例えば、寸法安定性、強度、取り扱い性などの作業性、薄層性などの点を考慮すると、10~500μmの範囲が好ましく、より好ましくは20~300μm、さらに好ましくは25~250μmの範囲であり、最適には、30~200μmの範囲である。本発明の基材の屈折率は、特に制限されないが、例えば、1.30~1.80の範囲であり、好ましくは、1.40~1.70の範囲である。 Although the thickness of the substrate of the present invention is not particularly limited, it is preferably in the range of 10 to 500 μm, more preferably in the range of 10 to 500 μm, considering dimensional stability, strength, workability such as handleability, thin layer property, and the like. It ranges from 20 to 300 μm, more preferably from 25 to 250 μm, optimally from 30 to 200 μm. The refractive index of the substrate 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.
 本発明の基材の第2面は、反射表面処理及び/又はアンチグレア処理が施されていることが好ましい。本発明の基材の第2面に反射表面処理及び/又はアンチグレア処理が施されているという構成は、外光の反射や像の映り込み等による視認性の低下を防止する、光沢度などの見栄えを調整するといった観点で好ましい。また、本発明の画像表示装置の基板上に配置された金属配線やITO配線などによる反射を防止できる点で好ましい。また、本発明の基材の第2面は、ハードコート処理が施されていることが好ましい。本発明の基材の第2面にハードコート処理が施されているという構成は、表面硬度、耐擦傷性が向上する点で好ましい。 The second surface of the substrate of the present invention is preferably subjected to reflective surface treatment and/or antiglare 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 deterioration of visibility due to reflection of external light and reflection of images, etc. This is preferable from the viewpoint of adjusting appearance. It is also preferable in that it can prevent reflection due to metal wiring, ITO wiring, and the like arranged on the substrate of the image display device of the present invention. Moreover, it is preferable that the second surface of the substrate of the present invention is subjected to a hard coat treatment. The configuration in which the second surface of the substrate of the present invention is hard-coated is preferable in that the surface hardness and scratch resistance are improved.
 前記反射防止処理としては、公知の反射防止処理を特に限定なく使用することができ、例えば、アンチリフレクション(AR)処理が挙げられる。 As the antireflection treatment, any known antireflection treatment can be used without particular limitation, and examples thereof include antireflection (AR) treatment.
 前記アンチリフレクション(AR)処理としては、公知のAR処理を特に制限なく適用することができ、具体的には、本発明の基材の第2面上に厚みおよび屈折率を厳密に制御した光学薄膜若しくは前記光学薄膜を二層以上積層した反射防止層(AR層)を形成することにより実施することができる。前記AR層は、光の干渉効果を利用して入射光と反射光の逆転した位相を互いに打ち消し合わせることで反射防止機能を発現する。反射防止機能を発現させる可視光線の波長領域は、例えば、380~780nmであり、特に視感度が高い波長領域は450~650nmの範囲であり、その中心波長である550nmの反射率を最小にするようにAR層を設計することが好ましい。 As the antireflection (AR) treatment, a known AR treatment can be applied without particular limitation. It can be carried out by forming an antireflection layer (AR layer) in which two or more layers of thin films or optical thin films are laminated. The AR layer exerts an antireflection function by canceling out the reversed phases of the incident light and the reflected light using the interference effect of light. The wavelength region of visible light that exhibits the antireflection function is, for example, 380 to 780 nm, and the wavelength region with particularly high luminosity is in the range of 450 to 650 nm. It is preferable to design the AR layer so that
 前記AR層としては、一般的に、二ないし五層の光学薄層(厚みおよび屈折率を厳密に制御した薄膜)を積層した構造の多層反射防止層が挙げられ、屈折率の異なる成分を所定の厚さだけ複数層形成することで、AR層の光学設計の自由度が上がり、より反射防止効果を向上させることができ、分光反射特性も可視光領域で均一(フラット)にすることが可能になる。前記光学薄膜において、高い厚み精度が要求されるため、一般的に、各層の形成は、ドライ方式である真空蒸着、スパッタリング、CVD等で実施される。 The AR layer generally includes a multilayer antireflection layer having a structure in which two to five optical thin layers (thin films with strictly controlled thickness and refractive index) are laminated. By forming multiple layers with a thickness of , the degree of freedom in the optical design of the AR layer increases, the anti-reflection effect can be further improved, and the spectral reflection characteristics can be made uniform (flat) in the visible light region. become. Since the optical thin film requires high thickness accuracy, each layer is generally formed by dry methods such as vacuum deposition, sputtering, and CVD.
 また、前記AR層は、反射防止層形成用塗工液により形成することもできる。前記反射防止層形成用塗工液は、例えば、樹脂、フッ素元素含有添加剤、中空粒子、中実粒子および希釈溶媒等を含んでいてもよく、例えば、これらを混合して製造できる。 In addition, the AR layer can also be formed using a coating solution for forming an antireflection layer. The antireflection layer-forming coating liquid may contain, for example, a resin, a fluorine element-containing additive, hollow particles, solid particles, a diluent solvent, and the like, and can be produced, for example, by mixing these.
 前記樹脂は、例えば、熱硬化性樹脂、紫外線や光で硬化する電離放射線硬化性樹脂があげられる。前記樹脂として、市販の熱硬化型樹脂や紫外線硬化型樹脂等を用いることも可能である。 Examples of the resin include thermosetting resins and ionizing radiation curable resins that are cured by ultraviolet light or light. As the resin, it is possible to use a commercially available thermosetting resin, ultraviolet curable resin, or the like.
 前記熱硬化型樹脂や紫外線硬化型樹脂としては、例えば、熱、光(紫外線等)または電子線等により硬化するアクリレート基およびメタクリレート基の少なくとも一方の基を有する硬化型化合物が使用でき、例えば、シリコーン樹脂、ポリエステル樹脂、ポリエーテル樹脂、エポキシ樹脂、ウレタン樹脂、アルキッド樹脂、スピロアセタール樹脂、ポリブタジエン樹脂、ポリチオールポリエン樹脂、多価アルコール等の多官能化合物のアクリレートやメタクリレート等のオリゴマーまたはプレポリマー等があげられる。これらは、1種類を単独で用いてもよく、2種類以上を併用してもよい。 As the thermosetting resin or UV-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 (ultraviolet rays, etc.), electron beams, or the like can be used. Silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiolpolyene resins, oligomers or prepolymers such as acrylates and methacrylates of polyfunctional compounds such as polyhydric alcohols. can give. These may be used individually by 1 type, and may use 2 or more types together.
 前記樹脂には、例えば、アクリレート基およびメタクリレート基の少なくとも一方の基を有する反応性希釈剤を用いることもできる。前記反応性希釈剤は、例えば、特開2008-88309号公報に記載の反応性希釈剤を用いることができ、例えば、単官能アクリレート、単官能メタクリレート、多官能アクリレート、多官能メタクリレート等を含む。前記反応性希釈剤としては、3官能以上のアクリレート、3官能以上のメタクリレートが好ましい。これは、本発明の基材の第2面の硬度を、優れたものにできるからである。前記反応性希釈剤としては、例えば、ブタンジオールグリセリンエーテルジアクリレート、イソシアヌル酸のアクリレート、イソシアヌル酸のメタクリレート等もあげられる。これらは、1種類を単独で用いてもよく、2種類以上を併用してもよい。前記樹脂は、硬化前の重量平均分子量が、例えば、100以上、300以上、500以上、1,000以上、または2,000以上であってもよく、100,000以下、70,000以下、50,000以下、30,000以下、または10,000以下であってもよい。前記硬化前の重量平均分子量が高ければ、硬度は低下するが、屈曲させた際に割れが起こり難くなる傾向がある。一方、前記硬化前の重量平均分子量が低ければ、分子間架橋密度が向上し、硬度が高くなる傾向がある。 For the resin, for example, a reactive diluent having at least one of an acrylate group and a methacrylate group can be used. As the reactive diluent, for example, reactive diluents described in JP-A-2008-88309 can be used, and examples include monofunctional acrylates, monofunctional methacrylates, polyfunctional acrylates, polyfunctional methacrylates, and the like. As the reactive diluent, tri- or more functional acrylates and tri- or more functional methacrylates are preferable. This is because the hardness of the second surface of the substrate of the present invention can be made excellent. Examples of the reactive diluent include butanediol glycerol ether diacrylate, isocyanuric acid acrylate, and isocyanuric acid methacrylate. These may be used individually by 1 type, and may use 2 or more types together. 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, 100,000 or less, 70,000 or less, 50 ,000 or less, 30,000 or less, or 10,000 or less. If the weight-average molecular weight before curing is high, the hardness tends to be low, but cracking tends to be less likely to occur when bent. On the other hand, when the weight-average molecular weight before curing is low, the intermolecular crosslink density tends to improve and the hardness tends to increase.
 前記樹脂としては、多官能アクリレート(例えば、ペンタスリトールトリアクリレート)を含むことが好ましい。 The resin preferably contains a polyfunctional acrylate (eg, pentathritol triacrylate).
 前記硬化型樹脂の硬化のために、例えば、硬化剤を添加してもよい。前記硬化剤は、特に限定されず、例えば、公知の重合開始剤(例えば、熱重合開始剤、光重合開始剤等)を適宜用いることができる。前記硬化剤の添加量は特に限定されないが、前記反射防止層形成用塗工液中の前記樹脂100重量部に対し、例えば、0.5重量部以上、1.0重量部以上、1.5重量部以上、2.0重量部以上、または2.5重量部以上であってもよく、15重量部以下、13重量部以下、10重量部以下、7重量部以下、または5重量部以下であってもよい。 For example, a curing agent may be added to cure the curable resin. The curing agent is not particularly limited, and for example, a known polymerization initiator (eg, thermal polymerization initiator, photopolymerization initiator, etc.) can be used as appropriate. The amount of the curing agent to be added is not particularly limited. 15 parts by weight or more, 13 parts by weight or less, 10 parts by weight or less, 7 parts by weight or less, or 5 parts by weight or less; There may be.
 前記フッ素元素含有添加剤は、特に限定されないが、例えば、分子中にフッ素を含む有機化合物または無機化合物であってもよい。前記有機化合物は、特に限定されないが、例えば、フッ素含有防汚コーティング剤、フッ素含有アクリル化合物、フッ素およびケイ素含有アクリル化合物等があげられる。前記有機化合物は、具体的には、例えば、信越化学工業株式会社製の商品名「KY-1203」、DIC株式会社製の商品名「メガファック」等があげられる。前記無機化合物も、特に限定されない。前記フッ素元素含有添加剤の添加量は、特に限定されないが、例えば、前記反射防止層形成用塗工液中の固形分全体の重量に対し、前記固形分中のフッ素元素の重量が、例えば、0.05重量%以上、0.1重量%以上、0.15重量%以上、0.20重量%以上、または0.25重量%以上であってもよく、20重量%以下、15重量%以下、10重量%以下、5重量%以下、または3重量%以下であってもよい。また、例えば、前記反射防止層形成用塗工液中の前記樹脂100重量部に対し、前記フッ素元素含有添加剤の重量が、例えば、0.05重量%以上、0.1重量%以上、0.15重量%以上、0.20重量%以上、または0.25重量%以上であってもよく、20重量%以下、15重量%以下、10重量%以下、5重量%以下、または3重量%以下であってもよい。 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. Examples of the organic compound include, but are not limited to, 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., "Megafac" (trade name) manufactured by DIC Corporation, and the like. The inorganic compound is also not particularly limited. The amount of the elemental fluorine-containing additive to be added is not particularly limited. 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 wt % or less, 5 wt % or less, or 3 wt % or less. Further, for example, the weight of the fluorine element-containing additive with respect to 100 parts by weight of the resin in the antireflection layer-forming coating liquid is, for example, 0.05 wt% or more, 0.1 wt% or more, 0 .15 wt% or more, 0.20 wt% or more, or 0.25 wt% or more, and 20 wt% or less, 15 wt% or less, 10 wt% or less, 5 wt% or less, or 3 wt% It may be below.
 前記中空粒子は、特に限定されないが、例えば、シリカ粒子、アクリル粒子、アクリル-スチレン共重合粒子等であってもよい。前記シリカ粒子は、例えば、日揮触媒化成工業株式会社製の商品名「スルーリア5320」、「スルーリア4320」等があげられる。前記中空粒子の重量平均粒子径は、特に限定されないが、例えば、30nm以上、40nm以上、50nm以上、60nm以上、または70nm以上であってもよく、150nm以下、140nm以下、130nm以下、120nm以下、または110nm以下であってもよい。前記中空粒子の形状は、特に制限されず、例えば、ビーズ状の略球形であってもよく、粉末等の不定形のものであってもよいが、略球形のものが好ましく、より好ましくは、アスペクト比が1.5以下の略球形の粒子であり、最も好ましくは球形の粒子である。前記中空粒子を添加することで、例えば、前記反射防止層の低屈折率、良好な反射防止特性等を実現できる。前記中空粒子の添加量は特に限定されないが、前記反射防止層形成用塗工液中の前記樹脂100重量部に対し、例えば、30重量部以上、50重量部以上、70重量部以上、90重量部以上、または100重量部以上であってもよく、300重量部以下、270重量部以下、250重量部以下、200重量部以下、または180重量部以下であってもよい。反射防止層の低屈折率化の観点からは、前記中空粒子の添加量が少なすぎないことが好ましく、反射防止層の機械特性確保の観点からは、前記中空粒子の添加量が多すぎないことが好ましい。 The hollow particles are not particularly limited, but may be, for example, silica particles, acrylic particles, acrylic-styrene copolymer particles, or the like. Examples of the silica particles include trade names "Sururia 5320" and "Sururia 4320" manufactured by Nikki Shokubai & 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, Alternatively, it may be 110 nm or less. The shape of the hollow particles is not particularly limited, and may be, for example, a substantially spherical shape such as a bead, or an irregular shape such as a powder. They are substantially spherical particles with an aspect ratio of 1.5 or less, most preferably spherical particles. By adding the hollow particles, for example, a low refractive index, good antireflection properties, etc. of the antireflection layer can be realized. The amount of the hollow particles to be added is not particularly limited. parts by weight or more, or 100 parts by weight or more, and may be 300 parts by weight or less, 270 parts by weight or less, 250 parts by weight or less, 200 parts by weight or less, or 180 parts by weight or less. From the viewpoint of lowering the refractive index of the antireflection layer, the amount of the hollow particles added is preferably not too small, and from the viewpoint of ensuring the mechanical properties of the antireflection layer, the amount of the hollow particles added should not be too large. is preferred.
 前記中実粒子は、特に限定されないが、例えば、シリカ粒子、酸化ジルコニウム粒子、チタン含有粒子(例えば、酸化チタン粒子)等であってもよい。前記シリカ粒子は、例えば、日産化学工業株式会社製の商品名「MEK-2140Z-AC」、「MIBK-ST」、「IPA-ST」等があげられる。前記中実粒子の重量平均粒子径は、特に限定されないが、例えば、5nm以上、10nm以上、15nm以上、20nm以上、または25nm以上であってもよく、3300nm以下、250nm以下、200nm以下、150nm以下、または100nm以下であってもよい。前記中実粒子の形状は、特に制限されず、例えば、ビーズ状の略球形であってもよく、粉末等の不定形のものであってもよいが、略球形のものが好ましく、より好ましくは、アスペクト比が1.5以下の略球形の粒子であり、最も好ましくは球形の粒子である。前記中実粒子を添加することで、例えば、前記フッ素元素含有添加剤が、塗工した前記反射防止層形成用塗工液の表面に偏在しやすくなり、反射防止層の耐擦傷性に優れ、低屈折率、良好な反射防止特性等を実現できる。前記中実粒子の添加量は特に限定されないが、前記反射防止層形成用塗工液中の前記樹脂100重量部に対し、例えば、5重量部以上、10重量部以上、15重量部以上、20重量部以上、または25重量部以上であってもよく、150重量部以下、120重量部以下、重量部以下、100重量部以下、または80重量部以下であってもよい。 The solid particles are not particularly limited, but may be, for example, silica particles, zirconium oxide particles, titanium-containing particles (eg, titanium oxide particles), and the like. Examples of the silica particles include trade names "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 3300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less. , or 100 nm or less. The shape of the solid particles is not particularly limited, and may be, for example, a substantially spherical bead shape, or an irregular shape such as a powder. , an aspect ratio of 1.5 or less, most preferably spherical particles. By adding the solid particles, for example, the fluorine element-containing additive tends to be unevenly distributed on the surface of the coated antireflection layer-forming coating liquid, and the antireflection layer has excellent scratch resistance, A low refractive index, good antireflection properties, and the like can be realized. The amount of the solid particles to be added is not particularly limited. It may be 150 parts by weight or less, 120 parts by weight or less, 100 parts by weight or less, or 80 parts by weight or less.
 前記希釈溶媒は、例えば、MIBK(メチルイソブチルケトン)およびPMA(プロピレングリコールモノメチルエーテルアセテート)を含む混合溶媒でもよい。この場合の混合比率は特に限定されないが、MIBKの重量を100重量%とした場合、PMAの重量が、例えば、20重量%以上、50重量%以上、100重量%以上、150重量%以上、または200重量%以上であってもよく、400重量%以下、350重量%以下、300重量%以下、または250重量%以下であってもよい。 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. It may be 200 wt% or more, 400 wt% or less, 350 wt% or less, 300 wt% or less, or 250 wt% or less.
 前記希釈溶媒は、例えば、MIBKおよびPMAに加え、さらにTBA(ターシャリーブチルアルコール)を含む混合溶媒でもよい。この場合の混合比率は特に限定されないが、MIBKの重量を100重量%とした場合、PMAの重量が、例えば、10重量%以上、30重量%以上、50重量%以上、80重量%以上、または100重量%以上であってもよく、200重量%以下、180重量%以下、150重量%以下、130重量%以下、または110重量%以下であってもよい。また、MIBKの重量を100重量%とした場合、TBAの重量が、例えば、10重量%以上、30重量%以上、50重量%以上、80重量%以上、または100重量%以上であってもよく、200重量%以下、180重量%以下、150重量%以下、130重量%以下、または110重量%以下であってもよい。 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. 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. Further, when the weight of MIBK is 100% by weight, 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 wt.% or less, 180 wt.% or less, 150 wt.% or less, 130 wt.% or less, or 110 wt.% or less.
 前記希釈溶媒の添加量も特に限定されないが、例えば、反射防止層形成用塗工液全体の重量に対する固形分の重量が、例えば、0.1重量%以上、0.3重量%以上、0.5重量%以上、1.0重量%以上、または1.5重量%以上となるようにしてもよく、20重量%以下、15重量%以下、10重量%以下、5重量%以下、または3重量%以下となるようにしてもよい。塗工性確保(ヌレ、レベリング)の観点からは、前記固形分の含有率が高すぎないことが好ましく、風乾ムラ、白化など乾燥起因の外観不良防止の観点からは、前記固形分の含有率が低すぎないことが好ましい。 The amount of the diluent solvent to be added is not particularly limited, either. 5 wt% or more, 1.0 wt% or more, or 1.5 wt% or more, and 20 wt% or less, 15 wt% or less, 10 wt% or less, 5 wt% or less, or 3 wt% % or less. From the viewpoint of ensuring coatability (wetness, leveling), it is preferable that the content of the solid content is not too high. is not too low.
 つぎに、本発明の基材の第2面の上に、前記反射防止層形成用塗工液を塗工する(前記塗工工程)。塗工方法は特に限定されず、例えば、ファンテンコート法、ダイコート法、スピンコート法、スプレーコート法、グラビアコート法、ロールコート法、バーコート法等の公知の塗工方法を適宜用いることができる。前記反射防止層形成用塗工液の塗工量も特に限定されないが、形成される前記反射防止層の厚みが、例えば、0.1μm以上、0.3μm以上、0.5μm以上、1.0μm以上、または2.0μm以上となるようにしてもよく、50μm以下、40μm以下、30μm以下、20μm以下、または10μm以下となるようにしてもよい。 Next, the antireflection layer-forming coating liquid is applied onto 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 can be used as appropriate. can. Although the coating amount of the antireflection layer-forming coating solution is not particularly limited, the thickness of the antireflection layer to be formed is, for example, 0.1 μm or more, 0.3 μm or more, 0.5 μm or more, or 1.0 μm. or 2.0 μm or more, or 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less.
 つぎに、塗工した前記反射防止層形成用塗工液を乾燥させて塗膜を形成する(前記塗膜形成工程)。乾燥温度は、特に限定されないが、例えば、30~200℃の範囲であってもよい。前記乾燥温度は、例えば、40℃以上、50℃以上、60℃以上、70℃以上、80℃以上、90℃以上、または100℃以上であってもよく、190℃以下、180℃以下、170℃以下、160℃以下、150℃以下、140℃以下、135℃以下、130℃以下、120℃以下、または110℃以下であってもよい。乾燥時間は特に限定されないが、例えば、30秒以上、40秒以上、50秒以上、または60秒以上であってもよく、150秒以下、130秒以下、110秒以下、または90秒以下であってもよい。 Next, the coated antireflection layer forming coating solution is dried to form a coating film (the coating film forming step). Although the drying temperature is not particularly limited, it may be in the range of 30 to 200°C, for example. 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, 170° C. °C or lower, 160 °C or lower, 150 °C or lower, 140 °C or lower, 135 °C or lower, 130 °C or lower, 120 °C or lower, or 110 °C or lower. The drying time is not particularly limited, but may be, for example, 30 seconds or longer, 40 seconds or longer, 50 seconds or longer, or 60 seconds or longer, and may be 150 seconds or shorter, 130 seconds or shorter, 110 seconds or shorter, or 90 seconds or shorter. may
 さらに、前記塗膜を硬化させてもよい(硬化工程)。前記硬化は、例えば、加熱、光照射等により行うことができる。前記光は、特に限定されないが、例えば、紫外線等であってもよい。前記光照射の光源も特に限定されないが、例えば、高圧水銀ランプ等であってもよい。前記紫外線硬化におけるエネルギー線源の照射量は、紫外線波長365nmでの積算露光量として、50~500mJ/cm2が好ましい。照射量が、50mJ/cm2以上であれば、硬化が十分に進行しやすく、形成される反射防止層の硬度が高くなりやすい。また、500mJ/cm2以下であれば、形成される反射防止層の着色を防止することができる。 Furthermore, the coating film may be cured (curing step). The curing can be performed, for example, by heating, light irradiation, or the like. Although the light is not particularly limited, it 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 beam source in the ultraviolet curing is preferably 50 to 500 mJ/cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation dose is 50 mJ/cm 2 or more, curing proceeds sufficiently and the hardness of the formed antireflection layer tends to increase. Also, if it is 500 mJ/cm 2 or less, coloring of the formed antireflection layer can be prevented.
 前記アンチグレア(AG)処理としては、公知のAG処理を特に制限なく適用することができ、例えば、本発明の基材の第2面上にアンチグレア層を形成することにより実施することができる。前記アンチグレア層としては、公知のものを制限なく採用することができ、一般的に、樹脂中にアンチグレア剤として無機又は有機の粒子を分散した層として形成される。また、前記アンチグレア層は、防眩性ハードコート層であってもよい。 As the anti-glare (AG) treatment, a 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. As the anti-glare layer, known layers can be employed without limitation, and it is generally formed as a layer in which inorganic or organic particles are dispersed as an anti-glare agent in a resin. Also, the antiglare layer may be an antiglare hard coat layer.
 前記アンチグレア層としては、特に限定されないが、例えば、樹脂、粒子およびチキソトロピー付与剤を含むアンチグレア層形成材料を用いて形成されており、前記粒子および前記チキソトロピー付与剤が凝集することによって、前記アンチグレア層の表面に凸状部が形成される。当該構成により、アンチグレア層は、アンチグレア性と、白ボケの防止とを両立した優れた表示特性を有するとともに、粒子の凝集を利用してアンチグレア層を形成しているにもかかわらず、外観欠点となるアンチグレア層表面の突起状物の発生を防止して製品の歩留まりを向上させることができる。 The anti-glare layer is not particularly limited. A convex portion is formed on the surface of the . With this configuration, the anti-glare layer has excellent display characteristics that achieve both anti-glare properties and prevention of white blurring, and despite the fact that the anti-glare layer is formed using aggregation of particles, there are no defects in appearance. It is possible to prevent the occurrence of protrusions on the surface of the anti-glare layer and improve the yield of products.
 前記樹脂は、例えば、熱硬化性樹脂、紫外線や光で硬化する電離放射線硬化性樹脂があげられる。前記樹脂として、市販の熱硬化型樹脂や紫外線硬化型樹脂等を用いることも可能である。 Examples of the resin include thermosetting resins and ionizing radiation curable resins that are cured by ultraviolet light or light. As the resin, it is possible to use a commercially available thermosetting resin, ultraviolet curable resin, or the like.
 前記熱硬化型樹脂や紫外線硬化型樹脂としては、例えば、熱、光(紫外線等)または電子線等により硬化するアクリレート基およびメタクリレート基の少なくとも一方の基を有する硬化型化合物が使用でき、例えば、シリコーン樹脂、ポリエステル樹脂、ポリエーテル樹脂、エポキシ樹脂、ウレタン樹脂、アルキッド樹脂、スピロアセタール樹脂、ポリブタジエン樹脂、ポリチオールポリエン樹脂、多価アルコール等の多官能化合物のアクリレートやメタクリレート等のオリゴマーまたはプレポリマー等があげられる。これらは、1種類を単独で用いてもよく、2種類以上を併用してもよい。 As the thermosetting resin or UV-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 (ultraviolet rays, etc.), electron beams, or the like can be used. Silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiolpolyene resins, oligomers or prepolymers such as acrylates and methacrylates of polyfunctional compounds such as polyhydric alcohols. can give. These may be used individually by 1 type, and may use 2 or more types together.
 前記樹脂には、例えば、アクリレート基およびメタクリレート基の少なくとも一方の基を有する反応性希釈剤を用いることもできる。前記反応性希釈剤は、例えば、特開2008-88309号公報に記載の反応性希釈剤を用いることができ、例えば、単官能アクリレート、単官能メタクリレート、多官能アクリレート、多官能メタクリレート等を含む。前記反応性希釈剤としては、3官能以上のアクリレート、3官能以上のメタクリレートが好ましい。これは、前記アンチグレア層の硬度を、優れたものにできるからである。前記反応性希釈剤としては、例えば、ブタンジオールグリセリンエーテルジアクリレート、イソシアヌル酸のアクリレート、イソシアヌル酸のメタクリレート等もあげられる。これらは、1種類を単独で用いてもよく、2種類以上を併用してもよい。 For the resin, for example, a reactive diluent having at least one of an acrylate group and a methacrylate group can be used. As the reactive diluent, for example, reactive diluents described in JP-A-2008-88309 can be used, and examples include monofunctional acrylates, monofunctional methacrylates, polyfunctional acrylates, polyfunctional methacrylates, and the like. As the reactive diluent, tri- or more functional acrylates and tri- or more functional methacrylates are preferable. This is because the hardness of the antiglare layer can be made excellent. Examples of the reactive diluent include butanediol glycerol ether diacrylate, isocyanuric acid acrylate, and isocyanuric acid methacrylate. These may be used individually by 1 type, and may use 2 or more types together.
 前記樹脂としては、ウレタンアクリレート樹脂を含むことが好ましく、硬化型ウレタンアクリレート樹脂および多官能アクリレート(例えば、ペンタスリトールトリアクリレート)の共重合物であることがより好ましい。 The resin preferably contains a urethane acrylate resin, more preferably a copolymer of a curable urethane acrylate resin and a polyfunctional acrylate (for example, pentathritol triacrylate).
 前記アンチグレア層を形成するための粒子は、形成されるアンチグレア層の表面を凹凸形状にしてアンチグレア性を付与し、また、アンチグレア層のヘイズ値を制御することを主な機能とする。アンチグレア層のヘイズ値は、前記粒子と前記樹脂との屈折率差を制御することで、設計することができる。前記粒子としては、例えば、無機粒子と有機粒子とがある。前記無機粒子は、特に制限されず、例えば、酸化ケイ素粒子、酸化チタン粒子、酸化アルミニウム粒子、酸化亜鉛粒子、酸化錫粒子、酸化ジルコニウム粒子、炭酸カルシウム粒子、硫酸バリウム粒子、タルク粒子、カオリン粒子、硫酸カルシウム粒子等があげられる。また、前記有機粒子は、特に制限されず、例えば、ポリメチルメタクリレート樹脂粉末(PMMA微粒子)、シリコーン樹脂粉末、ポリスチレン樹脂粉末、ポリカーボネート樹脂粉末、アクリルスチレン樹脂粉末、ベンゾグアナミン樹脂粉末、メラミン樹脂粉末、ポリオレフィン樹脂粉末、ポリエステル樹脂粉末、ポリアミド樹脂粉末、ポリイミド樹脂粉末、ポリフッ化エチレン樹脂粉末等があげられる。これらの無機粒子および有機粒子は、一種類を単独で使用してもよいし、二種類以上を併用してもよい。 The main functions of the particles for forming the anti-glare layer are to make the surface of the formed anti-glare layer uneven to impart anti-glare properties, and to control the haze value of the anti-glare layer. The haze value of the antiglare layer can be designed by controlling the refractive index difference between the particles and the resin. Examples of the particles include inorganic particles and organic particles. The inorganic particles are not particularly limited, and examples include 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 examples include 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. Examples thereof include resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyethylene fluoride 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.
 前記粒子の重量平均粒径(D)は、2.5~10μmの範囲内にあることが好ましい。前記粒子の重量平均粒径を、前記範囲とすることで、例えば、よりアンチグレア性に優れ、かつ白ボケが防止できる。前記粒子の重量平均粒径は、より好ましくは、3~7μmの範囲内である。なお、前記粒子の重量平均粒径は、例えば、コールターカウント法により測定できる。例えば、細孔電気抵抗法を利用した粒度分布測定装置(商品名:コールターマルチサイザー、ベックマン・コールター社製)を用い、粒子が前記細孔を通過する際の粒子の体積に相当する電解液の電気抵抗を測定することにより、前記粒子の数と体積を測定し、重量平均粒径を算出する。 The weight average particle size (D) of the particles is preferably within the range of 2.5 to 10 μm. By setting the weight-average particle size of the particles within the above range, for example, the anti-glare property is more excellent and white blurring can be prevented. The weight average particle size of the particles is more preferably in the range of 3-7 μm. 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, Inc.) using the pore electrical resistance method, the volume of the electrolyte solution corresponding to the volume of the particles when the particles pass through the pores. By measuring the electrical resistance, the number and volume of the particles are measured, and the weight average particle diameter is calculated.
 前記粒子の形状は、特に制限されず、例えば、ビーズ状の略球形であってもよく、粉末等の不定形のものであってもよいが、略球形のものが好ましく、より好ましくは、アスペクト比が1.5以下の略球形の粒子であり、最も好ましくは球形の粒子である。 The shape of the particles is not particularly limited, and may be, for example, a substantially spherical bead shape, or an irregular shape such as a powder. They are substantially spherical particles with a ratio of 1.5 or less, most preferably spherical particles.
 前記アンチグレア層における前記粒子の割合は、前記樹脂100重量部に対し、0.2~12重量部の範囲が好ましく、より好ましくは、0.5~12重量部の範囲であり、さらに好ましくは1~7重量部の範囲である。前記範囲とすることで、例えば、よりアンチグレア性に優れ、かつ白ボケが防止できる。 The proportion of the particles in the antiglare 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, still more preferably 1 part by weight, relative to 100 parts by weight of the resin. ~7 parts by weight. By setting it within the above range, for example, it is possible to achieve more excellent anti-glare properties and prevent white blurring.
 前記アンチグレア層は、チキソトロピー付与剤を含んでいてもよい。前記チキソトロピー付与剤を含むことで、前記粒子の凝集状態の制御を容易に行うことができる。前記アンチグレア層を形成するためのチキソトロピー付与剤としては、例えば、有機粘土、酸化ポリオレフィン、変性ウレア等があげられる。 The antiglare layer may contain a thixotropy-imparting agent. By containing the thixotropy-imparting agent, the aggregation state of the particles can be easily controlled. Examples of the thixotropy-imparting agent for forming the antiglare layer include organic clay, polyolefin oxide, and modified urea.
 前記有機粘土は、前記樹脂との親和性を改善するために、有機化処理した粘土であることが好ましい。有機粘土としては、例えば、層状有機粘土をあげることができる。前記有機粘土は、自家調製してもよいし、市販品を用いてもよい。前記市販品としては、例えば、ルーセンタイトSAN、ルーセンタイトSTN、ルーセンタイトSEN、ルーセンタイトSPN、ソマシフME-100、ソマシフMAE、ソマシフMTE、ソマシフMEE、ソマシフMPE(商品名、いずれもコープケミカル(株)製);エスベン、エスベンC、エスベンE、エスベンW、エスベンP、エスベンWX、エスベンN-400、エスベンNX、エスベンNX80、エスベンNO12S、エスベンNEZ、エスベンNO12、エスベンNE、エスベンNZ、エスベンNZ70、オルガナイト、オルガナイトD、オルガナイトT(商品名、いずれも(株)ホージュン製);クニピアF、クニピアG、クニピアG4(商品名、いずれもクニミネ工業(株)製);チクソゲルVZ、クレイトンHT、クレイトン40(商品名、いずれもロックウッド アディティブズ社製)等があげられる。 The organoclay is preferably an organically treated clay in order to improve the affinity with the resin. Examples of organic clays include layered organic clays. The organic clay may be self-prepared, 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 of which are manufactured by Co-op Chemical Co., Ltd.). ) manufactured); Organite, Organite D, Organite T (trade names, all manufactured by Hojun Co., Ltd.); Kunipia F, Kunipia G, Kunipia G4 (trade names, manufactured by Kunimine Industry Co., Ltd.); Thixogel VZ, Kraton HT , Clayton 40 (trade name, both manufactured by Rockwood Additives), and the like.
 前記酸化ポリオレフィンは、自家調製してもよいし、市販品を用いてもよい。前記市販品としては、例えば、ディスパロン4200-20(商品名、楠本化成(株)製)、フローノンSA300(商品名、共栄社化学(株)製)等があげられる。 The oxidized polyolefin may be prepared in-house, or a commercially available product may be used. Examples of the commercially available products include Disparlon 4200-20 (trade name, manufactured by Kusumoto Kasei Co., Ltd.) and Flownon SA300 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).
 前記変性ウレアは、イソシアネート単量体あるいはそのアダクト体と有機アミンとの反応物である。前記変性ウレアは、自家調製してもよいし、市販品を用いてもよい。前記市販品としては、例えば、BYK410(ビッグケミー社製)等があげられる。 The modified urea is a reaction product of an isocyanate monomer or its adduct and an organic amine. The modified urea may be self-prepared, or a commercially available product may be used. Examples of the commercial product include BYK410 (manufactured by Big Chemie).
 前記チキソトロピー付与剤は、一種類を単独で使用してもよいし、二種類以上を併用してもよい。 The thixotropy-imparting agents may be used singly or in combination of two or more.
 前記凸状部の前記アンチグレア層の粗さ平均線からの高さが、アンチグレア層の厚みの0.4倍未満であることが好ましい。より好ましくは、0.01倍以上0.4倍未満の範囲であり、さらに好ましくは、0.01倍以上0.3倍未満の範囲である。この範囲であれば、前記凸状部に外観欠点となる突起物が形成されることを好適に防止できる。前記アンチグレア層は、このような高さの凸状部を有することで、外観欠点を生じにくくすることができる。ここで、前記平均線からの高さは、例えば、特開2017-138620号公報に記載の方法により測定することができる。 The height of the convex portion from the roughness average line of the antiglare layer is preferably less than 0.4 times the thickness of the antiglare 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 projections that impair the appearance of the convex portion. Since the antiglare layer has convex portions with such heights, it is possible to make appearance defects less likely to occur. Here, the height from the average line can be measured, for example, by the method described in JP-A-2017-138620.
 前記アンチグレア層における前記チキソトロピー付与剤の割合は、前記樹脂100重量部に対し、0.1~5重量部の範囲が好ましく、より好ましくは、0.2~4重量部の範囲である。 The proportion of the thixotropy imparting agent in the antiglare 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, with respect to 100 parts by weight of the resin.
 前記アンチグレア層の厚み(d)は、特に制限されないが、3~12μmの範囲内にあることが好ましい。アンチグレア層の厚み(d)を、前記範囲とすることで、例えば、本発明の光学用粘着シートのカールの発生を防ぐことができ、搬送性不良等の生産性の低下の問題を回避できる。また、前記厚み(d)が前記範囲にある場合、前記粒子の重量平均粒径(D)は、前述のように、2.5~10μmの範囲内にあることが好ましい。前記アンチグレア層の厚み(d)と、前記粒子の重量平均粒径(D)とが、前述の組み合わせであることで、さらにアンチグレア性に優れるものとすることができる。前記アンチグレア層の厚み(d)は、より好ましくは、3~8μmの範囲内である。 Although the thickness (d) of the antiglare layer is not particularly limited, it is preferably in the range of 3 to 12 μm. By setting the thickness (d) of the antiglare layer within the above range, for example, the optical pressure-sensitive adhesive sheet of the present invention can be prevented from curling, and the problem of reduced productivity such as poor transportability can be avoided. Further, when the thickness (d) is within the above range, the weight average particle size (D) of the particles is preferably within the range of 2.5 to 10 μm as described above. When the thickness (d) of the anti-glare layer and the weight average particle size (D) of the particles are in the above-described combination, the anti-glare property can be further improved. The thickness (d) of the antiglare layer is more preferably in the range of 3-8 μm.
 前記アンチグレア層の厚み(d)と前記粒子の重量平均粒径(D)との関係は、0.3≦D/d≦0.9の範囲内にあることが好ましい。このような関係にあることにより、よりアンチグレア性に優れ、かつ白ボケが防止でき、さらに、外観欠点のないアンチグレア層とすることができる。 The relationship between the thickness (d) of the antiglare layer and the weight average particle diameter (D) of the particles is preferably within the range of 0.3≦D/d≦0.9. By having such a relationship, it is possible to obtain an anti-glare layer that is more excellent in anti-glare properties, can prevent white blurring, and has no defects in appearance.
 本発明の光学用粘着シートでは、前述のように、前記アンチグレア層は、前記粒子および前記チキソトロピー付与剤が凝集することによって、前記アンチグレア層の表面に凸状部を形成する。前記凸状部を形成する凝集部においては、前記粒子が、前記アンチグレア層の面方向に、複数集まった状態で存在する。これにより、前記凸状部が、なだらかな形状となっている。前記アンチグレア層は、このような形状の凸状部を有することで、アンチグレア性を維持しつつ、かつ、白ボケを防止することができ、さらに、外観欠点を生じにくくすることができる。 In the optical pressure-sensitive adhesive sheet of the present invention, as described above, the anti-glare layer forms convex portions on the surface of the anti-glare layer due to aggregation of the particles and the thixotropy-imparting agent. In the aggregated portion forming the convex portion, the particles are present in a state in which a plurality of the particles are aggregated in the surface direction of the antiglare layer. As a result, the convex portion has a gentle shape. Since the anti-glare layer has convex portions having such a shape, it is possible to maintain the anti-glare property, prevent white blurring, and make appearance defects less likely to occur.
 前記アンチグレア層の表面形状は、アンチグレア層形成材料に含まれる粒子の凝集状態を制御することで、任意に設計することができる。前記粒子の凝集状態は、例えば、前記粒子の材質(例えば、粒子表面の化学的修飾状態、溶媒や樹脂に対する親和性等)、樹脂(バインダー)または溶媒の種類、組合せ等により制御できる。ここで、前記アンチグレア層形成材料に含まれるチキソトロピー付与剤により、前記粒子の凝集状態をコントロールすることができる。この結果、前記粒子の凝集状態を前述のようにすることができ、前記凸状部を、なだらかな形状とすることができる。 The surface shape of the antiglare layer can be arbitrarily designed by controlling the aggregation state of the particles contained in the antiglare layer forming material. The aggregation state of the particles can be controlled by, for example, the material of the particles (for example, chemically modified state of the particle surface, affinity for solvent or resin, etc.), type of resin (binder) or solvent, combination, and the like. Here, the aggregation state of the particles can be controlled by the thixotropy imparting agent contained in the antiglare layer-forming material. As a result, the aggregated state of the particles can be made as described above, and the convex portion can be formed into a smooth shape.
 本発明の光学用粘着シートにおいて、本発明の基材が樹脂等から形成されている場合、本発明の基材と前記アンチグレア層との界面において、浸透層を有していることが好ましい。前記浸透層は、前記アンチグレア層の形成材料に含まれる樹脂成分が、本発明の基材に浸透して形成される。浸透層が形成されると、本発明の基材と前記アンチグレア層との密着性を向上させることができ、好ましい。前記浸透層は、厚みが0.2~3μmの範囲であることが好ましく、より好ましくは0.5~2μmの範囲である。例えば、本発明の基材がポリエステル系樹脂であり、前記アンチグレア層に含まれる樹脂がアクリル樹脂である場合には、前記浸透層を形成させることができる。前記浸透層は、例えば、本発明の光学用粘着シートの断面を、透過型電子顕微鏡(TEM)で観察することで、確認することができ、厚みを測定することができる。 In the optical pressure-sensitive adhesive sheet of the present invention, when the substrate of the present invention is made of a resin or the like, it preferably has a permeation layer at the interface between the substrate of the present invention and the antiglare layer. The permeation layer is formed by permeating the resin component contained in the material for forming the antiglare layer into the substrate of the present invention. The formation of the permeation layer is preferable because the adhesion between the substrate of the present invention and the antiglare layer can be improved. The penetration layer preferably has a thickness in the range of 0.2 to 3 μm, more preferably in the range of 0.5 to 2 μm. For example, when the base material of the present invention is a polyester-based resin and the resin contained in the antiglare layer is an acrylic resin, the permeation layer can be formed. The penetration layer can be confirmed and the thickness can be measured, for example, by observing the cross section of the optical pressure-sensitive adhesive sheet of the present invention with a transmission electron microscope (TEM).
 このような浸透層を有する本発明の光学用粘着シートに適用した場合であっても、アンチグレア性と、白ボケの防止とを両立した所望するなだらかな表面凹凸形状を容易に形成することができる。前記浸透層は、前記アンチグレア層との密着性が乏しい基材であるほど、密着性の向上のため、厚く形成することが好ましい。 Even when applied to the optical pressure-sensitive adhesive sheet of the present invention having such a permeation layer, it is possible to easily form a desired smooth uneven surface shape that achieves both anti-glare properties and prevention of white blurring. . It is preferable that the permeation layer is formed thicker in order to improve the adhesion of the base material with poor adhesion to the anti-glare layer.
 前記アンチグレア層において、最大径が200μm以上の外観欠点がアンチグレア層の1m2あたり1個以下であることが好ましい。より好ましくは、前記外観欠点が無いことである。 In the antiglare layer, it is preferable that the number of appearance defects having a maximum diameter of 200 μm or more is 1 or less per 1 m 2 of the antiglare layer. More preferably, it does not have the appearance defect.
 前記アンチグレア層表面の凹凸形状において、平均傾斜角θa(°)が.1~5.0の範囲であることが好ましく、0.3~4.5の範囲であることがより好ましく、1.0~4.0の範囲であることがさらに好ましく、1.6~4.0であることが特に好ましい。ここで、前記平均傾斜角θaは、下記数式(1)で定義される値である。前記平均傾斜角θaは、例えば、特開2017-138620に記載の方法により測定される値である。
  平均傾斜角θa=tan-1Δa      (1)
In the uneven shape of the surface of the antiglare layer, the average inclination angle θa (°) is . It is preferably in the range of 1 to 5.0, more preferably in the range of 0.3 to 4.5, even more preferably in the range of 1.0 to 4.0, and 1.6 to 4.0. .0 is particularly preferred. Here, the average tilt angle θa is a value defined by the following formula (1). The average tilt angle θa is, for example, a value measured by the method described in JP-A-2017-138620.
