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WO2020262340A1 - Feuille adhésive et son utilisation - Google Patents

Feuille adhésive et son utilisation Download PDF

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Publication number
WO2020262340A1
WO2020262340A1 PCT/JP2020/024499 JP2020024499W WO2020262340A1 WO 2020262340 A1 WO2020262340 A1 WO 2020262340A1 JP 2020024499 W JP2020024499 W JP 2020024499W WO 2020262340 A1 WO2020262340 A1 WO 2020262340A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
weight
adhesive layer
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/024499
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English (en)
Japanese (ja)
Inventor
あゆみ 西丸
普史 形見
崇弘 野中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2020107125A external-priority patent/JP7733975B2/ja
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to KR1020227002636A priority Critical patent/KR20220024977A/ko
Priority to CN202080047095.6A priority patent/CN114051521B/zh
Publication of WO2020262340A1 publication Critical patent/WO2020262340A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B32B2037/268—Release layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to an adhesive sheet, a film member with an adhesive sheet, and a method for producing a laminate.
  • This application claims priority based on Japanese Patent Application No. 2019-122284 filed on June 28, 2019 and Japanese Patent Application No. 2020-107125 filed on June 22, 2020. The entire contents of those applications are incorporated herein by reference.
  • an adhesive also referred to as a pressure-sensitive adhesive; the same applies hereinafter
  • the pressure-sensitive adhesive is widely used in various fields, typically in the form of a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer.
  • Patent Document 1 is mentioned as a technical document relating to the adhesive sheet.
  • an object of the present invention is to provide an adhesive sheet capable of forming a joint having high deformation resistance and high impact resistance. Another object of the present invention is to provide a film member with an adhesive sheet, which is configured to include the adhesive sheet. Still another object of the present invention is to provide a method for producing a laminate using the pressure-sensitive adhesive sheet.
  • a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer and having the following characteristics (a) and (b) is provided.
  • the elastic modulus measured by the following tensile test is 3.0 MPa or more.
  • the impact resistance measured by the following shear impact test is 2.0 J / (10 mm) 2 or more.
  • the pressure-sensitive adhesive layer was irradiated with ultraviolet rays under the conditions of an illuminance of 300 mW / cm 2 and an integrated light intensity of 3000 mJ / cm 2 , and after aging at 50 ° C. for 48 hours, the pressure-sensitive adhesive layer was 10 mm wide and 150 mm long. Cut to size to make a test piece.
  • a tensile test was performed on the test piece under the conditions of a chuck distance of 120 mm and a tensile speed of 50 mm / min using a tensile tester, and a stress-displacement curve (hereinafter, “SS”). (Also referred to as “curve”) is obtained, and the elastic coefficient [MPa] (hereinafter, also referred to as tensile elastic coefficient) is calculated from the initial inclination thereof.
  • SS stress-displacement curve
  • MPa hereinafter, also referred to as tensile elastic coefficient
  • the first surface of the 10 mm square adhesive layer is bonded to the central portion of a chemically strengthened glass plate having a thickness of 25 mm square and 1.7 mm thick, and then the second surface of the adhesive layer is 40 mm square.
  • the measurement sample is fixed so that the stainless steel plate is on the lower side, and in an environment of 23 ° C. and 50% RH, a hammer energy of 2.75 J and a hammer speed (impact speed) of 3.5 m are applied to the outer peripheral side surface of the glass plate.
  • the impact resistance [J / (10 mm) 2 ] is obtained by measuring the absorbed energy [J] when a hammer is applied under the condition of / sec.
  • the pressure-sensitive adhesive layer can exhibit high deformation resistance in the state of use of the pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet satisfying the above characteristics (a) and (b) can form a joint having high deformation resistance and high impact resistance, and thus can be preferably used for the purpose of joining or fixing members, for example.
  • a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer contains a polymer (A) and a photoreactive monomer (B).
  • the photoreactive monomer (B) comprises compound B1 having a ring structure and two or more ethylenically unsaturated groups in the molecule.
  • the compound B1 preferably has a molecular weight of 100 g / mol or more per ethylenically unsaturated group. According to the pressure-sensitive adhesive sheet having such a pressure-sensitive adhesive layer, a bond having high deformation resistance and high impact resistance can be preferably formed.
  • the pressure-sensitive adhesive sheet according to any of the embodiments disclosed herein may satisfy the following property (c).
  • the pressure-sensitive adhesive sheet satisfying the characteristic (c) can be preferably used for the purpose of joining or fixing members, for example.
  • the peel strength measured by the following peel test is 1.0 N / 10 mm or more.
  • the first surface of the adhesive layer is pressure-bonded to a glass plate by reciprocating a 2 kg rubber roller once, autoclaving (50 ° C., 0.5 MPa, 15 minutes), and then illuminance 300 mW from the glass plate side. Irradiate with ultraviolet rays under the conditions of / cm 2 and integrated light intensity of 3000 mJ / cm 2 . After aging this at 50 ° C.
  • test piece is pulled from the glass plate under the conditions of a peeling angle of 180 degrees and a tensile speed of 60 mm / min in an environment of 23 ° C. and 50% RH. Measure the peeling strength at the time of peeling.
  • a film member with an adhesive sheet which includes any of the adhesive sheets disclosed herein and a film member bonded to the adhesive layer of the adhesive sheet. According to the film member with an adhesive sheet, a bond having high deformation resistance and high impact resistance can be suitably formed.
  • one of the pressure-sensitive adhesive sheets disclosed herein is attached to an adherend, and the pressure-sensitive adhesive sheet is irradiated with ultraviolet rays to photo-cure the pressure-sensitive adhesive layer in this order.
  • a method for producing a laminate including the above is provided. According to such a method, a laminate having both impact resistance and high deformation resistance can be produced.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of the pressure-sensitive adhesive sheet according to the embodiment.
  • FIG. 2 is a cross-sectional view schematically showing the configuration of the pressure-sensitive adhesive sheet according to another embodiment.
  • FIG. 3 is a cross-sectional view schematically showing a film member with an adhesive sheet to which the adhesive sheet according to the embodiment is attached to the film member.
  • the "acrylic polymer” refers to a polymer derived from a monomer component containing an acrylic monomer in an amount of 50% by weight or more, and is also referred to as an acrylic polymer.
  • the acrylic monomer refers to a monomer having at least one (meth) acryloyl group in one molecule.
  • (meth) acryloyl means a comprehensively referring to acryloyl and methacryloyl.
  • “(meth) acrylate” means acrylate and methacrylate
  • “(meth) acrylic” means acrylic and methacrylic, respectively.
  • “mass” and "weight” are synonymous.
  • the "photoreactive monomer” is a compound having at least one functional group (photoreactive functional group) in which the reaction can proceed by light irradiation, and is typically the above-mentioned photoreactivity. It is a compound having at least one ethylenically unsaturated group in the molecule as a functional group.
  • the photoreactive monomer referred to here may be any one capable of causing a reaction as a monomer, and for example, it itself has a polymer such as an oligomer or a polymer (for example, at least one ethylenically unsaturated group in the molecule). It may be a polymer).
  • the adhesive sheet 1 includes an adhesive layer 10 in which one surface 10A is a surface (adhesive surface) to be attached to an adherend, and a support 20 laminated on the other surface 10B of the adhesive layer 10. It is configured as a single-sided adhesive sheet (single-sided adhesive sheet with a support) including.
  • the pressure-sensitive adhesive layer 10 is bonded to one surface 20A of the support 20.
  • a resin film such as a polyester film can be used.
  • the support 20 may be an optical film such as a polarizing plate.
  • the pressure-sensitive adhesive layer 10 has a single-layer structure.
  • the adhesive sheet 1 before use (before being attached to the adherend) has an adhesive surface 10A having a release liner 30 having at least the adhesive layer side as a release surface (release surface). It may be in the form of an adhesive sheet 50 with a release liner protected by.