Average tilt angle θa=tan-1Δa (1)
 前記数式(1)において、Δaは、下記数式(2)に示すように、JIS B 0601(1994年度版)に規定される粗さ曲線の基準長さLにおいて、隣り合う山の頂点と谷の最下点との差(高さh)の合計(h1+h2+h3・・・+hn)を前記基準長さLで割った値である。前記粗さ曲線は、断面曲線から、所定の波長より長い表面うねり成分を位相差補償形高域フィルタで除去した曲線である。また、前記断面曲線とは、対象面に直角な平面で対象面を切断したときに、その切り口に現れる輪郭である。
  Δa=(h1+h2+h3・・・+hn)/L      (2)
In the above formula (1), Δa is, as shown in the following formula (2), in the reference length L of the roughness curve defined in JIS B 0601 (1994 edition), the distance between the top and the valley of the adjacent peaks It is a value obtained by dividing the sum (h1+h2+h3 . The roughness curve is a curve obtained by removing surface waviness components longer than a predetermined wavelength from the cross-sectional curve with a phase difference compensation type high-pass filter. Further, the cross-sectional curve is a contour that appears at the cut end when the target plane is cut along a plane perpendicular to the target plane.
Δa=(h1+h2+h3...+hn)/L (2)
 θaが、上記範囲にあると、よりアンチグレア性に優れ、かつ白ボケが防止できる。 When θa is within the above range, the anti-glare property is more excellent and white blurring can be prevented.
 前記アンチグレア層を形成するにあたり、調製したアンチグレア層形成材料(塗工液)がチキソ性を示していることが好ましく、下記で規定されるTi値が、1.3~3.5の範囲にあることが好ましく、より好ましくは1.3~2.8の範囲である。
 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。
In forming the antiglare layer, the prepared antiglare layer forming material (coating solution) preferably exhibits thixotropy, and the Ti value defined below is in the range of 1.3 to 3.5. is preferred, and more preferably in the range of 1.3 to 2.8.
Ti value = β1/β2
Here, β1 is the viscosity measured at a shear rate of 20 (1/s) using HAAKE's Rheostress 6000, and β2 is the viscosity measured using HAAKE's Rheostress 6000 at a shear rate of 200 (1/s). Viscosity measured under conditions.
 Ti値が、1.3未満であると、外観欠点が生じやすくなり、アンチグレア性、白ボケについての特性が悪化する。また、Ti値が、3.5を超えると、前記粒子が凝集しにくく分散状態となりやすくなる。 If the Ti value is less than 1.3, defects in appearance are likely to occur, and anti-glare properties and white blur characteristics deteriorate. On the other hand, when the Ti value exceeds 3.5, the particles are less likely to agglomerate and more likely to be in a dispersed state.
 前記アンチグレア層の製造方法は、特に制限されず、いかなる方法で製造されてもよいが、例えば、前記樹脂、前記粒子、前記チキソトロピー付与剤および溶媒を含むアンチグレア層形成材料(塗工液)を準備し、前記アンチグレア層形成材料(塗工液)を本発明の基材の第2面に塗工して塗膜を形成し、前記塗膜を硬化させてアンチグレア層を形成することにより、製造できる。金型による転写方式や、サンドブラスト、エンボスロールなどの適宜な方式で凹凸形状を付与する方法などを、併せて用いることもできる。 The method for producing the anti-glare layer is not particularly limited, and it may be produced by any method. Then, the anti-glare layer-forming material (coating liquid) is applied to the second surface of the substrate of the present invention to form a coating film, and the coating film is cured to form an anti-glare layer. . A transfer method using a mold, a method of imparting an uneven shape by an appropriate method such as sandblasting, embossing roll, or the like can also be used together.
 前記溶媒は、特に制限されず、種々の溶媒を使用可能であり、一種類を単独で使用してもよいし、二種類以上を併用してもよい。前記樹脂の組成、前記粒子および前記チキソトロピー付与剤の種類、含有量等に応じて最適な溶媒種類や溶媒比率が存在する。溶媒としては、特に限定されないが、例えば、メタノール、エタノール、イソプロピルアルコール、ブタノール、2-メトキシエタノール等のアルコール類;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン等のケトン類;酢酸メチル、酢酸エチル、酢酸ブチル等のエステル類;ジイソプロピルエーテル、プロピレングリコールモノメチルエーテル等のエーテル類;エチレングリコール、プロピレングリコール等のグリコール類;エチルセロソルブ、ブチルセロソルブ等のセロソルブ類;ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類;ベンゼン、トルエン、キシレン等の芳香族炭化水素類等があげられる。 The solvent is not particularly limited, and various solvents can be used. One type may be used alone, or two or more types may be used in combination. There is an optimum solvent type and solvent ratio depending on the composition of the resin, the types and contents of the particles and the thixotropy-imparting agent, and the like. Examples of solvents 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, and xylene.
 本発明の基材として、例えば、ポリエステル系樹脂を採用して浸透層を形成する場合は、ポリエステル系樹脂に対する良溶媒が好適に使用できる。その溶媒としては、例えば、酢酸エチル、メチルエチルケトン、シクロペンタノンなどをあげることができる。 For example, when a polyester-based resin is used as the base material of the present invention to form the permeation layer, a good solvent for the polyester-based resin can be suitably used. Examples of the solvent include ethyl acetate, methyl ethyl ketone, cyclopentanone and the like.
 前記溶媒を適宜選択することによって、チキソトロピー付与剤によるアンチグレア層形成材料(塗工液)へのチキソ性を良好に発現させることができる。例えば、有機粘土を用いる場合には、トルエンおよびキシレンを好適に、単独使用または併用することができ、例えば、酸化ポリオレフィンを用いる場合には、メチルエチルケトン、酢酸エチル、プロピレングリコールモノメチルエーテルを好適に、単独使用または併用することができ、例えば、変性ウレアを用いる場合には、酢酸ブチルおよびメチルイソブチルケトンを好適に、単独使用または併用することができる。 By appropriately selecting the solvent, the thixotropy of the antiglare layer-forming material (coating liquid) by the thixotropy-imparting agent can be satisfactorily expressed. For example, when organoclays are used, toluene and xylene can be suitably used alone or in combination. They can be used or used in combination. For example, when modified urea is used, butyl acetate and methyl isobutyl ketone can be preferably used alone or in combination.
 前記アンチグレア層形成材料には、各種レベリング剤を添加することができる。前記レベリング剤としては、塗工ムラ防止(塗工面の均一化)を目的に、例えば、フッ素系またはシリコーン系のレベリング剤を用いることができる。前記アンチグレア層の表面に防汚性が求められる場合、または、反射防止層(低屈折率層)や層間充填剤を含む層がアンチグレア層上に形成される場合などに応じて、適宜レベリング剤を選定することができる。例えば、前記チキソトロピー付与剤を含ませることで塗工液にチキソ性を発現させることができるため、塗工ムラが発生しにくい。このため、例えば、前記レベリング剤の選択肢を広げられるという優位点を有している。 Various leveling agents can be added to the antiglare layer-forming material. As the leveling agent, for example, a fluorine-based or silicone-based leveling agent can be used for the purpose of preventing coating unevenness (uniformizing the coated surface). If antifouling properties are required on the surface of the antiglare layer, or if an antireflection layer (low refractive index layer) or a layer containing an interlayer filler is formed on the antiglare layer, a leveling agent is added as appropriate. can be selected. For example, the inclusion of the thixotropy-imparting agent makes it possible to express thixotropic properties in the coating liquid, so that unevenness in coating is less likely to occur. Therefore, for example, it has an advantage that the options for the leveling agent can be expanded.
 前記レベリング剤の配合量は、前記樹脂100重量部に対して、例えば、5重量部以下、好ましくは0.01~5重量部の範囲である。 The amount of the leveling agent compounded is, for example, 5 parts by weight or less, preferably in the range of 0.01 to 5 parts by weight, per 100 parts by weight of the resin.
 前記アンチグレア層形成材料には、必要に応じて、性能を損なわない範囲で、顔料、充填剤、分散剤、可塑剤、紫外線吸収剤、界面活性剤、防汚剤、酸化防止剤等が添加されてもよい。これらの添加剤は一種類を単独で使用してもよく、また二種類以上併用してもよい。 Pigments, fillers, dispersants, plasticizers, UV absorbers, surfactants, antifouling agents, antioxidants and the like are added to the antiglare layer-forming material as necessary within a range that does not impair the performance. may These additives may be used singly or in combination of two or more.
 前記アンチグレア層形成材料には、例えば、特開2008-88309号公報に記載されるような、従来公知の光重合開始剤を用いることができる。 For the anti-glare layer-forming material, conventionally known photopolymerization initiators, such as those described in JP-A-2008-88309, can be used.
 前記アンチグレア層形成材料を本発明の基材の第2面上に塗工する方法としては、例えば、ファンテンコート法、ダイコート法、スピンコート法、スプレーコート法、グラビアコート法、ロールコート法、バーコート法等の塗工法を用いることができる。 Examples of the method for applying the anti-glare layer-forming material onto the second surface of the substrate of the present invention include a fountain coating method, a die coating method, a spin coating method, a spray coating method, a gravure coating method, a roll coating method, A coating method such as a bar coating method can be used.
 前記アンチグレア層形成材料を塗工して本発明の基材の上に塗膜を形成し、前記塗膜を硬化させる。前記硬化に先立ち、前記塗膜を乾燥させることが好ましい。前記乾燥は、例えば、自然乾燥でもよいし、風を吹きつけての風乾であってもよいし、加熱乾燥であってもよいし、これらを組み合わせた方法であってもよい。 The anti-glare layer-forming material is applied to form a coating film on the substrate 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 air, heat drying, or a combination thereof.
 前記アンチグレア層形成材料の塗膜の硬化手段は、特に制限されないが、紫外線硬化が好ましい。エネルギー線源の照射量は、紫外線波長365nmでの積算露光量として、50~500mJ/cm2が好ましい。照射量が、50mJ/cm2以上であれば、硬化がより十分となり、形成されるアンチグレア層の硬度もより十分なものとなる。また、500mJ/cm2以下であれば、形成されるアンチグレア層の着色を防止することができる。 The means for curing the coating film of the anti-glare layer-forming material is not particularly limited, but ultraviolet curing is preferable. The irradiation amount of the energy beam source is preferably 50 to 500 mJ/cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation dose is 50 mJ/cm 2 or more, the curing becomes more sufficient, and the hardness of the formed anti-glare layer becomes more sufficient. Also, if it is 500 mJ/cm 2 or less, coloring of the formed antiglare layer can be prevented.
 以上のようにして、本発明の基材の第2面に、前記アンチグレア層を形成することができる。なお、前述の方法以外の製造方法でアンチグレア層を形成してもよい。前記アンチグレア層の硬度は、鉛筆硬度において、層の厚みにも影響されるが、2H以上の硬度を有することが好ましい。 As described above, the antiglare layer can be formed on the second surface of the substrate of the present invention. The anti-glare layer may be formed by a manufacturing method other than the method described above. The hardness of the anti-glare layer is preferably 2H or more in terms of pencil hardness, although it is also affected by the thickness of the layer.
 前記アンチグレア層は、二層以上が積層された複数層構造であってもよい。 The antiglare layer may have a multi-layer structure in which two or more layers are laminated.
 前記アンチグレア層の上に、上述のAR層(低屈折率層)を配置してもよい。例えば、画像表示装置に光学用粘着シートを装着した場合、画像の視認性を低下させる要因のひとつに空気とアンチグレア層界面での光の反射があげられる。AR層は、その表面反射を低減させるものである。なお、前記アンチグレア層および反射防止層は、それぞれ、二層以上が積層された複数層構造であってもよい。 The above-described AR layer (low refractive index layer) may be arranged on the antiglare layer. For example, when an optical pressure-sensitive adhesive sheet is attached to an image display device, one factor that reduces the visibility of the image is the reflection of light at the interface between the air and the anti-glare layer. The AR layer reduces the surface reflection. The antiglare layer and the antireflection layer may each have a multi-layer structure in which two or more layers are laminated.
 また、汚染物の付着防止および付着した汚染物の除去容易性の向上のために、フッ素基含有のシラン系化合物若しくはフッ素基含有の有機化合物等から形成される汚染防止層を前記反射防止層及び/又はアンチグレア層上に積層することが好ましい。 In addition, in order to prevent the adhesion of contaminants and improve the ease of removal of adhered contaminants, an anti-contamination layer formed of a fluorine group-containing silane compound, a fluorine group-containing organic compound, or the like is used as the antireflection layer and the anti-reflection layer. / Or lamination on the anti-glare layer is preferred.
 本発明の基材および前記アンチグレア層の少なくとも一方に対し表面処理を行うことが好ましい。本発明の基材の表面を表面処理すれば、前記アンチグレア層との密着性がさらに向上する。また、前記アンチグレア層の表面を表面処理すれば、前記AR層との密着性がさらに向上する。 It is preferable to subject at least one of the substrate of the present invention and the antiglare layer to surface treatment. By surface-treating the surface of the base material of the present invention, the adhesion to the anti-glare layer is further improved. Moreover, if the surface of the anti-glare layer is treated, the adhesion to the AR layer is further improved.
 本発明の基材のカール発生を防止するために、前記アンチグレア層の他方の面に対し溶剤処理を行ってもよい。また、カール発生を防止するために、前記アンチグレア層の他方の面に透明樹脂層を形成してもよい。 In order to prevent the base material of the present invention from curling, the other surface of the antiglare layer may be subjected to solvent treatment. Further, a transparent resin layer may be formed on the other surface of the antiglare layer in order to prevent curling.
 本発明の基材の第2面は帯電防止処理が施されていてもよい。本発明の基材の第2面に帯電処理が施されているという構成は、本発明の第1及び第2の側面の光学用粘着シートに静電気が帯電するのを抑制し、光学用粘着シートを画像表示装置に用いた場合に、静電気に起因する表示不良を抑制できる点で好ましい。 The second surface of the base material of the present invention may be subjected to antistatic treatment. The configuration in which the second surface of the base material of the present invention is subjected to electrification treatment suppresses static electricity charging of the optical pressure-sensitive adhesive sheets of the first and second aspects of the present invention. is used in an image display device, it is preferable in that display defects caused by static electricity can be suppressed.
 前記ハードコート(HC)処理としては、公知のHC処理を特に制限なく適用することができ、例えば、本発明の基材の第2面上にハードコート層を形成することにより実施することができる。前記ハードコート層としては、公知のものを制限なく採用することができ、例えば、上記のアンチグレア層形成材料において、粒子およびチキソトロピー付与剤を含まず、樹脂のみを含むハードコート層形成材料を用いること以外は、上記のアンチグレア層と同様にして、防眩性を有しないハードコート層を形成することができる。 As the hard coat (HC) treatment, a known HC treatment can be applied without particular limitation, and can be carried out, for example, by forming a hard coat layer on the second surface of the substrate of the present invention. . As the hard coat layer, known ones can be employed without limitation. For example, in the above anti-glare layer-forming material, a hard coat layer-forming material containing only a resin without particles and a thixotropy-imparting agent may be used. Except for this, a hard coat layer having no antiglare properties can be formed in the same manner as the above antiglare layer.
 前記帯電防止処理としては、公知の帯電防止処理を特に限定なく使用することができ、例えば、本発明の基材の第2面上に帯電防止層を形成することにより実施することができる。 As the antistatic treatment, a known antistatic treatment can be used without particular limitation, and can be carried out, for example, by forming an antistatic layer on the second surface of the substrate of the present invention.
 帯電防止層としては、帯電防止効果を奏することができる層であれば、本発明の効果を損なわない範囲で、任意の適切な帯電防止層を採用し得る。このような帯電防止層としては、好ましくは、導電性ポリマーを含む導電コート液を任意の適切な基材層上にコーティングして形成される帯電防止層である。具体的には、例えば、導電性ポリマーを含む導電コート液を基材上にコーティングして形成される帯電防止層である。具体的なコーティングの方法としては、ロールコート法、バーコート法、グラビアコート法などが挙げられる。 As the antistatic layer, any appropriate antistatic layer can be adopted as long as it is a layer capable of exhibiting an antistatic effect, as long as it does not impair the effects of the present invention. Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any suitable substrate layer. Specifically, for example, it is an antistatic layer formed by coating a substrate with a conductive coating liquid containing a conductive polymer. Specific coating methods include a roll coating method, a bar coating method, a gravure coating method, and the like.
 導電性ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切な導電性ポリマーを採用し得る。このような導電性ポリマーとしては、例えば、π共役系導電性ポリマーにポリアニオンがドープされた導電性ポリマーなどが挙げられる。π共役系導電性ポリマーとしては、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレンなどの鎖状導電性ポリマーが挙げられる。ポリアニオンとしては、ポリスチレンスルホン酸、ポリイソプレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリアクリル酸エチルスルホン酸、ポリメタクリルカルボン酸などが挙げられる。 Any suitable conductive polymer can be adopted as the conductive polymer as long as it does not impair the effects of the present invention. Examples of such a conductive polymer include a conductive polymer obtained by doping a π-conjugated conductive polymer with a polyanion. Examples of π-conjugated conductive polymers include linear conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Polyanions include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyethyl acrylate sulfonic acid, polymethacrylic carboxylic acid, and the like.
 帯電防止層の表面抵抗率は、温度23℃、湿度50%RHにおいて、好ましくは1.0×104Ω/□~1.0×109Ω/□であり、より好ましくは1.0×104Ω/□~5.0×108Ω/□であり、さらに好ましくは5.0×104Ω/□~1.0×108Ω/□であり、特に好ましくは1.0×105Ω/□~5.0×107Ω/□である。帯電防止層の表面抵抗率が上記範囲内にあれば、本発明の効果がより発現されやすくなる。 The surface resistivity of the antistatic layer is preferably 1.0×10 4 Ω/square to 1.0×10 9 Ω/square at a temperature of 23° C. and a humidity of 50% RH, more preferably 1.0× 10 4 Ω/□ to 5.0×10 8 Ω/□, more preferably 5.0×10 4 Ω/□ to 1.0×10 8 Ω/□, and particularly preferably 1.0×10 Ω/□. 10 5 Ω/□ to 5.0×10 7 Ω/□. If the surface resistivity of the antistatic layer is within the above range, the effects of the present invention are more likely to be exhibited.
 帯電防止層の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは1nm~1000nmであり、より好ましくは5nm~900nmであり、さらに好ましくは7.5nm~800nmであり、特に好ましくは10nm~700nmである。帯電防止層は、1層のみであってもよいし、2層以上であってもよい。 As the thickness of the antistatic layer, any appropriate thickness can be adopted according to the purpose as long as the effects of the present invention are not impaired. Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, even more preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm. The antistatic layer may consist of only one layer, or may consist of two or more layers.
 上記帯電防止層は、単独で本発明の基材の第2面に設けられていてもよく、帯電防止層の上に、さらにアンチグレア層及び/又はAR層を設けてもよい。或いは、トップコート層として、アンチグレア層及び/又はAR層の上に、帯電防止層を設けてもよい。 The antistatic layer may be provided alone on the second surface of the substrate of the present invention, or an antiglare layer and/or an AR layer may be provided on the antistatic layer. Alternatively, as a topcoat layer, an antistatic layer may be provided on the antiglare layer and/or the AR layer.
[2.粘着剤組成物及び粘着剤層]
 本発明の粘着剤層は、本発明の粘着剤組成物により形成される粘着剤層である。
 本発明の粘着剤組成物は、帯電防止剤と、アクリル系ポリマー(A)、アクリル系ポリマー(A)を構成するモノマー成分の混合物又はアクリル系ポリマー(A)を構成するモノマー成分の混合物の部分重合物とを含有し、前記帯電防止剤が、前記アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物である粘着剤組成物である。
[2. Adhesive composition and adhesive layer]
The pressure-sensitive adhesive layer of the present invention is a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
The pressure-sensitive adhesive composition of the present invention includes an antistatic agent, an acrylic polymer (A), a mixture of monomer components constituting the acrylic polymer (A), or a mixture of monomer components constituting the acrylic polymer (A). and the antistatic agent is an ionic compound having in its molecule a functional group capable of forming a covalent bond with the acrylic polymer (A).
 本発明の粘着剤組成物は、いずれの形態を有していてもよく、例えば、エマルジョン型、熱溶融型(ホットメルト型)、無溶剤型(活性エネルギー線硬化型、例えば、モノマー混合物、又はモノマー混合物とその部分重合物など)等が挙げられる。特に、本発明の粘着剤組成物は、溶剤型ではないことが好ましい。溶剤型の粘着剤組成物により粘着剤層を得ようとする場合、ゆず肌等の外観の不具合が発生しやすいためである。なお、「ゆず肌」とは、柑橘類の一種である「ゆず」の皮のような凹凸が生じる現象をいう。また、本発明の粘着剤組成物は、外観性の優れた粘着剤層を得る点からは、活性エネルギー線硬化型であることが好ましい。本明細書において、粘着剤組成物は、粘着剤層を形成するために用いる組成物を意味し、粘着剤を形成するために用いる組成物の意味を含むものとする。 The pressure-sensitive adhesive composition of the present invention may have any form, for example, emulsion type, hot melt type (hot melt type), non-solvent type (active energy ray curable type, e.g., monomer mixture, or monomer mixtures and partially polymerized products thereof) and the like. In particular, the pressure-sensitive adhesive composition of the present invention is preferably non-solvent type. This is because when a pressure-sensitive adhesive layer is to be obtained using a solvent-based pressure-sensitive adhesive composition, defects in appearance such as citrus peel are likely to occur. In addition, "yuzu skin" refers to a phenomenon in which unevenness occurs like the skin of "yuzu", which is a kind of citrus fruit. Moreover, the pressure-sensitive adhesive composition of the present invention is preferably active energy ray-curable from the viewpoint of obtaining a pressure-sensitive adhesive layer with excellent appearance. In this specification, the pressure-sensitive adhesive composition means a composition used for forming the pressure-sensitive adhesive layer, and includes the meaning of the composition used for forming the pressure-sensitive adhesive.
 上記有機溶剤としては、溶媒として用いられる有機化合物である限り特に限定されないが、例えば、シクロヘキサン、ヘキサン、ヘプタン等の炭化水素系溶剤;トルエン、キシレン等の芳香族系溶剤;酢酸エチル、酢酸メチル等のエステル系溶剤;アセトン、メチルエチルケトン等のケトン系溶剤;メタノール、エタノール、ブタノール、イソプロピルアルコール等のアルコール系溶剤等が挙げられる。なお、上記有機溶剤は、2種以上の有機溶剤を含む混合溶剤であってもよい。 The organic solvent is not particularly limited as long as it is an organic compound used as a solvent. Examples include hydrocarbon solvents such as cyclohexane, hexane, and heptane; aromatic solvents such as toluene and xylene; ethyl acetate, methyl acetate, and the like. ketone solvents such as acetone and methyl ethyl ketone; and alcohol solvents such as methanol, ethanol, butanol and isopropyl alcohol. In addition, the mixed solvent containing 2 or more types of organic solvents may be sufficient as the said organic solvent.
 本発明の粘着剤組成物において、有機溶剤を「実質的に含有しない」とは、有機溶剤が不可避的に混入する場合を除いて、有機溶剤を能動的に配合はしないことをいう。具体的には、粘着剤組成物中の有機溶剤の含有量が粘着剤組成物の全量(全重量、100重量%)に対して1.0重量%以下(好ましくは0.5重量%以下、さらに好ましくは0.2重量%以下)であるものは、実質的に含有しないということができる。 In the pressure-sensitive adhesive composition of the present invention, "substantially contains no organic solvent" means that the organic solvent is not actively blended, except when the organic solvent is unavoidably mixed. Specifically, the content of the organic solvent in the adhesive composition is 1.0% by weight or less (preferably 0.5% by weight or less, more preferably 0.2% by weight or less) can be said to be substantially free.
 本発明の粘着剤組成物が含有するベースポリマーは、アクリル系ポリマー(A)である。すなわち、本発明の粘着剤組成物は、アクリル系ポリマーをベースポリマーとして含有するアクリル系粘着剤組成物である。アクリル系ポリマーは、透明性、耐候性、接着信頼性、及びモノマーの種類が豊富なことから粘着剤層の機能設計が行いやすい等の点より、好ましい。つまり、本発明の粘着剤組成物は、後述のアクリル系ポリマー(A)をベースポリマーとして含有するアクリル系粘着剤組成物であることが好ましい。なお、アクリル系ポリマー(A)は、単独で又は2種以上組み合わせて用いることができる。 The base polymer contained in the adhesive composition of the present invention is acrylic polymer (A). That is, the pressure-sensitive adhesive composition of the present invention is an acrylic pressure-sensitive adhesive composition containing an acrylic polymer as a base polymer. Acrylic polymers are preferred because of their transparency, weather resistance, adhesion reliability, and ease of functional design of the pressure-sensitive adhesive layer due to the wide variety of monomers available. In other words, the pressure-sensitive adhesive composition of the present invention is preferably an acrylic pressure-sensitive adhesive composition containing the below-described acrylic polymer (A) as a base polymer. In addition, acrylic polymer (A) can be used individually or in combination of 2 or more types.
 本発明の粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)における上記アクリル系ポリマー(A)の含有量は、特に限定されないが、75重量%以上(例えば75~99.9重量%)であることが好ましく、より好ましくは85重量%以上(例えば85~99.9重量%)である。 The content of the acrylic polymer (A) in the pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is not particularly limited, but may be 75% by weight or more (for example, 75 to 99.9%). 9% by weight), more preferably 85% by weight or more (for example, 85 to 99.9% by weight).
 本発明の粘着剤組成物は、酸性基含有モノマー(例えば、カルボキシル基含有モノマー、スルホ基含有モノマー、リン酸基含有モノマーなど)を、含有しない又は実質的に含有しないことが好ましい。この構成は、優れた金属配線の腐食防止効果を得ることができる点で、好ましい。なお、酸性基含有モノマーの含有量は、本発明の粘着剤組成物全量に対して、0.05重量%以下(例えば、0~0.05重量%)が好ましく、より好ましくは0.01重量%以下(例えば、0~0.01重量%)、さらに好ましくは0.001重量%以下(例えば、0~0.001重量%)であるものは、実質的に含有しないということができる。 The adhesive composition of the present invention preferably does not contain or substantially does not contain acidic group-containing monomers (eg, carboxyl group-containing monomers, sulfo group-containing monomers, phosphoric acid group-containing monomers, etc.). This configuration is preferable in that an excellent effect of preventing corrosion of metal wiring can be obtained. The content of the acidic group-containing monomer is preferably 0.05% by weight or less (for example, 0 to 0.05% by weight), more preferably 0.01% by weight, based on the total amount of the adhesive composition of the present invention. % or less (eg, 0 to 0.01% by weight), more preferably 0.001% by weight or less (eg, 0 to 0.001% by weight), it can be said to be substantially free.
 本発明の粘着剤組成物は、ベースポリマーとして含有するアクリル系ポリマーを構成するモノマー成分として、カルボキシル基含有モノマーなどの酸性基含有モノマーを、含有しない又は実質的に含有しないことが好ましい。本発明の粘着剤組成物は、アクリル系ポリマー(A)を構成するモノマー成分としてカルボキシル基含有モノマーを含有しない又は実質的に含有しないことがより好ましい。このため、本発明の粘着剤組成物は、優れた腐食防止効果を得ることができる。カルボキシル基含有モノマーの意味、「実質的に含有しない」の意味、カルボキシル基以外の酸性基を有するモノマー等については、アクリル系ポリマー(A)を構成するモノマー成分である場合と同様であるものとする。また、カルボキシル基含有モノマーの含有量は、本発明の粘着剤組成物全量に対して、0.05重量%以下(例えば、0~0.05重量%)が好ましく、より好ましくは0.01重量%以下(例えば、0~0.01重量%)、さらに好ましくは0.001重量%以下(例えば、0~0.001重量%)であるものは、実質的に含有しないということができる。 The pressure-sensitive adhesive composition of the present invention preferably does not contain, or substantially does not contain, an acidic group-containing monomer such as a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer contained as the base polymer. More preferably, the pressure-sensitive adhesive composition of the present invention does not contain or substantially does not contain a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer (A). Therefore, the pressure-sensitive adhesive composition of the present invention can obtain an excellent anti-corrosion effect. The meaning of the carboxyl group-containing monomer, the meaning of "not containing substantially", the monomer having an acidic group other than the carboxyl group, etc. are the same as in the case of the monomer component constituting the acrylic polymer (A). do. In addition, the content of the carboxyl group-containing monomer is preferably 0.05% by weight or less (for example, 0 to 0.05% by weight), more preferably 0.01% by weight, based on the total amount of the pressure-sensitive adhesive composition of the present invention. % or less (eg, 0 to 0.01% by weight), more preferably 0.001% by weight or less (eg, 0 to 0.001% by weight), it can be said to be substantially free.
 本発明の粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)は、優れた帯電防止性能を有している。このため、本発明の粘着剤層を介して画像表示装置と光学部材を貼り合わせる際に、静電気による表示不良を抑制することができる。このように、本発明の粘着剤層は、画像表示装置の製造に好適に用いられる。 The adhesive layer of the present invention (the adhesive layer formed from the adhesive composition of the present invention) has excellent antistatic performance. Therefore, display defects due to static electricity can be suppressed when an image display device and an optical member are attached to each other via the pressure-sensitive adhesive layer of the present invention. Thus, the pressure-sensitive adhesive layer of the present invention is suitably used for manufacturing image display devices.
(表面抵抗率)
 本発明の粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)の表面抵抗率(JIS K 6271に準じる)は、優れた帯電防止性能の観点から、好ましくは1.0×1010Ω/□以下であり、より好ましくは0.5×1010Ω/□以下であり、さらに好ましくは1.0×109Ω/□以下であり、0.5×109Ω/□以下、又は1.0×108Ω/□以下である。本発明の粘着剤層の表面抵抗率の下限値は、特に限定されないが、1.0×105Ω/□以上、又は0.5×105Ω/□以上であってもよい。
(Surface resistivity)
The surface resistivity (according to JIS K 6271) of the pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is preferably 1.0× from the viewpoint of excellent antistatic performance. 10 10 Ω/□ or less, more preferably 0.5×10 10 Ω/□ or less, still more preferably 1.0×10 9 Ω/□ or less, and 0.5×10 9 Ω/□ or less or less, or 1.0×10 8 Ω/□ or less. The lower limit of the surface resistivity of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but may be 1.0×10 5 Ω/□ or more, or 0.5×10 5 Ω/□ or more.
 本発明の粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)は、湿熱環境でも、導電防止剤のブリードアウトを抑制して外観上の透明性を維持できるとともに、優れた帯電防止性能を安定付与し得る。このため、本発明の粘着剤層を介して画像表示装置と光学部材を貼り合わせた後の湿熱環境下でも、透明性を維持しつつ、静電気による表示不良を抑制することができる。このように、本発明の粘着剤層は、画像表示装置の製造に好適に用いられる。 The pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) can suppress the bleed-out of the anticonductive agent and maintain the transparency of the appearance even in a moist and hot environment, and has excellent It can stably impart antistatic performance. For this reason, display defects due to static electricity can be suppressed while maintaining transparency even in a moist and hot environment after bonding the image display device and the optical member via the pressure-sensitive adhesive layer of the present invention. Thus, the pressure-sensitive adhesive layer of the present invention is suitably used for manufacturing image display devices.
 本発明の粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)を、60℃、95%RH環境下に240時間投入して取り出した後、23℃、50%RH環境下で24時間調温・調湿を行った後に、23℃、50%RHの雰囲気下での湿熱試験後の粘着剤層表面の表面抵抗率は、湿熱環境においても導電防止剤のブリードアウトを抑制して外観上の透明性を維持できるとともに、湿熱試験前後における抵抗値の安定性を担保することで、優れた帯電防止性能を安定付与できる観点から、好ましくは5.0×1010Ω/□以下であり、より好ましくは3.0×1010Ω/□以下であり、さらに好ましくは1.0×1010Ω/□以下であり、0.5×1010Ω/□以下、1.0×109Ω/□以下、0.5×109Ω/□以下、又は1.0×108Ω/□以下である。本発明の粘着剤層の上記加湿試験後の表面抵抗率の下限値は、特に限定されないが、1.0×105Ω/□以上、又は0.5×105Ω/□以上であってもよい。 The pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) was placed in an environment of 60°C and 95% RH for 240 hours and then taken out, and then placed in an environment of 23°C and 50% RH. After controlling the temperature and humidity for 24 hours, the surface resistivity of the adhesive layer surface after a moist heat test in an atmosphere of 23 ° C and 50% RH suppresses the bleeding out of the anti-conductive agent even in a moist heat environment. 5.0×10 10 Ω/□ is preferable from the viewpoint of stably imparting excellent antistatic performance by ensuring the stability of the resistance value before and after the wet heat test while maintaining the transparency of the appearance. or less, more preferably 3.0×10 10 Ω/□ or less, still more preferably 1.0×10 10 Ω/□ or less, 0.5×10 10 Ω/□ or less, 1.0 ×10 9 Ω/□ or less, 0.5 × 10 9 Ω/□ or less, or 1.0 × 10 8 Ω/□ or less. The lower limit of the surface resistivity of the pressure-sensitive adhesive layer of the present invention after the humidification test is not particularly limited, but is 1.0×10 5 Ω/□ or more, or 0.5×10 5 Ω/□ or more. good too.
 上記湿熱試験前後の粘着剤層表面の表面抵抗率の割合(湿熱試験後の表面抵抗値/湿熱試験前の表面抵抗値)は、湿熱環境においても導電防止剤のブリードアウトを抑制して外観上の透明性を維持できるとともに、湿熱試験前後における抵抗値の安定性を担保することで、優れた帯電防止性能の安定性を付与できる観点から、好ましくは90以下であり、より好ましくは50以下であり、さらに好ましくは30以下であり、20以下、又は10以下である。 The ratio of the surface resistivity of the adhesive layer surface before and after the wet heat test (surface resistance value after the wet heat test / surface resistance value before the wet heat test) suppresses the bleeding out of the anti-conductive agent even in the wet heat environment, and the appearance While maintaining the transparency of, by ensuring the stability of the resistance value before and after the wet heat test, from the viewpoint of being able to impart the stability of excellent antistatic performance, preferably 90 or less, more preferably 50 or less. Yes, more preferably 30 or less, 20 or less, or 10 or less.
 本発明の粘着剤層の表面抵抗率、加湿試験後の表面抵抗率は、後掲の実施例に記載の方法により、測定できる。本発明の粘着剤層の表面抵抗率、加湿試験後の表面抵抗率は、アクリル系ポリマー(A)を構成するモノマー組成、架橋剤の量、本発明のイオン性化合物、その他添加剤の種類や量、硬化条件などを調整することによって、調整することができる。 The surface resistivity of the pressure-sensitive adhesive layer of the present invention and the surface resistivity after the humidification test can be measured by the method described in Examples below. The surface resistivity of the pressure-sensitive adhesive layer of the present invention and the surface resistivity after a humidification test are determined by the monomer composition constituting the acrylic polymer (A), the amount of the cross-linking agent, the ionic compound of the present invention, the type of other additives, and the like. Adjustments can be made by adjusting amounts, curing conditions, and the like.
(ヘイズ、全光線透過率)
 本発明の粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)は、透明であり、又は、透明性を有している。このため、本発明の粘着剤層を介しての視認性や外観性に優れる。このように、本発明の粘着剤層は、光学用に好適に用いられる。
(Haze, total light transmittance)
The pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is transparent or has transparency. Therefore, the visibility and appearance through the pressure-sensitive adhesive layer of the present invention are excellent. Thus, the pressure-sensitive adhesive layer of the present invention is suitable for optical applications.
 本発明の粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)のヘイズは、(JIS K7136に準じる)は、特に限定されないが、1.0%以下が好ましく、より好ましくは0.8%以下、0.7%以下、又は0.6%以下であってもよい。ヘイズが1.0%以下であると、優れた透明性や優れた外観が得られ、好ましい。なお、上記ヘイズは、例えば、粘着剤層(厚み:100μm)とし、これを常態(23℃、50%RH)に少なくとも24時間静置した後、スライドガラス(例えば、全光線透過率92%、ヘイズ0.2%のもの)に貼り合わせたものを試料とし、ヘイズメーター(株式会社村上色彩技術研究所製、商品名「HM-150N」)を用いて測定することができる。 The haze (according to JIS K7136) of the pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is not particularly limited, but is preferably 1.0% or less, more preferably It may be 0.8% or less, 0.7% or less, or 0.6% or less. A haze of 1.0% or less is preferable because excellent transparency and appearance can be obtained. Incidentally, the haze is, for example, an adhesive layer (thickness: 100 μm), which is allowed to stand in a normal state (23° C., 50% RH) for at least 24 hours, and then slide glass (for example, total light transmittance of 92%, Haze of 0.2%) can be used as a sample and measured using a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HM-150N").
 本発明の粘着剤層の可視光波長領域における全光線透過率(JIS K7361-1に準じる)は、特に限定されないが、90%以上が好ましく、より好ましくは91%以上、又は92%以上であってもよい。全光線透過率が90%以上であると、優れた透明性や優れた外観が得られ、好ましい。なお、上記全光線透過率は、例えば、粘着剤層(厚み:100μm)とし、これを常態(23℃、50%RH)に少なくとも24時間静置した後、セパレータを有する場合にはこれを剥離し、スライドガラス(例えば、全光線透過率92%、ヘイズ0.2%のもの)に貼り合わせたものを試料とし、ヘイズメーター(株式会社村上色彩技術研究所製、商品名「HM-150N」)を用いて測定することができる。 The total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the adhesive layer of the present invention is not particularly limited, but is preferably 90% or more, more preferably 91% or more, or 92% or more. may When the total light transmittance is 90% or more, excellent transparency and excellent appearance can be obtained, which is preferable. In addition, the above total light transmittance is, for example, an adhesive layer (thickness: 100 μm), which is allowed to stand in a normal state (23 ° C., 50% RH) for at least 24 hours, and then peeled off if it has a separator. Then, a slide glass (for example, total light transmittance of 92%, haze of 0.2%) is used as a sample, and a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HM-150N" ) can be measured using
 本発明の粘着剤層の全光線透過率及びヘイズは、後掲の実施例に記載の方法により、測定できる。本発明の粘着剤層の全光線透過率及びヘイズは、アクリル系ポリマー(A)を構成するモノマー組成、架橋剤の量、本発明のイオン性化合物、その他添加剤の種類や量、硬化条件などを調整することによって、調整することができる。 The total light transmittance and haze of the pressure-sensitive adhesive layer of the present invention can be measured by the methods described in Examples below. The total light transmittance and haze of the pressure-sensitive adhesive layer of the present invention are determined by the monomer composition constituting the acrylic polymer (A), the amount of the cross-linking agent, the ionic compound of the present invention, the type and amount of other additives, curing conditions, etc. can be adjusted by adjusting
(ゲル分率)
 本発明の粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)のゲル分率(溶剤不溶成分の割合)は、特に限定されないが、40~95%が好ましく、より好ましくは50~92%、さらに好ましくは55~90%である。ゲル分率が40%以上であると、上記粘着剤層の凝集力が向上し、高温環境下での被着体との界面での発泡や剥がれ、取り扱いでの打痕や、加工時の端部の汚染が抑制され、優れた耐発泡剥がれ性が得やすくなり好ましい。なお、ゲル分率が95%以下であると、適度な柔軟性が得られ、より接着性、段差追従性が向上し、好ましい。
(Gel fraction)
The gel fraction (proportion of solvent-insoluble components) of the pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is not particularly limited, but is preferably 40 to 95%, more preferably 50 to 92%, more preferably 55 to 90%. When the gel fraction is 40% or more, the cohesive force of the pressure-sensitive adhesive layer is improved, causing foaming and peeling at the interface with the adherend in a high-temperature environment, dents during handling, and edges during processing. Contamination of the part is suppressed, and excellent anti-foaming peeling property is easily obtained, which is preferable. In addition, when the gel fraction is 95% or less, appropriate flexibility can be obtained, and the adhesiveness and step followability are further improved, which is preferable.
 上記ゲル分率(溶剤不溶成分の割合)は、具体的には、例えば、以下の「ゲル分率の測定方法」により算出される値である。 Specifically, the gel fraction (ratio of solvent-insoluble components) is, for example, a value calculated by the following "Method for measuring gel fraction".
 粘着シートから粘着剤層:約0.1gを採取し、平均孔径0.2μmの多孔質テトラフルオロエチレンシート(商品名「NTF1122」、日東電工株式会社製)に包んだ後、凧糸で縛り、その際の重量を測定し、該重量を浸漬前重量とする。なお、該浸漬前重量は、粘着剤層(上記で採取した粘着剤層)と、テトラフルオロエチレンシートと、凧糸との総重量である。また、テトラフルオロエチレンシートと凧糸との合計重量も測定しておき、該重量を包袋重量とする。
 次に、粘着剤層をテトラフルオロエチレンシートで包み凧糸で縛ったもの(「サンプル」と称する)を、酢酸エチルで満たした50ml容器に入れ、23℃にて7日間静置する。その後、容器からサンプル(酢酸エチル処理後)を取り出して、アルミニウム製カップに移し、130℃で2時間、乾燥機中で乾燥して酢酸エチルを除去した後、重量を測定し、該重量を浸漬後重量とする。
 そして、下記の式からゲル分率を算出する。
    ゲル分率[%(重量%)]=(X-Y)/(Z-Y)×100
Adhesive layer: About 0.1 g was collected from the adhesive sheet, wrapped in a porous tetrafluoroethylene sheet (trade name “NTF1122”, manufactured by Nitto Denko Co., Ltd.) with an average pore size of 0.2 μm, and tied with a kite string. The weight at that time is measured, and the weight is taken as the weight before immersion. The weight before immersion is the total weight of the adhesive layer (the adhesive layer collected above), the tetrafluoroethylene sheet, and the kite string. Also, the total weight of the tetrafluoroethylene sheet and the kite string is measured, and this weight is taken as the weight of the package.
Next, the adhesive layer wrapped with a tetrafluoroethylene sheet and tied with kite string (referred to as a "sample") is placed in a 50 ml container filled with ethyl acetate and allowed to stand at 23°C for 7 days. After that, remove the sample (after ethyl acetate treatment) from the container, transfer it to an aluminum cup, dry it in a dryer at 130 ° C. for 2 hours to remove ethyl acetate, measure the weight, and immerse the weight. Rear weight.
Then, the gel fraction is calculated from the following formula.
Gel fraction [% (% by weight)] = (XY) / (ZY) x 100
 なお、上記ゲル分率は、例えば、アクリル系ポリマー(A)のモノマー組成、重量平均分子量、架橋剤の使用量(添加量)等により制御することができる。 The gel fraction can be controlled by, for example, the monomer composition of the acrylic polymer (A), the weight average molecular weight, the amount of cross-linking agent used (added amount), and the like.
(貯蔵弾性率)
 上記粘着剤層(特に、本発明の粘着剤組成物により形成される粘着剤層)の25℃、1Hzでの貯蔵弾性率は、特に限定されないが、3×104Pa以上であることが好ましい。本発明の粘着剤層の25℃、1Hzでの貯蔵弾性率が3×104Pa以上であるという構成は、取り扱いでの打痕が生じにくい点で好ましい。本発明の粘着剤層の打痕を抑制できる点で、本発明の粘着剤層の25℃、1Hzでの貯蔵弾性率は5×104Pa以上がより好ましく、1×105Pa以上であってもよい。本発明の粘着剤層の25℃、1Hzでの貯蔵弾性率の上限値は特に限定されないが、本発明の粘着剤層の段差追従性の観点から、5×106Pa以下が好ましく、1×106Pa以下であってもよい。
(storage modulus)
The storage modulus of the pressure-sensitive adhesive layer (especially the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) at 25° C. and 1 Hz is not particularly limited, but is preferably 3×10 4 Pa or more. . The configuration in which the pressure-sensitive adhesive layer of the present invention has a storage elastic modulus of 3×10 4 Pa or more at 25° C. and 1 Hz is preferable in that dents are less likely to occur during handling. The storage elastic modulus of the pressure-sensitive adhesive layer of the present invention at 25° C. and 1 Hz is more preferably 5×10 4 Pa or more, more preferably 1×10 5 Pa or more, in that dents on the pressure-sensitive adhesive layer of the present invention can be suppressed. may Although the upper limit of the storage elastic modulus at 25° C. and 1 Hz of the pressure-sensitive adhesive layer of the present invention is not particularly limited, it is preferably 5×10 6 Pa or less, and 1× It may be 10 6 Pa or less.
 本発明の光学用粘着シートの上記25℃、1Hzでの貯蔵弾性率は、動的粘弾性測定により測定でき具体的は、後掲の実施例に記載の方法により、測定できる。本発明の光学用粘着シートの上記25℃、1Hzでの貯蔵弾性率は、アクリル系ポリマー(A)を構成するモノマー組成、架橋剤の量、本発明のイオン性化合物、その他添加剤の種類や量、硬化条件などを調整することによって、調整することができる。 The storage elastic modulus of the optical pressure-sensitive adhesive sheet of the present invention at 25°C and 1 Hz can be measured by dynamic viscoelasticity measurement, and specifically by the method described in Examples below. The storage elastic modulus of the optical pressure-sensitive adhesive sheet of the present invention at 25° C. and 1 Hz is determined by the composition of the monomers constituting the acrylic polymer (A), the amount of the cross-linking agent, the ionic compound of the present invention, the type of other additives, and the like. Adjustments can be made by adjusting amounts, curing conditions, and the like.
(厚み)
 上記粘着剤層(特に、本発明の粘着剤組成物により形成される粘着剤層)は、特に限定されないが、5~250μmが好ましく、より好ましくは7~240μm、10~230μm、12~220μm、15~210μm、20~200μm、23~175μm、又は25~150μmであってもよい。厚みが一定以上であると段差追従性や接着信頼性が向上し、好ましい。また、厚みが一定以下であると、取扱い性や製造性に特に優れ、好ましい。
(thickness)
The pressure-sensitive adhesive layer (in particular, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is not particularly limited, but is preferably 5 to 250 μm, more preferably 7 to 240 μm, 10 to 230 μm, 12 to 220 μm, It may be 15-210 μm, 20-200 μm, 23-175 μm, or 25-150 μm. When the thickness is at least a certain value, the followability to unevenness and adhesion reliability are improved, which is preferable. In addition, when the thickness is a certain value or less, it is particularly excellent in handleability and manufacturability, which is preferable.
 本発明の粘着剤層の作製方法としては、特に限定されない。例えば、本発明の粘着剤組成物(前駆体組成物)を作製し、必要に応じて、活性エネルギー線の照射、加熱乾燥等を行うことにより作製できる。具体的には、モノマー成分の混合物又はその部分重合物に、本発明の帯電防止剤(アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物)と、必要に応じて、添加剤等を添加して、混合することを経て、作製されることなどが挙げられる。 The method for producing the pressure-sensitive adhesive layer of the present invention is not particularly limited. For example, it can be produced by preparing the pressure-sensitive adhesive composition (precursor composition) of the present invention and, if necessary, performing irradiation with active energy rays, heat drying, and the like. Specifically, a mixture of monomer components or a partial polymer thereof, the antistatic agent of the present invention (ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in the molecule), and, if necessary, Depending on the circumstances, it may be produced by adding additives and the like and mixing.
[2-1.本発明のイオン性化合物]
 本発明の粘着剤組成物は、少なくとも、帯電防止剤として、本発明のイオン性化合物(アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物)を必須成分として含有する。本発明のイオン性化合物とは、アクリル系ポリマー(A)と共有結合を形成できる官能基(以下、本明細書において、「官能基(A)」と称する場合がある)を、イオン性化合物を構成するカチオン部、及び/又は、アニオン部(いずれか、又は両方)に有するイオン性化合物である。また、本発明のイオン性化合物は、0~150℃の範囲内のいずれかで液体(液状)であり、不揮発性の溶融塩で、透明性を有するもの(イオン液体)が好ましい。なお、本発明のイオン性化合物は、単独で又は2種以上組み合わせて用いることができる。
[2-1. Ionic compound of the present invention]
The pressure-sensitive adhesive composition of the present invention contains at least the ionic compound of the present invention (an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in the molecule) as an antistatic agent as an essential component. contains. The ionic compound of the present invention is a functional group capable of forming a covalent bond with the acrylic polymer (A) (hereinafter, sometimes referred to as "functional group (A)" in the present specification). It is an ionic compound having a constituent cation part and/or an anion part (either or both). In addition, the ionic compound of the present invention is liquid (liquid) at any temperature within the range of 0 to 150° C., and is preferably a non-volatile molten salt having transparency (ionic liquid). In addition, the ionic compound of this invention can be used individually or in combination of 2 or more types.
 本発明の粘着剤組成物が、本発明のイオン性化合物を含有することにより、アクリル系ポリマー(A)と、本発明のイオン性化合物が有する官能基(A)が反応して共有結合を形成して、イオン性化合物がアクリル系ポリマー(A)の分子中に組み込まれるため、本発明のイオン性化合物を大量に配合しても、本発明の粘着剤層中での相溶性が損なわれることはなく透明性が維持しやすくなる。また、湿熱環境のような過酷な条件でも帯電防止成分のブリードアウトを抑制することができるため、粘着剤層の表面での析出、発泡、剥がれが抑制され、外観や接着信頼性などの耐久性の不良が生じにくい。従って、本発明のイオン性化合物を含有する本発明の粘着剤組成物から形成される粘着剤層は、優れた帯電防止性、透明性、耐湿熱性、及び低汚染性を満足でき、有用である。 When the pressure-sensitive adhesive composition of the present invention contains the ionic compound of the present invention, the acrylic polymer (A) reacts with the functional group (A) of the ionic compound of the present invention to form a covalent bond. As a result, the ionic compound is incorporated into the molecule of the acrylic polymer (A), so even if a large amount of the ionic compound of the present invention is blended, the compatibility in the pressure-sensitive adhesive layer of the present invention is impaired. It becomes easier to maintain transparency. In addition, since bleeding out of the antistatic component can be suppressed even under harsh conditions such as moist and hot environments, precipitation, foaming, and peeling on the surface of the adhesive layer are suppressed, and durability such as appearance and adhesion reliability is improved. defects are less likely to occur. Therefore, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention containing the ionic compound of the present invention can satisfy excellent antistatic properties, transparency, resistance to moist heat, and low staining properties, and is useful. .
 本発明のイオン性化合物のカチオン部としては、特に制限なく使用できるが、第4級アンモニウムカチオン、イミダゾリウムカチオン、ピリジニウムカチオン、ピペリニジニウムカチオン、ピロリジニウムカチオン、第4級ホスホニウムカチオン、トリアルキルスルホニウムカチオン、ピロールカチオン、ピラゾリウムカチオン、グアニジウムカチオン等があげられ、中でも、第4級アンモニウムカチオン、イミダゾリウムカチオン、ピリジニウムカチオン、ピペリニジニウムカチオン、ピロリジニウムカチオン、第4級ホスホニウムカチオン、トリアルキルスルホニウムカチオンを使用することがより好ましい。 The cation moiety of the ionic compound of the present invention can be used without particular limitation, and includes quaternary ammonium cations, imidazolium cations, pyridinium cations, piperinidinium cations, pyrrolidinium cations, quaternary phosphonium cations, tri Alkylsulfonium cations, pyrrole cations, pyrazolium cations, guanidinium cations, and the like, among which quaternary ammonium cations, imidazolium cations, pyridinium cations, piperinidinium cations, pyrrolidinium cations, quaternary Phosphonium cations and trialkylsulfonium cations are more preferably used.
 また、本発明のイオン性化合物を構成するアニオン部の内、前記アニオンとしては、SCN-、BF4 -、PF6 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(FSO22-、(CF3SO22-、(CF3SO23-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2-、C49SO3 -、(C25SO22-、C37COO-、(CF3SO2)(CF3CO)N-、B(CN)4 -、C(CN)3 -、N(CN)2 -、CH3OSO3 -、C25OSO3 -、C49OSO3 -、C613OSO3 -、C817OSO3 -、p-トルエンスルホネートアニオン、2-(2-メトキシエチル)エチルサルフェートアニオン、(C253PF3 -などが挙げられ、特に、フッ素原子を含むアニオン成分(含フッ素系アニオン)は、低融点のイオン性化合物を得られ、帯電防止性に優れる点で好ましい。なお、アニオンとして、塩素イオン、臭素イオンなどは、腐食性を有する点で、使用しないことが好ましい。 Among the anions constituting the ionic compound of the present invention, the anions include SCN , BF 4 , PF 6 , NO 3 , CH 3 COO , CF 3 COO , CH 3 SO 3 - , CF3SO3- , ( FSO2 ) 2N- , ( CF3SO2 ) 2N- , ( CF3SO2 ) 3C- , AsF6- , SbF6- , NbF6- , TaF6 - , F ( HF) n- , ( CN ) 2N- , C4F9SO3- , ( C2F5SO2 ) 2N- , C3F7COO- , ( CF3SO2 ) ( CF3CO )N- , B ( CN) 4- , C ( CN) 3- , N ( CN ) 2- , CH3OSO3- , C2H5OSO3- , C4H9OSO3- , C 6 H 13 OSO 3 - , C 8 H 17 OSO 3 - , p-toluenesulfonate anion, 2-(2-methoxyethyl)ethylsulfate anion, (C 2 F 5 ) 3 PF 3 - and the like, especially , an anion component containing a fluorine atom (fluorine-containing anion) is preferable in terms of obtaining an ionic compound having a low melting point and excellent antistatic properties. As anions, chlorine ions, bromide ions, etc. are preferably not used because they are corrosive.
 本発明のイオン性化合物が有する官能基(A)(アクリル系ポリマー(A)と共有結合を形成できる官能基)としては、例えば、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミノ基、ビニル基、アリル基、スチリル基、水酸基、アミノ基、メルカプト基、エポキシ基等があげられる。中でも、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミノ基、水酸基が好ましく、特に好ましくは、アクリル系ポリマー(A)と共重合可能な(メタ)アクリロイルオキシ基である。なお、本明細書において、「(メタ)アクリロイル」とは、「アクロイル」及び「メタクリロイル」のうち、何れか一方又は両方を表し、他も同様である。また、アミノ基には、-NH2、及び-NHR(Rは、炭素数1~6のアルキル基)も含まれる。 The functional group (A) (functional group capable of forming a covalent bond with the acrylic polymer (A)) possessed by the ionic compound of the present invention includes, for example, a (meth)acryloyloxy group, a (meth)acryloylamino group, and a vinyl group. , allyl group, styryl group, hydroxyl group, amino group, mercapto group, epoxy group and the like. Among them, a (meth)acryloyloxy group, a (meth)acryloylamino group and a hydroxyl group are preferred, and a (meth)acryloyloxy group copolymerizable with the acrylic polymer (A) is particularly preferred. In this specification, "(meth)acryloyl" represents either one or both of "acryloyl" and "methacryloyl", and the same applies to others. The amino group also includes --NH 2 and --NHR (R is an alkyl group having 1 to 6 carbon atoms).
 本発明のイオン性化合物が有する官能基(A)の数は、特に限定されないが、1~4個が好ましく、1~3個がより好ましく、1又は2個がさらに好ましく、1個が特に好ましい。官能基(A)の数が2個以上の場合、2個以上の官能基(A)は同一であっても、異なっていてもよい。なお、官能基(A)の数が2個以上の場合、本発明のイオン性化合物は、2つ以上のアクリル系ポリマー(A)を架橋する架橋剤としても機能し得る。 The number of functional groups (A) possessed by the ionic compound of the present invention is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. . When the number of functional groups (A) is two or more, two or more functional groups (A) may be the same or different. When the number of functional groups (A) is 2 or more, the ionic compound of the present invention can also function as a cross-linking agent for cross-linking two or more acrylic polymers (A).
 本発明のイオン性化合物としては、特に制限なく使用することができるが、下記一般式(A)で示されるイオン性化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000001
Although the ionic compound of the present invention can be used without any particular limitation, it is preferably an ionic compound represented by the following general formula (A).
Figure JPOXMLDOC01-appb-C000001
 上記式(A)中、X+はカチオン部である。Y-はアニオンである。Z1及びZ2は、同一又は異なって、単結合、又は炭素数1~16のアルキレン基である。A1及びA2は、同一又は異なって、アクリル系ポリマー(A)と共有結合を形成できる官能基である。n1は0又は1、n2は0又は1、但し、n1+n2は1又は2である。 In formula (A) above, X + is a cation moiety. Y is an anion. Z 1 and Z 2 are the same or different and each represents a single bond or an alkylene group having 1 to 16 carbon atoms. A 1 and A 2 are the same or different and are functional groups capable of forming a covalent bond with the acrylic polymer (A). n 1 is 0 or 1, n 2 is 0 or 1, provided that n 1 +n 2 is 1 or 2;
 一般式(A)で示されるイオン性化合物を構成するカチオン部(X+)としては、第4級アンモニウム基、イミダゾリウム基、ピリジニウム基、ピペリニジニウム基、ピロリジニウム基、ピロール基、第4級ホスホニウム基、トリアルキルスルホニウム基、ピラゾリウム基、グアニジウム基などが挙げられる。これらの中でも、特に、第4級アンモニウム基であることが、透明性に優れ、電子・光学用途に好ましい態様となる。また、第4級アンモニウム基は、紫外線(UV)硬化の際に、一般的なラジカル重合反応を阻害しにくく、硬化性が高いことが推測され、好適である。 The cation moiety (X + ) constituting the ionic compound represented by the general formula (A) includes a quaternary ammonium group, an imidazolium group, a pyridinium group, a piperinidinium group, a pyrrolidinium group, a pyrrole group and a quaternary phosphonium group. , a trialkylsulfonium group, a pyrazolium group, a guanidinium group, and the like. Among these, a quaternary ammonium group is particularly excellent in transparency and is a preferred embodiment for electronic and optical applications. In addition, quaternary ammonium groups are suitable because they are less likely to inhibit general radical polymerization reactions during ultraviolet (UV) curing and are presumed to have high curability.
 前記第4級アンモニウム基としては、n1+n2が1である場合、トリメチルアンモニウム基、トリエチルアンモニウム基、トリプロピルアンモニウム基、メチルジエチルアンモニウム基、エチルジメチルアンモニウム基、メチルジプロピルアンモニウム基、ジメチルベンジルアンモニウム基、ジエチルベンジルアンモニウム基、メチルジベンジルアンモニウム基、エチルジベンジルアンモニウム基、ジメチルオクタデシルアンモニウム基、ジメチルオレイルアンモニウム基等が挙げられるが、中でも特に、トリメチルアンモニウム基、ジメチルベンジルアンモニウム基が安価な工業材料を入手し易い点で、好ましい態様となる。 As the quaternary ammonium group, when n 1 +n 2 is 1, trimethylammonium group, triethylammonium group, tripropylammonium group, methyldiethylammonium group, ethyldimethylammonium group, methyldipropylammonium group, dimethylbenzyl ammonium group, diethylbenzylammonium group, methyldibenzylammonium group, ethyldibenzylammonium group, dimethyloctadecylammonium group, dimethyloleyl ammonium group, etc.; This is a preferred embodiment because the materials are readily available.
 前記第4級アンモニウム基としては、n1+n2が2である場合、ジメチルアンモニウム基、ジエチルアンモニウム基、ジプロピルアンモニウム基、メチルエチルアンモニウム基、メチルプロピルアンモニウム基、メチルベンジルアンモニウム基、エチルベンジルアンモニウム基、メチルオクタデシルアンモニウム基、エチルオクタデシルアンモニウム基、メチルオレイルアンモニウム、エチルオレイルアンモニウム基等が挙げられるが、中でも特に、ジメチルアンモニウム基、メチルオレイルアンモニウム基が安価な工業材料を入手し易い点で、好ましい態様となる。 As the quaternary ammonium group, when n 1 +n 2 is 2, dimethylammonium group, diethylammonium group, dipropylammonium group, methylethylammonium group, methylpropylammonium group, methylbenzylammonium group, ethylbenzylammonium group group, methyloctadecylammonium group, ethyloctadecylammonium group, methyloleyl ammonium group, ethyl oleyl ammonium group, etc. Among them, dimethyl ammonium group and methyl oleyl ammonium group are particularly preferable in terms of easy availability of inexpensive industrial materials. It becomes a mode.
 上記一般式(A)で示されるイオン性化合物を構成するアニオン(部位)(Y-)内、前記アニオンとしては、SCN-、BF4 -、PF6 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(FSO22-、(CF3SO22-、(CF3SO23-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2-、C49SO3 -、(C25SO22-、C37COO-、(CF3SO2)(CF3CO)N-、B(CN)4 -、C(CN)3 -、N(CN)2 -、CH3OSO3 -、C25OSO3 -、C49OSO3 -、C613OSO3 -、C817OSO3 -、p-トルエンスルホネートアニオン、2-(2-メトキシエチル)エチルサルフェートアニオン、(C253PF3 -などが挙げられ、特に、フッ素原子を含むアニオン成分(含フッ素系アニオン)は、低融点のイオン性化合物を得られ、帯電防止性に優れる点で好ましい。なお、アニオンとして、塩素イオン、臭素イオンなどは、腐食性を有する点で、使用しないことが好ましい。 Among the anions (sites) (Y ) constituting the ionic compound represented by the general formula (A), the anions include SCN , BF 4 , PF 6 , NO 3 , CH 3 COO , CF3COO- , CH3SO3- , CF3SO3- , ( FSO2 ) 2N- , ( CF3SO2 ) 2N- , ( CF3SO2 ) 3C- , AsF6- , SbF 6- , NbF6- , TaF6- , F ( HF) n- , ( CN ) 2N- , C4F9SO3- , ( C2F5SO2 ) 2N- , C3F7COO - , ( CF3SO2 ) ( CF3CO )N- , B(CN) 4- , C ( CN) 3- , N ( CN ) 2- , CH3OSO3- , C2H5OSO3- , C 4 H 9 OSO 3 , C 6 H 13 OSO 3 , C 8 H 17 OSO 3 , p-toluenesulfonate anion, 2-(2-methoxyethyl)ethylsulfate anion, (C 2 F 5 ) 3 PF 3 and the like are included, and in particular, an anion component containing a fluorine atom (fluorine-containing anion) is preferable because an ionic compound with a low melting point can be obtained and excellent antistatic properties can be obtained. As anions, chlorine ions, bromide ions, and the like are preferably not used because they are corrosive.
 上記一般式(A)で示されるイオン性化合物を構成するZ1及びZ2は、単結合、又は炭素数1~16のアルキレン基である。炭素数1~16のアルキレン基としては、好ましくは炭素数1~12のアルキレン基、さらに好ましくは炭素数1~6のアルキレン基、特に好ましくは炭素数1~3のアルキレン基である。具体的には、メチレン基、エチレン基、トリメチレン基、メチルエチレン基など挙げられ、エチレン基、トリメチレン基が好ましい。n1+n2が2である場合、Z1及びZ2は、同一でもよく、異なっていてもよい。 Z 1 and Z 2 constituting the ionic compound represented by the general formula (A) are single bonds or alkylene groups having 1 to 16 carbon atoms. The alkylene group having 1 to 16 carbon atoms is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms. Specific examples include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, etc., and an ethylene group and a trimethylene group are preferable. When n 1 +n 2 is 2, Z 1 and Z 2 may be the same or different.
 上記一般式(A)で示されるイオン性化合物を構成するA1及びA2は、アクリル系ポリマー(A)と共有結合を形成できる官能基であり、具体的には、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミノ基、ビニル基、アリル基、スチリル基、水酸基、アミノ基、メルカプト基、エポキシ基等があげられる。中でも、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミノ基、水酸基が好ましく、特に好ましくは、アクリル系ポリマー(A)と共重合可能な(メタ)アクリロイルオキシ基である。n1+n2が2である場合、A1及びA2は、同一でもよく、異なっていてもよい。 A 1 and A 2 constituting the ionic compound represented by the general formula (A) are functional groups capable of forming a covalent bond with the acrylic polymer (A), specifically, a (meth)acryloyloxy group , (meth)acryloylamino group, vinyl group, allyl group, styryl group, hydroxyl group, amino group, mercapto group, epoxy group and the like. Among them, a (meth)acryloyloxy group, a (meth)acryloylamino group and a hydroxyl group are preferred, and a (meth)acryloyloxy group copolymerizable with the acrylic polymer (A) is particularly preferred. When n 1 +n 2 is 2, A 1 and A 2 may be the same or different.
  上記一般式(A)で示されるイオン性化合物のうち、X+が第4級アンモニウム基であり、n1が1であり、n2が0であり、A1がビニル基、(メタ)アクリロイルオキシ基、又は(メタ)アクリロイルアミノ基である態様の具体例としては、N,N,N-トリアルキル-N-ビニルアンモニウムテトラフルオロボレート、N,N,N-トリアルキル-N-ビニルアンモニウムトリフルオロアセテート、N,N,N-トリアルキル-N-ビニルアンモニウムヘプタフルオロブチレート、N,N,N-トリアルキル-N-ビニルアンモニウムトリフルオロメタンスルホネート、N,N,N-トリアルキル-N-ビニルアンモニウムペルフルオロブタンスルホネート、N,N,N-トリアルキル-N-ビ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,N-トリアルキル-N-ビニ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、N,N,N-トリアルキル-N-ビニルアンモニウムトリス(トリフルオロメタンスルホニル)イミド、N,N,N-トリアルキル-N-ビニルアンモニウムヘキサフルオロホスフェート、N,N,N-トリアルキル-N-ビニルアンモニウム(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、N,N,N-トリアルキル-N-ビニルアンモニウムジシアンアミド、N,N,N-トリアルキル-N-ビニルアンモニウムチオシアネート等のN,N,N-トリアルキル-N-ビニルアンモニウムカチオン含有イオン性化合物;N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムテトラフルオロボレート、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムトリフルオロアセテート、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムヘプタフルオロブチレート、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムトリフルオロメタンスルホネート、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムペルフルオロブタンスルホネート、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキ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,N-トリアルキル-N-(メタ)アクリロイルオキシアルキ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、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムトリス(トリフルオロメタンスルホニル)イミド、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムヘキサフルオロホスフェート、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウム(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、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムジシアンアミド、N,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムチオシアネート、等のN,N,N-トリアルキル-N-(メタ)アクリロイルオキシアルキルアンモニウムカチオン含有イオン性化合物;N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムテトラフルオロボレート、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムトリフルオロアセテート、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムヘプタフルオロブチレート、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムトリフルオロメタンスルホネート、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムペルフルオロブタンスルホネート、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキ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,N-トリアルキル-N-(メタ)アクリロイルアミノアルキ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、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムトリス(トリフルオロメタンスルホニル)イミド、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムヘキサフルオロホスフェート、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウム(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、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムジシアンアミド、N,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムチオシアネート、等のN,N,N-トリアルキル-N-(メタ)アクリロイルアミノアルキルアンモニウムカチオン含有イオン性化合物があげられる。なお、前記アルキル置換基としては、炭素数1~16のアルキル基であることが好ましく、特に好ましくは炭素数1~12、更に好ましくは炭素数1~6である。 Among the ionic compounds represented by the general formula (A), X + is a quaternary ammonium group, n 1 is 1, n 2 is 0, A 1 is a vinyl group, and (meth)acryloyl Specific examples of embodiments that are oxy groups or (meth)acryloylamino groups include N,N,N-trialkyl-N-vinylammonium tetrafluoroborate, N,N,N-trialkyl-N-vinylammonium tri Fluoroacetate, N,N,N-trialkyl-N-vinylammonium heptafluorobutyrate, N,N,N-trialkyl-N-vinylammonium trifluoromethanesulfonate, N,N,N-trialkyl-N-vinyl ammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-vinylammonium bis(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-vinylammonium bis(pentafluoroethanesulfonyl)imide, N, N,N-trialkyl-N-vinylammonium tris(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-vinylammonium hexafluorophosphate, N,N,N-trialkyl-N-vinylammonium ( N,N,N-trialkyl- such as trifluoromethanesulfonyl)trifluoroacetamide, N,N,N-trialkyl-N-vinylammonium dicyanamide, N,N,N-trialkyl-N-vinylammonium thiocyanate N-Vinylammonium cation-containing ionic compounds; N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium tetrafluoroborate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium trifluoroacetate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium heptafluorobutyrate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium trifluoromethanesulfonate, N , N,N-trialkyl-N-(meth)acryloyloxyalkylammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium bis(trifluoromethanesulfonyl)imide, N,N , N-trialkyl-N-(meth)acryloyloxyalkylammonium bis(penta fluoroethanesulfonyl)imide, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium tris(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium Hexafluorophosphate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium di N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium cation-containing ionic compounds such as cyanamide, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium thiocyanate; N , N,N-trialkyl-N-(meth)acryloylaminoalkylammonium tetrafluoroborate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium trifluoroacetate, N,N,N-tri Alkyl-N-(meth)acryloylaminoalkylammonium heptafluorobutyrate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium trifluoromethanesulfonate, N,N,N-trialkyl-N-( meth)acryloylaminoalkylammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium bis(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-(meth) Acryloylaminoalkylammonium bis(pentafluoroethanesulfonyl)imide, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium tris(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N- (Meth) acryloylaminoalkylammonium hexafluorophosphate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N,N,N-trialkyl-N-( N,N such as meth)acryloylaminoalkylammonium dicyanamide, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium thiocyanate, etc. , N-trialkyl-N-(meth)acryloylaminoalkylammonium cation-containing ionic compounds. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
 上記一般式(A)で示されるイオン性化合物のうち、X+が第4級アンモニウム基であり、n1が1であり、n2が0であり、A1が(メタ)アクリロイルオキシ基である態様の好ましい具体例としては、(メタ)アクリロイルオキシプロピ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、(メタ)アクリロイルオキシプロピルジメチルベンジ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、(メタ)アクリロイルオキシエチ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、(メタ)アクリロイルオキシエチルジメチルベンジ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、(メタ)アクリロイルオキシエチルトリメチルアンモニウムビス(フルオロスルホニル)イミド、(メタ)アクリロイルオキシエチルジメチルベンジルアンモニウムビス(フルオロスルホニル)イミド、(メタ)アクリロイルオキシエチルトリメチルアンモニウムトリフルオロメタンスルホン酸、(メタ)アクリロイルオキシエチルジメチルベンジルアンモニウムトリフルオロメタンスルホン酸などが挙げられる。 Among the ionic compounds represented by the general formula (A), X + is a quaternary ammonium group, n 1 is 1, n 2 is 0, and A 1 is a (meth)acryloyloxy group. Preferred specific examples of certain embodiments include (meth)acryloyloxypropyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxypropyldimethylbenzylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxyethyltrimethylammonium Bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxyethyldimethylbenzylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxyethyltrimethylammonium bis(fluorosulfonyl)imide, (meth)acryloyloxyethyldimethylbenzylammonium bis (fluorosulfonyl)imide, (meth)acryloyloxyethyltrimethylammonium trifluoromethanesulfonic acid, (meth)acryloyloxyethyldimethylbenzylammonium trifluoromethanesulfonic acid and the like.
 上記一般式(A)で示されるイオン性化合物のうち、X+が第4級アンモニウム基であり、n1が1であり、n2が0であり、A1が(メタ)アクリロイルアミノ基である態様の好ましい具体例としては、(メタ)アクリロイルアミノプロピ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、(メタ)アクリロイルアミノプロピルジメチルベンジ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、(メタ)アクリロイルアミノプロピルトリメチルアンモニウムビス(フルオロスルホニル)イミド、(メタ)アクリロイルアミノプロピルジメチルベンジルアンモニウムビス(フルオロスルホニル)イミド、(メタ)アクリロイルアミノプロピルトリメチルアンモニウムトリフルオロメタンスルホン酸、(メタ)アクリロイルアミノプロピルジメチルベンジルアンモニウムトリフルオロメタンスルホン酸などが挙げられる。 Among the ionic compounds represented by the general formula (A), X + is a quaternary ammonium group, n 1 is 1, n 2 is 0, and A 1 is a (meth)acryloylamino group. Preferred specific examples of certain embodiments include (meth)acryloylaminopropyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloylaminopropyldimethylbenzylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloylaminopropyltrimethylammonium Bis(fluorosulfonyl)imide, (meth)acryloylaminopropyldimethylbenzylammonium bis(fluorosulfonyl)imide, (meth)acryloylaminopropyltrimethylammonium trifluoromethanesulfonic acid, (meth)acryloylaminopropyldimethylbenzylammonium trifluoromethanesulfonic acid, etc. are mentioned.
 上記一般式(A)で示されるイオン性化合物のうち、X+がイミダゾリウム基であり、n1が1であり、n2が0又は1であり、A1及びA2がビニル基である態様の具体例としては、1-アルキル-3-ビニルイミダゾリウムテトラフルオロボレート、1-アルキル-3-ビニルイミダゾリウムトリフルオロアセテート、1-アルキル-3-ビニルイミダゾリウムヘプタフルオロブチレート、1-アルキル-3-ビニルイミダゾリウムトリフルオロメタンスルホネート、1-アルキル-3-ビニルイミダゾリウムペルフルオロブタンスルホネート、1-アルキル-3-ビニ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、1-アルキル-3-ビニルイミダゾリウムビス(ペンタフルオロエタンスルホニル)イミド、1-アルキル-3-ビニルイミダゾリウムトリス(トリフルオロメタンスルホニル)イミド、1-アルキル-3-ビニルイミダゾリウムヘキサフルオロホスフェート、1-アルキル-3-ビニルイミダゾリウム(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、1-アルキル-3-ビニルイミダゾリウムジシアンアミド、1-アルキル-3-ビニルイミダゾリウムチオシアネート等の1-アルキル-3-ビニルイミダゾリウムカチオン含有イオン性化合物;1,2-ジアルキル-3-ビニルイミダゾリウムビス(フルオロスルホニル)イミド、1,2-ジアルキル-3-ビニ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、1,2-ジアルキル-3-ビニルイミダゾリウムジシアンアミド、1,2-ジアルキル-3-ビニルイミダゾリウムチオシアネート等の1,2-ジアルキル-3-ビニルイミダゾリウムカチオン含有イオン性化合物;2-アルキル-1,3-ジビニルイミダゾリウムビス(フルオロスルホニル)イミド、2-アルキル-1,3-ジビニ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、2-アルキル-1,3-ジビニルイミダゾリウムジシアンアミド、2-アルキル-1,3-ジビニルイミダゾリウムチオシアネート、等の2-アルキル-1,3-ジビニルイミダゾリウムカチオン含有イオン性化合物;1-ビニルイミダゾリウムビス(フルオロスルホニル)イミド、1-ビニ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、1-ビニルイミダゾリウムジシアンアミド、1-ビニルイミダゾリウムチオシアネート等の1-ビニルイミダゾリウムカチオン含有イオン性化合物等が挙げられる。 Among the ionic compounds represented by the general formula (A), X + is an imidazolium group, n 1 is 1, n 2 is 0 or 1, and A 1 and A 2 are vinyl groups. Specific examples of embodiments include 1-alkyl-3-vinylimidazolium tetrafluoroborate, 1-alkyl-3-vinylimidazolium trifluoroacetate, 1-alkyl-3-vinylimidazolium heptafluorobutyrate, 1-alkyl -3-vinylimidazolium trifluoromethanesulfonate, 1-alkyl-3-vinylimidazolium perfluorobutanesulfonate, 1-alkyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-vinylimidazolium bis (Pentafluoroethanesulfonyl)imide, 1-alkyl-3-vinylimidazolium tris(trifluoromethanesulfonyl)imide, 1-alkyl-3-vinylimidazolium hexafluorophosphate, 1-alkyl-3-vinylimidazolium (trifluoromethane 1-alkyl-3-vinylimidazolium cation-containing ionic compounds such as sulfonyl)trifluoroacetamide, 1-alkyl-3-vinylimidazolium dicyanamide, 1-alkyl-3-vinylimidazolium thiocyanate; dialkyl-3-vinylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dialkyl-3-vinylimidazolium dicyanamide, 1, 1,2-dialkyl-3-vinylimidazolium cation-containing ionic compounds such as 2-dialkyl-3-vinylimidazolium thiocyanate; 2-alkyl-1,3-divyvinylimidazolium bis(fluorosulfonyl)imide, 2-alkyl -2-alkyl- such as 1,3-divynylimidazolium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1,3-divynylimidazolium dicyanamide, 2-alkyl-1,3-divynylimidazolium thiocyanate, etc. 1,3-divinylimidazolium cation-containing ionic compounds; 1-vinylimidazolium bis(fluorosulfonyl)imide, 1-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-vinylimidazolium dicyanamide, 1-vinyl imidazoli and ionic compounds containing 1-vinylimidazolium cations such as umthiocyanate.