  • the second surface 20B of the support 20 (the surface opposite to the first surface 20A, also referred to as the back surface) is a peeling surface, and the adhesive surface 10A is on the second surface 20B of the support 20.
  • the adhesive surface 10A may be protected by being wound or laminated so as to be in contact with each other.
  • the release liner is not particularly limited, and for example, a release liner in which the surface of a liner base material such as a resin film or paper is peeled off, a fluoropolymer (polytetrafluoroethylene, etc.), a polyolefin resin (polyethylene, polypropylene, etc.), etc. ), A release liner made of a low-adhesive material or the like can be used.
  • a silicone-based or long-chain alkyl-based peeling agent can be used for the peeling treatment.
  • the stripped resin film can be preferably used as the strip liner.
  • the pressure-sensitive adhesive sheet disclosed herein may be in the form of a supportless double-sided pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer.
  • each side surface 10A, 10B of the pressure-sensitive adhesive layer 10 has at least a peelable surface (peeling surface) on the pressure-sensitive adhesive layer side. It may be in the form protected by the liners 31 and 32.
  • the back surface of the release liner 31 (the surface opposite to the adhesive side) is the release surface, and the adhesive surface is wound or laminated so that the adhesive surface 10B abuts on the back surface of the release liner 31.
  • 10A and 10B may be in a protected form.
  • Such a support-less double-sided pressure-sensitive adhesive sheet can be used, for example, by bonding a support to the surface of any one of the pressure-sensitive adhesive layers.
  • the pressure-sensitive adhesive sheet disclosed herein may be in the form of a double-sided pressure-sensitive adhesive sheet with a support in which a pressure-sensitive adhesive layer is laminated on each of one surface and the other surface of the sheet-shaped support.
  • the support in the pressure-sensitive adhesive sheet of this form may be a resin film such as a polyester film or an optical film such as a polarizing plate.
  • the pressure-sensitive adhesive sheet disclosed here may be a component of a film member with a pressure-sensitive adhesive sheet to which a film member is bonded to one surface of a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet 1 shown in FIG. 1 can be a component of the film member 100 with a pressure-sensitive adhesive sheet in which the film member 70 is bonded to one surface 10A of the pressure-sensitive adhesive layer 10, as shown in FIG.
  • the film member may be, for example, an electromagnetic wave transmitting metallic luster member as described in Japanese Patent Application Publication No. 2018-69462, a polarizing plate or other optical film.
  • the pressure-sensitive adhesive sheet disclosed herein has a tensile elastic modulus of 3.0 MPa or more in the pressure-sensitive adhesive layer (which may be a pressure-sensitive adhesive layer formed by using any of the pressure-sensitive adhesive compositions disclosed herein). Is preferable.
  • the tensile elastic modulus is measured by the above-mentioned tensile test, and more specifically, it is measured by the method described in Examples described later. Adhesive layers with higher tensile modulus tend to exhibit better deformation resistance.
  • the pressure-sensitive adhesive sheet having a high tensile elastic modulus can be preferably used for the purpose of joining or fixing members, for example.
  • the high deformation resistance of the adhesive layer is to maintain the relative position of the member with respect to the adherend with high accuracy.
  • the high deformation resistance of the adhesive layer means that the laminated body is locally from the film member side. It can be useful for suppressing an event in which the appearance of the laminate is changed by being pressed.
  • the adherend is a transparent rigid member (for example, a glass member)
  • the tensile elastic modulus may be, for example, 5.0 MPa or more, 7.0 MPa or more, 10.0 MPa or more, 15.0 MPa or more, 20. It may be 0 MPa or more. Deformation resistance tends to improve due to the increase in tensile elastic modulus.
  • the upper limit of the tensile elastic modulus is not particularly limited.
  • the tensile elastic modulus is usually 150 MPa or less from the viewpoint of facilitating balance with other characteristics (for example, one or more characteristics selected from impact resistance, peel strength, haze value, etc.). It is advantageous, preferably 120 MPa or less, 100 MPa or less, 80 MPa or less, or 60 MPa or less.
  • the tensile elastic modulus can be adjusted by selecting the composition of the pressure-sensitive adhesive layer and the like.
  • the treatment of irradiating the pressure-sensitive adhesive layer with ultraviolet rays is preferably performed with the pressure-sensitive adhesive layer sandwiched between transparent release liners.
  • a polyester resin film having at least one side peeled for example, a peeled polyethylene terephthalate resin (PET) film
  • PET polyethylene terephthalate resin
  • the thickness of the release liner may be, for example, about 10 ⁇ m or more and 125 ⁇ m or less, 10 ⁇ m or more and 75 ⁇ m or less, or 20 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the test piece used in the above tensile test may be about the same as or different from the thickness of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet disclosed herein.
  • a test piece prepared to have a thickness of 5 ⁇ m or more for example, about 5 ⁇ m to 200 ⁇ m
  • the result obtained by performing the tensile test can be adopted as the tensile elastic modulus of the pressure-sensitive adhesive layer.
  • the thickness of the test piece can be adjusted, for example, by appropriately superimposing the pressure-sensitive adhesive layers before irradiation with ultraviolet rays.
  • a test piece having a thickness that facilitates a tensile test is prepared, and the above-mentioned tensile test is performed on the test piece.
  • the obtained result can be adopted as the tensile elastic modulus of the pressure-sensitive adhesive layer.
  • the tensile test can be performed using, for example, a test piece having a thickness of about 10 ⁇ m to 50 ⁇ m (preferably about 15 ⁇ m to 25 ⁇ m).
  • the pressure-sensitive adhesive sheet disclosed herein preferably has an impact resistance of 2.0 J / (10 mm) 2 or more.
  • the impact resistance is measured by the shear impact test described above, and more specifically, by the method described in Examples described later.
  • a highly reliable bond can be formed. This can be an advantageous feature in, for example, an adhesive sheet used for joining or fixing members. Even if the adhesive sheet receives an impact due to, for example, dropping or collision, the adhesive sheet can withstand the impact and maintain good adhesion between the member and the adherend.
  • the impact resistance may be, for example, 2.1 J / (10 mm) 2 or more, 2.3 J / (10 mm) 2 or more, and 2.5 J / (10 mm). may be two or more, may be 2.7 J / (10 mm) 2 or more, may be 3.0 J / (10 mm) 2 or more.
  • the impact resistance may be preferably implemented in embodiments is 3.3J / (10mm) 2 or more, or 3.5J / (10mm) 2 or more.
  • the upper limit of the impact resistance is not particularly limited.
  • the impact resistance for example 20 J / (10 mm) may be two or less, 15 J / (10 mm) may be two or less, may be 10J / (10 mm) 2 or less , 8.0J / (10mm) 2 may be used, and 6.0J / (10mm) 2 or less may be used.
  • the impact resistance can be adjusted by selecting the composition and thickness of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet disclosed in the present specification includes an aspect in which the tensile elastic modulus is not limited, and in such an aspect, the pressure-sensitive adhesive sheet is not limited to one satisfying the tensile elastic modulus.
  • the pressure-sensitive adhesive sheet disclosed herein includes an unrestricted aspect of impact resistance, in which aspect the pressure-sensitive adhesive sheet is not limited to those that satisfy the impact resistance.
  • the peel strength of the pressure-sensitive adhesive sheet disclosed herein is not particularly limited and can be set according to the purpose.
  • the peel strength is measured by the peel test described above, and more specifically, it is measured by the method described in Examples described later.
  • the peel strength may be, for example, 0.5 N / 10 mm or more, preferably 1.0 N / 10 mm or more, and 1.5 N / 10 mm or more from the viewpoint of bonding reliability. Is more preferable, and it may be 2.0 N / 10 mm or more, 2.2 N / 10 mm or more, or 2.3 N / 10 mm or more.