 上記一般式(A)で示されるイオン性化合物のうち、X+がイミダゾリウム基であり、n1が1であり、n2が0又は1であり、A1及びA2が(メタ)アクリロイルオキシ基である態様の具体例としては、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムテトラフルオロボレート、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムトリフルオロアセテート、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムヘプタフルオロブチレート、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムトリフルオロメタンスルホネート、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムペルフルオロブタンスルホネート、1-アルキル-3-(メタ)アクリロイルオキシアルキ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、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムビス(ペンタフルオロエタンスルホニル)イミド、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムトリス(トリフルオロメタンスルホニル)イミド、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムヘキサフルオロホスフェート、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウム(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、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムジシアンアミド、1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムチオシアネート等の1-アルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムカチオン含有イオン性化合物;1,2-ジアルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムビス(フルオロスルホニル)イミド、1,2-ジアルキル-3-(メタ)アクリロイルオキシアルキ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、1,2-ジアルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムジシアンアミド、1,2-ジアルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムチオシアネート等の1,2-ジアルキル-3-(メタ)アクリロイルオキシアルキルイミダゾリウムカチオン含有イオン性化合物;2-アルキル-1,3-ジ(メタ)アクリロイルオキシアルキルイミダゾリウムビス(フルオロスルホニル)イミド、2-アルキル-1,3-ジ(メタ)アクリロイルオキシアルキ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、2-アルキル-1,3-ジ(メタ)アクリロイルオキシアルキルイミダゾリウムジシアンアミド、2-アルキル-1,3-ジ(メタ)アクリロイルオキシイミダゾリウムチオシアネート等の2-アルキル-1,3-ジ(メタ)アクリロイルオキシアルキルイミダゾリウムカチオン含有イオン性化合物;1-(メタ)アクリロイルオキシアルキルイミダゾリウムビス(フルオロスルホニル)イミド、1-(メタ)アクリロイルオキシアルキ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、1-(メタ)アクリロイルオキシアルキルイミダゾリウムジシアンアミド、1-(メタ)アクリロイルオキシアルキルイミダゾリウムチオシアネート等の1-(メタ)アクリロイルオキシアルキルイミダゾリウムカチオン含有イオン性化合物等が挙げられる。なお、前記アルキル置換基としては、炭素数1~16のアルキル基であることが好ましく、特に好ましくは炭素数1~12、更に好ましくは炭素数1~6である。 Among the ionic compounds represented by the general formula (A), X + is an imidazolium group, n 1 is 1, n 2 is 0 or 1, and A 1 and A 2 are (meth)acryloyl Specific examples of embodiments that are oxy groups include 1-alkyl-3-(meth)acryloyloxyalkylimidazolium tetrafluoroborate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium trifluoroacetate, 1-alkyl -3-(meth)acryloyloxyalkylimidazolium heptafluorobutyrate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium perfluorobutane Sulfonate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium bis(pentafluoroethanesulfonyl)imide, 1-alkyl -3-(meth)acryloyloxyalkylimidazolium tris(trifluoromethanesulfonyl)imide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium hexafluorophosphate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium 1-alkyl-3 such as lithium (trifluoromethanesulfonyl) trifluoroacetamide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium dicyanamide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium thiocyanate -(meth)acryloyloxyalkylimidazolium cation-containing ionic compound; 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-(meth)acryloyl Oxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium dicyanamide, 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium thiocyanate, etc. 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium cation-containing ionic compound; 2-alkyl-1,3-di (Meth) acryloyloxyalkylimidazolium bis(fluorosulfonyl)imide, 2-alkyl-1,3-di(meth)acryloyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1,3-di( 2-alkyl-1,3-di(meth)acryloyloxyalkylimidazolium cation-containing ions such as meth)acryloyloxyalkylimidazolium dicyanamide, 2-alkyl-1,3-di(meth)acryloyloxyimidazolium thiocyanate 1-(meth)acryloyloxyalkylimidazolium bis(fluorosulfonyl)imide, 1-(meth)acryloyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-(meth)acryloyloxyalkylimidazolium dicyanide Examples include ionic compounds containing 1-(meth)acryloyloxyalkylimidazolium cations such as amides and 1-(meth)acryloyloxyalkylimidazolium thiocyanate. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
 上記一般式(A)で示されるイオン性化合物のうち、X+がイミダゾリウム基であり、n1が1であり、n2が0又は1であり、A1及びA2が(メタ)アクリロイルアミノ基である態様の具体例としては、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムテトラフルオロボレート、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムトリフルオロアセテート、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムヘプタフルオロブチレート、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムトリフルオロメタンスルホネート、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムペルフルオロブタンスルホネート、1-アルキル-3-(メタ)アクリロイルアミノアルキ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、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムビス(ペンタフルオロエタンスルホニル)イミド、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムトリス(トリフルオロメタンスルホニル)イミド、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムヘキサフルオロホスフェート、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウム(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、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムジシアンアミド、1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムチオシアネート等の1-アルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムカチオン含有イオン性化合物;1,2-ジアルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムビス(フルオロスルホニル)イミド、1,2-ジアルキル-3-(メタ)アクリロイルアミノアルキ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、1,2-ジアルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムジシアンアミド、1,2-ジアルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムチオシアネート等の1,2-ジアルキル-3-(メタ)アクリロイルアミノアルキルイミダゾリウムカチオン含有イオン性化合物;2-アルキル-1,3-ジ(メタ)アクリロイルアミノアルキルイミダゾリウムビス(フルオロスルホニル)イミド、2-アルキル-1,3-ジ(メタ)アクリロイルアミノアルキ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、2-アルキル-1,3-ジ(メタ)アクリロイルアミノアルキルイミダゾリウムジシアンアミド、2-アルキル-1,3-ジ(メタ)アクリロイルアミノイミダゾリウムチオシアネート等の2-アルキル-1,3-ジ(メタ)アクリロイルアミノアルキルイミダゾリウムカチオン含有イオン性化合物;1-(メタ)アクリロイルアミノアルキルイミダゾリウムビス(フルオロスルホニル)イミド、1-(メタ)アクリロイルアミノアルキ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、1-(メタ)アクリロイルアミノアルキルイミダゾリウムジシアンアミド、1-(メタ)アクリロイルアミノアルキルイミダゾリウムチオシアネート等の1-(メタ)アクリロイルアミノアルキルイミダゾリウムカチオン含有イオン性化合物等が挙げられる。なお、前記アルキル置換基としては、炭素数1~16のアルキル基であることが好ましく、特に好ましくは炭素数1~12、更に好ましくは炭素数1~6である。 Among the ionic compounds represented by the general formula (A), X + is an imidazolium group, n 1 is 1, n 2 is 0 or 1, and A 1 and A 2 are (meth)acryloyl Specific examples of amino groups include 1-alkyl-3-(meth)acryloylaminoalkylimidazolium tetrafluoroborate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium trifluoroacetate, 1-alkyl -3-(meth)acryloylaminoalkylimidazolium heptafluorobutyrate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium perfluorobutane Sulfonate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium bis(pentafluoroethanesulfonyl)imide, 1-alkyl -3-(meth)acryloylaminoalkylimidazolium tris(trifluoromethanesulfonyl)imide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium hexafluorophosphate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium 1-alkyl-3 such as lithium (trifluoromethanesulfonyl) trifluoroacetamide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium dicyanamide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium thiocyanate -(meth)acryloylaminoalkylimidazolium cation-containing ionic compound; 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-(meth)acryloyl aminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium dicyanamide, 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium thiocyanate, etc. 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium cation-containing ionic compounds; 2-alkyl-1,3-di (Meth) acryloylaminoalkylimidazolium bis(fluorosulfonyl)imide, 2-alkyl-1,3-di(meth)acryloylaminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1,3-di( 2-alkyl-1,3-di(meth)acryloylaminoalkylimidazolium cation-containing ions such as meth)acryloylaminoalkylimidazolium dicyanamide, 2-alkyl-1,3-di(meth)acryloylaminoimidazolium thiocyanate 1-(meth)acryloylaminoalkylimidazolium bis(fluorosulfonyl)imide, 1-(meth)acryloylaminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-(meth)acryloylaminoalkylimidazolium dicyanide 1-(meth)acryloylaminoalkylimidazolium cation-containing ionic compounds such as amides and 1-(meth)acryloylaminoalkylimidazolium thiocyanate. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
 上記一般式(A)で示されるイオン性化合物のうち、X+がピリジニウム基であり、n1が1であり、n2が0であり、A1がビニル基、(メタ)アクリロイルオキシ基、又は(メタ)アクリロイルアミノ基である態様の具体例としては、1-ビニルピリジニウムビス(フルオロスルホニル)イミド、1-ビニ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、1-ビニルピリジニウムジシアンアミド、1-ビニルピリジニウムチオシアネート、等の1-ビニルピリジニウムカチオン含有イオン性化合物;1-(メタ)アクリロイルオキシアルキルピリジニウムビス(フルオロスルホニル)イミド、1-(メタ)アクリロイルオキシアルキ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、1-(メタ)アクリロイルオキシアルキルピリジニウムジシアンアミド、1-(メタ)アクリロイルオキシアルキルピリジニウムチオシアネート、等の1-(メタ)アクリロイルオキシアルキルピリジニウムカチオン含有イオン性化合物;1-(メタ)アクリロイルアミノアルキルピリジニウムビス(フルオロスルホニル)イミド、1-(メタ)アクリロイルアミノアルキ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、1-(メタ)アクリロイルアミノアルキルピリジニウムジシアンアミド、1-(メタ)アクリロイルアミノアルキルピリジニウムチオシアネート、等の1-(メタ)アクリロイルアミノアルキルピリジニウムカチオン含有イオン性化合物;2-アルキル-1-ビニルピリジニウムビス(フルオロスルホニル)イミド、2-アルキル-1-ビニ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、2-アルキル-1-ビニルピリジニウムジシアンアミド、2-アルキル-1-ビニルピリジニウムチオシアネート、等の2-アルキル-1-ビニルピリジニウムカチオン含有イオン性化合物;2-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムビス(フルオロスルホニル)イミド、2-アルキル-1-(メタ)アクリロイルオキシアルキ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、2-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムジシアンアミド、2-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムチオシアネート、等の2-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムカチオン含有イオン性化合物;2-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムビス(フルオロスルホニル)イミド、2-アルキル-1-(メタ)アクリロイルアミノアルキ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、2-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムジシアンアミド、2-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムチオシアネート、等の2-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムカチオン含有イオン性化合物;3-アルキル-1-ビニルピリジニウムビス(フルオロスルホニル)イミド、3-アルキル-1-ビニ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-アルキル-1-ビニルピリジニウムジシアンアミド、3-アルキル-1-ビニルピリジニウムチオシアネート、等の3-アルキル-1-ビニルピリジニウムカチオン含有イオン性化合物;3-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムビス(フルオロスルホニル)イミド、3-アルキル-1-(メタ)アクリロイルオキシアルキ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-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムジシアンアミド、3-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムチオシアネート等の3-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムカチオン含有イオン性化合物;3-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムビス(フルオロスルホニル)イミド、3-アルキル-1-(メタ)アクリロイルアミノアルキ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-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムジシアンアミド、3-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムチオシアネート、等の3-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムカチオン含有イオン性化合物;4-アルキル-1-ビニルピリジニウムビス(フルオロスルホニル)イミド、4-アルキル-1-ビニ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、4-アルキル-1-ビニルピリジニウムジシアンアミド、4-アルキル-1-ビニルピリジニウムチオシアネート等の4-アルキル-1-ビニルピリジニウムカチオン含有イオン性化合物;4-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムビス(フルオロスルホニル)イミド、4-アルキル-1-(メタ)アクリロイルオキシアルキ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、4-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムジシアンアミド、4-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムチオシアネート、等の4-アルキル-1-(メタ)アクリロイルオキシアルキルピリジニウムカチオン含有イオン性化合物;4-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムビス(フルオロスルホニル)イミド、4-アルキル-1-(メタ)アクリロイルアミノアルキ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、4-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムジシアンアミド、4-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムチオシアネート、等の4-アルキル-1-(メタ)アクリロイルアミノアルキルピリジニウムカチオン含有イオン性化合物等があげられる。なお、前記アルキル置換基としては、炭素数1~16のアルキル基であることが好ましく、特に好ましくは炭素数1~12、更に好ましくは炭素数1~6である。 Among the ionic compounds represented by the general formula (A), X + is a pyridinium group, n 1 is 1, n 2 is 0, A 1 is a vinyl group, a (meth)acryloyloxy group, or (meth)acryloylamino group, 1-vinylpyridinium bis(fluorosulfonyl)imide, 1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 1-vinylpyridinium dicyanamide, 1-vinyl 1-vinylpyridinium cation-containing ionic compounds such as pyridinium thiocyanate; 1-(meth)acryloyloxyalkylpyridinium cation-containing ionic compounds such as (meth)acryloyloxyalkylpyridinium dicyanamide, 1-(meth)acryloyloxyalkylpyridinium thiocyanate; 1-(meth)acryloylaminoalkylpyridinium bis( 1-(fluorosulfonyl)imide, 1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide, 1-(meth)acryloylaminoalkylpyridinium dicyanamide, 1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc. (Meth)acryloylaminoalkylpyridinium cation-containing ionic compounds; 2-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1- 2-alkyl-1-vinylpyridinium cation-containing ionic compounds such as vinylpyridinium dicyanamide, 2-alkyl-1-vinylpyridinium thiocyanate; 2-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl) imide, 2-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 2-alkyl-1-(meth)acryloyl 2-alkyl-1-(meth)acryloyloxyalkyl, such as oxyalkylpyridinium thiocyanate Lupyridinium cation-containing ionic compound; 2-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide, 2 - 2-alkyl-1-(meth)acryloylaminoalkylpyridinium cation-containing ionic such as alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 2-alkyl-1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc. Compound; 3-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 3-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 3-alkyl-1-vinylpyridinium dicyanamide, 3-alkyl-1 - 3-alkyl-1-vinylpyridinium cation-containing ionic compounds such as vinylpyridinium thiocyanate; 3-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl)imide, 3-alkyl-1-(meth) 3-alkyl-1 such as acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl)imide, 3-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 3-alkyl-1-(meth)acryloyloxyalkylpyridinium thiocyanate -(meth)acryloyloxyalkylpyridinium cation-containing ionic compounds; 3-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl)imide, 3-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(trifluoro) 3-alkyl-1-(meth)acryloylamino such as methanesulfonyl)imide, 3-alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 3-alkyl-1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc. Alkylpyridinium cation-containing ionic compounds; 4-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 4-alkyl-1-vinylpyridinium dicyanamide , 4-alkyl-1-vinylpyridinium thiocyanate 4-alkyl-1-vinylpyridinium cation-containing ionic compounds such as; 4-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium bis 4-alkyl-1-(meth), such as (trifluoromethanesulfonyl)imide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium thiocyanate, etc. Acryloyloxyalkylpyridinium cation-containing ionic compounds; 4-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide , 4-alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 4-alkyl-1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc. containing 4-alkyl-1-(meth)acryloylaminoalkylpyridinium cations Examples include ionic compounds. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
 上記一般式(A)で示されるイオン性化合物のうち、X+がピペリニジニウム基であり、n1が1であり、n2が0であり、A1がビニル基、(メタ)アクリロイルオキシ基、又は(メタ)アクリロイルアミノ基である態様の具体例としては、1-アルキル-1-ビニルアルキルピペリジニウムビス(フルオロスルホニル)イミド、1-アルキル-1-ビニルアルキルピペリジニウムビス(トリフルオロメタンスルホニル)イミド、1-アルキル-1-ビニルアルキルピペリジニウムジシアンアミド、1-アルキル-1-ビニルアルキルピペリジニウムチオシアネート等の1-アルキル-1-ビニルアルキルピペリジニウムカチオン含有イオン性化合物;1-アルキル-1-(メタ)アクリロイルオキシアルキルピペリジニウムビス(フルオロスルホニル)イミド、1-アルキル-1-(メタ)アクリロイルオキシアルキルピペリジニウムビス(トリフルオロメタンスルホニル)イミド、1-アルキル-1-(メタ)アクリロイルオキシアルキルピペリジニウムジシアンアミド、1-アルキル-1-(メタ)アクリロイルオキシアルキルピペリジニウムチオシアネート等の1-アルキル-1-(メタ)アクリロイルオキシアルキルピペリジニウムカチオン含有イオン性化合物;1-アルキル-1-(メタ)アクリロイルアミノアルキルピペリジニウムビス(フルオロスルホニル)イミド、1-アルキル-1-(メタ)アクリロイルアミノアルキルピペリジニウムビス(トリフルオロメタンスルホニル)イミド、1-アルキル-1-(メタ)アクリロイルアミノアルキルピペリジニウムジシアンアミド、1-アルキル-1-(メタ)アクリロイルアミノアルキルピペリジニウムチオシアネート等の1-アルキル-1-(メタ)アクリロイルアミノアルキルピペリジニウムカチオン含有イオン性化合物等があげられる。 なお、前記アルキル置換基としては、炭素数1~16のアルキル基であることが好ましく、特に好ましくは炭素数1~12、更に好ましくは炭素数1~6である。 Among the ionic compounds represented by the general formula (A), X + is a piperinidinium group, n 1 is 1, n 2 is 0, A 1 is a vinyl group, a (meth)acryloyloxy group, or a (meth)acryloylamino group, 1-alkyl-1-vinylalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-vinylalkylpiperidinium bis(trifluoromethanesulfonyl ) 1-alkyl-1-vinylalkylpiperidinium cation-containing ionic compounds such as imides, 1-alkyl-1-vinylalkylpiperidinium dicyanamides, 1-alkyl-1-vinylalkylpiperidinium thiocyanates; -alkyl-1-(meth)acryloyloxyalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloyloxyalkylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-alkyl-1- 1-Alkyl-1-(meth)acryloyloxyalkylpiperidinium cation-containing ionics such as (meth)acryloyloxyalkylpiperidinium dicyanamide, 1-alkyl-1-(meth)acryloyloxyalkylpiperidinium thiocyanate Compound; 1-alkyl-1-(meth)acryloylaminoalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloylaminoalkylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-alkyl -1-alkyl-1-(meth)acryloylaminoalkylpiperidinium cations such as 1-(meth)acryloylaminoalkylpiperidinium dicyanamide, 1-alkyl-1-(meth)acryloylaminoalkylpiperidinium thiocyanate Contained ionic compounds and the like can be mentioned. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
 上記一般式(A)で示されるイオン性化合物のうち、X+がピロリジニウム基であり、n1が1であり、n2が0であり、A1がビニル基、(メタ)アクリロイルオキシ基、又は(メタ)アクリロイルアミノ基である態様の具体例としては、1-アルキル-1-ビニルアルキルピロリジニウムビス(フルオロスルホニル)イミド、1-アルキル-1-ビニルアルキ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、1-アルキル-1-ビニルアルキルピロリジニウムジシアンアミド、1-アルキル-1-ビニルアルキルピロリジニウムチオシアネート、等の1-アルキル-1-ビニルアルキルピロリジニウムカチオン含有イオン性化合物;1-アルキル-1-(メタ)アクリロイルオキシアルキルピロリジニウムビス(フルオロスルホニル)イミド、1-アルキル-1-(メタ)アクリロイルオキシアルキ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、1-アルキル-1-(メタ)アクリロイルオキシアルキルピロリジニウムジシアンアミド、1-アルキル-1-(メタ)アクリロイルオキシアルキルピロリジニウムチオシアネート、等の1-アルキル-1-(メタ)アクリロイルオキシアルキルピロリジニウムカチオン含有イオン性化合物;1-アルキル-1-(メタ)アクリロイルアミノアルキルピロリジニウムビス(フルオロスルホニル)イミド、1-アルキル-1-(メタ)アクリロイルアミノアルキ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、1-アルキル-1-(メタ)アクリロイルアミノアルキルピロリジニウムジシアンアミド、1-アルキル-1-(メタ)アクリロイルアミノアルキルピロリジニウムチオシアネート等の1-アルキル-1-(メタ)アクリロイルアミノアルキルピロリジニウムカチオン含有イオン性化合物等があげられる。なお、前記アルキル置換基としては、炭素数1~16のアルキル基であることが好ましく、特に好ましくは炭素数1~12、更に好ましくは炭素数1~6である。 Among the ionic compounds represented by the general formula (A), X + is a pyrrolidinium group, n 1 is 1, n 2 is 0, A 1 is a vinyl group, a (meth)acryloyloxy group, or a (meth)acryloylamino group, 1-alkyl-1-vinylalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-vinylalkylpyrrolidinium bis(trifluoromethanesulfonyl ) 1-alkyl-1-vinylalkylpyrrolidinium cation-containing ionic compounds such as imides, 1-alkyl-1-vinylalkylpyrrolidinium dicyanamides, 1-alkyl-1-vinylalkylpyrrolidinium thiocyanates; 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-alkyl-1 - containing 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium cations such as (meth)acryloyloxyalkylpyrrolidinium dicyanamide, 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium thiocyanate, etc. Ionic compounds; 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1 -1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium such as alkyl-1-(meth)acryloylaminoalkylpyrrolidinium dicyanamide, 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium thiocyanate Examples include ionic compounds containing nium cations. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
 上記一般式(A)で示されるイオン性化合物のうち、X+がトリアルキルスルホニウム基であり、n1が1であり、n2が0であり、A1がビニル基、(メタ)アクリロイルオキシ基、又は(メタ)アクリロイルアミノ基である態様の具体例としては、ジアルキル(ビニル)スルホニウムビス(フルオロスルホニル)イミド、ジアルキル(ビニル)スルホニウムビス(トリフルオロメタンスルホニル)イミド、ジアルキル(ビニル)スルホニウムジシアンアミド、ジアルキル(ビニル)スルホニウムチオシアネート、等のジアルキル(ビニル)スルホニウムカチオン含有イオン性化合物;ジアルキル((メタ)アクリロイルオキシアルキル)スルホニウムビス(フルオロスルホニル)イミド、ジアルキル((メタ)アクリロイルオキシアルキル)スルホニウムビス(トリフルオロメタンスルホニル)イミド、ジアルキル((メタ)アクリロイルオキシアルキル)スルホニウムジシアンアミド、ジアルキル((メタ)アクリロイルオキシアルキル)スルホニウムチオシアネート等のジアルキル((メタ)アクリロイルオキシアルキル)スルホニウムカチオン含有イオン性化合物;ジアルキル((メタ)アクリロイルアミノアルキル)スルホニウムビス(フルオロスルホニル)イミド、ジアルキル((メタ)アクリロイルアミノアルキル)スルホニウムビス(トリフルオロメタンスルホニル)イミド、ジアルキル((メタ)アクリロイルアミノアルキル)スルホニウムジシアンアミド、ジアルキル((メタ)アクリロイルアミノアルキル)スルホニウムチオシアネート等のジアルキル((メタ)アクリロイルアミノアルキル)スルホニウムカチオン含有イオン性化合物等があげられる。なお、前記アルキル置換基としては、炭素数1~16のアルキル基であることが好ましく、特に好ましくは炭素数1~12、更に好ましくは炭素数1~6である。 Among the ionic compounds represented by the general formula (A), X + is a trialkylsulfonium group, n 1 is 1, n 2 is 0, A 1 is a vinyl group, (meth)acryloyloxy or (meth)acryloylamino group, dialkyl(vinyl)sulfonium bis(fluorosulfonyl)imide, dialkyl(vinyl)sulfonium bis(trifluoromethanesulfonyl)imide, dialkyl(vinyl)sulfonium dicyanide Dialkyl (vinyl) sulfonium cation-containing ionic compounds such as amides, dialkyl (vinyl) sulfonium thiocyanates; Dialkyl ((meth)acryloyloxyalkyl)sulfonium cation-containing ionic compounds such as (trifluoromethanesulfonyl)imide, dialkyl ((meth)acryloyloxyalkyl)sulfonium dicyanamide, dialkyl ((meth)acryloyloxyalkyl)sulfonium thiocyanate; dialkyl((meth)acryloylaminoalkyl)sulfoniumbis(fluorosulfonyl)imide, dialkyl((meth)acryloylaminoalkyl)sulfoniumbis(trifluoromethanesulfonyl)imide, dialkyl((meth)acryloylaminoalkyl)sulfonium dicyanamide, dialkyl dialkyl ((meth)acryloylaminoalkyl)sulfonium cation-containing ionic compounds such as ((meth)acryloylaminoalkyl)sulfonium thiocyanate; The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
 上記一般式(A)で示されるイオン性化合物のうち、X+が第4級ホスホニウム基であり、n1が1であり、n2が0であり、A1がビニル基、(メタ)アクリロイルオキシ基、又は(メタ)アクリロイルアミノ基である態様の具体例としては、トリアルキル(ビニル)ホスホニウムビス(フルオロスルホニル)イミド、トリアルキル(ビニル)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、トリアルキル(ビニル)ホスホニウムジシアンアミド、トリアルキル(ビニル)ホスホニウムチオシアネート、等のトリアルキル(ビニル)ホスホニウムカチオン含有イオン性化合物;トリアルキル((メタ)アクリロイルオキシアルキル)ホスホニウムビス(フルオロスルホニル)イミド、トリアルキル((メタ)アクリロイルオキシアルキル)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、トリアルキル((メタ)アクリロイルオキシアルキル)ホスホニウムジシアンアミド、トリアルキル((メタ)アクリロイルオキシアルキル)ホスホニウムチオシアネート等のトリアルキル((メタ)アクリロイルオキシアルキル)ホスホニウムカチオン含有イオン性化合物;トリアルキル((メタ)アクリロイルアミノアルキル)ホスホニウムビス(フルオロスルホニル)イミド、トリアルキル((メタ)アクリロイルアミノアルキル)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、トリアルキル((メタ)アクリロイルアミノアルキル)ホスホニウムジシアンアミド、トリアルキル((メタ)アクリロイルアミノアルキル)ホスホニウムチオシアネート等のトリアルキル((メタ)アクリロイルアミノアルキル)ホスホニウムカチオン含有イオン性化合物等があげられる。なお、前記アルキル置換基としては、炭素数1~16のアルキル基であることが好ましく、特に好ましくは炭素数1~12、更に好ましくは炭素数1~6である。 Among the ionic compounds represented by the general formula (A), X + is a quaternary phosphonium group, n 1 is 1, n 2 is 0, A 1 is a vinyl group, and (meth)acryloyl Specific examples of embodiments that are an oxy group or a (meth)acryloylamino group include trialkyl(vinyl)phosphonium bis(fluorosulfonyl)imide, trialkyl(vinyl)phosphonium bis(trifluoromethanesulfonyl)imide, trialkyl(vinyl ) phosphonium dicyanamide, trialkyl (vinyl) phosphonium thiocyanate, trialkyl (vinyl) phosphonium cation-containing ionic compounds; trialkyl ((meth) acryloyloxyalkyl) phosphonium bis (fluorosulfonyl) imide, trialkyl (( trialkyl ((meth)acryloyloxyalkyl)phosphonium bis(trifluoromethanesulfonyl)imide, trialkyl((meth)acryloyloxyalkyl)phosphonium dicyanamide, trialkyl((meth)acryloyloxyalkyl)phosphonium thiocyanate, etc. Acryloyloxyalkyl)phosphonium cation-containing ionic compounds; trialkyl((meth)acryloylaminoalkyl)phosphonium bis(fluorosulfonyl)imide, trialkyl((meth)acryloylaminoalkyl)phosphonium bis(trifluoromethanesulfonyl)imide, trialkyl trialkyl((meth)acryloylaminoalkyl)phosphonium cation-containing ionic compounds such as ((meth)acryloylaminoalkyl)phosphonium dicyanamide and trialkyl((meth)acryloylaminoalkyl)phosphonium thiocyanate; The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
 上記一般式(A)で示されるイオン性化合物のうち、X+が第4級アンモニウム基であり、n1が1であり、n2が1であり、A1及びA2が水酸基である態様の具体例としては、ビス(2-ヒドロキシエチル)-メチル-オク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、ビス(2-ヒドロキシエチル)-メチル-デ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、ビス(2-ヒドロキシエチル)-メチル-ドデ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、ビス(2-ヒドロキシエチル)-メチル-テトラデ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、ビス(2-ヒドロキシエチル)-メチル-ヘキサデ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、ビス(2-ヒドロキシエチル)-メチル-オクタデ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、ビス(2-ヒドロキシエチル)-メチル-(9-エン-オクタデシル)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、エチル-ビス(2-ヒドロキシエチル)-オク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、エチル-ビス(2-ヒドロキシエチル)-デ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、エチル-ビス(2-ヒドロキシエチル)-ドデ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、エチル-ビス(2-ヒドロキシエチル)-テトラデ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、エチル-ビス(2-ヒドロキシエチル)-ヘキサデ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、エチル-ビス(2-ヒドロキシエチル)-オクタデ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、オレイルビス(2-ヒドロキシエチル)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、オレイル-エチル-ビス(2-ヒドロキシエチル)アンモニウムビス(トリフルオロメタンスルホニル)イミド等が挙げられる。 Among the ionic compounds represented by the general formula (A), X + is a quaternary ammonium group, n 1 is 1, n 2 is 1, and A 1 and A 2 are hydroxyl groups. Specific examples include bis(2-hydroxyethyl)-methyl-octylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-decylammonium bis(trifluoromethanesulfonyl)imide, bis(2- Hydroxyethyl)-methyl-dodecylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-tetradecylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-hexadecylammonium Bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-octadecylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-(9-ene-octadecyl)ammonium bis(trifluoromethane sulfonyl)imide, ethyl-bis(2-hydroxyethyl)-octylammonium bis(trifluoromethanesulfonyl)imide, ethyl-bis(2-hydroxyethyl)-decylammonium bis(trifluoromethanesulfonyl)imide, ethyl-bis(2- hydroxyethyl)-dodecylammonium bis(trifluoromethanesulfonyl)imide, ethyl-bis(2-hydroxyethyl)-tetradecylammonium bis(trifluoromethanesulfonyl)imide, ethyl-bis(2-hydroxyethyl)-hexadecylammonium bis( trifluoromethanesulfonyl)imide, ethyl-bis(2-hydroxyethyl)-octadecylammonium bis(trifluoromethanesulfonyl)imide, oleylbis(2-hydroxyethyl)methylammonium bis(trifluoromethanesulfonyl)imide, oleyl-ethyl-bis(2 -hydroxyethyl)ammonium bis(trifluoromethanesulfonyl)imide and the like.
 上記一般式(A)で示されるイオン性化合物のうち、X+がピリジニウム基であり、n1が1であり、n2が0であり、A1が水酸基である態様の具体例としては、N-ヒドロキシエチルピリジニウムビス(トリフルオロメタスルホニル)イミド等が挙げられる。 Among the ionic compounds represented by the above general formula (A), specific examples of embodiments in which X + is a pyridinium group, n 1 is 1, n 2 is 0, and A 1 is a hydroxyl group include: and N-hydroxyethylpyridinium bis(trifluoromethasulfonyl)imide.
 上記一般式(A)で示されるイオン性化合物のうち、X+がイミダゾリウム基であり、n1が1であり、n2が0であり、A1が水酸基である態様の具体例としては、1-(2-ヒドロキシエチル)-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)イミド等が挙げられる。 Among the ionic compounds represented by the above general formula (A), as a specific example of an aspect in which X + is an imidazolium group, n 1 is 1, n 2 is 0, and A 1 is a hydroxyl group, , 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and the like.
 上記一般式(A)で示されるイオン性化合物のうち、X+がイミダゾリウム基、又は第4級アンモニウム基であり、n1が1であり、n2が0であり、A1及びA2がアミノ基である態様の具体例としては、1-アミノプロピル-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、1-アミノプロピル-3-メチルイミダゾリウムジシアノアミド、1-アミノプロピル-3-メチルイミダゾリウムテトラフルオロボレート、1-アミノヘキシル-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、1-アミノヘキシル-3-メチルイミダゾリウムジシアノアミド、1-アミノヘキシル-3-メチルイミダゾリウムテトラフルオロボレート、トリメチルアミノ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、トリメチルアミノヘキシルアンモニウムジシアノアミド、トリメチルアミノヘキシルアンモニウムテトラフルオロボレート等が挙げられる。 Among the ionic compounds represented by the general formula (A), X + is an imidazolium group or a quaternary ammonium group, n 1 is 1, n 2 is 0, A 1 and A 2 is an amino group, 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-aminopropyl-3-methylimidazolium dicyanoamide, 1-aminopropyl-3- Methylimidazolium tetrafluoroborate, 1-aminohexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-aminohexyl-3-methylimidazolium dicyanoamide, 1-aminohexyl-3-methylimidazolium tetrafluoro borate, trimethylaminohexylammonium bis(trifluoromethanesulfonyl)imide, trimethylaminohexylammonium dicyanoamide, trimethylaminohexylammonium tetrafluoroborate and the like.
 本発明のイオン性化合物の含有量は、特に限定されないが、本発明の粘着剤層に十分な帯電防止性能を付与できる点から、アクリル系ポリマー(A)100重量部に対して、好ましくは0.01重量部以上、より好ましくは0.05重量部以上、さらに好ましくは0.1重量部以上、0.5重量部以上又は0.5重量部以上、1.0重量部以上、2.0重量部以上、3.0重量部以上、4.0重量部以上、又は5.0重量部以上含んでいてもよい。本発明のイオン性化合物の含有量は、特に限定されないが、本発明の粘着剤層に透明性、外観、接着信頼性等の耐久性を確保しやすくなる点から、アクリル系ポリマー(A)100重量部に対して、好ましくは50重量部以下、より好ましくは40重量部以下、さらに好ましくは30重量部以下、25重量部以下、20重量部以下、又は15重量部以下含んでいてもよい。 The content of the ionic compound of the present invention is not particularly limited, but from the viewpoint of imparting sufficient antistatic performance to the pressure-sensitive adhesive layer of the present invention, it is preferably 0 per 100 parts by weight of the acrylic polymer (A). 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, 0.5 parts by weight or more, or 0.5 parts by weight or more, 1.0 parts by weight or more, 2.0 It may be included in parts by weight or more, 3.0 parts by weight or more, 4.0 parts by weight or more, or 5.0 parts by weight or more. Although the content of the ionic compound of the present invention is not particularly limited, the acrylic polymer (A) 100 It may be contained in an amount of preferably 50 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less.
[2-2.アクリル系ポリマー(A)]
 上記粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)は、アクリル系ポリマー(A)を主成分とするアクリル系粘着剤層である。アクリル系ポリマー(A)の具体的な含有量は、特に限定されないが、本発明の粘着剤層全量(全重量、100重量%)に対して75重量%以上(例えば75~99.9重量%)であることが好ましく、より好ましくは85重量%以上(例えば85~99.9重量%)である。
[2-2. Acrylic polymer (A)]
The pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is an acrylic pressure-sensitive adhesive layer containing the acrylic polymer (A) as a main component. Although the specific content of the acrylic polymer (A) is not particularly limited, it is 75% by weight or more (for example, 75 to 99.9% by weight) relative to the total amount of the pressure-sensitive adhesive layer of the present invention (total weight, 100% by weight). ), more preferably 85% by weight or more (for example, 85 to 99.9% by weight).
 アクリル系ポリマー(A)を主成分として含有する粘着剤層を形成する粘着剤組成物としては、特に限定されないが、例えば、アクリル系ポリマー(A)を必須成分とする組成物;アクリル系ポリマー(A)を構成するモノマー成分の混合物(「モノマー混合物」と称する場合がある)又はその部分重合物を必須成分とする組成物等が挙げられる。特に限定されないが、前者としては、例えば、いわゆる水分散型組成物(エマルジョン型組成物)等が挙げられ、後者としては、例えば、いわゆる活性エネルギー線硬化型組成物等が挙げられる。なお、上記粘着剤組成物は、必要に応じて、その他の添加剤を含んでいてもよい。 The adhesive composition for forming the adhesive layer containing the acrylic polymer (A) as a main component is not particularly limited, but for example, a composition containing the acrylic polymer (A) as an essential component; an acrylic polymer ( Examples thereof include a mixture of monomer components constituting A) (sometimes referred to as a "monomer mixture") or a composition containing a partial polymer thereof as an essential component. Although not particularly limited, examples of the former include so-called water-dispersible compositions (emulsion-type compositions), and examples of the latter include so-called active energy ray-curable compositions. In addition, the said adhesive composition may contain the other additive agent as needed.
 上記「モノマー混合物」とは、単一のモノマー成分で構成される場合、2以上のモノマー成分で構成される場合を含むものとする。また、上記「部分重合物」とは、上記モノマー混合物の構成成分のうち1又は2以上の成分が部分的に重合している組成物を意味する。なかでも、上記粘着剤組成物は、モノマー混合物又はその部分重合物を必須成分とする組成物が好ましい。 The above "monomer mixture" includes cases where it is composed of a single monomer component and cases where it is composed of two or more monomer components. Moreover, the above-mentioned "partially polymerized product" means a composition in which one or more of the components of the monomer mixture are partially polymerized. Among them, the pressure-sensitive adhesive composition is preferably a composition containing a monomer mixture or a partial polymer thereof as an essential component.
 アクリル系ポリマー(A)は、必須のモノマー単位(単量体単位、モノマー構成単位)としてアクリル系モノマー(アクリル系単量体)を含むポリマー(重合体)である。いいかえれば、アクリル系ポリマー(A)は、構成単位としてアクリル系モノマーに由来する構成単位を含むポリマーである。つまり、アクリル系ポリマー(A)は、アクリル系モノマーを必須のモノマー成分として構成(形成)された重合体である。なお、本明細書において、「(メタ)アクリル」とは、「アクリル」及び「メタクリル」のうち、何れか一方又は両方を表し、他も同様である。アクリル系ポリマー(A)の重量平均分子量は、特に限定されないが、100000~5000000であることが好ましい。 The acrylic polymer (A) is a polymer (polymer) containing an acrylic monomer (acrylic monomer) as an essential monomer unit (monomer unit, monomer structural unit). In other words, the acrylic polymer (A) is a polymer containing structural units derived from acrylic monomers as structural units. In other words, the acrylic polymer (A) is a polymer constituted (formed) with an acrylic monomer as an essential monomer component. In this specification, "(meth)acryl" means either one or both of "acryl" and "methacryl", and the same applies to others. Although the weight average molecular weight of the acrylic polymer (A) is not particularly limited, it is preferably from 100,000 to 5,000,000.
 アクリル系ポリマー(A)は、必須のモノマー単位として、直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステル(以下、単に「(メタ)アクリル酸アルキルエステル」と称する場合がある)を含むポリマーであることが好ましい。 The acrylic polymer (A) is a (meth)acrylic acid alkyl ester having a linear or branched alkyl group as an essential monomer unit (hereinafter sometimes simply referred to as "(meth)acrylic acid alkyl ester"). ) is preferred.
 上記(メタ)アクリル酸アルキルエステルとしては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸ブチル((メタ)アクリル酸n-ブチル)、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸イソペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸オクタデシル、(メタ)アクリル酸イソステアリル、(メタ)アクリル酸ノナデシル、(メタ)アクリル酸エイコシル等のアルキル基の炭素数が1~20の(メタ)アクリル酸アルキルエステル等が挙げられる。なお、(メタ)アクリル酸アルキルエステルは、単独で又は2種以上を組み合わせて用いてもよい。 Examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate ((meth) ) n-butyl acrylate), isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth) hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) ) Decyl acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, (meth) Hexadecyl acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, etc., where the alkyl group has 1 to 20 carbon atoms. (Meth)acrylic acid alkyl esters of. In addition, you may use a (meth)acrylic-acid alkylester individually or in combination of 2 or more types.
 なかでも、上記(メタ)アクリル酸アルキルエステルは、強接着性を得る点、残存応力を調整する点より、アルキル基の炭素数が1~18の(メタ)アクリル酸アルキルエステルが好ましく、より好ましくはメタクリル酸メチル(MMA)、アクリル酸ブチル(BA)、アクリル酸2-エチルヘキシル(2EHA)、アクリル酸イソステアリル(ISTA)である。 Among them, the (meth)acrylic acid alkyl ester is preferably a (meth)acrylic acid alkyl ester having an alkyl group with a carbon number of 1 to 18 from the viewpoint of obtaining strong adhesiveness and adjusting residual stress. are methyl methacrylate (MMA), butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), and isostearyl acrylate (ISTA).
 アクリル系ポリマー(A)の全モノマー単位(アクリル系ポリマー(A)を構成するモノマー成分全量)における上記(メタ)アクリル酸アルキルエステルの含有量(割合)は、特に限定されないが、接着性信頼性、特に低温での接着信頼性の点で、アクリル系ポリマー(A)を構成するモノマー成分全量(100重量部)に対して、30~95重量部が好ましく、より好ましくは35~90重量部、さらに好ましくは40~85重量部である。 The content (percentage) of the (meth)acrylic acid alkyl ester in the total monomer units of the acrylic polymer (A) (the total amount of the monomer components constituting the acrylic polymer (A)) is not particularly limited, but the adhesion reliability , Especially in terms of adhesion reliability at low temperatures, the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) is preferably 30 to 95 parts by weight, more preferably 35 to 90 parts by weight, More preferably 40 to 85 parts by weight.
 アクリル系ポリマー(A)は、モノマー単位として上記(メタ)アクリル酸アルキルエステルの他にも、共重合が可能なモノマー(共重合性モノマー)を含んでいてもよい。つまり、アクリル系ポリマー(A)は、構成するモノマー成分として、共重合性モノマーを含んでいてもよい。なお、共重合性モノマーは、単独で又は2種以上を組み合わせて用いられていてもよい。 The acrylic polymer (A) may contain a copolymerizable monomer (copolymerizable monomer) in addition to the (meth)acrylic acid alkyl ester as a monomer unit. In other words, the acrylic polymer (A) may contain a copolymerizable monomer as a constituent monomer component. The copolymerizable monomers may be used alone or in combination of two or more.
 上記共重合性モノマーとしては、水酸基含有モノマーが好ましく挙げられる。アクリル系ポリマー(A)がモノマー単位として水酸基含有モノマーを含んでいると、構成するモノマー成分を重合させる際に重合させやすくなり、また、良好な凝集力を得やすくなる。このため、強接着性を得やすくなり、また、ゲル分率を大きくして、優れた耐発泡剥がれ性を得やすくなる。さらに、高湿環境下で生じることのある粘着シートの白化を抑制しやすくなる。さらに、水酸基は、上記の本発明のイオン性化合物が有する官能基(A)との反応点にもなり得る。 As the copolymerizable monomer, a hydroxyl group-containing monomer is preferably mentioned. When the acrylic polymer (A) contains a hydroxyl group-containing monomer as a monomer unit, it becomes easy to polymerize the constituent monomer components, and it becomes easy to obtain good cohesive strength. For this reason, it becomes easy to obtain strong adhesiveness, and it becomes easy to obtain excellent anti-foaming peeling property by increasing the gel fraction. Furthermore, it becomes easy to suppress whitening of the adhesive sheet that may occur in a high-humidity environment. Furthermore, the hydroxyl group can also serve as a reaction point with the functional group (A) of the ionic compound of the present invention.
 アクリル系ポリマー(A)を構成するモノマー成分全量(100重量部)に対する上記水酸基含有モノマーの含有量(割合)は、特に限定されない。水酸基含有モノマーの量が一定以上であると、高湿環境下で生じることのある粘着シートの白化をより抑制でき、加湿白濁耐性等の透明性が確保できる。上記水酸基含有モノマーの含有量の下限は、1重量部以上であることが好ましく、より好ましくは2重量部以上、3重量部以上、4重量部以上、5重量部以上、6重量部以上、7重量部以上、8重量部以上、さらに好ましくは10重量部以上である。また、上記水酸基含有モノマーの含有量の上限は、凝集力の点、接着性、耐発泡剥がれ性等の接着信頼性の得やすさの点より、40重量部以下であること好ましく、35重量部以下、34重量部以下、33重量部以下、32重量部以下、又は31重量部以下であることがより好ましく、30重量部以下であることがさらに好ましい。  The content (proportion) of the hydroxyl group-containing monomer relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) is not particularly limited. When the amount of the hydroxyl group-containing monomer is at least a certain amount, the whitening of the pressure-sensitive adhesive sheet, which may occur in a high-humidity environment, can be further suppressed, and the transparency such as resistance to humid clouding can be ensured. The lower limit of the content of the hydroxyl group-containing monomer is preferably 1 part by weight or more, more preferably 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more. It is at least 8 parts by weight, more preferably at least 10 parts by weight. In addition, the upper limit of the content of the hydroxyl group-containing monomer is preferably 40 parts by weight or less, and 35 parts by weight, from the viewpoint of cohesive strength, adhesiveness, and ease of obtaining adhesion reliability such as resistance to foaming and peeling. It is more preferably 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, or 31 parts by weight or less, and even more preferably 30 parts by weight or less. 
 さらに、上記共重合性モノマーとしては、窒素原子含有モノマーが好ましく挙げられる。アクリル系ポリマー(A)がモノマー単位として窒素原子含有モノマーを含んでいると、適度な凝集力が得やすくなる。このため、ガラス板に対する180°(度)引き剥がし接着力及びアクリル板に対する180°引き剥がし接着力を大きくして、強接着性を得やすくなり、また、ゲル分率を大きくして、優れた耐発泡剥がれ性を得やすくなる。さらに、粘着剤層で適度な柔軟性を得やすくなり、300%引張残留応力を特定の範囲内に調整し、優れた応力緩和性及び優れた段差追従性を得やすくなる。 Furthermore, as the copolymerizable monomer, a nitrogen atom-containing monomer is preferably mentioned. When the acrylic polymer (A) contains a nitrogen atom-containing monomer as a monomer unit, it becomes easy to obtain an appropriate cohesive force. For this reason, the 180° (degree) peeling adhesive force to the glass plate and the 180° peeling adhesive force to the acrylic plate are increased, making it easier to obtain strong adhesiveness, and increasing the gel fraction to achieve excellent adhesion. It becomes easy to obtain anti-foaming peeling property. Furthermore, it becomes easy to obtain appropriate flexibility in the pressure-sensitive adhesive layer, adjust the 300% tensile residual stress within a specific range, and easily obtain excellent stress relaxation properties and excellent conformability to unevenness.
 アクリル系ポリマー(A)を構成するモノマー成分全量(100重量部)に対する上記窒素原子含有モノマーの含有量(割合)は、特に限定されないが、5重量部以上であることが好ましい。上記窒素原子含有モノマーの含有量の下限は、凝集力、接着性、耐発泡剥がれ性の点より、アクリル系ポリマー(A)を構成するモノマー成分全量(100重量部)に対して、7重量部以上であることが好ましく、8重量部以上であることがより好ましく、9重量部以上、又は10重量部以上であることがさらに好ましい。また、上記窒素原子含有モノマーの含有量の上限は、粘着剤層で適度な柔軟性をより得やすくなり、優れた応力緩和性及び優れた段差追従性をより得やすくなる点より、40重量部以下であることが好ましく、35重量部以下であることがより好ましく、30重量部以下であることがさらに好ましい。 The content (proportion) of the nitrogen atom-containing monomer relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) is not particularly limited, but is preferably 5 parts by weight or more. The lower limit of the content of the nitrogen atom-containing monomer is 7 parts by weight with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) from the viewpoint of cohesive strength, adhesiveness, and resistance to foaming and peeling. It is preferably 8 parts by weight or more, more preferably 9 parts by weight or more, or even more preferably 10 parts by weight or more. In addition, the upper limit of the content of the nitrogen atom-containing monomer is 40 parts by weight from the point that it becomes easier to obtain appropriate flexibility in the pressure-sensitive adhesive layer, and it becomes easier to obtain excellent stress relaxation and excellent step conformability. It is preferably 35 parts by weight or less, more preferably 30 parts by weight or less.
 上記アクリル系ポリマー(A)は、上記モノマー単位(モノマー成分)を公知乃至慣用の重合方法により重合することにより、得ることができる。上記アクリル系ポリマー(A)の重合方法としては、例えば、溶液重合方法、乳化重合方法、塊状重合方法、活性エネルギー線照射による重合方法(活性エネルギー線重合方法)等が挙げられる。なかでも、粘着剤層の透明性、耐水性、コスト等の点で、溶液重合方法、活性エネルギー線重合方法が好ましく、より好ましくは活性エネルギー線重合方法である。 The above acrylic polymer (A) can be obtained by polymerizing the above monomer units (monomer components) by a known or commonly used polymerization method. Examples of the polymerization method of the acrylic polymer (A) include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method). Among them, the solution polymerization method and the active energy ray polymerization method are preferable, and the active energy ray polymerization method is more preferable, from the viewpoints of the transparency, water resistance, cost, etc. of the pressure-sensitive adhesive layer.
 上記活性エネルギー線重合(光重合)に際して照射される活性エネルギー線としては、例えば、α線、β線、γ線、中性子線、電子線等の電離性放射線や、紫外線等が挙げられ、特に紫外線が好ましい。また、活性エネルギー線の照射エネルギー、照射時間、照射方法等は特に限定されず、光重合開始剤を活性化させて、モノマー成分の反応を生じさせることができればよい。 Examples of the active energy ray irradiated during the active energy ray polymerization (photopolymerization) include ionizing radiation such as α-ray, β-ray, γ-ray, neutron beam, and electron beam, and ultraviolet rays, particularly ultraviolet rays. is preferred. Moreover, the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the photopolymerization initiator can be activated to cause the reaction of the monomer components.
 上記アクリル系ポリマー(A)の重合に際しては、各種の一般的な溶剤が用いられてもよい。このような溶剤としては、例えば、酢酸エチル、酢酸n-ブチル等のエステル類;トルエン、ベンゼン等の芳香族炭化水素類;n-ヘキサン、n-ヘプタン等の脂肪族炭化水素類;シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類;メチルエチルケトン、メチルイソブチルケトン等のケトン類等の有機溶剤が挙げられる。なお、溶剤は、単独で又は2種以上を組み合わせて用いられてもよい。 Various common solvents may be used in the polymerization of the acrylic polymer (A). Examples of such solvents 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; Alicyclic hydrocarbons such as cyclohexane; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone. In addition, a solvent may be used individually or in combination of 2 or more types.
 また、上記アクリル系ポリマー(A)の重合に際しては、重合反応の種類に応じて、熱重合開始剤や光重合開始剤(光開始剤)等の重合開始剤が用いられてもよい。なお、重合開始剤は、単独で又は2種以上を組み合わせて用いられてもよい。 In addition, when polymerizing the acrylic polymer (A), a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) may be used depending on the type of polymerization reaction. In addition, a polymerization initiator may be used individually or in combination of 2 or more types.
 上記光重合開始剤としては、特に限定されないが、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α-ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤等が挙げられる。なお、光重合開始剤は、単独で又は2種以上を組み合わせて用いられてもよい。 The photopolymerization initiator is not particularly limited. Active oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like can be mentioned. In addition, a photoinitiator may be used individually or in combination of 2 or more types.
 上記ベンゾインエーテル系光重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、アニソールメチルエーテル等が挙げられる。上記アセトフェノン系光重合開始剤としては、例えば、2,2-ジエトキシアセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、4-フェノキシジクロロアセトフェノン、4-(t-ブチル)ジクロロアセトフェノン等が挙げられる。上記α-ケトール系光重合開始剤としては、例えば、2-メチル-2-ヒドロキシプロピオフェノン、1-[4-(2-ヒドロキシエチル)フェニル]-2-メチルプロパン-1-オン等が挙げられる。上記芳香族スルホニルクロリド系光重合開始剤としては、例えば、2-ナフタレンスルホニルクロライド等が挙げられる。上記光活性オキシム系光重合開始剤としては、例えば、1-フェニル-1,1-プロパンジオン-2-(o-エトキシカルボニル)-オキシム等が挙げられる。上記ベンゾイン系光重合開始剤としては、例えば、ベンゾイン等が挙げられる。上記ベンジル系光重合開始剤としては、例えば、ベンジル等が挙げられる。上記ベンゾフェノン系光重合開始剤としては、例えば、ベンゾフェノン、ベンゾイル安息香酸、3,3'-ジメチル-4-メトキシベンゾフェノン、ポリビニルベンゾフェノン、α-ヒドロキシシクロヘキシルフェニルケトン等が挙げられる。上記ケタール系光重合開始剤としては、例えば、ベンジルジメチルケタール等が挙げられる。上記チオキサントン系光重合開始剤としては、例えば、チオキサントン、2-クロロチオキサントン、2-メチルチオキサントン、2,4-ジメチルチオキサントン、イソプロピルチオキサントン、2,4-ジイソプロピルチオキサントン、ドデシルチオキサントン等が挙げられる。 Examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, anisole methyl ether and the like. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4-(t-butyl ) and dichloroacetophenone. Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like. 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-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenyl ketone, and the like. Examples of the ketal-based 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.