  • the peel strength may be, for example, 10 N / 10 mm or less, 8.0 N / 10 mm or less, 6.0 N / 10 mm or less. It may be 0N / 10mm or less, or 4.0N / 10mm or less.
  • the peel strength can be adjusted by selecting the composition and thickness of the pressure-sensitive adhesive layer.
  • the haze value of the pressure-sensitive adhesive layer is not particularly limited.
  • the haze value of the pressure-sensitive adhesive layer may be, for example, 10% or less, 5.0% or less, 3.0% or less, 1.0% or less. It may be.
  • a usage mode in which the pressure-sensitive adhesive layer is required to be transparent a member is bonded to a transparent adherend via a pressure-sensitive adhesive layer, and the above-mentioned is described from the adherend side through the pressure-sensitive adhesive layer.
  • the usage mode in which the member is visually recognized the usage mode in which the pressure-sensitive adhesive sheet having the support is joined to the transparent adherend, and the support is visually recognized from the adherend side through the pressure-sensitive adhesive layer.
  • the haze value of the pressure-sensitive adhesive layer may be less than 1.0%, less than 0.7%, 0.5% or less (eg 0-0.5%). There may be.
  • the "haze value” refers to the ratio of diffuse transmitted light to total transmitted light when the measurement target is irradiated with visible light. Also called cloudy value.
  • the haze value is measured by irradiating ultraviolet rays under the conditions of an illuminance of 300 mW / cm 2 and an integrated light intensity of 3000 mJ / cm 2 , and aging at 50 ° C. for 48 hours, using the adhesive layer as a measurement sample as a haze meter (for example).
  • a haze meter for example.
  • "MR-100" manufactured by Murakami Color Technology Research Institute) can be used for measurement.
  • the haze value can be adjusted by selecting, for example, the composition and thickness of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer is sandwiched between transparent release liners (for example, a PET film that has been peeled off), as in the tensile test in the above-mentioned tensile elastic modulus measurement. It is preferable to carry out in a state of being.
  • the pressure-sensitive adhesive sheet in the techniques disclosed herein includes a pressure-sensitive adhesive layer.
  • the composition of the pressure-sensitive adhesive layer can be selected so that a bond having high deformation resistance and high impact resistance can be formed.
  • the pressure-sensitive adhesive layer contains a polymer (A).
  • materials that can be used as the polymer (A) include acrylic polymers, rubber-based polymers, polyester-based polymers, urethane-based polymers, polyether-based polymers, silicone-based polymers, and polyamide-based polymers known in the field of pressure-sensitive adhesives. Examples thereof include polymers that exhibit rubber elasticity in the room temperature range, such as fluoropolymers. These can be used alone or in combination of two or more.
  • the weight ratio of the polymer (A) to the total weight of the pressure-sensitive adhesive layer is usually preferably 40% by weight or more, preferably 50% by weight or more, preferably 60% by weight. % Or more, and 70% by weight or more.
  • the weight ratio of the polymer (A) to the total weight of the pressure-sensitive adhesive layer is typically less than 100% by weight, and is usually 95% by weight or less from the viewpoint of facilitating the balance of characteristics. Is advantageous, and is preferably 92% by weight or less, 90% by weight or less, or 87% by weight or less.
  • the pressure-sensitive adhesive layer in the technique disclosed herein may be an acrylic pressure-sensitive adhesive layer containing an acrylic polymer as a base polymer (a main component in the polymer component, that is, a component accounting for more than 50% by weight).
  • the acrylic polymer as the polymer (A) (hereinafter, may be referred to as “acrylic polymer (A)”) is a linear or branched alkyl group having 1 to 20 carbon atoms at the ester terminal. It is preferable that the acrylic polymer is composed of a monomer component containing 40% by weight or more of the (meth) acrylic acid alkyl ester having.
  • (meth) acrylic acid alkyl ester having an alkyl group having an number of carbon atoms of X or more and Y or less at the ester terminal may be referred to as "(meth) acrylic acid CXY alkyl ester".
  • the proportion of (meth) acrylic acid C 1-20 alkyl ester in the total monomer component of the acrylic polymer (A) is preferably greater than 40% by weight because it is easy to balance the properties. For example, it may be 45% by weight or more, 50% by weight or more, 55% by weight or more, or 60% by weight or more.
  • the proportion of the (meth) acrylic acid C 1-20 alkyl ester in the monomer component can be 100% by weight, but it is usually suitable to be 98% by weight or less because it is easy to balance the characteristics. For example, it may be 95% by weight or less, or 90% by weight or less.
  • the proportion of C 1-20 (meth) acrylic acid alkyl ester in the total monomer component of the acrylic polymer (A) is, for example, 85% by weight or less from the viewpoint of improving the cohesiveness of the pressure-sensitive adhesive layer. It may be 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, or 60% by weight or less.
  • Non-limiting specific examples of (meth) acrylic acid C 1-20 alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, ( 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, Isodecy
  • At least (meth) acrylic acid C 4-20 alkyl ester it is preferable to use at least (meth) acrylic acid C 4-20 alkyl ester, and it is more preferable to use at least (meth) acrylic acid C 4-18 alkyl ester.
  • Particularly preferred (meth) acrylic acid C 4-18 alkyl esters include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
  • Other specific examples of (meth) acrylic acid C 4-20 alkyl esters that may be preferably used include isononyl acrylate, n-butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2EHMA), isostearyl acrylate ( iSTA) and the like.
  • BMA n-butyl methacrylate
  • EHMA 2-ethylhexyl methacrylate
  • iSTA isostearyl acrylate
  • the monomer component preferably contains, for example, either one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
  • the monomer component preferably comprises at least BA.
  • at least the example of the monomer component containing BA includes a monomer component having a composition containing BA and not containing 2EHA, BA and 2EHA, and the content of 2EHA is less than the content of BA (for example, the content of 2EHA). Contains monomer components of composition (the amount is less than 0.5 times or less than 0.3 times the content of BA).
  • the monomer component constituting the acrylic polymer (A) may contain (meth) acrylic acid C 4-18 alkyl ester in a proportion of 40% by weight or more.
  • the ratio of the (meth) acrylic acid C 4-18 alkyl ester to the monomer component may be, for example, 50% by weight or more, 60% by weight or more, or 65% by weight or more. Further, from the viewpoint of enhancing the cohesiveness of the pressure-sensitive adhesive layer, it is usually appropriate that the ratio of the (meth) acrylic acid C 4-18 alkyl ester to the monomer component is 99.5% by weight or less, and 95% by weight. It may be% or less, 85% by weight or less, and 75% by weight or less.
  • the monomer component constituting the acrylic polymer (A) contains a (meth) acrylic acid alkyl ester and, if necessary, another monomer (copolymerizable monomer) copolymerizable with the (meth) acrylic acid alkyl ester.
  • a monomer having a polar group for example, a carboxy group, a hydroxyl group, a nitrogen atom-containing ring, etc.
  • a monomer having a relatively high glass transition temperature of a homopolymer for example, 10 ° C. or higher
  • the monomer having a polar group can be useful for introducing a cross-linking point in the acrylic polymer (A) and increasing the cohesive force of the pressure-sensitive adhesive.
  • the copolymerizable monomer may be used alone or in combination of two or more.
  • Non-limiting specific examples of the copolymerizable monomer include the following.
  • Carboxylic group-containing monomer For example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.
  • Acid anhydride group-containing monomer For example, maleic anhydride, itaconic anhydride.
  • Hydroxyl group-containing monomers for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic.
  • Monomer containing sulfonic acid group or phosphoric acid group For example, styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfo Propyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, 2-hydroxyethylacryloyl phosphate, etc.
  • styrene sulfonic acid allyl sulfonic acid, sodium vinyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfo Propyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, 2-hydroxyethy
  • Epoxy group-containing monomer For example, an epoxy group-containing acrylate such as glycidyl (meth) acrylate or -2-ethylglycidyl ether (meth) acrylate, allyl glycidyl ether, glycidyl ether (meth) acrylate and the like.
  • Cyano group-containing monomer For example, acrylonitrile, methacrylonitrile, etc.
  • Isocyanate group-containing monomer For example, 2-isocyanate ethyl (meth) acrylate and the like.
  • Amide group-containing monomers (meth) acrylamide; for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) N, N-dialkyl (meth) acrylamide such as acrylamide, N, N-di (n-butyl) (meth) acrylamide, N, N-di (t-butyl) (meth) acrylamide; N-ethyl (meth) acrylamide , N-alkyl (meth) acrylamide such as N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, Nn-butyl (meth) acrylamide; N-vinylcarboxylic acid amides such as N-vinylacetamide; Monomers having a hydroxyl group and an amide group, for example
  • N-alkoxyalkyl (meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide, N- (meth) acryloylmorpholine and the like.
  • Amino group-containing monomer For example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate.
  • Monomers having an epoxy group for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether.
  • N-vinyl-2-pyrrolidone N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N- Vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N- (meth) acryloyl-2-pyrrolidone, N- (meth) acryloyl piperidine, N- (meth) acryloyl pyrrolidine, N- (meth) acryloyl morpholine, N- Vinyl morpholin, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxadin-2-one, N-vinyl-3,5-morpholindione, N-vinylpyrazole, N -Vinyl
  • Monomers having a succinimide skeleton for example, N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyhexamethylene succinimide and the like.
  • Maleimides For example, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like.
  • Itaconimides For example, N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-lauryl. Itaconimide, etc.
  • Aminoalkyl (meth) acrylates For example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t (meth) acrylate. -Butylaminoethyl.
  • Alkoxy group-containing monomers for example, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, (meth) acrylate.
  • Alkoxyalkyl (alkoxyalkyl (meth) acrylate) such as butoxyethyl, ethoxypropyl (meth) acrylate; (meth) methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, (meth) (Meta) Alkoxyalkylene glycol acrylate (for example, alkoxypolyalkylene glycol (meth) acrylate) such as methoxypolypropylene glycol acrylate.
  • Alkoxysilyl group-containing monomers for example 3- (meth) acryloxipropyltrimethoxysilane, 3- (meth) acryloxipropyltriethoxysilane, 3- (meth) acryloxipropylmethyldimethoxysilane, 3- (meth) acryloxy Alkoxysilyl group-containing (meth) acrylates such as propylmethyldiethoxysilane, alkoxysilyl group-containing vinyl compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, and the like.
  • Vinyl esters For example, vinyl acetate, vinyl propionate and the like.
  • Vinyl ethers For example, vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether.
  • Aromatic vinyl compounds for example, styrene, ⁇ -methylstyrene, vinyltoluene and the like.
  • Olefins For example, ethylene, butadiene, isoprene, isobutylene and the like.
  • (Meta) acrylic acid ester having an alicyclic hydrocarbon group For example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate and the like. Acrylate-type hydrocarbon group-containing (meth) acrylate.
  • acrylic acid ester having an aromatic hydrocarbon group For example, an aromatic hydrocarbon group-containing (meth) acrylate such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and benzyl (meth) acrylate.
  • heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, halogen atom-containing (meth) acrylates such as vinyl chloride and fluorine atom-containing (meth) acrylates, and silicon atom-containing silicone (meth) acrylates.
  • the amount used is not particularly limited, but it is usually appropriate to use 0.01% by weight or more of the total monomer component. From the viewpoint of better exerting the effect of using the copolymerizable monomer, the amount of the copolymerizable monomer used may be 0.1% by weight or more of the total monomer component, or 0.5% by weight or more. Further, from the viewpoint of facilitating the balance of the adhesive properties, the amount of the copolymerizable monomer used is usually preferably 50% by weight or less of the total monomer component, and preferably 40% by weight or less.
  • the monomer component constituting the acrylic polymer (A) may include a monomer having a nitrogen atom.
  • a monomer having a nitrogen atom By using a monomer having a nitrogen atom, the cohesive force of the pressure-sensitive adhesive can be increased, and the peel strength after photocuring can be preferably improved.
  • a preferred example of a monomer having a nitrogen atom is a monomer having a nitrogen atom-containing ring.
  • the monomer having a nitrogen atom-containing ring those exemplified above can be used, and for example, the general formula (1):
  • the N-vinyl cyclic amide represented by is used.
  • R 1 is a divalent organic group, and specific examples thereof include ⁇ (CH 2 ) n ⁇ .
  • n is an integer of 2 to 7 (preferably 2, 3 or 4).
  • N-vinyl-2-pyrrolidone can be preferably adopted.
  • Other preferred examples of monomers having a nitrogen atom include amide group-containing monomers such as (meth) acrylamide.
  • the amount of the monomer having a nitrogen atom (preferably the monomer having a nitrogen atom-containing ring) is not particularly limited, and may be, for example, 1% by weight or more of the total monomer component, or 3% by weight or more. Further, it can be 5% by weight or more or 7% by weight or more. In one aspect, the amount of the monomer having a nitrogen atom used may be 10% by weight or more, 15% by weight or more, or 20% by weight or more of the total monomer component. Further, the amount of the monomer having a nitrogen atom to be used is appropriately set to, for example, 40% by weight or less of the total monomer component, 35% by weight or less, 30% by weight or less, or 25% by weight or less. May be good. In another aspect, the amount of the monomer having a nitrogen atom used may be, for example, 20% by weight or less of the total monomer component, or 15% by weight or less.
  • the monomer component constituting the acrylic polymer (A) may contain a hydroxyl group-containing monomer.
  • the hydroxyl group-containing monomer By using the hydroxyl group-containing monomer, the cohesive force of the pressure-sensitive adhesive and the degree of cross-linking (for example, cross-linking with an isocyanate cross-linking agent) can be suitably adjusted.
  • the amount used is not particularly limited, and may be, for example, 0.01% by weight or more, 0.1% by weight or more, or 0.5% by weight or more of the entire monomer component. It may be 1% by weight or more, 5% by weight or more, or 10% by weight or more.
  • the amount of the hydroxyl group-containing monomer used is preferably, for example, 40% by weight or less of the total monomer component, and is 30% by weight or less. It may be 25% by weight or less, or 20% by weight or less. In another aspect, the amount of the hydroxyl group-containing monomer used may be, for example, 15% by weight or less of the total monomer component, 10% by weight or less, or 5% by weight or less.
  • the proportion of the carboxy group-containing monomer in the monomer component of the acrylic polymer (A) may be, for example, 2% by weight or less, 1% by weight or less, and 0.5% by weight or less (for example). It may be less than 0.1% by weight). It is not necessary to substantially use a carboxy group-containing monomer as the monomer component of the acrylic polymer (A).
  • the fact that the carboxy group-containing monomer is not substantially used means that the carboxy group-containing monomer is not used at least intentionally.
  • the pressure-sensitive adhesive layer containing the acrylic polymer (A) in which the amount of the carboxy group-containing monomer used is limited as described above is preferable from the viewpoint of preventing metal corrosion.
  • the pressure-sensitive adhesive sheet having such a pressure-sensitive adhesive layer is also preferably in an embodiment in which the pressure-sensitive adhesive layer is in contact with an adherend and / or a support (which may be a metal foil or a support film containing a metal material) having a metal material. Can be used.
  • the monomer component constituting the acrylic polymer (A) may contain an alicyclic hydrocarbon group-containing (meth) acrylate.
  • an alicyclic hydrocarbon group-containing (meth) acrylate those exemplified above can be used, and for example, cyclohexyl acrylate and isobornyl acrylate can be preferably adopted.