 上記光重合開始剤の使用量は、特に限定されないが、例えば、アクリル系ポリマー(A)の全モノマー単位(アクリル系ポリマー(A)を構成するモノマー成分全量)100重量部に対して、0.001~1重量部が好ましく、より好ましくは0.01~0.50重量部である。 The amount of the photopolymerization initiator to be used is not particularly limited. 001 to 1 part by weight, more preferably 0.01 to 0.50 part by weight.
 また、上記熱重合開始剤としては、特に限定されないが、例えば、アゾ系重合開始剤、過酸化物系重合開始剤(例えば、ジベンゾイルペルオキシド、tert-ブチルペルマレエート等)、レドックス系重合開始剤等が挙げられる。なかでも、特開2002-69411号公報に開示されたアゾ系重合開始剤が好ましい。上記アゾ系重合開始剤としては、2,2'-アゾビスイソブチロニトリル(以下、「AIBN」と称する場合がある)、2,2'-アゾビス-2-メチルブチロニトリル(以下、「AMBN」と称する場合がある)、2,2'-アゾビス(2-メチルプロピオン酸)ジメチル、4,4'-アゾビス-4-シアノバレリアン酸等が挙げられる。 Further, the thermal polymerization initiator is not particularly limited, but for example, an azo polymerization initiator, a peroxide polymerization initiator (e.g., dibenzoyl peroxide, tert-butyl permaleate, etc.), a redox polymerization initiator agents and the like. Among them, the azo polymerization initiator disclosed in JP-A-2002-69411 is preferable. Examples of the azo polymerization initiator include 2,2'-azobisisobutyronitrile (hereinafter sometimes referred to as "AIBN"), 2,2'-azobis-2-methylbutyronitrile (hereinafter, " AMBN”), 2,2′-azobis(2-methylpropionate)dimethyl, 4,4′-azobis-4-cyanovaleric acid and the like.
 上記熱重合開始剤の使用量は、特に限定されないが、例えば、上記アゾ系重合開始剤の場合、アクリル系ポリマー(A)の全モノマー単位(アクリル系ポリマー(A)を構成するモノマー成分全量)100重量部に対して、0.05~0.5重量部が好ましく、より好ましくは0.1~0.3重量部である。 The amount of the thermal polymerization initiator used is not particularly limited. For example, in the case of the azo polymerization initiator, all monomer units of the acrylic polymer (A) (the total amount of monomer components constituting the acrylic polymer (A)) It is preferably 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight, per 100 parts by weight.
[2-3.カルボキシル基含有モノマー等]
 上記粘着剤層は、アクリル系ポリマー(A)を構成するモノマー成分として、カルボキシル基含有モノマーを実質的に含有しないことが好ましい。なお、「実質的に含有しない」とは、不可避的に混入する場合を除いて能動的に配合はしないことをいう。また、カルボキシル基含有モノマーとは、分子内にカルボキシル基を少なくとも1つ有するモノマーを意味する。より優れた腐食防止効果が得られるという観点から、具体的には、カルボキシル基含有モノマーの含有量が、アクリル系ポリマー(A)を構成するモノマー成分全量(100重量部)に対して、0.05重量部以下(例えば、0~0.05重量部)が好ましく、より好ましくは0.01重量部以下(例えば、0~0.01重量部)、さらに好ましくは0.001重量部以下(例えば、0~0.001重量部)であるものは、実質的に含有しないということができる。なお、上記カルボキシル基含有モノマーとしては、例えば、(メタ)アクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等が挙げられる、また、上記カルボキシル基含有モノマーには、例えば、無水マレイン酸、無水イタコン酸等の酸無水物基含有モノマーも含まれるものとする。
[2-3. Carboxyl group-containing monomer, etc.]
Preferably, the pressure-sensitive adhesive layer does not substantially contain a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer (A). The phrase "substantially does not contain" means that it is not actively blended except when it is unavoidably mixed. A carboxyl group-containing monomer means a monomer having at least one carboxyl group in the molecule. From the viewpoint of obtaining a more excellent anti-corrosion effect, specifically, the content of the carboxyl group-containing monomer is 0.00% relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A). 05 parts by weight or less (e.g., 0 to 0.05 parts by weight), more preferably 0.01 parts by weight or less (e.g., 0 to 0.01 parts by weight), still more preferably 0.001 parts by weight or less (e.g., , 0 to 0.001 parts by weight) can be said to be substantially free. Examples of the carboxyl group-containing monomer include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Acid anhydride group-containing monomers such as maleic acid and itaconic anhydride are also intended to be included.
 さらに、上記粘着剤層がアクリル系粘着剤層である場合、より優れた腐食防止効果が得られるという観点から、上記粘着剤層は、アクリル系ポリマー(A)を構成するモノマー成分として、カルボキシル基含有モノマーを実質的に含有しないのみならず、カルボキシル基以外の酸性基(スルホ基、リン酸基等)を有するモノマーについても、アクリル系ポリマー(A)を構成するモノマー成分として、実質的に含有しないことが好ましい。すなわち、アクリル系ポリマー(A)は、好ましくは、構成するモノマー成分として、カルボキシル基含有モノマーとその他の酸性基を有するモノマーとを何れも実質的に含有しないことが好ましい。具体的には、アクリル系ポリマー(A)を構成するモノマー成分としてのカルボキシル基含有モノマー及びその他の酸性基を有するモノマーの総量が、アクリル系ポリマー(A)を構成するモノマー成分全量(100重量部)に対して、0.05重量部以下(例えば、0~0.05重量部)が好ましく、より好ましくは0.01重量部以下(例えば、0~0.01重量部)、さらに好ましくは0.001重量部以下(例えば、0~0.001重量部)であるものは、実質的に含有しないということができる。 Furthermore, when the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer, from the viewpoint of obtaining a more excellent anti-corrosion effect, the pressure-sensitive adhesive layer contains a carboxyl group as a monomer component constituting the acrylic polymer (A). In addition to substantially not containing contained monomers, monomers having acidic groups other than carboxyl groups (sulfo groups, phosphoric acid groups, etc.) are also substantially contained as monomer components constituting the acrylic polymer (A). preferably not. That is, the acrylic polymer (A) preferably contains substantially no carboxyl group-containing monomers and other monomers having acidic groups as constituent monomer components. Specifically, the total amount of the carboxyl group-containing monomers and other monomers having an acidic group as the monomer components constituting the acrylic polymer (A) is the total amount of the monomer components constituting the acrylic polymer (A) (100 parts by weight ), preferably 0.05 parts by weight or less (e.g., 0 to 0.05 parts by weight), more preferably 0.01 parts by weight or less (e.g., 0 to 0.01 parts by weight), more preferably 0 It can be said that the content of 0.001 part by weight or less (for example, 0 to 0.001 part by weight) is substantially absent.
 また、上記粘着剤層は、同様の観点から、アクリル系ポリマー(A)以外のポリマー(例えば、後述のアクリル系ポリマー(B)など)を構成するモノマー成分としても、酸性基含有モノマーを含有しない又は実質的に含有しないことが好ましい。例えば、カルボキシル基含有モノマーを実質的に含有しないことが好ましい。なお、「実質的に含有しない」の意味、好ましい程度、及びカルボキシル基以外の酸性基を有するモノマー等については、アクリル系ポリマー(A)を構成するモノマー成分である場合と同様であるものとする。 In addition, from the same viewpoint, the pressure-sensitive adhesive layer does not contain an acidic group-containing monomer as a monomer component constituting a polymer other than the acrylic polymer (A) (for example, an acrylic polymer (B) described later). Or it is preferable not to contain substantially. For example, it is preferred that substantially no carboxyl group-containing monomer is contained. The meaning of "not containing substantially", the preferred degree, and the monomer having an acidic group other than a carboxyl group are the same as in the case of the monomer component constituting the acrylic polymer (A). .
[2-4.塩基性基含有モノマー]
 なお、上記粘着剤層は、ベースポリマーを構成するモノマー成分として、塩基性基含有モノマーを含有しない又は実質的に含有しないことが好ましい。例えば、上記粘着剤層がベースポリマーとしてアクリル系ポリマー(A)を含有するアクリル系粘着剤層である場合、アクリル系ポリマー(A)以外のポリマーを構成するモノマー成分として、塩基性基含有モノマーを実質的に含有しないことが好ましく、各種ポリマーを構成するモノマー成分でない場合であっても、上記粘着剤層中に塩基性基含有モノマーを実質的に含有しないことが好ましい点は、カルボキシル基含有モノマーの場合と同様である。また、「実質的に含有しない」の意味、好ましい程度等についても、同様であるものとする。
[2-4. Basic group-containing monomer]
In addition, it is preferable that the pressure-sensitive adhesive layer does not contain, or substantially does not contain, a basic group-containing monomer as a monomer component constituting the base polymer. For example, when the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer containing an acrylic polymer (A) as a base polymer, a basic group-containing monomer is added as a monomer component constituting a polymer other than the acrylic polymer (A). It is preferable that it does not substantially contain, and even if it is not a monomer component constituting various polymers, it is preferable that the pressure-sensitive adhesive layer does not substantially contain a basic group-containing monomer. is the same as for In addition, the same applies to the meaning of "substantially free of", the preferred degree, and the like.
[2-5.水酸基含有モノマー]
 水酸基含有モノマーとは、分子内に水酸基を少なくとも1つ有するモノマーを意味する。また、分子内に水酸基を少なくとも1つ有し、且つ、分子内にカルボキシル基を少なくとも1つ有するモノマーはカルボキシル基含有モノマーであり、水酸基含有モノマーではないものとする。上記水酸基含有モノマーとしては、特に限定されないが、具体的には、例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル、(メタ)アクリル酸ヒドロキシオクチル、(メタ)アクリル酸ヒドロキシデシル、(メタ)アクリル酸ヒドロキシラウリル、(メタ)アクリル酸(4-ヒドロキシメチルシクロヘキシル)等の水酸基含有(メタ)アクリル酸エステル;ビニルアルコール、アリルアルコール等が挙げられる。なかでも、上記水酸基含有モノマーとしては、水酸基含有(メタ)アクリル酸エステルが好ましく、より好ましくはアクリル酸2-ヒドロキシエチル(HEA)、(メタ)アクリル酸2-ヒドロキシプロピル(HPA)、アクリル酸4-ヒドロキシブチル(4HBA)である。なお、水酸基含有モノマーは、単独で又は2種以上を組み合わせて用いられていてもよい。
[2-5. Hydroxyl Group-Containing Monomer]
A hydroxyl group-containing monomer means a monomer having at least one hydroxyl group in the molecule. Also, a monomer having at least one hydroxyl group in the molecule and at least one carboxyl group in the molecule is a carboxyl group-containing monomer and is not a hydroxyl group-containing monomer. The hydroxyl group-containing monomer is not particularly limited, but specific examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 3-hydroxypropyl meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, (meth)acrylic acid hydroxyl group-containing (meth)acrylic acid esters such as hydroxyllauryl and (meth)acrylic acid (4-hydroxymethylcyclohexyl); vinyl alcohol, allyl alcohol and the like. Among them, the hydroxyl group-containing monomer is preferably a hydroxyl group-containing (meth)acrylic acid ester, more preferably 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl (meth)acrylate (HPA), acrylic acid 4 - hydroxybutyl (4HBA). Incidentally, the hydroxyl group-containing monomers may be used alone or in combination of two or more.
[2-6.窒素原子含有モノマー]
 窒素原子含有モノマーとは、分子内(1分子内)に窒素原子を少なくとも1つ有するモノマーを意味する。ただし、上記水酸基含有モノマーには、上記窒素原子含有モノマーは含まれないものとする。すなわち、本明細書において、分子内に水酸基及び窒素原子を有するモノマーは、窒素原子含有モノマーに含まれるものとする。また、分子内に窒素原子を少なくとも1つ有し、且つ、分子内にカルボキシル基を少なくとも1つ有するモノマーはカルボキシル基含有モノマーであり、窒素原子含有モノマーではないものとする。
[2-6. Nitrogen Atom-Containing Monomer]
A nitrogen atom-containing monomer means a monomer having at least one nitrogen atom in its molecule (in one molecule). However, the hydroxyl group-containing monomer does not include the nitrogen atom-containing monomer. That is, in this specification, a monomer having a hydroxyl group and a nitrogen atom in its molecule is included in the nitrogen atom-containing monomer. Also, a monomer having at least one nitrogen atom in the molecule and at least one carboxyl group in the molecule is a carboxyl group-containing monomer and is not a nitrogen atom-containing monomer.
 上記窒素原子含有モノマーとしては、耐発泡剥がれ性を向上させる観点から、N-ビニル環状アミド、(メタ)アクリルアミド類等が好ましい。なお、窒素原子含有モノマーは、単独で又は2種以上を組み合わせて用いられていてもよい。 From the viewpoint of improving resistance to foaming and peeling, N-vinyl cyclic amides, (meth)acrylamides, and the like are preferable as the nitrogen atom-containing monomer. Incidentally, the nitrogen atom-containing monomers may be used alone or in combination of two or more.
 上記N-ビニル環状アミドとしては、下記式(1)で表されるN-ビニル環状アミドが好ましい。
Figure JPOXMLDOC01-appb-C000002
(式(1)中、R1は2価の有機基を示す)
As the N-vinyl cyclic amide, an N-vinyl cyclic amide represented by the following formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000002
(In formula (1), R 1 represents a divalent organic group)
 上記式(1)におけるR1は2価の有機基であり、好ましくは2価の飽和炭化水素基又は不飽和炭化水素基であり、より好ましくは2価の飽和炭化水素基(例えば、炭素数3~5のアルキレン基等)である。 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., carbon number 3 to 5 alkylene groups, etc.).
 上記式(1)で表されるN-ビニル環状アミドとしては、さらに耐発泡剥がれ性を向上させる観点から、N-ビニル-2-ピロリドン(NVP)、N-ビニル-2-ピペリドン、N-ビニル-2-カプロラクタム、N-ビニル-3-モルホリノン、N-ビニル-1,3-オキサジン-2-オン、N-ビニル-3,5-モルホリンジオン等が好ましく、より好ましくはN-ビニル-2-ピロリドン、N-ビニル-2-カプロラクタムであり、さらに好ましくはN-ビニル-2-ピロリドンである。 As the N-vinyl cyclic amide represented by the above formula (1), N-vinyl-2-pyrrolidone (NVP), N-vinyl-2-piperidone, N-vinyl -2-caprolactam, N-vinyl-3-morpholinone, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione and the like are preferred, more preferably N-vinyl-2- pyrrolidone, N-vinyl-2-caprolactam, more preferably N-vinyl-2-pyrrolidone.
 上記(メタ)アクリルアミド類としては、例えば、(メタ)アクリルアミド、N-アルキル(メタ)アクリルアミド、N,N-ジアルキル(メタ)アクリルアミド等が挙げられる。上記N-アルキル(メタ)アクリルアミドとしては、例えば、N-エチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-n-ブチル(メタ)アクリルアミド、N-オクチルアクリルアミド等が挙げられる。さらに、上記N-アルキル(メタ)アクリルアミドには、ジメチルアミノエチル(メタ)アクリルアミド、ジエチルアミノエチル(メタ)アクリルアミド、ジメチルアミノプロピル(メタ)アクリルアミドのようなアミノ基を有する(メタ)アクリルアミドも含まれる。上記N,N-ジアルキル(メタ)アクリルアミドとしては、例えば、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N,N-ジプロピル(メタ)アクリルアミド、N,N-ジイソプロピル(メタ)アクリルアミド、N,N-ジ(n-ブチル)(メタ)アクリルアミド、N,N-ジ(t-ブチル)(メタ)アクリルアミド等が挙げられる。 Examples of the (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, and N,N-dialkyl(meth)acrylamide. Examples of the N-alkyl(meth)acrylamide include N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-octylacrylamide and the like. Furthermore, the above N-alkyl(meth)acrylamides also include (meth)acrylamides having an amino group such as dimethylaminoethyl(meth)acrylamide, diethylaminoethyl(meth)acrylamide, and dimethylaminopropyl(meth)acrylamide. Examples of the N,N-dialkyl(meth)acrylamides include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl (Meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide and the like.
 また、上記(メタ)アクリルアミド類には、例えば、各種のN-ヒドロキシアルキル(メタ)アクリルアミドも含まれる。上記N-ヒドロキシアルキル(メタ)アクリルアミドとしては、例えば、N-メチロール(メタ)アクリルアミド、N-(2-ヒドロキシエチル)(メタ)アクリルアミド、N-(2-ヒドロキシプロピル)(メタ)アクリルアミド、N-(1-ヒドロキシプロピル)(メタ)アクリルアミド、N-(3-ヒドロキシプロピル)(メタ)アクリルアミド、N-(2-ヒドロキシブチル)(メタ)アクリルアミド、N-(3-ヒドロキシブチル)(メタ)アクリルアミド、N-(4-ヒドロキシブチル)(メタ)アクリルアミド、N-メチル-N-2-ヒドロキシエチル(メタ)アクリルアミド等が挙げられる。 The (meth)acrylamides also include, for example, various N-hydroxyalkyl(meth)acrylamides. Examples of the N-hydroxyalkyl(meth)acrylamide 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, N-(4-hydroxybutyl)(meth)acrylamide, N-methyl-N-2-hydroxyethyl(meth)acrylamide and the like.
 また、上記(メタ)アクリルアミド類には、例えば、各種のN-アルコキシアルキル(メタ)アクリルアミドも含まれる。上記N-アルコキシアルキル(メタ)アクリルアミドとしては、例えば、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド等が挙げられる。 The (meth)acrylamides also include, for example, various N-alkoxyalkyl(meth)acrylamides. Examples of the N-alkoxyalkyl(meth)acrylamides include N-methoxymethyl(meth)acrylamide and N-butoxymethyl(meth)acrylamide.
 また、上記N-ビニル環状アミド、上記(メタ)アクリルアミド類以外の窒素原子含有モノマーとしては、例えば、(メタ)アクリル酸アミノエチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸ジメチルアミノプロピル、(メタ)アクリル酸t-ブチルアミノエチル等のアミノ基含有モノマー;アクリロニトリル、メタクリロニトリル等のシアノ基含有モノマー;(メタ)アクリロイルモルホリン、N-ビニルピペラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルピラジン、N-ビニルモルホリン、N-ビニルピラゾール、ビニルピリジン、ビニルピリミジン、ビニルオキサゾール、ビニルイソオキサゾール、ビニルチアゾール、ビニルイソチアゾール、ビニルピリダジン、(メタ)アクリロイルピロリドン、(メタ)アクリロイルピロリジン、(メタ)アクリロイルピペリジン、N-メチルビニルピロリドン等の複素環含有モノマー;N-シクロヘキシルマレイミド、N-イソプロピルマレイミド、N-ラウリルマレイミド、N-フェニルマレイミド等のマレイミド系モノマー、N-メチルイタコンイミド、N-エチルイタコンイミド、N-ブチルイタコンイミド、N-オクチルイタコンイミド、N-2-エチルヘキシルイタコンイミド、N-ラウリルイタコンイミド、N-シクロヘキシルイタコンイミド等のイタコンイミド系モノマー、N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、N-(メタ)アクリロイル-8-オキシオクタメチレンスクシンイミド等のスクシンイミド系モノマー等のイミド基含有モノマー;2-(メタ)アクリロイルオキシエチルイソシアネート等のイソシアネート基含有モノマー等が挙げられる。 Nitrogen atom-containing monomers other than the N-vinyl cyclic amides and the (meth)acrylamides include, for example, aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylamino (meth)acrylate propyl, amino group-containing monomers such as t-butylaminoethyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; (meth)acryloylmorpholine, N-vinylpiperazine, N-vinylpyrrole, N-vinyl imidazole, N-vinylpyrazine, N-vinylmorpholine, N-vinylpyrazole, vinylpyridine, vinylpyrimidine, vinyloxazole, vinylisoxazole, vinylthiazole, vinylisothiazole, vinylpyridazine, (meth)acryloylpyrrolidone, (meth)acryloyl heterocyclic ring-containing monomers such as pyrrolidine, (meth)acryloylpiperidine and N-methylvinylpyrrolidone; maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide, N-methylitaconimide , N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-laurylitaconimide, N-cyclohexylitaconimide and other itaconimide monomers, N-(meth)acryloyl imide group-containing monomers such as succinimide monomers such as oxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyoctamethylenesuccinimide; 2-(meth)acryloyloxy Examples thereof include isocyanate group-containing monomers such as ethyl isocyanate.
[2-7.脂環構造含有モノマー]
 窒素原子含有モノマー及び水酸基含有モノマー以外の共重合性モノマーとしては、さらに、脂環構造含有モノマーが挙げられる。上記脂環構造含有モノマーは、(メタ)アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつ脂環構造を有するものであれば特に限定されない。例えば、シクロアルキル基を有するアルキル(メタ)アクリレートは、上記脂環構造含有モノマーに含まれる。なお、脂環構造含有モノマーは、単独で又は2種以上組み合わせて用いることができる。
[2-7. Alicyclic Structure-Containing Monomer]
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. For example, an alkyl (meth)acrylate having a cycloalkyl group is included in the alicyclic structure-containing monomer. In addition, an alicyclic structure containing monomer can be used individually or in combination of 2 or more types.
 上記脂環構造含有モノマーにおける脂環構造は、環状の炭化水素構造であり、炭素数5以上であることが好ましく、炭素数6~24がより好ましく、炭素数6~15がさらに好ましく、炭素数6~10が特に好ましい。 The alicyclic structure in the alicyclic structure-containing monomer is a cyclic hydrocarbon structure, preferably having 5 or more carbon atoms, more preferably 6 to 24 carbon atoms, further preferably 6 to 15 carbon atoms, and 6 to 10 are particularly preferred.
 上記脂環構造含有モノマーとしては、例えば、シクロプロピル(メタ)アクリレート、シクロブチル(メタ)アクリレート、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、シクロヘプチル(メタ)アクリレート、シクロオクチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、下記式(2)で表されるHPMPA、下記式(3)で表されるTMA-2、下記式(4)で表されるHCPAなどの(メタ)アクリル系モノマーが挙げられる。なお、下記式(4)において、線でつないだシクロヘキシル環と括弧内の構造式との結合場所は特に限定されない。これらの中でも、イソボルニル(メタ)アクリレートが好ましい。
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
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. (Meth)acrylic monomers. In the following formula (4), there is no particular limitation on the bonding position between the cyclohexyl ring connected by a line and the structural formula in parentheses. Among these, isobornyl (meth)acrylate is preferred.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
 上記アクリル系ポリマーが、ポリマーを構成するモノマー成分として上記脂環構造含有モノマーを含有する場合、上記アクリル系ポリマー(A)を構成する全モノマー成分(100重量%)中の、上記脂環構造含有モノマーの割合は、特に限定されないが、耐久性向上、高い接着信頼性を得る点より、10重量%以上であることが好ましい。また、上記脂環構造含有モノマーの割合の上限は、適度な柔軟性を有する粘着剤層を得る点より、50重量%以下が好ましく、より好ましくは40重量%以下、さらに好ましくは30重量%以下である。 When the acrylic polymer contains the alicyclic structure-containing monomer as a monomer component constituting the polymer, the alicyclic structure-containing monomer in all the monomer components (100% by weight) constituting the acrylic polymer (A) Although the proportion of the monomer is not particularly limited, it is preferably 10% by weight or more from the viewpoint of improving durability and obtaining high adhesion reliability. In addition, the upper limit of the ratio of the alicyclic structure-containing monomer is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 30% by weight or less, from the viewpoint of obtaining a pressure-sensitive adhesive layer having appropriate flexibility. is.
[2-8.その他の共重合性モノマー]
 アクリル系ポリマー(A)における共重合性モノマーとしては、上記の窒素原子含有モノマー、水酸基含有モノマーの他に、例えば、(メタ)アクリル酸アルコキシアルキルエステル[例えば、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸2-エトキシエチル、(メタ)アクリル酸メトキシトリエチレングリコール、(メタ)アクリル酸3-メトキシプロピル、(メタ)アクリル酸3-エトキシプロピル、(メタ)アクリル酸4-メトキシブチル、(メタ)アクリル酸4-エトキシブチル等];エポキシ基含有モノマー[例えば、(メタ)アクリル酸グリシジル、(メタ)アクリル酸メチルグリシジル等];スルホン酸基含有モノマー[例えば、ビニルスルホン酸ナトリウム等];リン酸基含有モノマー;芳香族炭化水素基を有する(メタ)アクリル酸エステル[例えば、(メタ)アクリル酸フェニル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸ベンジル等];ビニルエステル類[例えば、酢酸ビニル、プロピオン酸ビニル等];芳香族ビニル化合物[例えば、スチレン、ビニルトルエン等];オレフィン類又はジエン類[例えば、エチレン、プロピレン、ブタジエン、イソプレン、イソブチレン等];ビニルエーテル類[例えば、ビニルアルキルエーテル等];塩化ビニル等が挙げられる。
[2-8. Other copolymerizable monomers]
Examples of copolymerizable monomers in the acrylic polymer (A) include, in addition to the above nitrogen atom-containing monomers and hydroxyl group-containing monomers, (meth)acrylic acid alkoxyalkyl esters [for example, 2-methoxyethyl (meth)acrylate , 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate , 4-ethoxybutyl (meth)acrylate, etc.]; epoxy group-containing monomers [e.g., glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, etc.]; sulfonic acid group-containing monomers [e.g., sodium vinyl sulfonate, etc. ]; phosphoric acid group-containing monomer; (meth) acrylic acid ester having an aromatic hydrocarbon group [e.g., phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, etc.]; vinyl ester analogues [e.g., vinyl acetate, vinyl propionate, etc.]; aromatic vinyl compounds [e.g., styrene, vinyltoluene, etc.]; olefins or dienes [e.g., ethylene, propylene, butadiene, isoprene, isobutylene, etc.]; vinyl ethers [e.g. For example, vinyl alkyl ether, etc.]; vinyl chloride, etc. may be mentioned.
 さらに、上記アクリル系ポリマー(A)における共重合性モノマーとしては、多官能性モノマーも挙げられる。多官能性モノマーは、架橋成分として作用する。上記多官能性モノマーとしては、例えば、ヘキサンジオールジ(メタ)アクリレート、ブタンジオールジ(メタ)アクリレート、(ポリ)エチレングリコールジ(メタ)アクリレート、(ポリ)プロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、アリル(メタ)アクリレート、ビニル(メタ)アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート等が挙げられる。なお、多官能性モノマーは、単独で又は2種以上を組み合わせて用いられていてもよい。 Furthermore, the copolymerizable monomers in the acrylic polymer (A) also include polyfunctional monomers. A polyfunctional monomer acts as a cross-linking component. 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, Allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate and the like. In addition, a polyfunctional monomer may be used individually or in combination of 2 or more types.
 アクリル系ポリマー(A)の全モノマー単位における上記多官能性モノマーの含有量(割合)は、特に限定されないが、アクリル系ポリマー(A)を構成するモノマー成分全量(100重量部)に対して、0.5重量部以下(例えば、0~0.5重量部)が好ましく、より好ましくは0~0.35重量部、さらに好ましくは0~0.3重量部である。多官能性モノマーの含有量が0.5重量部以下であると、粘着剤層が適度な凝集力を有し、粘着力や段差吸収性が向上しやすく、好ましい。なお、架橋剤を使用する場合には多官能性モノマーを使用しなくてもよいが、架橋剤を使用しない場合の多官能性モノマーの含有量は、0.001~0.5重量部が好ましく、より好ましくは0.001~0.35重量部、さらに好ましくは0.002~0.3重量部である。 The content (proportion) of the polyfunctional monomer in all monomer units of the acrylic polymer (A) is not particularly limited, but with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A), It is preferably 0.5 parts by weight or less (for example, 0 to 0.5 parts by weight), more preferably 0 to 0.35 parts by weight, still more preferably 0 to 0.3 parts by weight. When the content of the polyfunctional monomer is 0.5 parts by weight or less, the pressure-sensitive adhesive layer has appropriate cohesive strength, and the pressure-sensitive adhesive strength and step absorbability are easily improved, which is preferable. In addition, when using a cross-linking agent, the polyfunctional monomer may not be used, but the content of the multi-functional monomer when the cross-linking agent is not used is preferably 0.001 to 0.5 parts by weight. , more preferably 0.001 to 0.35 parts by weight, more preferably 0.002 to 0.3 parts by weight.
[2-9.アクリル系ポリマー(B)]
 上記粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)がベースポリマーとしてアクリル系ポリマー(A)を含有する場合、上記粘着剤層は、上記アクリル系ポリマー(A)とともに、重量平均分子量が1000~30000であるアクリル系ポリマー(B)を含有することが好ましい。アクリル系ポリマー(B)を含有していると、粘着シートにおける界面における被着体への接着性が向上するので、強接着性を得やすくなり、また優れた耐発泡剥がれ性を得やすくなる。なお、本明細書では、「重量平均分子量が1000~30000であるアクリル系ポリマー(B)」を単に「アクリル系ポリマー(B)」と称する場合がある。
[2-9. Acrylic polymer (B)]
When the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) contains an acrylic polymer (A) as a base polymer, the pressure-sensitive adhesive layer, together with the acrylic polymer (A), It preferably contains an acrylic polymer (B) having a weight average molecular weight of 1,000 to 30,000. When the acrylic polymer (B) is contained, the adhesion to the adherend at the interface of the pressure-sensitive adhesive sheet is improved, so that it becomes easy to obtain strong adhesion and excellent resistance to foaming and peeling. In this specification, "acrylic polymer (B) having a weight average molecular weight of 1000 to 30000" may be simply referred to as "acrylic polymer (B)".
 上記アクリル系ポリマー(B)としては、分子内に環状構造を有する(メタ)アクリル酸エステルを必須のモノマー成分として構成されたアクリル系ポリマーが好ましく挙げられ、分子内に環状構造を有する(メタ)アクリル酸エステル及び直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルを必須のモノマー成分として構成されたアクリル系ポリマーがより好ましく挙げられる。すなわち、上記アクリル系ポリマー(B)としては、モノマー単位として分子内に環状構造を有する(メタ)アクリル酸エステルを含むアクリル系ポリマーが好ましく挙げられ、モノマー単位として分子内に環状構造を有する(メタ)アクリル酸エステル及び直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルを含むアクリル系ポリマーがより好ましく挙げられる。 As the acrylic polymer (B), an acrylic polymer composed of a (meth)acrylic ester having a cyclic structure in the molecule as an essential monomer component is preferably mentioned, and a (meth) having a cyclic structure in the molecule. An acrylic polymer composed of an acrylic acid ester and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group as essential monomer components is more preferable. That is, the acrylic polymer (B) preferably includes an acrylic polymer containing a (meth)acrylic acid ester having a cyclic structure in the molecule as a monomer unit, and has a cyclic structure in the molecule as a monomer unit (meth) ) Acrylic polymers containing acrylic acid esters and (meth)acrylic acid alkyl esters having linear or branched alkyl groups are more preferred.
 上記分子内(1分子内)に環状構造を有する(メタ)アクリル酸エステル(以下、「環含有(メタ)アクリル酸エステル」と称する場合がある)の環状構造(環)は、芳香族性環、非芳香族性環の何れであってもよく、特に限定されない。上記芳香族性環としては、例えば、芳香族性炭素環[例えば、ベンゼン環等の単環炭素環や、ナフタレン環等の縮合炭素環等]、各種の芳香族性複素環等が挙げられる。上記非芳香族性環としては、例えば、非芳香族性脂肪族環(非芳香族性脂環式環)[例えば、シクロペンタン環、シクロヘキサン環、シクロヘプタン環、シクロオクタン環等のシクロアルカン環;シクロヘキセン環等のシクロアルケン環等]、非芳香族性橋かけ環[例えば、ピナン、ピネン、ボルナン、ノルボルナン、ノルボルネン等における二環式炭化水素環;アダマンタン等における三環以上の脂肪族炭化水素環(橋かけ式炭化水素環)等]、非芳香族性複素環[例えば、エポキシ環、オキソラン環、オキセタン環等]等が挙げられる。 The cyclic structure (ring) of the (meth)acrylic acid ester having a cyclic structure in the molecule (in one molecule) (hereinafter sometimes referred to as "ring-containing (meth)acrylic acid ester") is an aromatic ring , a non-aromatic ring, and is not particularly limited. Examples of the aromatic ring include aromatic carbocyclic rings [eg, monocyclic carbocyclic rings such as benzene ring, condensed carbocyclic rings such as naphthalene ring, etc.], various aromatic heterocyclic rings, and the like. Examples of the non-aromatic ring include non-aromatic aliphatic rings (non-aromatic alicyclic rings) [e.g., cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring cycloalkene rings such as cyclohexene rings], non-aromatic bridging rings [e.g., bicyclic hydrocarbon rings in pinane, pinene, bornane, norbornane, norbornene, etc.; tricyclic or higher aliphatic hydrocarbons in adamantane, etc. ring (bridged hydrocarbon ring), etc.], non-aromatic heterocyclic ring [eg, epoxy ring, oxolane ring, oxetane ring, etc.], and the like.
 上記三環以上の脂肪族炭化水素環(三環以上の橋かけ式炭化水素環)としては、例えば、下記式(5a)で表されるジシクロペンタニル基、下記式(5b)で表されるジシクロペンテニル基、下記式(5c)で表されるアダマンチル基、下記式(5d)で表されるトリシクロペンタニル基、下記式(5e)で表されるトリシクロペンテニル基等が挙げられる。
Figure JPOXMLDOC01-appb-C000006
Examples of the tricyclic or higher aliphatic hydrocarbon ring (tricyclic or higher bridged hydrocarbon ring) include, for example, a dicyclopentanyl group represented by the following formula (5a), and a dicyclopentanyl group represented by the following formula (5b). a dicyclopentenyl group represented by the following formula (5c), an adamantyl group represented by the following formula (5d), a tricyclopentenyl group represented by the following formula (5d), a tricyclopentenyl group represented by the following formula (5e), and the like. .
Figure JPOXMLDOC01-appb-C000006
 すなわち、上記環含有(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸シクロペンチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸シクロヘプチル、(メタ)アクリル酸シクロオクチル等の(メタ)アクリル酸シクロアルキルエステル;(メタ)アクリル酸イソボルニル等の二環式の脂肪族炭化水素環を有する(メタ)アクリル酸エステル;ジシクロペンタニル(メタ)アクリレート、ジシクロペンタニルオキシエチル(メタ)アクリレート、トリシクロペンタニル(メタ)アクリレート、1-アダマンチル(メタ)アクリレート、2-メチル-2-アダマンチル(メタ)アクリレート、2-エチル-2-アダマンチル(メタ)アクリレート等の三環以上の脂肪族炭化水素環を有する(メタ)アクリル酸エステル;(メタ)アクリル酸フェニル等の(メタ)アクリル酸アリールエステル、(メタ)アクリル酸フェノキシエチル等の(メタ)アクリル酸アリールオキシアルキルエステル、(メタ)アクリル酸ベンジル等の(メタ)アクリル酸アリールアルキルエステル等の芳香族性環を有する(メタ)アクリル酸エステル等が挙げられる。なかでも、上記環含有(メタ)アクリル酸エステルとしては、特に、非芳香族性環含有(メタ)アクリル酸エステルが好ましく、より好ましくはアクリル酸シクロヘキシル(CHA)、メタクリル酸シクロヘキシル(CHMA)、アクリル酸ジシクロペンタニル(DCPA)、メタクリル酸ジシクロペンタニル(DCPMA)であり、さらに好ましくはアクリル酸ジシクロペンタニル(DCPA)、メタクリル酸ジシクロペンタニル(DCPMA)である。なお、環含有(メタ)アクリル酸エステルは、単独で又は2種以上を組み合わせて用いられてもよい。 That is, examples of the ring-containing (meth)acrylic acid ester include (meth)acrylic esters such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate. Acrylic acid cycloalkyl ester; (meth)acrylic acid ester having a bicyclic aliphatic hydrocarbon ring such as isobornyl (meth)acrylate; dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth) Tricyclic or higher aliphatics such as acrylates, tricyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate (Meth)acrylic acid esters having a hydrocarbon ring; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate, (meth)acrylic acid aryloxyalkyl esters such as phenoxyethyl (meth)acrylate, (meth)acrylic acid esters Examples thereof include (meth)acrylic acid esters having an aromatic ring, such as (meth)acrylic acid arylalkyl esters such as benzyl acrylate. Among them, the ring-containing (meth)acrylic acid ester is particularly preferably a non-aromatic ring-containing (meth)acrylic acid ester, more preferably cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHMA), acrylic Dicyclopentanyl acid (DCPA) and dicyclopentanyl methacrylate (DCPMA), more preferably dicyclopentanyl acrylate (DCPA) and dicyclopentanyl methacrylate (DCPMA). In addition, ring-containing (meth)acrylic acid esters may be used alone or in combination of two or more.
 上記非芳香族性環含有(メタ)アクリル酸エステルのなかでも、三環以上の脂肪族炭化水素環(特に、三環以上の橋かけ式炭化水素環)を有する(メタ)アクリル酸エステルを使用した場合、特に、重合阻害を起こしにくい点で好ましい。また、不飽和結合を有しない上記式(5a)で表されるジシクロペンタニル基、上記式(5c)で表されるアダマンチル基、上記式(5d)で表されるトリシクロペンタニル基を有する(メタ)アクリル酸エステルを使用した場合には、耐発泡剥がれ性をより高めることができ、さらに、ポリエチレンやポリプロプレン等の低極性の被着体に対する接着性を顕著に向上させることができる。 Among the non-aromatic ring-containing (meth)acrylic acid esters, a (meth)acrylic acid ester having a tricyclic or higher aliphatic hydrocarbon ring (particularly, a tricyclic or higher bridging hydrocarbon ring) is used. This is particularly preferable in that polymerization inhibition is less likely to occur. Further, a dicyclopentanyl group having no unsaturated bond 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) When using a (meth) acrylic acid ester having, it is possible to further increase the resistance to foaming and peeling, and furthermore, the adhesion to low-polar adherends such as polyethylene and polypropylene can be significantly improved. .
 アクリル系ポリマー(B)の全モノマー単位(アクリル系ポリマー(B)を構成するモノマー成分全量)における上記環含有(メタ)アクリル酸エステルの含有量(割合)は、特に限定されないが、アクリル系ポリマー(B)を構成するモノマー成分全量(100重量部)に対して、10~90重量部が好ましく、より好ましくは20~80重量部である。上記環含有(メタ)アクリル酸エステルの含有量を10重量部以上であると、耐発泡剥がれ性が向上しやすくなり、好ましい。また、含有量を90重量部以下であると、粘着剤層が適度な柔軟性を有し、粘着力や段差吸収性等が向上しやすくなり、好ましい。 The content (percentage) of the ring-containing (meth)acrylic acid ester in the total monomer units of the acrylic polymer (B) (the total amount of the monomer components constituting the acrylic polymer (B)) is not particularly limited, but the acrylic polymer It is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting (B). When the content of the ring-containing (meth)acrylic acid ester is 10 parts by weight or more, the resistance to foaming and peeling is easily improved, which is preferable. Moreover, when the content is 90 parts by weight or less, the pressure-sensitive adhesive layer has appropriate flexibility, and the pressure-sensitive adhesive strength, step absorbability, etc. are likely to be improved, which is preferable.
 また、アクリル系ポリマー(B)のモノマー単位としての上記直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルとしては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸イソペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸オクタデシル、(メタ)アクリル酸ノナデシル、(メタ)アクリル酸エイコシル等のアルキル基の炭素数が1~20の(メタ)アクリル酸アルキルエステル等が挙げられる。なかでも、アクリル系ポリマー(A)との相溶性が良好となる点で、メタクリル酸メチル(MMA)が好ましい。なお、上記の(メタ)アクリル酸アルキルエステルは、単独で又は2種以上を組み合わせて用いられてもよい。 Examples of the (meth)acrylic acid alkyl ester having a linear or branched alkyl group as the monomer unit of the acrylic polymer (B) include methyl (meth)acrylate and ethyl (meth)acrylate. , propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, (meth)acrylate Pentyl acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, (meth) ) nonyl acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, (meth)acrylate Alkyl groups such as tetradecyl acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. Examples thereof include (meth)acrylic acid alkyl esters having 1 to 20 carbon atoms. Among them, methyl methacrylate (MMA) is preferable because it has good compatibility with the acrylic polymer (A). In addition, said (meth)acrylic-acid alkylester may be used individually or in combination of 2 or more types.
 アクリル系ポリマー(B)の全モノマー単位(アクリル系ポリマー(B)を構成するモノマー成分全量)における上記直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルの含有量(割合)は、特に限定されないが、耐発泡剥がれ性の点で、アクリル系ポリマー(B)を構成するモノマー成分全量(100重量部)に対して、10~90重量部が好ましく、より好ましくは20~80重量部、さらに好ましくは20~60重量部である。含有量が10重量部以上であると、特に、アクリル樹脂やポリカーボネート製の被着体に対する粘着力が向上しやすくなり、好ましい。 Content (percentage) of (meth)acrylic acid alkyl ester having a linear or branched alkyl group in all monomer units of acrylic polymer (B) (total amount of monomer components constituting acrylic polymer (B)) is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (B) in terms of resistance to foaming and peeling. parts by weight, more preferably 20 to 60 parts by weight. When the content is 10 parts by weight or more, the adhesive strength to an adherend made of acrylic resin or polycarbonate tends to be improved, which is preferable.
 アクリル系ポリマー(B)のモノマー単位としては、上記環含有(メタ)アクリル酸エステル及び直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルの他にも、これらのモノマーと共重合が可能なモノマー(共重合性モノマー)が含まれていてもよい。なお、アクリル系ポリマー(B)の全モノマー単位(アクリル系ポリマー(B)を構成するモノマー成分全量)における上記共重合性モノマーの含有量(割合)は、特に限定されないが、アクリル系ポリマー(B)を構成するモノマー成分全量(100重量部)に対して、49.9重量部以下(例えば、0~49.9重量部)が好ましく、より好ましくは30重量部以下である。また、共重合性モノマーは、単独で又は2種以上を組み合わせて用いられてもよい。 As the monomer unit of the acrylic polymer (B), in addition to the ring-containing (meth)acrylic acid ester and the (meth)acrylic acid alkyl ester having a linear or branched alkyl group, these monomers and A polymerizable monomer (copolymerizable monomer) may be included. The content (proportion) of the copolymerizable monomer in the total monomer units of the acrylic polymer (B) (the total amount of the monomer components constituting the acrylic polymer (B)) is not particularly limited, but the acrylic polymer (B ) is preferably 49.9 parts by weight or less (eg, 0 to 49.9 parts by weight), more preferably 30 parts by weight or less, relative to the total amount (100 parts by weight) of the monomer components constituting Also, the copolymerizable monomers may be used alone or in combination of two or more.