  • the amount used is not particularly limited, and may be, for example, 1% by weight or more, 3% by weight or more, or 5% by weight or more of the total monomer component.
  • the amount of the alicyclic hydrocarbon group-containing (meth) acrylate used may be 10% by weight or more of the total monomer component, or 15% by weight or more.
  • the upper limit of the amount of the alicyclic hydrocarbon group-containing (meth) acrylate used is appropriately about 40% by weight or less, for example, 30% by weight or less, and 25% by weight or less (for example, 15% by weight). % Or less, and even 10% by weight or less).
  • the polymerization method for forming (synthesizing) the polymer (A) from the monomer component is not particularly limited, and various conventionally known polymerization methods can be appropriately adopted.
  • thermal polymerization such as solution polymerization, emulsion polymerization, bulk polymerization (typically performed in the presence of a thermal polymerization initiator); photopolymerization performed by irradiating light such as ultraviolet rays (typically).
  • a polymerization method such as radiation polymerization carried out by irradiating radiation such as ⁇ -ray or ⁇ -ray; which is carried out in the presence of a photopolymerization initiator; can be appropriately adopted. Two or more polymerization methods may be combined (eg, stepwise).
  • solvent for solution polymerization examples include aromatic compounds such as toluene (typically aromatic hydrocarbons); esters such as ethyl acetate and butyl acetate; aliphatic compounds such as hexane and cyclohexane or Aromatic hydrocarbons; Alkane halides such as 1,2-dichloroethane; Lower alcohols such as isopropyl alcohol (for example, monovalent alcohols having 1 to 4 carbon atoms); Ethers such as tert-butylmethyl ether Class; Ketones such as methyl ethyl ketone; Any one solvent selected from the above, or a mixed solvent of two or more kinds can be used.
  • aromatic compounds such as toluene (typically aromatic hydrocarbons); esters such as ethyl acetate and butyl acetate; aliphatic compounds such as hexane and cyclohexane or Aromatic hydrocarbons; Alkane halides such as 1,2-dichloroe
  • thermal polymerization initiator or photopolymerization initiator can be used depending on the polymerization method, polymerization mode, and the like.
  • a polymerization initiator may be used alone or in combination of two or more.
  • the thermal polymerization initiator is not particularly limited, but is, for example, an azo-based polymerization initiator, a peroxide-based initiator, a redox-based initiator by a combination of a peroxide and a reducing agent, and a substituted ethane-based initiator.
  • Etc. can be used. More specifically, for example, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (2-amidinopropane).
  • Thermal polymerization can be preferably carried out at a temperature of, for example, about 20 to 100 ° C. (typically 40 to 80 ° C.), but is not limited thereto.
  • the photopolymerization initiator is not particularly limited, but for example, a ketal-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, a benzoin ether-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, ⁇ - Ketol-based photopolymerization initiator, aromatic sulfonyl chloride-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzyl-based photopolymerization initiator, benzophenone-based photopolymerization initiator, thioxanthone-based light
  • a polymerization initiator or the like can be used.
  • the amount of the polymerization initiator used can be a normal amount according to the polymerization method, polymerization mode, etc., and is not particularly limited. For example, about 0.001 to 5 parts by weight of the polymerization initiator (typically about 0.01 to 2 parts by weight, for example, about 0.01 to 1 part by weight) is used with respect to 100 parts by weight of the monomer to be polymerized. Can be done.
  • chain transfer agents which can also be grasped as a molecular weight adjusting agent or a degree of polymerization adjusting agent
  • chain transfer agent mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, and ⁇ -thioglycerol
  • a chain transfer agent containing no sulfur atom non-sulfur chain transfer agent
  • non-sulfur chain transfer agent examples include anilins such as N, N-dimethylaniline and N, N-diethylaniline; terpenoids such as ⁇ -pinene and turpinolene; ⁇ -methylstyrene and ⁇ -methylstyrene dimer.
  • the chain transfer agent may be used alone or in combination of two or more. It should be noted that the technique disclosed herein can be preferably implemented even in an embodiment in which a chain transfer agent is not used.
  • the amount used can be, for example, about 0.005 part by weight to 1 part by weight with respect to 100 parts by weight of the monomer component.
  • the amount of the chain transfer agent used per 100 parts by weight of the monomer component can be, for example, 0.01 parts by weight or more, 0.03 parts by weight or more, and 0. It may be 0.05 parts by weight or more, or 0.07 parts by weight or more.
  • the amount of the chain transfer agent used with respect to 100 parts by weight of the monomer component may be, for example, 0.5 parts by weight or less, or 0.2 parts by weight or less. It may be 0.1 parts by weight or less, or less than 0.1 parts by weight (for example, 0.09 parts by weight or less).
  • the glass transition temperature (Tg) of the polymer (A) is not particularly limited, but is usually preferably less than 0 ° C, preferably less than -10 ° C, and -20. It is preferably less than ° C.
  • the impact resistance tends to be improved by reducing the Tg of the polymer (A).
  • the Tg of the polymer (A) may be less than -25 ° C or less than -30 ° C.
  • the Tg of the polymer (A) is typically ⁇ 80 ° C. or higher, for example, ⁇ 70 ° C. or higher, ⁇ 60 ° C. or higher, or ⁇ 55 ° C. or higher.
  • the Tg of the polymer (A) is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 45 ° C. or higher, and may be ⁇ 40 ° C. or higher, or ⁇ 38 ° C. It may be more than that, and it may be more than -35 ° C.
  • the Tg of the polymer means the Tg obtained by the Fox formula based on the composition of the monomer component used for the preparation of the polymer.
  • Tg is the glass transition temperature (unit: K) of the copolymer
  • Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio based on the weight)
  • Tgi is the homopolymer of the monomer i.
  • the glass transition temperature of the homopolymer used for calculating Tg the value described in the publicly known material shall be used.
  • the monomers listed below the following values are used as the glass transition temperature of the homopolymer of the monomer.
  • the weight average molecular weight (Mw) of the polymer (A) is not particularly limited.
  • the upper limit of Mw of the polymer (A) may be normally be about 500 ⁇ 10 4 or less.
  • the Mw of the polymer (A) may be, for example, 150 ⁇ 10 4 or less, 100 ⁇ 10 4 or less, or 90 ⁇ 10 4 it may be below or at 75 ⁇ 10 4 or less.
  • Mw refers to a standard polystyrene-equivalent value obtained by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Mw may be applied to the Mw of the polymer (A) in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet disclosed herein, and the polymer (A) in the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer. ) May be applied to Mw.
  • the pressure-sensitive adhesive layer in the technique disclosed herein may include a photoreactive monomer (B) in addition to the polymer (A) as described above (eg, acrylic polymer (A)).
  • a photoreactive monomer (B) a compound having two or more ethylenically unsaturated groups contained in the molecule (hereinafter, also referred to as “functional group number”) can be used.
  • the upper limit of the number of functional groups of the compound used as the photoreactive monomer (B) is not particularly limited.
  • the number of functional groups may be, for example, 50 or less, 40 or less, 30 or less, 20 or less, or 15 or less.
  • a compound having an ethylenically unsaturated group having, for example, 2 to 10 functional groups can be used, preferably a compound having 2 to 8 functional groups, and a compound having 2 to 6 functional groups. Is more preferable to use.
  • the photoreactive monomer (B) may be used alone or in combination of two or more.
  • the photoreactive monomer (B) contained in the pressure-sensitive adhesive layer can form a crosslinked structure by reacting the ethylenically unsaturated group with light (for example, ultraviolet rays) irradiation after being attached to the adherend.
  • the pressure-sensitive adhesive sheet containing the photoreactive monomer (B) in the pressure-sensitive adhesive layer is subjected to ultraviolet irradiation or the like after being attached to the adherend to cure the pressure-sensitive adhesive layer, thereby enhancing the deformation resistance of the pressure-sensitive adhesive layer. Can be done.
  • Examples of the ethylenically unsaturated group include, but are not limited to, an acryloyl group, a methacryloyl group, a vinyl group and an allyl group.
  • the two or more ethylene unsaturated groups that the photoreactive monomer (B) has in the molecule may be the same group or two or more different groups.
  • Preferred ethylenically unsaturated groups from the viewpoint of photoreactivity include acryloyl group and methacryloyl group. Of these, the acryloyl group is preferable.
  • the functional group equivalent of the compound used as the photoreactive monomer (B) is not particularly limited.
  • the functional group equivalent may be, for example, about 50 to 10000 g / mol, about 50 to 8000 g / mol, about 50 to 5000 g / mol, about 50 to 3000 g / mol, or about 50 to 2000 g / mol. It may be about.
  • a compound having a functional group equivalent of about 60 to 800 g / mol (more preferably about 80 to 600 g / mol) is preferably used from the viewpoint of photocurability. Can be done.
  • the functional group equivalent of the photoreactive monomer (B) is obtained by dividing the molecular weight [g / mol] of the photoreactive monomer (B) by the number of ethylene unsaturated functional groups of the photoreactive monomer (B). It is calculated by.
  • the molecular weight of the photoreactive monomer (B) can be obtained, for example, by a gel permeation chromatography (GPC) method as a weight average molecular weight in terms of standard polystyrene. Further, as the molecular weight [g / mol] of the photoreactive monomer (B), the molecular weight calculated from the manufacturer's nominal value or the molecular structure may be adopted.
  • the molecular weight of the photoreactive monomer (B) is not particularly limited and can be selected so as to preferably exert the desired effect.
  • the photoreactive monomer (B) one having a molecular weight of about 20000 or less can be used.
  • the molecular weight of the photoreactive monomer (B) may be, for example, 16000 or less, 10,000 or less, or 4000 or less in some embodiments. Well, it may be 1500 or less, or 1000 or less.
  • the molecular weight of the photoreactive monomer (B) is, for example, 100 or more, and typically 120 or more.
  • the molecular weight of the photoreactive monomer (B) may be, for example, 150 or more, 200 or more, 280 or more, 350 or more. However, it may be 420 or more, 480 or more, or 550 or more.
  • the amount of the photoreactive monomer (B) contained in the pressure-sensitive adhesive layer is not particularly limited, and depends on the target performance (for example, the tensile elastic modulus of the pressure-sensitive adhesive layer after photo-curing). It can be set appropriately.
  • the amount of photoreactive monomer (B) relative to 100 parts by weight of the polymer (A) contained in the pressure-sensitive adhesive layer is For example, it may be 1 part by weight or more, and usually 3 parts by weight or more is suitable.
  • the amount of the photoreactive monomer (B) with respect to 100 parts by weight of the polymer (A) may be 5 parts by weight or more, or 10 parts by weight or more. , 15 parts by weight or more, or 20 parts by weight or more.
  • the amount of the photoreactive monomer (B) with respect to 100 parts by weight of the polymer (A) is usually 80% by weight. It is appropriate that the amount is 60 parts by weight or less, preferably 50 parts by weight or less, 40 parts by weight or less, and 35 parts by weight or less.
  • the pressure-sensitive adhesive layer preferably contains, as the photoreactive monomer (B), at least compound B1 having a ring structure and two or more ethylenically unsaturated groups in the molecule.
  • the deformation resistance of the pressure-sensitive adhesive layer can be effectively enhanced by light irradiation.
  • the ring in the above ring structure may be an aliphatic ring or an aromatic ring. Further, the ring may be a carbon ring or a heterocycle.
  • the number of rings contained in one molecule of compound B1 may be 1, or may be 2 or more.
  • the upper limit of the number of rings contained in compound B1 is not particularly limited, and may be, for example, 100 or less, 70 or less, 50 or less, 30 or less, 15 or less, 8 or less, 6 It may be less than or equal to, 5 or less, or 4 or less.
  • compound B1 contains two or more rings, those rings may form fused rings of one or more rings (typically bicyclic or tricyclic fused rings). It does not have to be formed.
  • the ring is preferably contained in the main chain of compound B1. That is, it is preferable that one ethylenically unsaturated group of compound B1 and at least one other ethylenically unsaturated group are linked via the ring structure.
  • Compound B1 may be used alone or in combination of two or more.
  • a compound having a ring structure and two or more ethylenically unsaturated groups in the molecule and having a functional group equivalent of 100 g / mol or more can be preferably used.
  • a bond having high deformation resistance and high impact resistance can be suitably formed.
  • the reason why such an effect is obtained is not particularly limited, but according to Compound B1, the tensile elastic modulus of the pressure-sensitive adhesive layer after light irradiation is effectively increased by the rigidity of the ring structure.
  • the functional group equivalent of compound B1 may be, for example, 120 g / mol or more, 150 g / mol or more, 180 g / mol or more, 230 g / mol or more, or 280 g / mol or more. It may be 320 g / mol or more, or 350 g / mol or more. Impact resistance tends to improve as the functional group equivalent of compound B1 increases.
  • the functional group equivalent of compound B1 may be, for example, 10000 g / mol or less, 8000 g / mol or less, 5000 g / mol or less, 3000 g / mol or 2000 g / mol or less.
  • the functional group equivalent of compound B1 is preferably 800 g / mol or less, more preferably 600 g / mol or less, from the viewpoint of photocurability and the like.
  • the functional group equivalent of compound B1 may be 500 g / mol or less, 400 g / mol or less, or 300 g / mol or less.
  • the number of functional groups of compound B1 (ie, the number of ethylenically unsaturated groups contained in the molecule) may be, for example, 2 to 50, 2 to 40, or 2 to 30. It may be 2 to 10, for example, 2 to 6, preferably 2 to 4, or 2 to 3. In some embodiments, compound B1 having 2 functional groups may be preferably employed.
  • Compound B1 may have a functional group other than the ethylenically unsaturated group.
  • functional groups other than ethylenically unsaturated groups include hydroxyl groups, carboxy groups, amino groups and the like.
  • Preferable examples of functional groups other than ethylenically unsaturated groups include hydroxyl groups and amino groups.
  • compound B1 examples include bisphenol A glycidyl ether (meth) acrylic acid adduct, bisphenol A glycidylamine (meth) acrylic acid adduct, bisphenol A glycidyl ester (meth) acrylic acid adduct, and the like.
  • alkylene oxide-modified bisphenol A (meth) acrylate such as ethylene oxide (EO) -modified bisphenol A di (meth) acrylate, propylene oxide (PO) -modified bisphenol A di (meth) acrylate
  • bisphenol F glycidyl ether (meth) ) Bisphenol F type epoxy (meth) acrylate such as acrylic acid adduct, bisphenol F glycidylamine (meth) acrylic acid adduct, bisphenol F glycidyl ester (meth) acrylic acid adduct
  • EO-modified bisphenol F di (meth) acrylate PO-modified bisphenol F di (meth) acrylate, alkylene oxide-modified bisphenol F (meth) acrylate
  • bisphenol E glycidyl ether (meth) acrylic acid adduct bisphenol E glycidylamine (meth) acrylic acid adduct, bisphenol E glycidyl
  • Acrylates containing fluorene skeletons such as 9,9-bis (4-hydroxyphenyl) full orange (meth) acrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] full orange (meth) acrylate ( Meta) acrylate; tricyclodecanedimethanol di (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) acrylate, hydrogenated bisphenol F type epoxy (meth) acrylate, hydrogenated bisphenol E type epoxy (meth) acrylate, hydrogenated An aliphatic ring (which may be an alicyclic condensed ring) such as phthalic acid type epoxy (meth) acrylate, hydrogenated terpenephenol (meth) acrylate, and 1,4-cyclohexanedimethanol diglycidyl ether (meth) acrylate.