 アクリル系ポリマー(B)のモノマー単位としての上記共重合性モノマー(アクリル系ポリマー(B)を構成する上記共重合性モノマー)としては、例えば、(メタ)アクリル酸アルコキシアルキルエステル[例えば、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸2-エトキシエチル、(メタ)アクリル酸メトキシトリエチレングリコール、(メタ)アクリル酸3-メトキシプロピル、(メタ)アクリル酸3-エトキシプロピル、(メタ)アクリル酸4-メトキシブチル、(メタ)アクリル酸4-エトキシブチル等];ヒドロキシル基(水酸基)含有モノマー[例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル等の(メタ)アクリル酸ヒドロキシアルキル、ビニルアルコール、アリルアルコール等];アミド基含有モノマー[例えば、(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-ヒドロキシエチル(メタ)アクリルアミド等];アミノ基含有モノマー[例えば、(メタ)アクリル酸アミノエチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチル等];シアノ基含有モノマー[例えば、アクリロニトリル、メタクリロニトリル等];スルホン酸基含有モノマー[例えば、ビニルスルホン酸ナトリウム等];リン酸基含有モノマー[例えば、2-ヒドロキシエチルアクリロイルフォスフェート等];イソシアネート基含有モノマー[例えば、2-メタクリロイルオキシエチルイソシアネート等]、イミド基含有モノマー[シクロヘキシルマレイミド、イソプロピルマレイミド等]等が挙げられる。 Examples of the copolymerizable monomer (the copolymerizable monomer constituting the acrylic polymer (B)) as monomer units of the acrylic polymer (B) include (meth)acrylic acid alkoxyalkyl esters [for example, (meth) ) 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, (meth) ) 4-methoxybutyl acrylate, 4-ethoxybutyl (meth)acrylate, etc.]; hydroxyl group (hydroxyl group)-containing monomers [e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate, vinyl alcohol, allyl alcohol, etc.]; amide group-containing monomers [e.g., (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, etc.]; amino group-containing monomers [e.g., aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate etc.]; cyano group-containing monomers [e.g., acrylonitrile, methacrylonitrile, etc.]; sulfonic acid group-containing monomers [e.g., sodium vinyl sulfonate, etc.]; ; isocyanate group-containing monomers [eg, 2-methacryloyloxyethyl isocyanate], imide group-containing monomers [cyclohexylmaleimide, isopropylmaleimide, etc.], and the like.
 上記のように、アクリル系ポリマー(B)は、モノマー単位として分子内に環状構造を有する(メタ)アクリル酸エステル及び直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルを含むアクリル系ポリマーであることが好ましい。なかでも、モノマー単位として、環含有(メタ)アクリル酸エステル、及び、上記の直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルを含むアクリル系ポリマーであることが好ましい。上記のモノマー単位として環含有(メタ)アクリル酸エステル及び直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルを含むアクリル系ポリマーにおいて、アクリル系ポリマー(B)を構成するモノマー成分全量(100重量部)に対する環含有(メタ)アクリル酸エステルの量は、特に限定されないが、10~90重量部が好ましく、より好ましくは20~80重量部である。また、直鎖又は分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルの含有量は、特に限定されないが、10~90重量部が好ましく、より好ましくは20~80重量部、さらに好ましくは20~60重量部である。 As described above, the acrylic polymer (B) includes, as monomer units, a (meth)acrylic acid ester having a cyclic structure in the molecule and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group. Acrylic polymers are preferred. Among them, an acrylic polymer containing, as monomer units, a ring-containing (meth)acrylic acid ester and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group is preferred. In the 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 monomer units, a monomer component constituting the acrylic polymer (B) The amount of the ring-containing (meth)acrylic acid ester relative to the total amount (100 parts by weight) 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, and even more preferably 20 to 60 parts by weight.
 さらに、アクリル系ポリマー(B)の特に好ましい具体的構成としては、モノマー単位として(1)アクリル酸ジシクロペンタニル、メタクリル酸ジシクロペンタニル、アクリル酸シクロヘキシル、及びメタクリル酸シクロヘキシルからなる群より選ばれた少なくとも1種のモノマー、ならびに(2)メタクリル酸メチルを含むアクリル系ポリマーが挙げられる。上記の特に好ましい具体的構成のアクリル系ポリマー(B)における、アクリル系ポリマー(B)の全モノマー単位中の、(1)アクリル酸ジシクロペンタニル、メタクリル酸ジシクロペンタニル、アクリル酸シクロヘキシル、及びメタクリル酸シクロヘキシルの含有量(2種以上を含む場合はこれらの合計量)は、アクリル系ポリマー(B)を構成するモノマー成分全量(100重量部)に対して、30~70重量部、(2)メタクリル酸メチルの含有量は30~70重量部であることが好ましい。ただし、上記アクリル系ポリマー(B)は、上記具体的構成に限定されるものではない。 Furthermore, as a particularly preferred specific structure of the acrylic polymer (B), the monomer unit is (1) selected from the group consisting of dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate. and (2) an acrylic polymer containing methyl methacrylate. Among all the monomer units of the acrylic polymer (B) having a particularly preferred specific configuration, (1) dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and the content of cyclohexyl methacrylate (the total amount of these when two or more are included) is 30 to 70 parts by weight with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (B), 2) The content of methyl methacrylate is preferably 30 to 70 parts by weight. However, the acrylic polymer (B) is not limited to the above specific configuration.
 アクリル系ポリマー(B)は、上記モノマー成分を公知乃至慣用の重合方法により重合することにより得ることができる。上記アクリル系ポリマー(B)の重合方法としては、例えば、溶液重合方法、乳化重合方法、塊状重合方法、活性エネルギー線照射による重合方法(活性エネルギー線重合方法)等が挙げられる。なかでも、塊状重合方法、溶液重合方法が好ましく、より好ましくは溶液重合方法である。 The acrylic polymer (B) can be obtained by polymerizing the above monomer components by a known or commonly used polymerization method. Examples of the polymerization method of the acrylic polymer (B) include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method). Among them, the bulk polymerization method and the solution polymerization method are preferable, and the solution polymerization method is more preferable.
 アクリル系ポリマー(B)の重合に際しては、各種の一般的な溶剤が用いられてもよい。上記溶剤としては、例えば、酢酸エチル、酢酸n-ブチル等のエステル類;トルエン、ベンゼン等の芳香族炭化水素類;n-ヘキサン、n-ヘプタン等の脂肪族炭化水素類;シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類;メチルエチルケトン、メチルイソブチルケトン等のケトン類等の有機溶剤が挙げられる。なお、このような溶剤は、単独で又は2種以上を組み合わせて用いられてもよい。 Various common solvents may be used in the polymerization of the acrylic polymer (B). Examples of 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, methylcyclohexane and the like. alicyclic hydrocarbons; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone. In addition, such a solvent may be used individually or in combination of 2 or more types.
 さらに、アクリル系ポリマー(B)の重合に際しては、公知乃至慣用の重合開始剤(例えば、熱重合開始剤や光重合開始剤等)が使用されてもよい。なお、重合開始剤は、単独で又は2種以上を組み合わせて用いられてもよい。 Furthermore, a known or commonly used polymerization initiator (for example, a thermal polymerization initiator, a photopolymerization initiator, etc.) may be used in the polymerization of the acrylic polymer (B). In addition, a polymerization initiator may be used individually or in combination of 2 or more types.
 熱重合開始剤としては、例えば、2,2'-アゾビスイソブチロニトリル(AIBN)、2,2'-アゾビス-2-メチルブチロニトリル(AMBN)、2,2'-アゾビス(2-メチルプロピオン酸)ジメチル、4,4'-アゾビス-4-シアノバレリアン酸、2,2'-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2'-アゾビス(2,4-ジメチルバレロニトリル)、1,1'-アゾビス(シクロヘキサン-1-カルボニトリル)、2,2'-アゾビス(2,4,4-トリメチルペンタン)等のアゾ系開始剤;ベンゾイルパーオキサイド、t-ブチルハイドロパーオキサイド、ジ-t-ブチルパーオキサイド、t-ブチルパーオキシベンゾエート、ジクミルパーオキサイド、1,1-ビス(t-ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、1,1-ビス(t-ブチルパーオキシ)シクロドデカン等の過酸化物系開始剤等が挙げられる。なお、溶液重合を行う場合には、油溶性の重合開始剤を使用することが好ましい。また、熱重合開始剤は、単独で又は2種以上を組み合わせて用いられてもよい。 Examples of thermal polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile (AMBN), 2,2'-azobis(2- methylpropionate) dimethyl, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4- dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4,4-trimethylpentane) and other azo initiators; 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 bis(t-butylperoxy)cyclododecane. In addition, when performing solution polymerization, it is preferable to use an oil-soluble polymerization initiator. Moreover, a thermal polymerization initiator may be used individually or in combination of 2 or more types.
 上記熱重合開始剤の使用量としては、特に限定されないが、例えば、アクリル系ポリマー(B)の全モノマー単位(アクリル系ポリマー(B)を構成するモノマー成分全量)100重量部に対して、0.1~15重量部である。 The amount of the thermal polymerization initiator to be used is not particularly limited. .1 to 15 parts by weight.
 また、上記光重合開始剤としては、特に限定されないが、例えば、上記で挙げられたアクリル系ポリマー(A)の重合に際して用いられる光重合開始剤と同じ光重合開始剤が挙げられる。上記光重合開始剤の使用量は、特に限定されず、適宜選択される。 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 (A) mentioned above. The amount of the photopolymerization initiator to be used is not particularly limited, and is appropriately selected.
 上記アクリル系ポリマー(B)の重合に際しては、分子量を調整するため(具体的には、重量平均分子量を1000~30000に調整するため)に、連鎖移動剤が使用されてもよい。上記連鎖移動剤としては、例えば、2-メルカプトエタノール、α-チオグリセロール、2,3-ジメルカプト-1-プロパノール、オクチルメルカプタン、t-ノニルメルカプタン、ドデシルメルカプタン(ラウリルメルカプタン)、t-ドデシルメルカプタン、グリシジルメルカプタン、チオグリコール酸、チオグリコール酸メチル、チオグリコール酸エチル、チオグリコール酸プロピル、チオグリコール酸ブチル、チオグリコール酸t-ブチル、チオグリコール酸2-エチルヘキシル、チオグリコール酸オクチル、チオグリコール酸イソオクチル、チオグリコール酸デシル、チオグリコール酸ドデシル、エチレングリコールのチオグリコール酸エステル、ネオペンチルグリコールのチオグリコール酸エステル、ペンタエリスリトールのチオグリコール酸エステル、α-メチルスチレンダイマー等が挙げられる。なかでも、加湿による粘着シートの白化を抑制する観点から、α-チオグリセロール、チオグリコール酸メチルが好ましく、α-チオグリセロールが特に好ましい。なお、連鎖移動剤は、単独で又は2種以上を組み合わせて用いられてもよい。 A chain transfer agent may be used in the polymerization of the acrylic polymer (B) to adjust the molecular weight (specifically, to adjust the weight average molecular weight to 1000 to 30000). Examples of the chain transfer agent include 2-mercaptoethanol, α-thioglycerol, 2,3-dimercapto-1-propanol, octyl mercaptan, t-nonyl mercaptan, dodecyl mercaptan (lauryl mercaptan), t-dodecyl mercaptan, glycidyl mercaptan, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene glycol thioglycolate, neopentyl glycol thioglycolate, pentaerythritol thioglycolate, α-methylstyrene dimer and the like. Among them, α-thioglycerol and methyl thioglycolate are preferred, and α-thioglycerol is particularly preferred, from the viewpoint of suppressing whitening of the adhesive sheet due to humidification. In addition, a chain transfer agent may be used individually or in combination of 2 or more types.
 上記連鎖移動剤の含有量(使用量)は、特に限定されないが、アクリル系ポリマー(B)の全モノマー単位(アクリル系ポリマー(B)を構成するモノマー成分全量)100重量部に対して、0.1~20重量部が好ましく、より好ましくは0.2~15重量部、さらに好ましくは0.3~10重量部である。連鎖移動剤の含有量(使用量)を上記範囲とすることにより、重量平均分子量が1000~30000に制御されたアクリル系ポリマーを容易に得ることができる。 The content (amount used) of the chain transfer agent is not particularly limited, but is 0 per 100 parts by weight of all monomer units of the acrylic polymer (B) (the total amount of the monomer components constituting the acrylic polymer (B)). .1 to 20 parts by weight is preferred, more preferably 0.2 to 15 parts by weight, and still more preferably 0.3 to 10 parts by weight. By setting the content (use amount) of the chain transfer agent within the above range, an acrylic polymer having a weight average molecular weight controlled to 1,000 to 30,000 can be easily obtained.
 上記アクリル系ポリマー(B)の重量平均分子量(Mw)は、1000~30000であり、好ましくは1000~20000、より好ましくは1500~10000、さらに好ましくは2000~8000である。アクリル系ポリマー(B)の重量平均分子量が1000以上であるので、粘着力や保持特性が向上し、耐発泡剥がれ性が向上する。一方、アクリル系ポリマー(B)の重量平均分子量を30000以下であるので、粘着力を高くしやすく、耐発泡剥がれ性が向上する。 The weight average molecular weight (Mw) of the acrylic polymer (B) is 1,000 to 30,000, preferably 1,000 to 20,000, more preferably 1,500 to 10,000, and still more preferably 2,000 to 8,000. Since the acrylic polymer (B) has a weight-average molecular weight of 1000 or more, the adhesive strength and holding properties are improved, and the resistance to foaming and peeling is improved. On the other hand, since the acrylic polymer (B) has a weight-average molecular weight of 30,000 or less, the adhesive strength is easily increased, and the resistance to foaming and peeling is improved.
 上記アクリル系ポリマー(B)の重量平均分子量(Mw)は、GPC法によりポリスチレン換算して求めることができる。例えば、東ソー株式会社製の高速GPC装置「HPLC-8120GPC」を用いて、下記の条件により測定することができる。
 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
The weight-average molecular weight (Mw) of the acrylic polymer (B) can be determined by the GPC method in terms of polystyrene. For example, it can be measured under the following conditions using a high-speed GPC apparatus "HPLC-8120GPC" manufactured by Tosoh Corporation.
Column: TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000
Solvent: Tetrahydrofuran Flow rate: 0.6 ml/min
 上記アクリル系ポリマー(B)のガラス転移温度(Tg)は、特に限定されないが、20~300℃が好ましく、より好ましくは30~300℃、さらに好ましくは40~300℃である。アクリル系ポリマー(B)のガラス転移温度を20℃以上であると、耐発泡剥がれ性が向上しやすく、好ましい。また、アクリル系ポリマー(B)のガラス転移温度が300℃以下であると、粘着剤層が適度な柔軟性を有し、良好な粘着力や良好な段差吸収性が得やすくなり、優れた接着信頼性を得やすくなるので、好ましい。 Although the glass transition temperature (Tg) of the acrylic polymer (B) is not particularly limited, it is preferably 20 to 300°C, more preferably 30 to 300°C, and even more preferably 40 to 300°C. When the glass transition temperature of the acrylic polymer (B) is 20° C. or higher, the resistance to foaming and peeling is likely to be improved, which is preferable. In addition, when the glass transition temperature of the acrylic polymer (B) is 300° C. or less, the pressure-sensitive adhesive layer has appropriate flexibility, and it becomes easy to obtain good adhesive strength and good step absorbability, resulting in excellent adhesion. This is preferable because it makes it easier to obtain reliability.
 上記アクリル系ポリマー(B)のガラス転移温度(Tg)は、下記式で表されるガラス転移温度(理論値)である。
 1/Tg = W1/Tg1+W2/Tg2+・・・+Wn/Tgn
 上記式中、Tgはアクリル系ポリマー(B)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(B)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。
The glass transition temperature (Tg) of the acrylic polymer (B) is the glass transition temperature (theoretical value) represented by the following formula.
1 /Tg = W1 / Tg1 + W2/Tg2+...+ Wn / Tgn
In the above formula, Tg is the glass transition temperature (unit: K) of the acrylic polymer (B), Tg is the glass transition temperature (unit: K) when the monomer i forms a homopolymer, and W is the temperature of the monomer i . It represents the weight fraction in the total amount of monomer components (i=1, 2, . . . n).
As the Tg of the homopolymer of the monomers constituting the acrylic polymer (B), the values shown in Table 1 below can be adopted. As the Tg of homopolymers of monomers not listed in Table 1, values described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) can be used. Furthermore, as the Tg of a homopolymer of a monomer not described in the above literature, the value obtained by the above-described measuring method (tan δ peak top temperature by viscoelasticity test) can be employed.
Figure JPOXMLDOC01-appb-T000007
 なお、表1における「DCPMA/MMA=60/40」のコポリマーは、DCPMA60重量部とMMA40重量部のコポリマーを意味する。
Figure JPOXMLDOC01-appb-T000007
The copolymer "DCPMA/MMA=60/40" in Table 1 means a copolymer of 60 parts by weight of DCPMA and 40 parts by weight of MMA.
 上記粘着剤層がアクリル系ポリマー(A)及び(B)を含有する場合のアクリル系ポリマー(B)の含有量は、特に限定されないが、上記アクリル系ポリマー(A)100重量部に対して、1~30重量部が好ましく、より好ましくは2~20重量部であり、さらに好ましくは2~10重量部である。すなわち、上記粘着剤層におけるアクリル系ポリマー(B)の含有量は、特に限定されないが、上記アクリル系ポリマー(A)の全モノマー単位100重量部に対して、1~30重量部が好ましく、より好ましくは2~20重量部であり、さらに好ましくは2~10重量部である。粘着剤層におけるアクリル系ポリマー(B)の含有量は、特に限定されないが、例えば、上記モノマー混合物100重量部に対して、1~30重量部が好ましく、より好ましくは2~20重量部であり、さらに好ましくは2~10重量部である。アクリル系ポリマー(B)の含有量が1重量部以上であると、優れた接着性及び優れた耐発泡剥がれ性が得やすくなり、好ましい。また、アクリル系ポリマー(B)の含有量が30重量部以下であると、優れた透明性と接着信頼性が得やすくなり、好ましい。 The content of the acrylic polymer (B) when the pressure-sensitive adhesive layer contains the acrylic polymers (A) and (B) is not particularly limited. It is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, still more preferably 2 to 10 parts by weight. That is, the content of the acrylic polymer (B) in the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 30 parts by weight with respect to 100 parts by weight of all monomer units of the acrylic polymer (A), and more It is preferably 2 to 20 parts by weight, more preferably 2 to 10 parts by weight. The content of the acrylic polymer (B) in the adhesive layer is not particularly limited. , more preferably 2 to 10 parts by weight. When the content of the acrylic polymer (B) is 1 part by weight or more, excellent adhesiveness and excellent resistance to foaming and peeling can be easily obtained, which is preferable. Moreover, when the content of the acrylic polymer (B) is 30 parts by weight or less, excellent transparency and adhesion reliability can be easily obtained, which is preferable.
 アクリル系ポリマー(A)及び(B)を含有する上記粘着剤層の作製方法としては、特に限定されない。例えば、アクリル系ポリマー(A)を構成するモノマー成分の混合物又はアクリル系ポリマー(A)を構成するモノマー成分の混合物の部分重合物(アクリル系ポリマー(A)を形成するモノマー混合物又はその部分重合物)に、アクリル系ポリマー(B)、添加剤等を必要に応じて添加して、混合することを経て、作製される。 The method for producing the pressure-sensitive adhesive layer containing the acrylic polymers (A) and (B) is not particularly limited. For example, a mixture of monomer components constituting the acrylic polymer (A) or a partial polymer of a mixture of monomer components constituting the acrylic polymer (A) (a monomer mixture forming the acrylic polymer (A) or a partial polymer thereof ), the acrylic polymer (B), additives and the like are added as necessary and mixed.
[2-10.本発明のイオン性化合物以外の帯電防止剤]
 本発明の粘着剤層には、必要に応じて、本発明のイオン性化合物以外の帯電防止剤(本明細書において、「その他の帯電防止剤」と称する場合がある)を含んでいてもよい。
 その他の帯電防止剤としては、例えば、イオン性化合物、イオン性界面活性剤、導電性ポリマー、導電性微粒子等の帯電防止性を付与できる材料が挙げられる。これら中でも、アクリル系ポリマー(A)との相溶性、粘着剤層の透明性の点から、イオン性化合物が好ましい。
[2-10. Antistatic agent other than the ionic compound of the present invention]
The pressure-sensitive adhesive layer of the present invention may optionally contain an antistatic agent other than the ionic compound of the present invention (herein, may be referred to as "other antistatic agent"). .
Examples of other antistatic agents include materials capable of imparting antistatic properties, such as ionic compounds, ionic surfactants, conductive polymers, and conductive fine particles. Among these, ionic compounds are preferred from the viewpoint of compatibility with the acrylic polymer (A) and transparency of the pressure-sensitive adhesive layer.
 イオン性化合物としては、無機カチオンアニオン塩、及び/または、有機カチオンアニオン塩を好ましく用いることができ、特に無機カチオンアニオン塩を用いることが好ましい態様である。無機カチオンを含むイオン性化合物(無機カチオンアニオン塩)は、有機カチオンアニオン塩と比較して、使用した場合に、粘着剤層の密着性(投錨力)の低下が抑制でき、より好ましい。なお、本発明でいう、「無機カチオンアニオン塩」とは、一般的には、アルカリ金属カチオンとアニオンから形成されるアルカリ金属塩を示し、アルカリ金属塩は、アルカリ金属の有機塩および無機塩を用いることができる。また、本発明でいう、「有機カチオンアニオン塩」とは、有機塩であって、そのカチオン部が有機物で構成されているものを示し、アニオン部は有機物であっても良いし、無機物であっても良い。「有機カチオンアニオン塩」は、イオン性液体、イオン性固体とも言われる。また、イオン性化合物を構成するアニオン成分としては、フッ素含有アニオンを使用するものが、帯電防止機能の点から好ましい。 As the ionic compound, an inorganic cation anion salt and/or an organic cation anion salt can be preferably used, and it is particularly preferable to use an inorganic cation anion salt. An ionic compound containing an inorganic cation (inorganic cation anion salt) is more preferable than an organic cation anion salt because it can suppress a decrease in adhesiveness (anchor force) of the pressure-sensitive adhesive layer when used. The term "inorganic cation anion salt" as used in the present invention generally indicates an alkali metal salt formed from an alkali metal cation and an anion, and the alkali metal salt includes an organic salt and an inorganic salt of an alkali metal. can be used. In addition, the term "organic cation anion salt" as used in the present invention means an organic salt, the cation portion of which is composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. can be "Organic cation anion salts" are also referred to as ionic liquids and ionic solids. As the anion component constituting the ionic compound, it is preferable to use a fluorine-containing anion from the viewpoint of antistatic function.
 アルカリ金属塩のカチオン部を構成するアルカリ金属イオンとしては、リチウム、ナトリウム、カリウムの各イオンが挙げられる。これらアルカリ金属イオンのなかでもリチウムイオンが好ましい。 Examples of alkali metal ions that make up the cation portion of the alkali metal salt include ions of lithium, sodium, and potassium. Among these alkali metal ions, lithium ions are preferred.
 アルカリ金属塩のアニオン部は有機物で構成されていてもよく、無機物で構成されていてもよい。有機塩を構成するアニオン部としては、例えば、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO23-、C49SO3 -、C37COO-、(CF3SO2)(CF3CO)N--3S(CF23SO3 -、PF6 -、CO3 2-、や下記一般式(1)乃至(4)、
(1):(Cn2n+1SO22- (但し、nは1~10の整数)、
(2):CF2(Cm2mSO22- (但し、mは1~10の整数)、
(3):-3S(CF2lSO3 - (但し、lは1~10の整数)、
(4):(Cp2p+1SO2)N-(Cq2q+1SO2)、(但し、p、qは1~10の整数)、及び、(FSO22-で表わされるもの等が用いられる。特に、フッ素原子を含むアニオン部は、イオン解離性の良いイオン化合物が得られることから好ましく用いられる。無機塩を構成するアニオン部としては、Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2-、等が用いられる。フッ素原子を含むアニオンの中でも、フッ素含有イミドアニオンが好ましく、その中でも、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオンであることが好ましい。特に、ビス(フルオロスルホニル)イミドアニオンは、比較的少量添加で優れた帯電防止性を付与でき、粘着特性を維持して加湿や加熱環境下での耐久性に有利となり、好ましい。
The anion portion of the alkali metal salt may be composed of an organic substance or may be composed of an inorganic substance. Examples of the anion moiety constituting the organic salt include CH 3 COO , CF 3 COO , CH 3 SO 3 , CF 3 SO 3 , (CF 3 SO 2 ) 3 C , C 4 F 9 SO 3 - , C3F7COO- , ( CF3SO2 ) ( CF3CO ) N- , -O3S ( CF2 ) 3SO3- , PF6- , CO32- , or the following general formula ( 1) to (4),
(1): (C n F 2n+1 SO 2 ) 2 N (where n is an integer of 1 to 10),
(2): CF 2 (C m F 2m SO 2 ) 2 N (where m is an integer of 1 to 10),
(3): - O 3 S(CF 2 ) l SO 3 - (where l is an integer of 1 to 10),
(4): (C p F 2p+1 SO 2 )N (C q F 2q+1 SO 2 ), (where p and q are integers from 1 to 10), and (FSO 2 ) 2 N Those represented by are used. In particular, an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained. Examples of the anion moiety constituting the inorganic salt include Cl , Br , I , AlCl 4 , Al 2 Cl 7 , BF 4 , PF 6 , ClO 4 , NO 3 , AsF 6 , SbF 6 , NbF 6 , TaF 6 , (CN) 2 N , etc. are used. Among anions containing a fluorine atom, fluorine-containing imide anions are preferable, and among these, bis(trifluoromethanesulfonyl)imide anions and bis(fluorosulfonyl)imide anions are preferable. In particular, a bis(fluorosulfonyl)imide anion is preferable because it can impart excellent antistatic properties even when added in a relatively small amount, maintains adhesive properties, and is advantageous for durability in a humidified or heated environment.
 アルカリ金属の有機塩としては、具体的には、酢酸ナトリウム、アルギン酸ナトリウム、リグニンスルホン酸ナトリウム、トルエンスルホン酸ナトリウム、LiCF3SO3、Li(CF3SO22N、Li(CF3SO22N、Li(C25SO22N、Li(C49SO22N、Li(CF3SO23C、KO3S(CF23SO3K、LiO3S(CF23SO3K等が挙げられ、これらのうちLiCF3SO3、Li(FSO22N、Li(CF3SO22N、Li(C25SO22N、Li(C49SO22N、Li(CF3SO23C等が好ましく、Li(CF3SO22N、Li(C25SO22N、Li(C49SO22N等のフッ素含有リチウムイミド塩がより好ましく、特にビス(トリフルオロメタンスルホニル)イミドリチウム、ビス(フルオロスルホニル)イミドリチウムが好ましい。 Specific examples of alkali metal organic salts include sodium acetate, sodium alginate, sodium ligninsulfonate , sodium toluenesulfonate, LiCF3SO3 , Li ( CF3SO2 )2N, Li ( CF3SO2 ). )2N, Li ( C2F5SO2 )2N , Li ( C4F9SO2 ) 2N , Li ( CF3SO2 ) 3C , KO3S ( CF2 ) 3SO3K , LiO 3 S(CF 2 ) 3 SO 3 K, among others, LiCF 3 SO 3 , Li(FSO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, etc. are preferred, and Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N , Li(C 4 F 9 SO 2 ) 2 N and the like are more preferred, and bis(trifluoromethanesulfonyl)imidelithium and bis(fluorosulfonyl)imidelithium are particularly preferred.
 また、アルカリ金属の無機塩としては、過塩素酸リチウム、ヨウ化リチウムが挙げられる。 Inorganic salts of alkali metals include lithium perchlorate and lithium iodide.
 有機カチオンアニオン塩は、カチオン成分とアニオン成分とから構成されており、前記カチオン成分は有機物からなるものである。カチオン成分として、具体的には、ピリジニウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、ピロリン骨格を有するカチオン、ピロール骨格を有するカチオン、イミダゾリウムカチオン、テトラヒドロピリミジニウムカチオン、ジヒドロピリミジニウムカチオン、ピラゾリウムカチオン、ピラゾリニウムカチオン、テトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオン、テトラアルキルホスホニウムカチオン等が挙げられる。 An organic cation anion salt is composed of a cation component and an anion component, and the cation component is composed of an organic substance. Specific examples of cationic components include pyridinium cations, piperidinium cations, pyrrolidinium cations, cations having a pyrroline skeleton, cations having a pyrrole skeleton, imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, Examples include pyrazolium cations, pyrazolinium cations, tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and the like.
 アニオン成分としては、例えば、Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO23-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2-、C49SO3 -、C37COO-、((CF3SO2)(CF3CO)N--3S(CF23SO3 -、や下記一般式(1)乃至(4)、
(1):(Cn2n+1SO22- (但し、nは1~10の整数)、
(2):CF2(Cm2mSO22- (但し、mは1~10の整数)、
(3):-3S(CF2lSO3 - (但し、lは1~10の整数)、
(4):(Cp2p+1SO2)N-(Cq2q+1SO2)、(但し、p、qは1~10の整数)、及び、(FSO22-で表わされるもの等が用いられる。なかでも特に、フッ素原子を含むアニオン(フッ素含有アニオン)は、イオン解離性の良いイオン化合物が得られることから好ましく用いられる。フッ素原子を含むアニオンの中でも、フッ素含有イミドアニオンが好ましく、その中でも、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオンであることが好ましい。特に、ビス(フルオロスルホニル)イミドアニオンは、比較的少量添加で優れた帯電防止性を付与でき、粘着特性を維持して加湿や加熱環境下での耐久性に有利となり、好ましい。
Examples of anion components include Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , ClO 4 - , NO 3 - , CH 3 COO - , CF 3 COO - , CH3SO3- , CF3SO3- , ( CF3SO2 ) 3C- , AsF6- , SbF6- , NbF6- , TaF6- , ( CN) 2N- , C4F 9 SO 3 , C 3 F 7 COO , ((CF 3 SO 2 )(CF 3 CO) N , —O 3 S(CF 2 ) 3 SO 3 , and compounds represented by the following general formulas (1) to (4) ),
(1): (C n F 2n+1 SO 2 ) 2 N (where n is an integer of 1 to 10),
( 2 ): CF2 ( CmF2mSO2 ) 2N- ( where m is an integer of 1 to 10),
(3): - O 3 S(CF 2 ) l SO 3 - (where l is an integer of 1 to 10),
(4): (C p F 2p+1 SO 2 )N (C q F 2q+1 SO 2 ), (where p and q are integers from 1 to 10), and (FSO 2 ) 2 N Those represented by are used. Among these, anions containing a fluorine atom (fluorine-containing anions) are particularly preferred because they yield ionic compounds with good ion dissociation properties. Among anions containing a fluorine atom, fluorine-containing imide anions are preferable, and among these, bis(trifluoromethanesulfonyl)imide anions and bis(fluorosulfonyl)imide anions are preferable. In particular, a bis(fluorosulfonyl)imide anion is preferable because it can impart excellent antistatic properties even when added in a relatively small amount, maintains adhesive properties, and is advantageous for durability in a humidified or heated environment.
 また、イオン性化合物としては、前記無機カチオンアニオン塩(アルカリ金属塩)、有機カチオンアニオン塩の他に、塩化アンモニウム、塩化アルミニウム、塩化銅、塩化第一鉄、塩化第二鉄、硫酸アンモニウム等の無機塩が挙げられる。これらイオン性化合物は単独でまたは複数を併用することができる。 In addition to the above inorganic cation anion salts (alkali metal salts) and organic cation anion salts, the ionic compounds include inorganic compounds such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate. salt. These ionic compounds can be used alone or in combination.
 イオン性界面活性剤としては、カチオン系(例えば、4級アンモニウム塩型、ホスホニウム塩型、スルホニウム塩型等)、アニオン系(カルボン酸型、スルホネート型、サルフェート型、ホスフェート型、ホスファイト型等)、両性イオン系(スルホベタイン型、アルキルベタイン型、アルキルイミダゾリウムベタイン型等)またはノニオン系(多価アルコール誘導体、β-シクロデキストリン包接化合物、ソルビタン脂肪酸モノエステル・ジエステル、ポリアルキレンオキシド誘導体、アミンオキシド等)の各種界面活性剤が挙げられる。 Examples of ionic surfactants include cationic surfactants (e.g., quaternary ammonium salt type, phosphonium salt type, sulfonium salt type, etc.) and anionic surfactants (carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphite type, etc.). , Zwitterionic (sulfobetaine type, alkylbetaine type, alkylimidazolium betaine type, etc.) or nonionic (polyhydric alcohol derivative, β-cyclodextrin inclusion compound, sorbitan fatty acid monoester/diester, polyalkylene oxide derivative, amine oxide, etc.).
 導電性ポリマーとしては、ポリアニリン系、ポリチオフェン系、ポリピロール系、ポリキノキサリン系等のポリマーがあげられるが、これらのなかでも、ポリアニリン、ポリチオフェン等が好ましく使用される。特にポリチオフェンが好ましい。 Examples of conductive polymers include polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoxaline-based polymers. Among these, polyaniline, polythiophene, and the like are preferably used. Polythiophene is particularly preferred.
 導電性微粒子としては、酸化スズ系、酸化アンチモン系、酸化インジウム系、酸化亜鉛系等の金属酸化物があげられる。これらのなかでも酸化スズ系が好ましい。酸化スズ系のものとしては、たとえば、酸化スズの他、アンチモンドープ酸化スズ、インジウムドープ酸化スズ、アルミニウムドープ酸化スズ、タングステンドープ酸化スズ、酸化チタン-酸化セリウム-酸化スズの複合体、酸化チタン-酸化スズの複合体等があげられる。微粒子の平均粒径は1~100nm程度、好ましくは2~50nmである。 Examples of conductive fine particles include metal oxides such as tin oxide, antimony oxide, indium oxide, and zinc oxide. Among these, the tin oxide type is preferable. Tin oxides include, in addition to tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide-tin oxide composite, titanium oxide- Composites of tin oxide and the like can be mentioned. The fine particles have an average particle size of about 1 to 100 nm, preferably 2 to 50 nm.
 さらに前記以外の帯電防止剤として、アセチレンブラック、ケッチェンブラック、天然グラファイト、人造グラファイト、チタンブラックや、カチオン型(4級アンモニウム塩等)、両性イオン型(ベタイン化合物等)、アニオン型(スルホン酸塩等)またはノニオン型(グリセリン等)のイオン導電性基を有する単量体の単独重合体若しくは前記単量体と他の単量体との共重合体、4級アンモニウム塩基を有するアクリレートまたはメタクリレート由来の部位を有する重合体等のイオン導電性を有する重合体;ポリエチレンメタクリレート共重合体等の親水性ポリマーをアクリル系樹脂等にアロイ化させたタイプの永久帯電防止剤を例示できる。 Furthermore, as antistatic agents other than the above, acetylene black, ketjen black, natural graphite, artificial graphite, titanium black, cationic type (quaternary ammonium salt, etc.), amphoteric ion type (betaine compound, etc.), anionic type (sulfonic acid salts, etc.), homopolymers of monomers having nonionic (glycerin, etc.) ion-conductive groups or copolymers of the above monomers with other monomers, acrylates or methacrylates having a quaternary ammonium base Polymers having ionic conductivity such as polymers having sites of origin; and permanent antistatic agents of the type in which hydrophilic polymers such as polyethylene methacrylate copolymers are alloyed with acrylic resins or the like.
 本発明の粘着剤組成物がその他の帯電防止剤を含有する場合、その含有量は、特に限定されないが、本発明の粘着剤層の透明性、外観、接信頼性等の耐久性を確保する観点から、アクリル系ポリマー(A)100重量部に対して、1重量部以下が好ましく、より好ましくは0.5重量部以下、0.4重量部以下、0.3重量部以下、又は0.2重量部以下である。本発明の粘着剤組成物がその他の帯電防止剤を含有する場合、含有量の下限値は、特に限定されないが、アクリル系ポリマー(A)100重量部に対して、0.01重量部以上、又は0.05重量部以上であってもよい。 When the pressure-sensitive adhesive composition of the present invention contains other antistatic agents, the content is not particularly limited, but the transparency, appearance, and durability such as contact reliability of the pressure-sensitive adhesive layer of the present invention are ensured. From the point of view, it is preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, 0.4 parts by weight or less, 0.3 parts by weight or less, or 0.3 part by weight or less with respect to 100 parts by weight of the acrylic polymer (A). 2 parts by weight or less. When the pressure-sensitive adhesive composition of the present invention contains other antistatic agents, the lower limit of the content is not particularly limited. Alternatively, it may be 0.05 parts by weight or more.
[2-11.添加剤]
 上記粘着剤層には、必要に応じて、架橋剤、架橋促進剤、シランカップリング剤、粘着付与樹脂(ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノール等)、老化防止剤、充填剤、着色剤(顔料や染料等)、紫外線吸収剤、酸化防止剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、防錆剤等の公知の添加剤が、本発明の特性を損なわない範囲で含まれていてもよい。なお、このような添加剤は、単独で又は2種以上を組み合わせて用いられてもよい。
[2-11. Additive]
In the pressure-sensitive adhesive layer, if necessary, a cross-linking agent, a cross-linking accelerator, a silane coupling agent, a tackifying resin (rosin derivative, polyterpene resin, petroleum resin, oil-soluble phenol, etc.), an anti-aging agent, a filler, Known additives such as colorants (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, rust inhibitors, etc., within the range that does not impair the characteristics of the present invention. may be included in In addition, such an additive may be used individually or in combination of 2 or more types.
 上記粘着剤層に架橋剤が含まれていると、ベースポリマーを架橋してゲル分率を大きくし、耐発泡剥がれ性を向上させやすくなる。例えば、アクリル系ポリマー(特に、アクリル系ポリマー(A))を架橋して、ゲル分率のコントロールを容易に大きくすることができるので、耐発泡剥がれ性を向上させやすくなる。また、アクリル系ポリマー(A)と本発明のイオン性化合物が、架橋剤を介して共有結合を形成し得る。 When the pressure-sensitive adhesive layer contains a cross-linking agent, the base polymer is cross-linked to increase the gel fraction, making it easier to improve the resistance to foaming and peeling. For example, the acrylic polymer (especially the acrylic polymer (A)) can be crosslinked to easily increase the control of the gel fraction. Also, the acrylic polymer (A) and the ionic compound of the present invention can form a covalent bond via a cross-linking agent.
 上記架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤の他、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤等が挙げられる。なかでも、上記粘着剤層がベースポリマーとしてアクリル系ポリマー(A)を含有する粘着剤層である場合、耐発泡剥がれ性向上の点で、イソシアネート系架橋剤、エポキシ系架橋剤が好ましく、より好ましくはイソシアネート系架橋剤である。なお、架橋剤は、単独で又は2種以上を組み合わせて用いられてもよい。 Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal Examples include salt-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and amine-based cross-linking agents. Among them, when the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer containing an acrylic polymer (A) as a base polymer, isocyanate-based cross-linking agents and epoxy-based cross-linking agents are preferable and more preferable from the viewpoint of improving resistance to foaming and peeling. is an isocyanate cross-linking agent. In addition, a crosslinking agent may be used individually or in combination of 2 or more types.
 上記イソシアネート系架橋剤(多官能イソシアネート化合物)としては、例えば、1,2-エチレンジイソシアネート、1,4-ブチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネート等の低級脂肪族ポリイソシアネート類;シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加キシレンジイソシアネート等の脂環族ポリイソシアネート類;2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、4,4'-ジフェニルメタンジイソシアネート、キシリレンジイソシアネート等の芳香族ポリイソシアネート類等が挙げられる。また、上記イソシアネート系架橋剤としては、例えば、トリメチロールプロパン/トリレンジイソシアネート付加物[日本ポリウレタン工業(株)製、商品名「コロネートL」]、トリメチロールプロパン/ヘキサメチレンジイソシアネート付加物[日本ポリウレタン工業(株)製、商品名「コロネートHL」]、トリメチロールプロパン/キシリレンジイソシアネート付加物[三井化学(株)製、商品名「タケネートD-110N」]等の市販品も挙げられる。 Examples of the isocyanate-based crosslinking agent (polyfunctional isocyanate compound) 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 , xylylene diisocyanate and other aromatic polyisocyanates. Examples of the isocyanate-based cross-linking agent include trimethylolpropane/tolylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"], trimethylolpropane/hexamethylene diisocyanate adduct [Nippon Polyurethane Kogyo Co., Ltd., trade name “Coronate HL”], trimethylolpropane/xylylene diisocyanate adduct [Mitsui Chemicals Co., Ltd., trade name “Takenate D-110N”].
 上記エポキシ系架橋剤(多官能エポキシ化合物)としては、例えば、N,N,N',N'-テトラグリシジル-m-キシレンジアミン、ジグリシジルアニリン、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、1,6-ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、アジピン酸ジグリシジルエステル、o-フタル酸ジグリシジルエステル、トリグリシジル-トリス(2-ヒドロキシエチル)イソシアヌレート、レゾルシンジグリシジルエーテル、ビスフェノール-S-ジグリシジルエーテルの他、分子内にエポキシ基を2つ以上有するエポキシ系樹脂等が挙げられる。また、上記エポキシ系架橋剤としては、例えば、三菱ガス化学(株)製、商品名「テトラッドC」等の市販品も挙げられる。 Examples of the epoxy-based cross-linking agent (polyfunctional epoxy compound) include N,N,N',N'-tetraglycidyl-m-xylenediamine, 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, adipate diglycidyl ester, o-phthalate diglycidyl ester, triglycidyl-tris(2 -hydroxyethyl)isocyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. Examples of the epoxy-based cross-linking agent include commercially available products such as those manufactured by Mitsubishi Gas Chemical Company, Inc. under the trade name of "Tetrad C".
 上記粘着剤層における架橋剤の含有量としては、特に限定されないが、例えば、アクリル系ポリマー(A)100重量部に対して、0.001~10重量部が好ましく、より好ましくは0.01~5重量部である。架橋剤の含有量が0.001重量部以上であると、耐発泡剥がれ性が向上しやすくなり、好ましい。一方、架橋剤の含有量が10重量部以下であると、粘着剤層が適度な柔軟性を有し、粘着力が向上しやすくなるので、好ましい。 The content of the cross-linking agent in the pressure-sensitive adhesive layer is not particularly limited. 5 parts by weight. When the content of the cross-linking agent is 0.001 parts by weight or more, the resistance to foaming and peeling is easily improved, which is preferable. On the other hand, when the content of the cross-linking agent is 10 parts by weight or less, the pressure-sensitive adhesive layer has appropriate flexibility and the pressure-sensitive adhesive strength is easily improved, which is preferable.
 上記粘着剤層に、シランカップリング剤が含まれていると、ガラスに対する優れた接着性(特に、高温高湿でのガラスに対する優れた接着信頼性)が得やすくなり好ましい。上記シランカップリング剤としては、特に限定されないが、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-アミノプロピルトリメトキシシラン、N-フェニル-アミノプロピルトリメトキシシラン等が挙げられる。なかでも、γ-グリシドキシプロピルトリメトキシシランが好ましい。さらに、上記シランカップリング剤としては、例えば、商品名「KBM-403」(信越化学工業(株)製)等の市販品も挙げられる。なお、シランカップリング剤は、単独で又は2種以上を組み合わせて用いられてもよい。 If the pressure-sensitive adhesive layer contains a silane coupling agent, excellent adhesion to glass (in particular, excellent adhesion reliability to glass at high temperature and high humidity) can be easily obtained, which is preferable. Examples of the silane coupling agent include, but are not limited to, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-aminopropyltrimethoxysilane. etc. Among them, γ-glycidoxypropyltrimethoxysilane is preferred. Furthermore, examples of the silane coupling agent include commercially available products such as the product name "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.). In addition, a silane coupling agent may be used individually or in combination of 2 or more types.
 上記粘着剤層における上記シランカップリング剤の含有量は、特に限定されないが、例えば、上記粘着剤層がベースポリマーとしてアクリル系ポリマー(A)を含有する粘着剤層である場合、ガラスに対する接着信頼性向上の点から、アクリル系ポリマー(A)100重量部に対して、0.01~1重量部が好ましく、より好ましくは0.03~0.5重量部である。 The content of the silane coupling agent in the adhesive layer is not particularly limited, but for example, when the adhesive layer is an adhesive layer containing an acrylic polymer (A) as a base polymer, the adhesion reliability to glass From the viewpoint of improving properties, it is preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight, per 100 parts by weight of the acrylic polymer (A).
[2-12.共有結合]
 アクリル系ポリマー(A)と本発明のイオン性化合物の官能基(A)が共有結合を形成する反応は、当該共有結合を形成し得る限り、その形態は特に限定されない。例えば、官能基(A)がアクリル系ポリマー(A)のモノマー単位として取り込まれる形態であってもよく、或いは、アクリル系ポリマー(A)が側鎖鎖に有する官能基と反応して共有結合を形成する形態であってもよい。さらには、アクリル系ポリマー(A)と本発明のイオン性化合物の官能基(A)が、上記の架橋剤を介して反応して、共有結合を形成する形態であってもよい。
[2-12. Covalent bond]
The form of the reaction in which the acrylic polymer (A) and the functional group (A) of the ionic compound of the present invention form a covalent bond is not particularly limited as long as the covalent bond can be formed. For example, the functional group (A) may be incorporated as a monomer unit of the acrylic polymer (A), or the acrylic polymer (A) reacts with the functional group in the side chain to form a covalent bond. It may be in the form of forming. Furthermore, the acrylic polymer (A) and the functional group (A) of the ionic compound of the present invention may react via the above-mentioned cross-linking agent to form a covalent bond.
 例えば、本発明のイオン性化合物の官能基(A)が、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミノ基、ビニル基、アリル基、スチリル基等の共重合性を有する官能基であり、アクリル系ポリマー(A)を構成するモノマー成分の混合物に含まれる場合は、アクリル系ポリマー(A)を重合する過程でモノマー単位として取り込まれ、共有結合が形成される。 For example, the functional group (A) of the ionic compound of the present invention is a copolymerizable functional group such as (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, allyl group, styryl group, When it is contained in the mixture of monomer components constituting the acrylic polymer (A), it is incorporated as a monomer unit in the process of polymerizing the acrylic polymer (A) to form a covalent bond.
 また、本発明のイオン性化合物の官能基(A)が、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミノ基、ビニル基、アリル基、スチリル基等の共重合性を有する官能基であり、アクリル系ポリマー(A)を構成するモノマー成分の混合物の部分重合物に含まれる場合は、部分重合物の重合末端ラジカルとリビングラジカル重合して、共有結合が形成される。 Further, the functional group (A) of the ionic compound of the present invention is a copolymerizable functional group such as (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, allyl group, styryl group, etc. When it is contained in the partially polymerized product of the mixture of the monomer components constituting the acrylic polymer (A), it undergoes living radical polymerization with the polymerized terminal radical of the partially polymerized product to form a covalent bond.
 また、本発明のイオン性化合物の官能基(A)が、水酸基、アミノ基、メルカプト基 等であり、アクリル系ポリマー(A)が、側鎖に、イソシアネート基、チオイソシアネート基、エポキシ基等の官能基(A)と反応し得る官能基を有する場合、或いは、官能基(A)が、エポキシ基等であり、アクリル系ポリマー(A)が、側鎖に、水酸基、アミノ基、メルカプト基等の官能基(A)と反応し得る官能基を有する場合は、官能基(A)と反応して、共有結合が形成される。 In addition, the functional group (A) of the ionic compound of the present invention is a hydroxyl group, an amino group, a mercapto group, etc., and the acrylic polymer (A) has an isocyanate group, a thioisocyanate group, an epoxy group, etc. in the side chain. When it has a functional group that can react with the functional group (A), or the functional group (A) is an epoxy group or the like, and the acrylic polymer (A) has a hydroxyl group, an amino group, a mercapto group, or the like in the side chain. When it has a functional group capable of reacting with the functional group (A) of, it reacts with the functional group (A) to form a covalent bond.
 さらに、本発明のイオン性化合物の官能基(A)が、水酸基、アミノ基、メルカプト基 等であり、アクリル系ポリマー(A)が、側鎖に、水酸基、アミノ基、メルカプト基 等を有する場合、上記の架橋剤を配合し、官能基(A)とアクリル系ポリマー(A)の側鎖官能基が、架橋剤のイソシアネート基、チオイソシアネート基、エポキシ基等と反応して、架橋剤を介して共有結合を形成し得る。 Furthermore, when the functional group (A) of the ionic compound of the present invention is a hydroxyl group, an amino group, a mercapto group, etc., and the acrylic polymer (A) has a hydroxyl group, an amino group, a mercapto group, etc. in the side chain. , The above-mentioned cross-linking agent is blended, and the functional group (A) and the side chain functional group of the acrylic polymer (A) react with the isocyanate group, thioisocyanate group, epoxy group, etc. of the cross-linking agent, and through the cross-linking agent can form a covalent bond.
 本発明の光学用粘着シートは、本発明の基材、本発明の粘着剤層以外にも、本発明の効果を損なわない範囲で、他の層、例えば、本発明の基材以外の基材、本発明の粘着剤層以外の粘着剤層、中間層、下塗り層(アンカー層)、セパレータ、表面保護フィルムなどを、表面又は任意の層間に有していてもよい。 In addition to the base material of the present invention and the pressure-sensitive adhesive layer of the present invention, the optical pressure-sensitive adhesive sheet of the present invention includes other layers, for example, a base material other than the base material of the present invention, as long as the effects of the present invention are not impaired. , a pressure-sensitive adhesive layer other than the pressure-sensitive adhesive layer of the present invention, an intermediate layer, an undercoat layer (anchor layer), a separator, a surface protective film, and the like on the surface or between any layers.
[3.下塗り層(アンカー層)]
 本発明の基材の第1面と本発明の粘着剤層の間には、密着性の観点より、下塗り層(アンカー層)が設けられていてもよい。
 前記アンカー層の厚さは、粘着剤層との密着性の観点から0.01~0.5μmであり、0.01~0.4μmであるのが好ましく、さらに0.02~0.3μmであるのが好ましい。
[3. Undercoat layer (anchor layer)]
From the viewpoint of adhesion, an undercoat layer (anchor layer) may be provided between the first surface of the base material of the present invention and the pressure-sensitive adhesive layer of the present invention.
The thickness of the anchor layer is 0.01 to 0.5 μm, preferably 0.01 to 0.4 μm, more preferably 0.02 to 0.3 μm, from the viewpoint of adhesion with the pressure-sensitive adhesive layer. It is preferable to have
 前記アンカー層の形成材料としては、本発明の基材への皮膜形成性、密着性の向上等を目的に、バインダー成分を添加することもできる。バインダーの例としては、オキサゾリン基含有ポリマー、ポリウレタン系樹脂、ポリエステル系樹脂、アクリル系樹脂、ポリエーテル系樹脂、セルロース系樹脂、ポリビニルアルコール系樹脂、エポキシ樹脂、ポリビニルピロリドン、ポリスチレン系樹脂、ポリエチレングリコール、ペンタエリスリトール等があげられる。特にポリウレタン系樹脂、ポリエステル系樹脂、アクリル系樹脂が好ましい。これらバインダーは1種または2種以上を適宜その用途に合わせて用いることができる。 As the material for forming the anchor layer, a binder component can be added for the purpose of improving the film-forming property and adhesion to the base material of the present invention. Examples of binders include oxazoline group-containing polymers, polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polyvinylpyrrolidone, polystyrene resins, polyethylene glycol, pentaerythritol and the like. Polyurethane-based resins, polyester-based resins, and acrylic-based resins are particularly preferred. One or more of these binders can be used as appropriate depending on the application.
 前記アンカー層は導電性(帯電防止性)を有していてもよい。前記アンカー層は導電性(帯電防止性)することで、粘着剤層単独で帯電防止性を付与する場合に比べて、帯電防止機能が優れ、前記粘着剤層に使用する帯電防止剤の使用量を少量に抑えることも可能となり、帯電防止剤の析出・偏析や加湿環境下での白濁等の外観の不具合や、耐久性の観点で好ましい態様となる。前記アンカー層が帯電防止性を有する場合、その表面抵抗は、1.0×108~1.0×1010Ω/□であるのが好ましく、1.0×108~8.0×109Ω/□であるのがより好ましく、2.0×108~6.0×109Ω/□であるのがさらに好ましい。 The anchor layer may have conductivity (antistatic property). By making the anchor layer conductive (antistatic), the antistatic function is excellent compared to the case where the adhesive layer alone imparts antistatic properties, and the amount of antistatic agent used in the adhesive layer can be suppressed to a small amount, and this is a preferable embodiment from the viewpoint of durability and appearance defects such as precipitation and segregation of the antistatic agent and cloudiness under a humidified environment. When the anchor layer has antistatic properties, the surface resistance thereof is preferably 1.0×10 8 to 1.0×10 10 Ω/□, more preferably 1.0×10 8 to 8.0×10 Ω/□. 9 Ω/□ is more preferable, and 2.0×10 8 to 6.0×10 9 Ω/□ is even more preferable.
 前記アンカー層が帯電防止性を有する場合、上記バインダー成分に導電ポリマーを含有することで、帯電防止性を付与することができる。前記導電性ポリマーは、光学特性、外観、帯電防止効果および帯電防止効果の熱時、加湿時での安定性という観点から好ましく使用される。特に、ポリアニリン、ポリチオフェン等の導電性ポリマーが好ましく使用される。導電性ポリマーは有機溶剤可溶性、水溶性、水分散性のものを適宜使用可能だが、水溶性導電性ポリマーまたは水分散性導電性ポリマーが好ましく使用される。水溶性導電性ポリマーや水分散性導電性ポリマーは帯電防止層を形成する際の塗布液を水溶液または水分散液として調製でき、前記塗布液は非水系の有機溶剤を用いる必要がなく、前記有機溶剤による光学フィルム基材の変質を抑えることができるためである。なお、水溶液または水分散液は、水のほかに水系の溶媒を含有できる。たとえば、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、sec-ブタノール、tert-ブタノール、n-アミルアルコール、イソアミルアルコール、sec-アミルアルコール、tert-アミルアルコール、1-エチル-1-プロパノール、2-メチル-1-ブタノール、n-ヘキサノール、シクロヘキサノール等のアルコール類があげられる。 When the anchor layer has antistatic properties, the antistatic properties can be imparted by including a conductive polymer in the binder component. The conductive polymer is preferably used from the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect when heated and when humidified. In particular, conductive polymers such as polyaniline and polythiophene are preferably used. An organic solvent-soluble, water-soluble, or water-dispersible conductive polymer can be appropriately used, but a water-soluble conductive polymer or a water-dispersible conductive polymer is preferably used. A water-soluble conductive polymer or a water-dispersible conductive polymer can be prepared as an aqueous solution or an aqueous dispersion when forming an antistatic layer, and the coating solution does not need to use a non-aqueous organic solvent, and the organic This is because deterioration of the optical film substrate due to the solvent can be suppressed. The aqueous solution or aqueous dispersion can contain an aqueous solvent in addition to water. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1 -propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and other alcohols.
 また、前記ポリアニリン、ポリチオフェン等の水溶性導電性ポリマーまたは水分散性導電性ポリマーは、分子中に親水性官能基を有することが好ましい。親水性官能基としては、たとえばスルホン基、アミノ基、アミド基、イミノ基、四級アンモニウム塩基、ヒドロキシル基、メルカプト基、ヒドラジノ基、カルボキシル基、硫酸エステル基、リン酸エステル基、またはそれらの塩等があげられる。分子内に親水性官能基を有することにより水に溶けやすくなったり、水に微粒子状で分散しやすくなり、前記水溶性導電性ポリマーまたは水分散性導電性ポリマーを容易に調製することができる。なお、ポリチオフェン系ポリマーを用いる際は、通常、ポリスチレンスルホン酸を併用する。 In addition, the water-soluble conductive polymer or water-dispersible conductive polymer such as polyaniline and polythiophene preferably has a hydrophilic functional group in the molecule. Hydrophilic functional groups include, for example, a sulfone group, an amino group, an amide group, an imino group, a quaternary ammonium base, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfate group, a phosphate group, or salts thereof. etc. Having a hydrophilic functional group in the molecule makes it easier to dissolve in water or easier to disperse in water in the form of fine particles, making it possible to easily prepare the water-soluble conductive polymer or water-dispersible conductive polymer. In addition, when using a polythiophene-based polymer, polystyrene sulfonic acid is usually used together.
 前記アンカー層としては、例えば、上記バインダー成分に、必要に応じて、導電性ポリマーを配合して得られる導電コート液を本発明の基材の第1面にコーティングして形成できる。具体的なコーティングの方法としては、ロールコート法、バーコート法、グラビアコート法などが挙げられる。 The anchor layer can be formed, for example, by coating the first surface of the substrate of the present invention with a conductive coating liquid obtained by blending a conductive polymer with the above binder component, if necessary. Specific coating methods include a roll coating method, a bar coating method, a gravure coating method, and the like.
[4.セパレータ(剥離ライナー)]
 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、使用時まではセパレータにより保護されていてもよい。セパレータ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。なお、セパレータは必ずしも設けられなくてもよい。
[4. Separator (release liner)]
In the optical pressure-sensitive adhesive sheet of the present invention, the surface of the pressure-sensitive adhesive layer of the present invention (adhesive surface of the pressure-sensitive adhesive layer of the present invention) may be protected by a separator until use. The separator is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when the optical pressure-sensitive adhesive sheet of the present invention is attached to an adherend. Note that the separator does not necessarily have to be provided.
 上記セパレータとしては、慣用の剥離紙などを利用でき、具体的には、例えば、剥離処理剤による剥離処理層を少なくとも一方の表面に有する基材の他、フッ素系ポリマー(例えば、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、クロロフルオロエチレン-フッ化ビニリデン共重合体など)からなる低接着性基材や、無極性ポリマー(例えば、ポリエチレン、ポリプロピレンなどのオレフィン系樹脂など)からなる低接着性基材などを用いることができる。 As the separator, a conventional release paper or the like can be used. Specifically, for example, in addition to a substrate having a release treatment layer with a release treatment agent on at least one surface, a fluorine-based polymer (e.g., polytetrafluoroethylene) , polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.). A low-adhesive base material made of (for example, olefin resin such as polyethylene, polypropylene, etc.) can be used.
 上記セパレータとしては、例えば、セパレータ用基材の少なくとも一方の面に剥離処理層が形成されているセパレータを好適に用いることができる。このようなセパレータ用基材としては、ポリエステルフィルム(ポリエチレンテレフタレートフィルムなど)、オレフィン系樹脂フィルム(ポリエチレンフィルム、ポリプロピレンフィルムなど)、ポリ塩化ビニルフィルム、ポリイミドフィルム、ポリアミドフィルム(ナイロンフィルム)、レーヨンフィルムなどのプラスチック系基材フィルム(合成樹脂フィルム)や紙類(上質紙、和紙、クラフト紙、グラシン紙、合成紙、トップコート紙など)の他、これらを、ラミネートや共押し出しなどにより、複層化したもの(2~3層の複合体)などが挙げられる。 As the separator, for example, a separator in which a release treatment layer is formed on at least one surface of a separator substrate can be suitably used. Base materials for such separators include polyester film (polyethylene terephthalate film, etc.), olefin resin film (polyethylene film, polypropylene film, etc.), polyvinyl chloride film, polyimide film, polyamide film (nylon film), rayon film, etc. In addition to the plastic base film (synthetic resin film) and paper (wooden paper, Japanese paper, kraft paper, glassine paper, synthetic paper, top coat paper, etc.), these are multi-layered by lamination or co-extrusion. (composite of 2 to 3 layers) and the like.
 上記剥離処理層を構成する剥離処理剤としては、特に限定されないが、例えば、シリコーン系剥離処理剤、フッ素系剥離処理剤、長鎖アルキル系剥離処理剤などを用いることができる。剥離処理剤は単独でまたは2種以上組み合わせて使用することができる。 The release treatment agent that constitutes the release treatment layer is not particularly limited, but for example, a silicone-based release treatment agent, a fluorine-based release treatment agent, a long-chain alkyl-based release treatment agent, or the like can be used. The release agents can be used alone or in combination of two or more.
 前記セパレータの厚さは、特に限定されず、5~100μmの範囲から適宜選択すればよい。 The thickness of the separator is not particularly limited, and may be appropriately selected from the range of 5 to 100 μm.
 上記セパレータは、画像表示パネル等の被着体の破損を防止するため、セパレータ用基材の少なくとも一方の面に帯電防止層が形成されていてもよい。帯電防止層はセパレータの一方の面(剥離処理面または未処理面)に形成されていてもよく、セパレータの両面(剥離処理面及び未処理面)に形成されていてもよい。 The above separator may have an antistatic layer formed on at least one surface of the separator substrate in order to prevent damage to an adherend such as an image display panel. The antistatic layer may be formed on one surface of the separator (release-treated surface or untreated surface) or may be formed on both surfaces of the separator (release-treated surface and untreated surface).
 前記帯電防止層としては、特に限定されないが、例えば、導電性ポリマーを含む導電コート液をセパレータ上にコーティングして形成される帯電防止層である。具体的には、例えば、導電性ポリマーを含む導電コート液をセパレータ上(剥離処理面及び/又は未処理面)にコーティングして形成される帯電防止層である。具体的なコーティングの方法としては、ロールコート法、バーコート法、グラビアコート法などが挙げられる。 The antistatic layer is not particularly limited, but is, for example, an antistatic layer formed by coating a separator with a conductive coating liquid containing a conductive polymer. Specifically, for example, it is an antistatic layer formed by coating a separator (release-treated surface and/or untreated surface) with a conductive coating liquid containing a conductive polymer. Specific coating methods include a roll coating method, a bar coating method, a gravure coating method, and the like.
前記導電性ポリマーとしては、上記の本発明の光学用粘着シートに含まれていてもよい帯電防止剤を構成する導電性ポリマーと同様のものを使用することができる。 As the conductive polymer, the same conductive polymer that constitutes the antistatic agent that may be contained in the optical pressure-sensitive adhesive sheet of the present invention can be used.
 前記帯電防止層の厚みとしては、好ましくは1nm~1000nmであり、より好ましくは5nm~900nmである。前記帯電防止層は、1層のみであってもよいし、2層以上であってもよい。 The thickness of the antistatic layer is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm. The antistatic layer may consist of only one layer, or may consist of two or more layers.
[5.光学用粘着シートの製造方法]
 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。
[5. Manufacturing method of optical pressure-sensitive adhesive sheet]
The 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 substrate of the present invention.
 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方法は、特に限定されず、例えば、上記粘着剤組成物をセパレータ上に塗布(塗工)し、得られた粘着剤組成物層を乾燥硬化させることや、上記粘着剤組成物をセパレータ上に塗布(塗工)し、得られた粘着剤組成物層に活性エネルギー線を照射して硬化させることにより、セパレータ上にシート状の粘着剤層に成形し、本発明の基材の第1面上に前記粘着剤層を貼り合わせることにより行うことができる。また、必要に応じて、さらに、加熱乾燥してもよい。
 活性エネルギー線の照射により硬化を行う際は、塗膜の表面にさらにセパレータを付設して、粘着剤組成物を2枚のセパレータ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。
The method for laminating the pressure-sensitive adhesive layer of the present invention on the first surface of the base material of the present invention is not particularly limited. By drying and curing the adhesive composition layer, or by applying (coating) the adhesive composition on the separator and curing the obtained adhesive composition layer by irradiating it with an active energy ray, on the separator It can be carried out by molding into a sheet-like pressure-sensitive adhesive layer, and bonding the pressure-sensitive adhesive layer on the first surface of the substrate of the present invention. Moreover, you may heat-dry further as needed.
When curing by irradiation with active energy rays, a separator is further attached to the surface of the coating film, and the adhesive composition is sandwiched between two separators and irradiated with active energy rays to polymerize with oxygen. It is preferred to prevent inhibition.
 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別の方法は、例えば、上記粘着剤組成物を本発明の基材の第1面上に塗布(塗工)し、得られた粘着剤組成物層を乾燥硬化させることや、上記粘着剤組成物を本発明の基材の第1面上に塗布(塗工)し、得られた粘着剤組成物層に活性エネルギー線を照射して硬化させることにより行うこともできる。また、必要に応じて、さらに、加熱乾燥してもよい。
 活性エネルギー線の照射により硬化を行う際は、塗膜の表面にセパレータを付設して、粘着剤組成物を本発明の基材とセパレータ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。
Another method for laminating the pressure-sensitive 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 pressure-sensitive adhesive composition onto the first surface of the substrate of the present invention. , drying and curing the obtained pressure-sensitive adhesive composition layer, or applying (coating) the above-mentioned pressure-sensitive adhesive composition on the first surface of the substrate of the present invention, and applying an active agent to the obtained pressure-sensitive adhesive composition layer. It can also be cured by irradiation with energy rays. Moreover, you may heat-dry further as needed.
When curing by irradiation with active energy rays, a separator is attached to the surface of the coating film, and the adhesive composition is irradiated with active energy rays while being sandwiched between the base material of the present invention and the separator. It is preferable to prevent polymerization inhibition by oxygen.
 活性エネルギー線照射の前に、溶媒の除去等を目的として、シート状の塗膜を加熱してもよい。加熱による溶媒等の除去を行う場合は、セパレータを付設する前に実施することが好ましい。 The sheet-like coating film may be heated for the purpose of removing the solvent, etc., before the active energy ray irradiation. If the solvent or the like is removed by heating, it is preferably carried out before attaching the separator.
 上記活性エネルギー線としては、例えば、α線、β線、γ線、中性子線、電子線などの電離性放射線や、紫外線などが挙げられ、特に、紫外線が好ましい。また、活性エネルギー線の照射エネルギー、照射時間、照射方法などは特に制限されない。 Examples of the active energy rays include ionizing radiation such as α-rays, β-rays, γ-rays, neutron beams and electron beams, and ultraviolet rays, with ultraviolet rays being particularly preferred. Moreover, the irradiation energy of the active energy ray, the irradiation time, the irradiation method, etc. are not particularly limited.
 上記粘着剤組成物は、公知乃至慣用の方法で作製することができる。例えば、溶剤型のアクリル系粘着剤組成物は、アクリル系ポリマー(A)と本発明のイオン性化合物を含有する溶液に、必要に応じて、添加剤を混合することにより、作製することができる。例えば、活性エネルギー線硬化型のアクリル系粘着剤組成物は、上記アクリル系モノマー(A)の混合物又はその部分重合物と本発明のイオン性化合物に、必要に応じて、添加剤を混合することにより、作製することができる。 The above pressure-sensitive adhesive composition can be produced by a known or commonly used method. For example, a solvent-based acrylic pressure-sensitive adhesive composition can be prepared by mixing additives, if necessary, with a solution containing the acrylic polymer (A) and the ionic compound of the present invention. . For example, an active energy ray-curable acrylic pressure-sensitive adhesive composition can be prepared by mixing the mixture of the acrylic monomer (A) or a partial polymer thereof and the ionic compound of the present invention with additives, if necessary. can be produced by
 なお、上記粘着剤組成物の塗布(塗工)には、公知のコーティング法が用いられてもよい。例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーター等のコーターが用いられてもよい。 A known coating method may be used for applying (coating) the pressure-sensitive adhesive composition. For example, coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, comma coaters, and direct coaters may be used.
 特に、活性エネルギー線硬化型の粘着剤組成物により粘着剤層を形成する場合、活性エネルギー線硬化型の粘着剤組成物は光重合開始剤を含むことが好ましい。なお、活性エネルギー線硬化型の粘着剤組成物が紫外線吸収剤を含有する場合には、光重合開始剤として、広い波長範囲で吸光特性を有する光重合開始剤を少なくとも含むことが好ましい。例えば、紫外光に加え、可視光でも吸光特性を有する光重合開始剤を少なくとも含むことが好ましい。これは、紫外線吸収剤の作用により活性エネルギー線による硬化の阻害が懸念されるところ、広い波長範囲で吸光特性を有する光重合開始剤を含んでいると、粘着剤組成物において高い光硬化性が得やすくなるからである。 In particular, when the adhesive layer is formed from an active energy ray-curable adhesive composition, the active energy ray-curable adhesive composition preferably contains a photopolymerization initiator. When the active energy ray-curable pressure-sensitive adhesive composition contains an ultraviolet absorber, it preferably contains at least a photopolymerization initiator having light absorption properties in a wide wavelength range as a photopolymerization initiator. For example, it preferably contains at least a photopolymerization initiator that absorbs not only ultraviolet light but also visible light. This is because there is concern that curing by active energy rays may be inhibited due to the action of the ultraviolet absorber, and if the adhesive composition contains a photopolymerization initiator that has light absorption characteristics in a wide wavelength range, high photocurability will be achieved in the adhesive composition. This is because it becomes easier to obtain.
[6.光学用粘着シートの用途等]
 本発明の光学用粘着シートは、上記粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)を有するので、帯電防止性能に優れる。このため、光学部材や画像表示装置との貼り合わせに用いる場合、静電気による表示不良が生じにくい。また、また、湿熱環境のような過酷な条件でも帯電防止成分のブリードアウトを抑制することができるため、粘着剤層の表面での析出、発泡、剥がれが抑制され、外観や接着信頼性などの耐久性の不良が生じにくい。従って、本発明の光学用粘着シートは、優れた帯電防止性、透明性、耐湿熱性、及び低汚染性を満足でき、画像表示装置の製造に有用である。
[6. Applications, etc. of Optical Adhesive Sheets]
Since the optical pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention), it has excellent antistatic performance. Therefore, display defects due to static electricity are less likely to occur when used for lamination with an optical member or an image display device. In addition, since bleeding out of the antistatic component can be suppressed even under harsh conditions such as a moist and hot environment, precipitation, foaming, and peeling on the surface of the adhesive layer are suppressed, and appearance and adhesion reliability are improved. Poor durability is less likely to occur. Therefore, the optical pressure-sensitive adhesive sheet of the present invention satisfies excellent antistatic properties, transparency, moist heat resistance, and low staining properties, and is useful for the production of image display devices.
 さらに、本発明の光学用粘着シートは、接着性、耐発泡剥がれ性、応力緩和性に優れ、段差追従性、接着信頼性、特に高温時の接着信頼性に優れる。また、外観性に優れる。このため、本発明の光学用粘着シートは、高温時に界面での発泡の生じやすい被着体に対して有用に用いられる。例えば、ポリメタクリル酸メチル樹脂(PMMA)は、未反応モノマーを含むことがあり、高温時に異物による発泡が生じやすい。また、ポリカーボネート(PC)は、高温時に水と二酸化炭素のアウトガスを生じやすい。本発明の粘着シートは、耐発泡剥がれ性に優れるので、このような樹脂を含むプラスチック被着体に対しても有用に用いられる。 Furthermore, the optical pressure-sensitive adhesive sheet of the present invention is excellent in adhesiveness, resistance to foaming and peeling, and stress relaxation, as well as step followability and adhesion reliability, especially at high temperatures. Moreover, it is excellent in external appearance. Therefore, the optical pressure-sensitive adhesive sheet of the present invention is useful for adherends that tend to foam at the interface at high temperatures. For example, polymethyl methacrylate (PMMA) may contain unreacted monomers, and foaming due to foreign matter is likely to occur at high temperatures. Polycarbonate (PC) also tends to outgas water and carbon dioxide at high temperatures. Since the pressure-sensitive adhesive sheet of the present invention is excellent in resistance to foaming and peeling, it is also useful for plastic adherends containing such resins.
 また、本発明の光学用粘着シートは、線膨張係数の小さい被着体に加えて、線膨張係数の大きい被着体に対しても、有用に用いられる。なお、上記線膨張係数の小さい被着体としては、特に限定されないが、例えば、ガラス板(線膨張係数:0.3×10-5~0.8×10-5/℃)、ポリエチレンテレフタレート基材(PETフィルム、線膨張係数:1.5×10-5~2×10-5/℃)等が挙げられる。また、上記線膨張係数の大きい被着体としては、特に限定されないが、例えば、線膨張係数の大きい樹脂基材が挙げられ、より具体的には、ポリカーボネート樹脂基材(PC、線膨張係数:7×10-5~8×10-5/℃)、ポリメタクリル酸メチル樹脂基材(PMMA、線膨張係数:7×10-5~8×10-5/℃)、シクロオレフィンポリマー基材(COP、線膨張係数:6×10-5~7×10-5/℃)、商品名「ゼオノア」(日本ゼオン株式会社製)、商品名「アートン」(JSR株式会社製)等が挙げられる。 Moreover, the optical pressure-sensitive adhesive sheet of the present invention is useful not only for adherends with a small coefficient of linear expansion, but also for adherends with a large coefficient of linear expansion. The adherend having a small coefficient of linear expansion is not particularly limited. material (PET film, coefficient of linear expansion: 1.5×10 −5 to 2×10 −5 /° C.). The adherend having a large coefficient of linear expansion is not particularly limited, but examples thereof include resin substrates having a large coefficient of linear expansion. 7×10 −5 to 8×10 −5 /° C.), polymethyl methacrylate resin substrate (PMMA, linear expansion coefficient: 7×10 −5 to 8×10 −5 /° C.), cycloolefin polymer substrate ( COP, linear expansion coefficient: 6×10 −5 to 7×10 −5 /° C.), trade name “Zeonor” (manufactured by Nippon Zeon Co., Ltd.), trade name “Arton” (manufactured by JSR Corporation), and the like.
 このように、本発明の光学用粘着シートは、様々な素材の被着体との貼り合わせに有用であり、特にガラス被着体とプラスチック被着体との貼り合わせに有用に用いられる。なお、プラスチック被着体は、表面にITO(インジウムとすずの酸化物)層を有するプラスチックフィルムのような光学フィルムであってもよい。 Thus, the optical pressure-sensitive adhesive sheet of the present invention is useful for lamination with adherends made of various materials, and is particularly useful for lamination with glass adherends and plastic adherends. The plastic adherend may be an optical film such as a plastic film having an ITO (indium tin oxide) layer on its surface.
 さらに、本発明の光学用粘着シートは、表面が平滑な被着体に加えて、表面に段差を有する被着体に対しても、有用に用いられる。特に、本発明の光学用粘着シートは、ガラス被着体及び上記の線膨張係数の大きい樹脂基材のうち少なくとも一方が表面に段差を有していても、ガラス被着体と上記の線膨張係数の大きい樹脂基材との貼り合わせに有用に用いられる。 Furthermore, the optical pressure-sensitive adhesive sheet of the present invention is useful not only for adherends with smooth surfaces, but also for adherends with uneven surfaces. In particular, in the optical pressure-sensitive adhesive sheet of the present invention, even if at least one of the glass adherend and the resin substrate having a large coefficient of linear expansion has steps on the surface, the glass adherend and the linear expansion coefficient It is useful for bonding with a resin base material having a large modulus.
 本発明の光学用粘着シートは、携帯電子機器の製造用途に好ましく用いられる。上記携帯電子機器としては、例えば、携帯電話、PHS、スマートフォン、タブレット(タブレット型コンピューター)、モバイルコンピューター(モバイルPC)、携帯情報端末(PDA)、電子手帳、携帯型テレビや携帯型ラジオ等の携帯型放送受信機 、携帯型ゲーム機、ポータブルオーディオプレーヤー、ポータブルDVDプレーヤー、デジタルカメラ等のカメラ、カムコーダ型のビデオカメラ等が挙げられる。 The optical pressure-sensitive adhesive sheet of the present invention is preferably used for manufacturing portable electronic devices. Examples of the portable electronic devices include mobile phones, PHS, smartphones, tablets (tablet computers), mobile computers (mobile PCs), personal digital assistants (PDA), electronic notebooks, portable televisions, portable radios, and the like. type broadcast receivers, portable game machines, portable audio players, portable DVD players, cameras such as digital cameras, and camcorder type video cameras.
[7.光学積層体]
 本発明の光学積層体は、本発明の光学用粘着シートと、光学部材とが積層された積層構造を有する。図2において、光学積層体20は、光学用粘着シート10の粘着剤層2において、光学部材5が積層されている。
 本発明の光学積層体は、上記粘着剤層(本発明の粘着剤組成物により形成される粘着剤層)を有するので、帯電防止性能に優れる。このため、さらに別の光学部材の貼り合わせに用いる場合、静電気が生じにくい。また、湿熱環境のような過酷な条件でも帯電防止成分のブリードアウトを抑制することができるため、粘着剤層の表面での析出、発泡、剥がれが抑制され、外観や接着信頼性などの耐久性の不良が生じにくい。従って、本発明の光学積層体は、優れた帯電防止性、透明性、耐湿熱性、及び低汚染性を満足できる。
[7. Optical laminate]
The optical laminate of the present invention has a laminate structure in which the optical pressure-sensitive adhesive sheet of the present invention and an optical member are laminated. In FIG. 2, the optical layered body 20 has an optical member 5 laminated on the pressure-sensitive adhesive layer 2 of the optical pressure-sensitive adhesive sheet 10 .
Since the optical layered body of the present invention has the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention), it has excellent antistatic performance. Therefore, static electricity is less likely to occur when used to bond another optical member. In addition, since bleeding out of the antistatic component can be suppressed even under harsh conditions such as moist and hot environments, precipitation, foaming, and peeling on the surface of the adhesive layer are suppressed, and durability such as appearance and adhesion reliability is improved. defects are less likely to occur. Therefore, the optical laminate of the present invention can satisfy excellent antistatic properties, transparency, moist heat resistance, and low staining properties.
 光学部材とは、光学的特性(例えば、偏光性、光屈折性、光散乱性、光反射性、光透過性、光吸収性、光回折性、旋光性、視認性等)を有する部材をいう。上記光学部材を構成する基板としては、特に限定されないが、例えば、表示装置(画像表示装置)、入力装置等の機器(光学機器)を構成する基板又はこれらの機器に用いられる基板が挙げられ、例えば、偏光板、波長板、位相差板、光学補償フィルム、輝度向上フィルム、導光板、反射フィルム、反射防止フィルム、ハードコートフィルム(PETフィルム等のプラスチックフィルムの少なくとも片面にハードコート処理が施されたフィルム)、透明導電フィルム(例えば、表面にITO層を有するプラスチックフィルム(好ましくは、PET-ITO、ポリカーボネート、シクロオレフィンポリマー等のITOフィルム)等)、意匠フィルム、装飾フィルム、表面保護板、プリズム、レンズ、カラーフィルター、透明基板(ガラスセンサー、ガラス製表示パネル(LCD等)、透明電極付きガラス板等のガラス基板等)や、さらにはこれらが積層されている基板(これらを総称して「機能性フィルム」と称する場合がある)等が挙げられる。また、これらのフィルムは、金属ナノワイヤ層や導電性高分子層等を有していても良い。また、これらのフィルムには、金属細線がメッシュ印刷されていても良い。なお、上記の「板」及び「フィルム」は、それぞれ板状、フィルム状、シート状等の形態を含むものとし、例えば、「偏光フィルム」は、「偏光板」及び「偏光シート」等を含むものとする。また、「フィルム」はフィルムセンサー等を含むものとする。 An optical member refers to a member having optical properties (e.g., polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, optical rotation, visibility, etc.). . The substrate constituting the optical member is not particularly limited. For example, polarizing plate, wave plate, retardation plate, optical compensation film, brightness enhancement film, light guide plate, reflective film, antireflection film, hard coat film (hard coat treatment is applied to at least one side of plastic film such as PET film). films), transparent conductive films (for example, plastic films having an ITO layer on the surface (preferably ITO films such as PET-ITO, polycarbonate, cycloolefin polymer, etc.), design films, decorative films, surface protection plates, prisms , lenses, color filters, transparent substrates (glass sensors, glass display panels (LCD, etc.), glass substrates such as glass plates with transparent electrodes, etc.), and substrates on which these are laminated (these are collectively referred to as " may be referred to as "functional film") and the like. Moreover, these films may have a metal nanowire layer, a conductive polymer layer, or the like. Further, these films may be mesh-printed with thin metal wires. The above-mentioned "plate" and "film" include forms such as plate-like, film-like, and sheet-like, respectively. For example, "polarizing film" includes "polarizing plate" and "polarizing sheet". . In addition, "film" shall include film sensors and the like.
 上記表示装置としては、例えば、液晶表示装置、有機EL(エレクトロルミネッセンス)表示装置、PDP(プラズマディスプレイパネル)、電子ペーパー等が挙げられる。また、上記入力装置としては、タッチパネル等が挙げられる。 Examples of the display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), electronic paper, and the like. Moreover, a touch panel etc. are mentioned as said input device.
 上記光学部材を構成する基板としては、特に限定されないが、例えば、ガラス、アクリル樹脂、ポリカーボネート、ポリエチレンテレフタレート、シクロオレフィンポリマー、金属薄膜等からなる基板(例えば、シート状やフィルム状、板状の基板等)等が挙げられる。なお、本発明における「光学部材」には、上記の通り、表示装置や入力装置の視認性を保ちながら加飾や保護の役割を担う部材(意匠フィルム、装飾フィルムや表面保護フィルム等)も含むものとする。 The substrate constituting the optical member is not particularly limited. etc.). As described above, the "optical member" in the present invention includes members (design films, decorative films, surface protective films, etc.) that play a role of decoration and protection while maintaining the visibility of display devices and input devices. shall be taken.
 上記光学部材は、透明であることが好ましい。上記光学部材の可視光波長領域における全光線透過率(JIS K7361-1に準じる)は、特に限定されないが、85%以上が好ましく、より好ましくは88%以上である。また、上記光学部材のヘイズ(JIS K7136に準じる)は、特に限定されないが、1.0%以下が好ましく、より好ましくは0.8%以下である。このような透明な基材としては、例えば、PETフィルムや、商品名「アートン」、商品名「ゼオノア」等の無配向フィルム等が挙げられる。 The optical member is preferably transparent. The total light transmittance (according to JIS K7361-1) of the optical member in the visible light wavelength region is not particularly limited, but is preferably 85% or more, more preferably 88% or more. In addition, the haze (according to JIS K7136) of the optical member is not particularly limited, but is preferably 1.0% or less, more preferably 0.8% or less. Examples of such transparent substrates include PET films and non-oriented films such as the trade name "Arton" and the trade name "Zeonor".
 上記光学部材の厚みは、特に限定されないが、例えば、12~500μmが好ましい。なお、上記光学部材は単層及び複層のいずれの形態を有していてもよい。また、上記光学部材の表面には、例えば、コロナ放電処理、プラズマ処理等の物理的処理、下塗り処理等の化学的処理等の公知慣用の表面処理が適宜施されていてもよい。 Although the thickness of the optical member is not particularly limited, it is preferably 12 to 500 μm, for example. The optical member may have either a single-layer structure or a multilayer structure. Further, the surface of the optical member may be appropriately subjected to a known and commonly used surface treatment such as physical treatment such as corona discharge treatment and plasma treatment, and chemical treatment such as undercoating treatment.
 本発明の光学積層体は、前記光学部材と、本発明の光学用粘着シートの粘着剤層を貼り合わせることのより製造するにより製造することができる。 The optical laminate of the present invention can be produced by laminating the optical member and the pressure-sensitive adhesive layer of the optical pressure-sensitive adhesive sheet of the present invention.
 具体的には、光学部材と本発明の光学用粘着シートの貼り付けは、加熱及び/又は加圧下で積層させるにより実施することができる。加熱及び/又は加圧下で積層させた後に活性エネルギー線を照射して硬化を行ってもよい。活性エネルギー線の照射は、本発明の粘着剤層の形成と同様に行うことができる。 Specifically, the optical member and the optical pressure-sensitive adhesive sheet of the present invention can be attached by laminating them under heat and/or pressure. Curing may be performed by irradiating active energy rays after lamination under heat and/or pressure. Irradiation with active energy rays can be performed in the same manner as in the formation of the pressure-sensitive adhesive layer of the present invention.
[8.画像表示装置]
 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30は、光学用粘着シート10の粘着剤層1において、画像表示パネル6が積層されている。
 本発明の画像表示装置は、帯電防止性能に優れる本発明の光学用粘着シートを積層構造中に有するので、静電気による表示不良が生じにくい。また、また、湿熱環境のような過酷な条件でも帯電防止成分のブリードアウトを抑制することができるため、粘着剤層の表面での析出、発泡、剥がれが抑制され、外観や接着信頼性などの耐久性の不良が生じにくい。従って、本発明の画像表示装置は、優れた帯電防止性、透明性、耐湿熱性、及び低汚染性を満足できる。
[8. Image display device]
The image display device of the present invention has a laminate structure in which the optical pressure-sensitive adhesive sheet of the present invention and an image display panel are laminated. In FIG. 3, the image display device 30 has an image display panel 6 laminated on the adhesive layer 1 of the optical adhesive sheet 10 .
Since the image display device of the present invention has the optical pressure-sensitive adhesive sheet of the present invention having excellent antistatic performance in the laminated structure, display defects due to static electricity are less likely to occur. In addition, since it is possible to suppress bleeding out of the antistatic component even under harsh conditions such as a moist and hot environment, precipitation, foaming, and peeling on the surface of the adhesive layer are suppressed, and appearance and adhesion reliability are improved. Poor durability is less likely to occur. Therefore, the image display device of the present invention can satisfy excellent antistatic properties, transparency, moist heat resistance, and low staining properties.
 また、本発明の粘着剤層は、画像表示装置の収縮又は膨張に十分に追従して、浮きや剥がれが生じにくい。さらに、画像表示パネルに配線などによる凹凸形状の段差がある場合、当該段差に本発明の粘着剤層が十分に追従し、気泡などを残すことなく、充填することができる。 In addition, the pressure-sensitive 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. Furthermore, when the image display panel has uneven steps due to wiring or the like, the pressure-sensitive adhesive layer of the present invention can sufficiently follow the steps and can be filled without leaving air bubbles.
 前記画像表示パネルとしては、特に限定されないが、例えば、液晶画像表示パネル、自発光型画像表示パネル(例えば、有機EL(エレクトロルミネッセンス)画像表示パネル、LED画像表示パネル)などが挙げられる。 The image display panel is not particularly limited, but includes, for example, a liquid crystal image display panel, a self-luminous image display panel (eg, an organic EL (electroluminescence) image display panel, an LED image display panel), and the like.
 前記画像表示パネルは、RGBの素子が交互に配列されて形成されており、コントラストを向上するために、RGBの素子間は、ブラックマトリックス(BM)で充填されていることが好ましい。 The image display panel is formed by alternately arranging RGB elements, and in order to improve the contrast, it is preferable that the spaces between the RGB elements be filled with a black matrix (BM).
 本発明の画像表示装置は、本発明の光学用粘着シート及び上記画像表示パネル以外の光学部材を、表面又は任意の層間に備えていてもよい。上記光学部材としては、特に限定されないが、偏光板、位相差板、反射防止フィルム、視野角調整フィルム、光学補償フィルムなどが挙げられる。なお、上記光学部材には、画像表示装置や入力装置の視認性を保ちながら加飾や保護の役割を担う部材(意匠フィルム、装飾フィルムや表面保護板等)も含むものとする。 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 any layers. Examples of the optical member include, but are not particularly limited to, a polarizing plate, a retardation plate, an antireflection film, a viewing angle adjusting film, and an optical compensation film. Note that the optical member includes members (design film, decorative film, surface protection plate, etc.) that play a role of decoration and protection while maintaining the visibility of the image display device and the input device.
 本発明の画像表示装置は、前記画像表示パネルと、本発明の光学用粘着シートの粘着剤層を貼り合わせることのより製造するにより製造することができる。 The image display device of the present invention can be manufactured by laminating the image display panel and the pressure-sensitive adhesive layer of the optical pressure-sensitive adhesive sheet of the present invention.