  • fluorene skeletons such as 9,9-bis (4-hydroxyphenyl) full orange (meth) acrylate, 9,9-bis
  • Isocyanurate-type (meth) acrylate divinylbenzene; hydroquinone di (meth) acrylate; resorcindi (meth) acrylate; modified products of any of the above-mentioned materials (for example, amine-modified products, acid-modified products, halogen-modified products); etc.
  • the present invention is not limited to these.
  • compound B1 having an aromatic carbocycle may be preferably employed.
  • the compound B1 include compounds containing a bisphenol A structure, such as a bisphenol A type epoxy (meth) acrylate, an alkylene oxide-modified bisphenol A (meth) acrylate, and a modified product thereof (for example, an amine-modified product).
  • a bisphenol A structure such as a bisphenol A type epoxy (meth) acrylate, an alkylene oxide-modified bisphenol A (meth) acrylate, and a modified product thereof (for example, an amine-modified product).
  • the amount of compound B1 with respect to 100 parts by weight of the polymer (A) contained in the pressure-sensitive adhesive layer is not particularly limited, and may be, for example, 0.5 parts by weight or more. From the viewpoint of facilitating the acquisition of a pressure-sensitive adhesive layer having both deformation resistance and impact resistance in a well-balanced manner, in some embodiments, the amount of compound B1 with respect to 100 parts by weight of the polymer (A) is, for example, 1 part by weight or more. It may be 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, or 15 parts by weight or more.
  • the amount of the compound B1 with respect to 100 parts by weight of the polymer (A) is usually preferably 80 parts by weight or less. It is preferably 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, and 35 parts by weight or less.
  • the pressure-sensitive adhesive layer may contain, as the photoreactive monomer (B), compound B2 having two or more functional groups and having no intramolecular ring structure.
  • Compound B2 is preferably used in combination with compound B1. Thereby, the crosslinked structure of the pressure-sensitive adhesive layer can be adjusted, and a bond having both deformation resistance and impact resistance can be formed more preferably.
  • Compound B2 can be used alone or in combination of two or more.
  • the number of functional groups of compound B2 may be, for example, 50 or less, 40 or less, 30 or less, 20 or less, or 15 or less.
  • the number of functional groups of compound B2 used in some embodiments may be, for example, 2-10, preferably 3-10, 3-8, or 4-6. ..
  • compound B2 having 3 or more functional groups preferably 4 or more, more preferably 5 or more, still more preferably 6 or more.
  • the functional group equivalent of compound B2 is not particularly limited, and may be, for example, 5000 g / mol or less, 2000 g / mol or less, or 1000 g / mol or less. In some embodiments, the functional group equivalent of compound B2 may be, for example, 600 g / mol or less, 400 g / mol or less, or 300 g / mol or less from the viewpoint of improving photocurability and hardness of the cured product. , 200 g / mol or less, 150 g / mol or less, 100 g / mol or less.
  • the functional group equivalent of compound B2 is typically 50 g / mol or more, preferably 60 g / mol or more, 70 g / mol or more, 80 g / mol or more, or 90 g / mol or more.
  • Examples of compounds that can be used as compound B2 include pentaerythritol trimethylolpropane (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa.
  • the amount of the compound B2 with respect to 100 parts by weight of the polymer (A) contained in the pressure-sensitive adhesive layer is not particularly limited and may be, for example, 0.1 part by weight or more.
  • the amount of compound B2 with respect to 100 parts by weight of the polymer (A) is, for example, 1 part by weight or more. It may be 2 parts by weight or more, 4 parts by weight or more, 6 parts by weight or more, 10 parts by weight or more, or 12 parts by weight or more.
  • the amount of compound B2 with respect to 100 parts by weight of the polymer (A) may be, for example, 25 parts by weight or less. It is suitable, preferably 17 parts by weight or less, 15 parts by weight or less, 13 parts by weight or less, and 9 parts by weight or less.
  • the compound B2 is a compound having 3 or more functional groups and having a functional group equivalent smaller than the functional group equivalent of the compound B1 used in combination thereof. It can be preferably adopted.
  • the ratio of the functional group equivalent FE 2 of compound B2 to the functional group equivalent FE 1 of compound B1 (FE 2 / FE 1 ) may be, for example, 0.9 or less, or 0.7 or less. , 0.5 or less, or 0.4 or less. According to this aspect, the effect of improving the tensile elastic modulus by the photoreactive monomer (B) can be efficiently exhibited.
  • the lower limit of the above ratio (FE 2 / FE 1 ) is not particularly limited, and may be, for example, 0.01 or more, 0.1 or more, or 0.2 or more.
  • the weight ratio (W 2 / W 1 ) of the usage amount W 2 of the compound B2 to the usage amount W 1 of the compound B1 is not particularly limited.
  • the weight ratio (W 2 / W 1 ) may be, for example, 0.05-10, 0.1-5, 0.2-3, 0.3-2. It may be.
  • the effect of using the compound B1 and the compound B2 in combination tends to be preferably exhibited.
  • the photoreactive monomer (B) can be included in the pressure-sensitive adhesive layer in free form.
  • a pressure-sensitive adhesive layer can be suitably formed by using a pressure-sensitive adhesive composition containing the photoreactive monomer (B) in a free form.
  • the "free form” means that the photoreactive monomer (B) is not chemically bonded to another component (for example, the polymer (A)) contained in the pressure-sensitive adhesive layer or the pressure-sensitive adhesive composition. ..
  • the pressure-sensitive adhesive composition containing the photoreactive monomer (B) in a free form can be advantageous from the viewpoint of ease of preparation and suppression of gelation.
  • the photoreactive monomer (B) is contained in the pressure-sensitive adhesive layer or the pressure-sensitive adhesive composition from the viewpoint of improving the processability of the pressure-sensitive adhesive sheet. It can be contained in the pressure-sensitive adhesive layer in the form of being chemically bonded to other components (for example, polymer (A), cross-linking agent described later, etc.).
  • the chemical bond is, for example, a functional group F1 other than the ethylenically unsaturated group that the photoreactive monomer (B) has in the molecule, and a functional group that the other component has in the molecule and is the functional group F1. It can be a bond formed by reaction with a reactive functional group F2.
  • the other component may be a cross-linking agent, and the photoreactive monomer (B) may be bonded to the polymer (A) via the cross-linking agent.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet disclosed herein includes improved cohesive force, a surface adjacent to the pressure-sensitive adhesive layer (for example, the surface of a support on the pressure-sensitive adhesive sheet, the surface of an adherend to which the pressure-sensitive adhesive sheet is attached, and the like. From the viewpoint of improving the adhesiveness with (), an acrylic oligomer can be contained.
  • the pressure-sensitive adhesive layer containing the acrylic oligomer can be preferably formed by using the pressure-sensitive adhesive composition containing the acrylic oligomer.
  • the acrylic oligomer those having a higher Tg than the Tg of the polymer (A) described above can be preferably adopted.
  • the Tg of the acrylic oligomer is not particularly limited, and may be, for example, about 20 ° C. or higher and 300 ° C. or lower.
  • the Tg may be, for example, about 30 ° C. or higher, about 40 ° C. or higher, about 60 ° C. or higher, about 80 ° C. or higher, or about 100 ° C. or higher.
  • the Tg of the acrylic oligomer may be, for example, about 250 ° C. or lower, about 200 ° C. or lower, about 180 ° C. or lower, or about 150 ° C. or lower. But it may be.
  • the Tg of the acrylic oligomer is a value calculated based on the Fox formula, like the Tg of the polymer (A).