 具体的には、画像表示パネルと本発明の光学用粘着シートの貼り付けは、加熱及び/又は加圧下で積層させるにより実施することができる。加熱及び/又は加圧下で積層させた後に活性エネルギー線を照射して硬化を行ってもよい。活性エネルギー線の照射は、本発明の粘着剤層の形成と同様に行うことができる。 Specifically, the image display panel and the optical pressure-sensitive adhesive sheet of the present invention can be attached by laminating them under heat and/or pressure. Curing may be performed by irradiating active energy rays after lamination under heat and/or pressure. Irradiation with active energy rays can be performed in the same manner as in the formation of the pressure-sensitive adhesive layer of the present invention.
 以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。 The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples.
 製造例1
 (防眩性フィルム1の調製)
〔防眩層1形成用塗工液の調製〕
 防眩層形成材料に含まれる樹脂として、紫外線硬化型ウレタンアクリレート樹脂(新中村化学社製、商品名「NKオリゴ UA-53H-80BK」40重量部と、ペンタエリスリトールトリアクリレートを主成分とする多官能アクリレート(大阪有機化学工業株式会社製、商品名「ビスコート#300」)57.5重量部と、ジルコニア粒子と紫外線硬化性樹脂とを含有する光学調整層用組成物の希釈液(「オプスターZ7540」、JSR社製)2.5重量部と、シリコーン粒子(モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社制、商品名「トスパール130ND」2.8重量部と、チキソトロピー付与剤として有機粘土である合成スメクタイト(クニミネ工業株式会社製、商品名「スメクトンSAN」)2.5重量部と、光重合開始剤(BASF社製、商品名「OMNIRAD907」)を3重量部、架橋アクリルスチレン共重合樹脂の微粒子(積水化成品工業社製 商品名「SSX-103DXE」)を6.5重量部、レベリング剤(共栄社化学株式会社製、商品名「LE-303」)0.1重量部とを混合した。なお、前記有機粘土は、トルエンで固形分が6重量%になるよう希釈して用いた。この混合物を、固形分濃度が38重量%となるように、トルエン/シクロペンタノン(CPN)混合溶媒(重量比64/36)で希釈して、超音波分散機を用いて、防眩層形成材料(塗工液)を調製した。
Production example 1
(Preparation of antiglare film 1)
[Preparation of coating solution for forming antiglare layer 1]
As the resin contained in the antiglare layer forming material, 40 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Oligo UA-53H-80BK”) A diluted solution of a composition for an optical adjustment layer containing 57.5 parts by weight of a functional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat #300"), zirconia particles, and an ultraviolet curable resin ("OPSTAR Z7540 ”, manufactured by JSR), 2.5 parts by weight of silicone particles (Momentive Performance Materials Japan LLC, trade name “Tospearl 130ND”, and 2.8 parts by weight of organic clay as a thixotropy-imparting agent. 2.5 parts by weight of smectite (manufactured by Kunimine Industries Co., Ltd., trade name "Smecton SAN") and 3 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name "OMNIRAD907"), fine particles of crosslinked acrylic styrene copolymer resin (trade name “SSX-103DXE” manufactured by Sekisui Plastics Co., Ltd.) was mixed with 6.5 parts by weight of a leveling agent (trade name “LE-303” manufactured by Kyoeisha Chemical Co., Ltd.) and 0.1 part by weight. , The organoclay was diluted with toluene so that the solid content was 6% by weight.This mixture was added to a toluene/cyclopentanone (CPN) mixed solvent ( (weight ratio: 64/36) to prepare an antiglare layer-forming material (coating liquid) using an ultrasonic disperser.
〔防眩層1の形成〕
 基材として、透明プラスチックフィルム基材(PETフィルム、東レ株式会社製、商品名「38U413」、厚さ:38μm)を準備した。前記透明プラスチックフィルム基材の片面に、前記防眩層形成材料(塗工液)を、ワイヤーバーを用いて塗布して塗膜を形成した(塗工工程)。ついで、95℃で1分間加熱することにより前記塗膜を乾燥させた(乾燥工程)。その後、高圧水銀ランプにて積算光量300mJ/cm2の紫外線を照射し、前記塗膜を硬化処理して厚み6.5μmの防眩層を形成した。このようにして、前記光透過性基材と前記防眩層1との積層体を得た。
[Formation of antiglare layer 1]
As a substrate, a transparent plastic film substrate (PET film, manufactured by Toray Industries, Inc., trade name “38U413”, thickness: 38 μm) was prepared. The antiglare layer-forming material (coating solution) was applied to one side of the transparent plastic film substrate using a wire bar to form a coating film (coating step). Then, the coating film was dried by heating at 95° C. for 1 minute (drying step). After that, the coating film was cured by irradiating ultraviolet light with an accumulated light amount of 300 mJ/cm 2 with a high-pressure mercury lamp to form an antiglare layer having a thickness of 6.5 μm. Thus, a laminate of the light transmissive substrate and the antiglare layer 1 was obtained.
〔反射防止層1形成用塗工液の調製〕
 ペンタエリスリトールトリアクリレートを主成分とする多官能アクリレート(大阪有機化学工業株式会社製、商品名「ビスコート#300」)100重量部と、中空ナノシリカ粒子(日揮触媒化成工業株式会社製、商品名「スルーリア5320」)100重量部と、中実ナノシリカ粒子(日産化学工業株式会社製、商品名「MIBK-ST」、固形分30重量%、重量平均粒子径10nm)40重量部と、フッ素元素含有添加剤(信越化学工業株式会社製、商品名「KY-1203」)12重量部と、光重合開始剤(BASF社製、商品名「OMNIRAD907」)5重量部と、光重合開始剤(BASF社製、商品名「OMNIRAD2959」)5重量部とを混合した。その混合物に、希釈溶媒としてMIBK(メチルイソブチルケトン)およびPMA(プロピレングリコールモノメチルエーテルアセテート)を70:30重量比で混合した混合溶媒を添加して全体の固形分が1.5重量%となるようにし、攪拌して反射防止層形成用塗工液を調製した。
〔反射防止層1の形成〕
 前記光透過性基材と前記防眩層1との積層体の防眩層面に、前記反射防止層形成用塗工液をワイヤーバーで塗工した(塗工工程)。前記塗工した塗工液を80℃で1分間加熱し、乾燥させて塗膜を形成した(乾燥工程)。乾燥後の前記塗膜に、高圧水銀ランプで積算光量300mJ/cm2の紫外線を照射して硬化処理した(硬化工程)。これにより、前記塗膜を硬化させ、厚み0.1μmの反射防止層を形成した(反射防止層形成工程)。以上のようにして、本製造例1の防眩性フィルム1を製造した。
[Preparation of coating solution for forming antireflection layer 1]
100 parts by weight of polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Viscoat #300”) mainly composed of pentaerythritol triacrylate, and hollow nano silica particles (manufactured by Nikki Shokubai Kasei Kogyo Co., Ltd., trade name “Sururia 5320") 100 parts by weight, solid nanosilica particles (manufactured by Nissan Chemical Industries, Ltd., trade name "MIBK-ST", solid content 30% by weight, weight average particle diameter 10 nm) 40 parts by weight, fluorine element-containing additive (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KY-1203") 12 parts by weight, a photopolymerization initiator (manufactured by BASF, trade name "OMNIRAD907") 5 parts by weight, a photopolymerization initiator (manufactured by BASF, Trade name "OMNIRAD2959") was mixed with 5 parts by weight. To this mixture, a mixed solvent of MIBK (methyl isobutyl ketone) and PMA (propylene glycol monomethyl ether acetate) mixed at a weight ratio of 70:30 was added as a dilution solvent so that the total solid content was 1.5% by weight. and stirred to prepare a coating solution for forming an antireflection layer.
[Formation of antireflection layer 1]
The antireflection layer-forming coating liquid was applied to the antiglare layer surface of the laminate of the light transmissive substrate and the antiglare layer 1 with a wire bar (coating step). The applied coating liquid was heated at 80° C. for 1 minute and dried to form a coating film (drying step). After drying, the coating film was cured by irradiating ultraviolet light with an accumulated light amount of 300 mJ/cm 2 from a high-pressure mercury lamp (curing step). Thereby, the coating film was cured to form an antireflection layer having a thickness of 0.1 μm (antireflection layer forming step). Antiglare film 1 of Production Example 1 was produced as described above.
 製造例2:粘着剤シートAの作製
 モノマー混合物として、アクリル酸ブチル(BA)58重量部、アクリル酸4-ヒドロキシブチル(4HBA)23重量部、アクリル酸2-ヒドロキシエチル(HEA)7重量部、及びアクリル酸シクロヘキシル(CHA)12重量から構成されるモノマー混合物に、光重合開始剤(商品名「Omnirad184」、IGM Resins B.V.社製)0.05重量部、及び光重合開始剤(商品名「Omnirad651」、IGM Resins B.V.社製)0.05重量部を配合した後、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になるまで紫外線を照射して、上記モノマー成分の一部が重合したプレポリマー組成物を得た。
 次に、該プレポリマー組成物100重量部に、ジペンタエリスリトールヘキサアクリレート(DPHA)0.025重量部、及び反応性官能基としてアクロイル基を有する4級アンモニウム塩(2-アクリロイルオキシエチル)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)(富士フィルム和光純薬(株)製:CAS RN.827027-31-6)10重量部を添加して混合し、アクリル系粘着剤組成物を得た。上記アクリル系粘着剤組成物を、剥離フィルム(商品名「MRF#38」、三菱樹脂株式会社製)の剥離処理された面上に、粘着剤層形成後の厚さが20μmとなるように塗布して、粘着剤組成物層を形成し、次いで、該粘着剤組成物層の表面に、剥離フィルム(商品名「MRN#38」、三菱樹脂株式会社製)を貼り合わせた。その後、照度:5mW/cm2、光量:1500mJ/cm2の条件で紫外線照射を行い、粘着剤組成物層を光硬化させて、粘着剤層のみからなり、粘着剤層の両面がセパレータで保護されている基材レス両面粘着剤シートAを形成した。
Production Example 2: Production of PSA Sheet A As a monomer mixture, 58 parts by weight of butyl acrylate (BA), 23 parts by weight of 4-hydroxybutyl acrylate (4HBA), 7 parts by weight of 2-hydroxyethyl acrylate (HEA), and 12 parts by weight of cyclohexyl acrylate (CHA), 0.05 parts by weight of a photopolymerization initiator (trade name "Omnirad 184", manufactured by IGM Resins B.V.), and a photopolymerization initiator (trade name Name "Omnirad 651", manufactured by IGM Resins B.V.) After blending 0.05 parts by weight, the viscosity (measurement conditions: BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30 ° C.) was about 20 Pa s. A prepolymer composition in which a part of the monomer component was polymerized was obtained by irradiating with ultraviolet rays until the temperature reached 100%.
Next, 0.025 parts by weight of dipentaerythritol hexaacrylate (DPHA) and a quaternary ammonium salt (2-acryloyloxyethyl)trimethylammonium having an acroyl group as a reactive functional group are added to 100 parts by weight of the prepolymer composition. =Bis(trifluoromethanesulfonyl)imide) (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.: CAS RN.827027-31-6) was added and mixed to obtain an acrylic pressure-sensitive adhesive composition. The above acrylic pressure-sensitive adhesive composition is applied onto the release-treated surface of a release film (trade name “MRF #38”, manufactured by Mitsubishi Plastics, Inc.) so that the thickness after forming the pressure-sensitive adhesive layer is 20 μm. Then, a release film (trade name: "MRN#38", manufactured by Mitsubishi Plastics, Inc.) was attached to the surface of the adhesive composition layer. After that, ultraviolet irradiation is performed under the conditions of illuminance: 5 mW/cm 2 and light amount: 1500 mJ/cm 2 , and the adhesive composition layer is photocured to consist of only the adhesive layer, and both sides of the adhesive layer are protected by separators. A substrate-less double-sided pressure-sensitive adhesive sheet A was formed.
 製造例3:粘着剤シートBの作製
 反応性官能基としてアクロイル基を有する4級アンモニウム塩(2-アクリロイルオキシエチル)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)(富士フィルム和光純薬(株)製:CAS RN.827027-31-6)を15重量部添加し、粘着剤層形成後の厚さが50μmとなるように塗布したこと以外は、粘着剤シートAと同様にして、粘着剤シートBを形成した。
Production Example 3: Preparation of Adhesive Sheet B Quaternary ammonium salt having an acroyl group as a reactive functional group (2-acryloyloxyethyl) trimethylammonium = bis (trifluoromethanesulfonyl) imide) (Fujifilm Wako Pure Chemical Industries, Ltd.) CAS RN.827027-31-6) was added in 15 parts by weight and applied so that the thickness after forming the adhesive layer was 50 μm. formed B.
 製造例4:粘着剤シートCの作製
 反応性官能基としてアクロイル基を有する4級アンモニウム塩(2-アクリロイルオキシエチル)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)(富士フィルム和光純薬(株)製:CAS RN.827027-31-6)を20重量部添加し、粘着剤層形成後の厚さが50μmとなるように塗布したこと以外は、粘着剤シートAと同様にして、粘着剤シートCを形成した。
Production Example 4: Preparation of Adhesive Sheet C Quaternary ammonium salt having an acroyl group as a reactive functional group (2-acryloyloxyethyl) trimethylammonium = bis (trifluoromethanesulfonyl) imide) (Fujifilm Wako Pure Chemical Industries, Ltd.) CAS RN.827027-31-6) was added in 20 parts by weight, and the pressure-sensitive adhesive sheet was prepared in the same manner as for pressure-sensitive adhesive sheet A, except that the adhesive layer was coated so that the thickness after forming the pressure-sensitive adhesive layer was 50 μm. formed C.
 製造例5:粘着剤シートDの作製
 反応性官能基としてアクロイル基を有する4級アンモニウム塩(2-アクリロイルオキシエチル)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)(富士フィルム和光純薬(株)製:CAS RN.827027-31-6)を15重量部添加し、粘着剤層形成後の厚さが100μmとなるように塗布したこと以外は、粘着剤シートAと同様にして、粘着剤シートDを形成した。
Production Example 5: Preparation of Adhesive Sheet D Quaternary ammonium salt having an acroyl group as a reactive functional group (2-acryloyloxyethyl) trimethylammonium = bis (trifluoromethanesulfonyl) imide) (Fujifilm Wako Pure Chemical Industries, Ltd.) CAS RN.827027-31-6) was added in 15 parts by weight, and the pressure-sensitive adhesive sheet was prepared in the same manner as for pressure-sensitive adhesive sheet A except that the adhesive layer was coated so that the thickness after forming the pressure-sensitive adhesive layer was 100 μm. formed D.
 製造例6:粘着剤シートEの作製
 反応性官能基としてアクロイル基を有する4級アンモニウム塩(2-アクリロイルオキシエチル)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)(富士フィルム和光純薬(株)製:CAS RN.827027-31-6)に代えて、反応性官能基としてメタクロイル基を有する4級アンモニウム塩(2-メタクリロイルオキシエチル)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)(富士フィルム和光純薬(株)製:CAS RN.676257-10-6)を15重量部添加し、粘着剤層形成後の厚さが50μmとなるように塗布したこと以外は、粘着剤シートAと同様にして、粘着剤シートEを形成した。
Production Example 6: Preparation of Adhesive Sheet E Quaternary ammonium salt having an acroyl group as a reactive functional group (2-acryloyloxyethyl) trimethylammonium = bis (trifluoromethanesulfonyl) imide) (Fujifilm Wako Pure Chemical Industries, Ltd.) CAS RN.827027-31-6) instead of quaternary ammonium salt having a methacryloyl group as a reactive functional group (2-methacryloyloxyethyl) trimethylammonium = bis (trifluoromethanesulfonyl) imide) (Fuji Film Wada Kojunyaku Co., Ltd.: CAS RN.676257-10-6) was added in the same manner as in Adhesive Sheet A, except that 15 parts by weight was added and the adhesive layer was applied so that the thickness after forming the adhesive layer was 50 μm. to form an adhesive sheet E.
 比較製造例1:粘着剤シートFの作製
 反応性官能基としてアクロイル基を有する4級アンモニウム塩(2-アクリロイルオキシエチル)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)(富士フィルム和光純薬(株)製:CAS RN.827027-31-6)を添加しなかったこと以外は、粘着剤シートAと同様にして、粘着剤シートFを形成した。
Comparative Production Example 1: Preparation of Adhesive Sheet F Quaternary ammonium salt having an acroyl group as a reactive functional group (2-acryloyloxyethyl) trimethylammonium = bis (trifluoromethanesulfonyl) imide) (Fujifilm Wako Pure Chemical Industries, Ltd. ) manufactured by: CAS RN.827027-31-6) was formed in the same manner as the adhesive sheet A, except that the adhesive sheet F was formed.
 比較製造例2:粘着剤シートGの作製
 反応性官能基としてアクロイル基を有する4級アンモニウム塩(2-アクリロイルオキシエチル)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)(富士フィルム和光純薬(株)製:CAS RN.827027-31-6)に代えて、1-エチル-1-メチルピロリジウム=ビス(トリフルオロメタンスルホニル)イミド(関東化学(株)製:CAS RN.223436-99-5)を15重量部添加したこと以外は、粘着剤シートAと同様にして、粘着剤シートGを形成した。
Comparative Production Example 2: Preparation of Adhesive Sheet G Quaternary ammonium salt having an acroyl group as a reactive functional group (2-acryloyloxyethyl) trimethylammonium = bis (trifluoromethanesulfonyl) imide) (Fujifilm Wako Pure Chemical Industries, Ltd. ) manufactured by: CAS RN.827027-31-6) instead of 1-ethyl-1-methylpyrrolidium=bis(trifluoromethanesulfonyl)imide (manufactured by Kanto Chemical Co., Ltd.: CAS RN.223436-99-5) A pressure-sensitive adhesive sheet G was formed in the same manner as the pressure-sensitive adhesive sheet A, except that 15 parts by weight of was added.
 上記の製造例2~6、比較製造例1~2で得られた粘着剤シートを用いて以下の評価を行った。 The following evaluations were performed using the pressure-sensitive adhesive sheets obtained in Production Examples 2-6 and Comparative Production Examples 1-2 above.
<全光線透過率及びヘイズの評価>
 製造例2~6、比較製造例1~2で得られた粘着剤シートから一方のセパレータを剥離して、該両面粘着シートをスライドガラス(松浪硝子工業株式会社製、「白研磨 No.1」、厚さ0.8~1.0mm、全光線透過率92%、ヘイズ0.2%)に貼り合わせ、さらに他方のセパレータを剥離して、両面粘着シート(粘着剤層)/スライドガラスの層構成を有する試験片を作製した。上記試験片の可視光領域における全光線透過率及びヘイズを、ヘイズメーター(装置名「HM-150N」、株式会社村上色彩研究所製)を用いて測定した。測定結果は表2に記載した。
<Evaluation of total light transmittance and haze>
One separator was peeled off from the pressure-sensitive adhesive sheets obtained in Production Examples 2-6 and Comparative Production Examples 1-2, and the double-sided pressure-sensitive adhesive sheet was applied to a slide glass (manufactured by Matsunami Glass Industry Co., Ltd., "White polishing No. 1". , thickness 0.8 to 1.0 mm, total light transmittance 92%, haze 0.2%), and the other separator is peeled off, double-sided adhesive sheet (adhesive layer) / slide glass layer Test specimens having configurations were prepared. The total light transmittance and haze in the visible light region of the test piece were measured using a haze meter (apparatus name "HM-150N", manufactured by Murakami Color Research Institute). The measurement results are shown in Table 2.
<対ガラス粘着力評価>
 製造例2~6、比較製造例1~2で得られた粘着剤シートを幅100mm、長さ100mmにカットし、次いで、粘着剤層の一方の剥離フィルムを剥離して、PETフィルム(商品名:ルミラー S-10、厚さ:25μm、東レ(株)製)を貼付(裏打ち)した。次に、他方の剥離フィルムを剥離して、試験板としてガラス板(商品名:ソーダライムガラス♯0050、松浪硝子工業(株)製)に貼り合わせ、2kgローラー、1往復の圧着条件で貼り合わせ、試験板/粘着剤層/PETフィルムから構成されるサンプルを作製した。
 (初期接着力)
 サンプル作成後、23℃、50%RHの雰囲気下で30分間エージングした後、JIS Z0237に準拠して、23℃、50%RHの雰囲気下、引張試験機(装置名:オートグラフ AG-IS、(株)島津製作所製)を用いて引張速度300mm/分、剥離角度180°の条件で、試験板から粘着シート(粘着剤層/PETフィルム)を引きはがし、180°引き剥がし接着力(初期接着力)(N/20mm)を測定した。
 (貼り付け保存接着力)
 サンプル作成後、23℃、50%RHの雰囲気下で240時間エージングした後、JIS Z0237に準拠して、23℃、50%RHの雰囲気下、引張試験機(装置名:オートグラフ AG-IS、(株)島津製作所製)を用いて引張速度300mm/分、剥離角度180°の条件で、試験板から粘着シート(粘着剤層/PETフィルム)を引きはがし、180°引き剥がし接着力(貼り付け保存240時間後接着力)(N/20mm)を測定した。
 測定は各条件について3つの試料を作製し、それらの数平均値をとった。測定結果は表2に記載した。
<Evaluation of adhesive strength to glass>
The pressure-sensitive adhesive sheets obtained in Production Examples 2-6 and Comparative Production Examples 1-2 were cut into a width of 100 mm and a length of 100 mm. : Lumirror S-10, thickness: 25 μm, manufactured by Toray Industries, Inc.) was attached (backed). Next, the other release film was peeled off, and it was laminated to a glass plate (trade name: soda lime glass #0050, manufactured by Matsunami Glass Industry Co., Ltd.) as a test plate, and laminated under the conditions of one reciprocating pressure bonding with a 2 kg roller. , a sample composed of a test plate/adhesive layer/PET film was prepared.
(initial adhesive strength)
After sample preparation, after aging for 30 minutes in an atmosphere of 23 ° C. and 50% RH, in accordance with JIS Z0237, in an atmosphere of 23 ° C. and 50% RH, a tensile tester (device name: Autograph AG-IS, (manufactured by Shimadzu Corporation), the adhesive sheet (adhesive layer/PET film) was peeled off from the test plate under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 °, and 180 ° peeling adhesive strength (initial adhesion force) (N/20 mm) was measured.
(Paste storage adhesive strength)
After sample preparation, after aging for 240 hours in an atmosphere of 23 ° C. and 50% RH, in accordance with JIS Z0237, under an atmosphere of 23 ° C. and 50% RH, a tensile tester (device name: Autograph AG-IS (manufactured by Shimadzu Corporation), the adhesive sheet (adhesive layer/PET film) was peeled off from the test plate under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 °, and 180 ° peeling adhesive strength (sticking After 240 hours of storage, the adhesive strength) (N/20 mm) was measured.
For the measurement, three samples were prepared for each condition and their numerical average was taken. The measurement results are shown in Table 2.
<表面抵抗率(Ω/□):帯電防止性>
 製造例2~6、比較製造例1~2で得られた粘着剤シートの一方のセパレータフィルムを剥がした後、粘着剤層表面の表面抵抗率(R0)を測定した。測定は、23℃、50%RHの雰囲気下で、三菱化学アナリテック社製MCP-HT450を用いて行った。測定結果は表2に記載した。
<Surface resistivity (Ω/□): antistatic property>
After peeling off the separator film on one side of the pressure-sensitive adhesive sheets obtained in Production Examples 2-6 and Comparative Production Examples 1-2, the surface resistivity (R0) of the surface of the pressure-sensitive adhesive layer was measured. The measurement was performed in an atmosphere of 23° C. and 50% RH using MCP-HT450 manufactured by Mitsubishi Chemical Analytic Tech. The measurement results are shown in Table 2.
 <外観:常温保管、湿熱試験後>
 製造例2~6、比較製造例1~2で得られた粘着剤シート(セパレータ/粘着剤/セパレータの構成)を15×15cmに切り出し、23℃50%RHの環境で7日間保管した後、粘着剤シートの外観を目視確認し、以下の評価基準で評価した。測定結果は表2に記載した。
 (評価基準)
 〇 白濁など、光学的欠陥が全く見られない
 × 粘着剤に斑状の白化・ブリードアウトが見られる
<Appearance: Stored at normal temperature, after moist heat test>
The pressure-sensitive adhesive sheets (structure of separator/adhesive/separator) obtained in Production Examples 2-6 and Comparative Production Examples 1-2 were cut into pieces of 15×15 cm and stored in an environment of 23° C. and 50% RH for 7 days. The appearance of the pressure-sensitive adhesive sheet was visually confirmed and evaluated according to the following evaluation criteria. The measurement results are shown in Table 2.
(Evaluation criteria)
〇 No optical defects such as white turbidity observed × Patchy whitening/bleed-out observed on the adhesive
 次に、製造例2~6、比較製造例1~2で得られた粘着剤シートから一方のセパレータを剥離して、該両面粘着シートをスライドガラス(松浪硝子工業株式会社製、「白研磨 No.1」、厚さ0.8~1.0mm、全光線透過率92%、ヘイズ0.2%)に貼り合わせ、セパレータ/両面粘着シート(粘着剤層)/スライドガラスの層構成を有する試験片を作製した。85℃、85%RHの雰囲気下に240時間投入し、室温に取り出して、23℃、50%RH環境下で24時間調温・調湿を行った後に、セパレータを剥がして、両面粘着シート(粘着剤層)/スライドガラスの層構成にて、ヘイズメーター(装置名「HM-150N」、株式会社村上色彩研究所製)を用いて測定し、以下の評価基準で評価した。測定結果は表2に記載した。
 (評価基準)
 〇:ヘイズ1.0以下       特に良好
 △:ヘイズ1.0超~2.0以下  良好
 ×:ヘイズ2.0超        実用上問題のあるレベル
Next, one separator is peeled off from the pressure-sensitive adhesive sheets obtained in Production Examples 2-6 and Comparative Production Examples 1-2, and the double-sided pressure-sensitive adhesive sheet is applied to a slide glass (manufactured by Matsunami Glass Industry Co., Ltd., "White polishing No. .1”, thickness 0.8 to 1.0 mm, total light transmittance 92%, haze 0.2%), and a test having a layer configuration of separator / double-sided adhesive sheet (adhesive layer) / slide glass A piece was made. Put in an atmosphere of 85 ° C. and 85% RH for 240 hours, take out to room temperature, adjust temperature and humidity for 24 hours in an environment of 23 ° C. and 50% RH, then peel off the separator and use a double-sided adhesive sheet ( Adhesive layer)/slide glass layer structure was measured using a haze meter (apparatus name "HM-150N", manufactured by Murakami Color Laboratory Co., Ltd.) and evaluated according to the following evaluation criteria. The measurement results are shown in Table 2.
(Evaluation criteria)
○: Haze of 1.0 or less, particularly good △: Haze of more than 1.0 to 2.0 or less, good ×: Haze of more than 2.0, practically problematic level
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
 <表面抵抗率(Ω/□)の湿熱安定性評価>
 製造例4及び6、比較製造例2で得られた粘着剤シート(セパレータフィルム/粘着剤層/セパレータフィルム)を100mm角に切り出し、片面のセパレータフィルムを剥がした後に、粘着剤層表面の表面抵抗率(R0)を測定した。測定は、23℃、50%RHの雰囲気下で、三菱化学アナリテック社製MCP-HT450を用いて行った。各条件について3つの試料を作成して測定し、それらの数平均値をとった。測定後、セパレータフィルムを貼り直してから60℃、95%RH環境下に240時間投入した。取り出した後、23℃、50%RH環境下で24時間調温・調湿を行った後、片面のセパレータフィルムを剥がして、湿熱試験後の粘着剤層表面の表面抵抗率(R1)を測定し、3つの試料の数平均値をとった。測定結果より、以下の評価基準で評価した。測定結果を表3に記載した。
(評価基準)
〇: 湿熱試験後の表面抵抗値(R1)/湿熱試験前の表面抵抗値(R0)≦20
△: 20<湿熱試験後の表面抵抗値(R1)/湿熱試験前の表面抵抗値(R0)≦100
×: 100<湿熱試験後の表面抵抗値(R1)/湿熱試験前の表面抵抗値(R0)
<Wet heat stability evaluation of surface resistivity (Ω/□)>
The pressure-sensitive adhesive sheets (separator film/adhesive layer/separator film) obtained in Production Examples 4 and 6 and Comparative Production Example 2 were cut into 100 mm squares, and after peeling off the separator film on one side, the surface resistance of the pressure-sensitive adhesive layer surface was measured. The rate (R0) was measured. The measurement was performed in an atmosphere of 23° C. and 50% RH using MCP-HT450 manufactured by Mitsubishi Chemical Analytic Tech. Three samples were prepared and measured for each condition, and their numerical averages were taken. After the measurement, the separator film was reattached, and then placed in an environment of 60° C. and 95% RH for 240 hours. After taking it out, the temperature and humidity were adjusted for 24 hours in an environment of 23°C and 50% RH, then the separator film on one side was peeled off, and the surface resistivity (R1) of the adhesive layer surface after the wet heat test was measured. and a numerical average of three samples was taken. Based on the measurement results, evaluation was made according to the following evaluation criteria. The measurement results are shown in Table 3.
(Evaluation criteria)
○: Surface resistance value after wet heat test (R1) / Surface resistance value before wet heat test (R0) ≤ 20
△: 20<Surface resistance value after wet heat test (R1) / Surface resistance value before wet heat test (R0) ≤ 100
×: 100<Surface resistance value after wet heat test (R1) / Surface resistance value before wet heat test (R0)
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
 実施例1:光学用粘着シートAの作製
 上記製造例2で得られた粘着剤シートAから一方の剥離フィルムを剥離して露出させた粘着面を、製造例1で示した防眩性フィルム1の非防眩層面に貼り付けることにより、防眩性フィルム1/粘着剤層/剥離フィルムからなる光学用粘着シートAを得た。
Example 1 Preparation of Optical Adhesive Sheet A One release film was peeled off from the adhesive sheet A obtained in Production Example 2 above, and the exposed adhesive surface was coated with the antiglare film 1 shown in Production Example 1. Optical adhesive sheet A consisting of antiglare film 1/adhesive layer/release film was obtained by attaching to the non-antiglare layer surface of .
 実施例2:光学用粘着シートBの作製
 上記製造例4で得られた粘着剤シートCから一方の剥離フィルムを剥離して露出させた粘着面を、反射防止フィルム(TACフィルム;大日本印刷(株)製;商品名「DSG-17V1」;基材厚さ:60μm;総厚さ:70μm)の非反射防止面に貼り付けることにより、反射防止フィルム/粘着剤層/剥離フィルムからなる光学用粘着シートBを得た。
Example 2: Preparation of optical adhesive sheet B The adhesive surface exposed by peeling one release film from the adhesive sheet C obtained in Production Example 4 above was coated with an antireflection film (TAC film; Dai Nippon Printing ( Co., Ltd.; product name “DSG-17V1”; substrate thickness: 60 μm; total thickness: 70 μm). An adhesive sheet B was obtained.
 上記の実施例1~2で得られた光学用粘着シートを用いて以下の評価を行った。 The following evaluations were performed using the optical pressure-sensitive adhesive sheets obtained in Examples 1 and 2 above.
<ヘイズの評価>
 実施例1~2で得られた光学用粘着シートを、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。測定結果は表3に記載した。
<Evaluation of Haze>
The optical pressure-sensitive adhesive sheets obtained in Examples 1 and 2 were measured at room temperature (23° C.) using a haze measuring device (HR-100 manufactured by Murakami Color Laboratory). Measurement was repeated 3 times, and the average value was used as the measured value. The measurement results are shown in Table 3.
<反射率の評価>
 実施例1~2で得られた光学用粘着シートの粘着面を、黒色のアクリル板に貼り付けて、試験片とした。得られた試験片を、分光光度計U4100(日立ハイテクノロジー社製)へ粘着剤層側を光源側に設置し、5°正反射の可視光領域の反射率(%)を測定した。測定結果は表3に記載した。
<Evaluation of reflectance>
The adhesive surface of the optical pressure-sensitive adhesive sheet obtained in Examples 1 and 2 was attached to a black acrylic plate to prepare a test piece. The obtained test piece was placed in a spectrophotometer U4100 (manufactured by Hitachi High-Technology Co., Ltd.) with the pressure-sensitive adhesive layer side facing the light source side, and the reflectance (%) of the visible light region of 5° specular reflection was measured. The measurement results are shown in Table 3.
<表面抵抗率(Ω/□):帯電防止性>
 実施例1~2で得られた光学用粘着シートのセパレータフィルムを剥がした後、粘着剤層表面の表面抵抗率(R0)を測定した。測定は、23℃、50%RHの雰囲気下で、三菱化学アナリテック社製MCP-HT450を用いて行った。測定結果は表4に記載した。
<Surface resistivity (Ω/□): antistatic property>
After peeling off the separator film of the optical pressure-sensitive adhesive sheets obtained in Examples 1 and 2, the surface resistivity (R0) of the surface of the pressure-sensitive adhesive layer was measured. The measurement was performed in an atmosphere of 23° C. and 50% RH using MCP-HT450 manufactured by Mitsubishi Chemical Analytic Tech. The measurement results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
 以下に、本発明のバリエーションを付記する。
〔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、
 前記粘着剤層が、帯電防止剤と、アクリル系ポリマー(A)を構成するモノマー成分の混合物又はアクリル系ポリマー(A)を構成するモノマー 成分の混合物の部分重合物とを含有する粘着剤組成物により形成され、
 前記帯電防止剤が、前記アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物であることを特徴とする光学用粘着シート。
〔付記2〕 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、
 前記粘着剤層が、帯電防止剤とアクリル系ポリマー(A)とを含有する粘着剤組成物により形成され、
 前記帯電防止剤が、前記アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物であることを特徴とする光学用粘着シート。
〔付記3〕前記官能基が、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミノ基、ビニル基、アリル基、スチリル基、水酸基、アミノ基、メルカプト基  、及びエポキシ基からなる群から選ばれる少なくとも1種である、付記1又は2に記載の光学用粘着シート。
〔付記4〕前記アクリル系ポリマー(A)が構成するモノマー成分としてカルボキシル基含有モノマーを含有せず又は実質的に含有しない、付記1~3の何れか1つに記載の光学用粘着シート。
〔付記5〕前記粘着剤組成物が、有機溶剤を含有しない又は実質的に含有しない、付記1~4の何れか1つに記載の光学用粘着シート。
〔付記6〕前記粘着剤層のヘイズ(JIS K7136に準じる)が1.0%以下である、付記1~5の何れか1つに記載の光学用粘着シート。
〔付記7〕前記粘着剤層の全光線透過率(JIS K7361-1に準じる)が90%以上である、付記1~6の何れか1つに記載の光学用粘着シート。
〔付記8〕ガラス板に対する23℃での180°引き剥がし接着力が4N/20mm以上である、付記1~7の何れか1つに記載の光学用粘着シート。
〔付記9〕厚みが12~350μmである、付記1~8の何れか1つに記載の光学用粘着シート。
〔付記10〕前記基材の第2面は、反射防止処理、アンチグレア処理、ハードコート処理及び/又は帯電防止処理されている、付記1~9の何れか1つに記載の光学用粘着シート。
〔付記11〕付記1~10の何れか1つに記載の光学用粘着シートと、光学部材とが積層された光学積層体。
〔付記12〕付記1~10の何れか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。
Variations of the present invention are described below.
[Appendix 1] An optical pressure-sensitive adhesive sheet having a laminated structure in which a substrate having a first surface and a second surface and an adhesive layer is laminated on the first surface of the substrate,
A pressure-sensitive adhesive composition in which the pressure-sensitive adhesive layer contains an antistatic agent and a mixture of monomer components constituting the acrylic polymer (A) or a partial polymer of a mixture of monomer components constituting the acrylic polymer (A). formed by
The optical pressure-sensitive adhesive sheet, wherein the antistatic agent is an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in its molecule.
[Appendix 2] An optical pressure-sensitive adhesive sheet having a laminated structure in which a substrate having a first surface and a second surface and a pressure-sensitive adhesive layer is laminated on the first surface of the substrate,
The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing an antistatic agent and an acrylic polymer (A),
The optical pressure-sensitive adhesive sheet, wherein the antistatic agent is an ionic compound having a functional group capable of forming a covalent bond with the acrylic polymer (A) in its molecule.
[Appendix 3] The functional group is at least selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, an allyl group, a styryl group, a hydroxyl group, an amino group, a mercapto group, and an epoxy group. The optical pressure-sensitive adhesive sheet according to Appendix 1 or 2, which is one type.
[Appendix 4] The optical adhesive sheet according to any one of Appendices 1 to 3, wherein the acrylic polymer (A) does not contain or substantially does not contain a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer (A).
[Appendix 5] The optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 4, wherein the pressure-sensitive adhesive composition contains no or substantially no organic solvent.
[Appendix 6] The optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 5, wherein the pressure-sensitive adhesive layer has a haze (according to JIS K7136) of 1.0% or less.
[Appendix 7] The optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 6, wherein the pressure-sensitive adhesive layer has a total light transmittance (according to JIS K7361-1) of 90% or more.
[Appendix 8] The optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 7, which has a 180° peeling adhesive force to a glass plate at 23° C. of 4 N/20 mm or more.
[Appendix 9] The optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 8, which has a thickness of 12 to 350 μm.
[Appendix 10] The optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 9, wherein the second surface of the substrate is subjected to antireflection treatment, antiglare treatment, hard coat treatment and/or antistatic treatment.
[Appendix 11] An optical laminate obtained by laminating the optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 10 and an optical member.
[Appendix 12] An image display device in which the optical pressure-sensitive adhesive sheet according to any one of Appendices 1 to 10 and an image display panel are laminated.
 本発明の光学用粘着シートは、透明性、外観、耐久性に不良が生じにくく、且つ低い表面抵抗率を示し、優れた帯電防止性能を有するため、画像表示装置の製造に適する。 The optical pressure-sensitive adhesive sheet of the present invention is less likely to cause defects in transparency, appearance, and durability, exhibits a low surface resistivity, and has excellent antistatic performance, so it is suitable for manufacturing image display devices.
  10 光学用粘着シート
  1  基材
  2  粘着剤層
  3  反射防止処理、アンチグレア処理、及び/又は帯電防止処理
  4  セパレータ
  20 光学積層体
  5  光学部材
  30 画像表示装置
  6  画像表示パネル
REFERENCE SIGNS LIST 10 optical pressure-sensitive adhesive sheet 1 substrate 2 pressure-sensitive adhesive layer 3 antireflection treatment, anti-glare treatment, and/or antistatic treatment 4 separator 20 optical laminate 5 optical member 30 image display device 6 image display panel

Claims (12)

  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、
     前記粘着剤層が、帯電防止剤と、アクリル系ポリマー(A)を構成するモノマー成分の混合物又はアクリル系ポリマー(A)を構成するモノマー成分の混合物の部分重合物とを含有する粘着剤組成物により形成され、
     前記帯電防止剤が、前記アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物であることを特徴とする光学用粘着シート。
    An optical pressure-sensitive adhesive sheet having a laminated structure in which a substrate having a first surface and a second surface and a pressure-sensitive adhesive layer is laminated on the first surface of the substrate,
    A pressure-sensitive adhesive composition in which the pressure-sensitive adhesive layer contains an antistatic agent and a mixture of monomer components constituting the acrylic polymer (A) or a partial polymer of a mixture of monomer components constituting the acrylic polymer (A). formed by
    The optical pressure-sensitive adhesive sheet, wherein the antistatic agent is an ionic compound having in its molecule a functional group capable of forming a covalent bond with the acrylic polymer (A).
  2.  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、
     前記粘着剤層が、帯電防止剤とアクリル系ポリマー(A)とを含有する粘着剤組成物により形成され、
     前記帯電防止剤が、前記アクリル系ポリマー(A)と共有結合を形成できる官能基を分子内に有するイオン性化合物であることを特徴とする光学用粘着シート。
    An optical pressure-sensitive adhesive sheet having a laminated structure in which a substrate having a first surface and a second surface and a pressure-sensitive adhesive layer is laminated on the first surface of the substrate,
    The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing an antistatic agent and an acrylic polymer (A),
    The optical pressure-sensitive adhesive sheet, wherein the antistatic agent is an ionic compound having in its molecule a functional group capable of forming a covalent bond with the acrylic polymer (A).
  3.  前記官能基が、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミノ基、ビニル基、アリル基、スチリル基、水酸基、アミノ基、メルカプト基、及びエポキシ基からなる群から選ばれる少なくとも1種である、請求項1又は2に記載の光学用粘着シート。 The functional group is at least one selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, an allyl group, a styryl group, a hydroxyl group, an amino group, a mercapto group, and an epoxy group. The optical pressure-sensitive adhesive sheet according to claim 1 or 2.
  4.  前記アクリル系ポリマー(A)が構成するモノマー成分としてカルボキシル基含有モノマーを含有せず又は実質的に含有しない、請求項1~3の何れか1項に記載の光学用粘着シート。 The optical pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the acrylic polymer (A) does not contain or substantially does not contain a carboxyl group-containing monomer as a monomer component constituting the acrylic polymer (A).
  5.  前記粘着剤組成物が、有機溶剤を含有しない又は実質的に含有しない、請求項1~4の何れか1項に記載の光学用粘着シート。 The optical pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive composition contains no or substantially no organic solvent.
  6.  前記粘着剤層のヘイズ(JIS K7136に準じる)が1.0%以下である、請求項1~5の何れか1項に記載の光学用粘着シート。 The optical pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the pressure-sensitive adhesive layer has a haze (according to JIS K7136) of 1.0% or less.
  7.  前記粘着剤層の全光線透過率(JIS K7361-1に準じる)が90%以上である、請求項1~6の何れか1項に記載の光学用粘着シート。 The optical pressure-sensitive adhesive sheet according to any one of claims 1 to 6, wherein the pressure-sensitive adhesive layer has a total light transmittance (according to JIS K7361-1) of 90% or more.
  8.  ガラス板に対する23℃での180°引き剥がし接着力が4N/20mm以上である、請求項1~7の何れか1項に記載の光学用粘着シート。 The optical pressure-sensitive adhesive sheet according to any one of claims 1 to 7, which has a 180° peeling adhesive force to a glass plate at 23°C of 4 N/20 mm or more.
  9.  厚みが12~350μmである、請求項1~8の何れか1項に記載の光学用粘着シート。 The optical pressure-sensitive adhesive sheet according to any one of claims 1 to 8, which has a thickness of 12 to 350 µm.
  10.  前記基材の第2面は、反射防止処理、アンチグレア処理、ハードコート処理及び/又は帯電防止処理されている、請求項1~9の何れか1項に記載の光学用粘着シート。 The optical pressure-sensitive adhesive sheet according to any one of claims 1 to 9, wherein the second surface of the base material is subjected to antireflection treatment, antiglare treatment, hard coat treatment and/or antistatic treatment.
  11.  請求項1~10の何れか1項に記載の光学用粘着シートと、光学部材とが積層された光学積層体。 An optical laminate in which the optical pressure-sensitive adhesive sheet according to any one of claims 1 to 10 and an optical member are laminated.
  12.  請求項1~10の何れか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。 An image display device in which the optical pressure-sensitive adhesive sheet according to any one of claims 1 to 10 and an image display panel are laminated.
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