  • the Mw of the acrylic oligomer is not particularly limited, and may be, for example, about 1000 or more, usually about 1500 or more, about 2000 or more, or about 3000 or more. Further, the Mw of the acrylic oligomer may be, for example, less than about 30,000, usually less than about 10,000, may be less than about 7,000, and may be less than about 5,000. When Mw is within the above range, the effect of improving the cohesiveness of the pressure-sensitive adhesive layer and the adhesiveness with the adjacent surface is likely to be suitably exhibited.
  • the Mw of the acrylic oligomer can be measured by gel permeation chromatography (GPC) and determined as a standard polystyrene-equivalent value.
  • Examples of the monomer components constituting the acrylic oligomer include the various (meth) acrylic acid C 1-20 alkyl esters described above; the various alicyclic hydrocarbon group-containing (meth) acrylates described above; and the various fragrances described above. Examples thereof include (meth) acrylate monomers containing a group hydrocarbon group; (meth) acrylate obtained from a terpene compound derivative alcohol; and the like. These can be used alone or in combination of two or more.
  • Acrylic oligomers include alkyl (meth) acrylates in which alkyl groups such as isobutyl (meth) acrylate and t-butyl (meth) acrylate have a branched structure; alicyclic hydrocarbon group-containing (meth) acrylate and aromatic hydrocarbons. It is preferable to contain an acrylic monomer having a relatively bulky structure as a monomer unit, such as a group-containing (meth) acrylate; from the viewpoint of improving adhesiveness. Further, when ultraviolet rays are used when synthesizing an acrylic oligomer or when producing an adhesive layer, a monomer having a saturated hydrocarbon group at the ester terminal is preferable because it is unlikely to cause polymerization inhibition, for example, alkyl. Alkyl (meth) acrylates having a branched group or saturated alicyclic hydrocarbon group-containing (meth) acrylates can be preferably used.
  • the ratio of the (meth) acrylate monomer to all the monomer components constituting the acrylic oligomer is typically more than 50% by weight, preferably 60% by weight or more, and more preferably 70% by weight or more (for example, 80% by weight). And more, 90% by weight or more).
  • the acrylic oligomer has a monomer composition consisting substantially of only one or more (meth) acrylate monomers.
  • the monomer component constituting the acrylic oligomer contains an alicyclic hydrocarbon group-containing (meth) acrylate and a (meth) acrylic acid C 1-20 alkyl ester, their weight ratios are not particularly limited.
  • the weight ratio of the alicyclic hydrocarbon group-containing (meth) acrylate / (meth) acrylic acid C 1-20 alkyl ester is, for example, 10/90 or higher, 20/80 or higher, or 30/70 or higher. It can also be 90/10 or less, 80/20 or less, or 70/30 or less.
  • a functional group-containing monomer As the constituent monomer component of the acrylic oligomer, in addition to the above (meth) acrylate monomer, a functional group-containing monomer can be used if necessary.
  • the functional group-containing monomer include a monomer having a nitrogen atom-containing heterocycle such as N-vinyl-2-pyrrolidone and N-acryloylmorpholin; an amino group-containing monomer such as N, N-dimethylaminoethyl (meth) acrylate; N, Examples thereof include an amide group-containing monomer such as N-diethyl (meth) acrylamide; a carboxy group-containing monomer such as acrylic acid (AA) and methacrylic acid (MAA); and a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate.
  • these functional group-containing monomers may be used alone or in combination of two or more.
  • the ratio of the functional group-containing monomer to all the monomer components constituting the acrylic oligomer can be, for example, 1% by weight or more, 2% by weight or more, or 3% by weight or more, and also. For example, it can be 15% by weight or less, 10% by weight or less, or 7% by weight or less.
  • the acrylic oligomer may be one in which a functional group-containing monomer is not used.
  • Suitable acrylic oligomers include, for example, dicyclopentanyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), dicyclopentanyl acrylate (DCPA), and the like.
  • DCPMA dicyclopentanyl methacrylate
  • CHMA cyclohexyl methacrylate
  • IBXMA isobornyl methacrylate
  • IBXA isobornyl acrylate
  • DCPA dicyclopentanyl acrylate
  • ADAM 1-adamantyl methacrylate
  • ADA 1-adamantyl methacrylate
  • ADA 1-adamantyl acrylate
  • MMA methyl methacrylate
  • a polymer of CHMA and isobutyl methacrylate IBMA
  • a polymer of CHMA and IBXMA a polymer of CHMA and acryloylmorpholin (ACMO)
  • a polymer of CHMA and diethylacrylamide DEA
  • Examples thereof include a copolymer of CHMA and AA.
  • Acrylic oligomers can be formed by polymerizing their constituent monomer components.
  • the polymerization method and the polymerization mode are not particularly limited, and various conventionally known polymerization methods (for example, solution polymerization, emulsion polymerization, bulk polymerization, photopolymerization, radiation polymerization, etc.) can be adopted in an appropriate manner.
  • the types of polymerization initiators for example, azo-based polymerization initiators
  • the types of polymerization initiators that can be used as needed are generally as illustrated for the synthesis of the acrylic polymer (A), and the amount of the polymerization initiator and the chain that is arbitrarily used. Since the amount of the transfer agent (for example, mercaptans) is appropriately set based on the common general knowledge so as to have a desired molecular weight, detailed description thereof will be omitted.
  • the content thereof can be, for example, 0.01 part by weight or more with respect to 100 parts by weight of the polymer (A), and a higher effect can be obtained. From the viewpoint of obtaining, it may be 0.05 parts by weight or more, 0.1 parts by weight or more, or 0.2 parts by weight or more. From the viewpoint of compatibility with the polymer (A), the content of the acrylic oligomer with respect to 100 parts by weight of the polymer (A) is usually preferably less than 50 parts by weight, preferably 30 parts by weight. Less than, more preferably 25 parts by weight or less, for example, 10 parts by weight or less, 5 parts by weight or less, or 1 part by weight or less. It may be a pressure-sensitive adhesive layer or a pressure-sensitive adhesive composition that does not contain an acrylic oligomer.
  • the pressure-sensitive adhesive layer or pressure-sensitive adhesive composition of the pressure-sensitive adhesive sheet disclosed herein includes, if necessary, a pressure-imparting resin (for example, a rosin-based, petroleum-based, terpene-based, phenol-based, ketone-based, or other tack-imparting resin).
  • a pressure-imparting resin for example, a rosin-based, petroleum-based, terpene-based, phenol-based, ketone-based, or other tack-imparting resin.
  • Various additions common in the field of adhesives such as viscosity modifiers (for example, thickeners), leveling agents, plasticizers, fillers, colorants such as pigments and dyes, stabilizers, preservatives, anti-aging agents, etc.
  • the agent may be included as any other optional ingredient.
  • the content of the tackifier resin in the pressure-sensitive adhesive layer or the pressure-sensitive adhesive composition is, for example, less than 10 parts by weight, or even 5 parts by weight, based on 100 parts by weight of the polymer (A). Can be less than.
  • the content of the tackifier resin may be less than 1 part by weight (for example, less than 0.5 parts by weight) or less than 0.1 parts by weight (0 parts by weight or more and less than 0.1 parts by weight). Good.
  • the pressure-sensitive adhesive layer or pressure-sensitive adhesive composition may not contain a tackifier resin.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet may have predetermined optical properties (for example, transparency). From the viewpoint of such optical properties, other than the polymer (A) occupying the pressure-sensitive adhesive layer (and thus the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer) and the above-mentioned photoreactive monomer (B) used as necessary.
  • the amount of the component of is preferably limited. In the techniques disclosed herein, the amount of components other than the polymer (A) and the photoreactive monomer (B) in the pressure-sensitive adhesive layer is usually about 30% by weight or less, and about 15% by weight or less.
  • the amount of the components other than the polymer (A) and the photoreactive monomer (B) in the pressure-sensitive adhesive layer may be about 5% by weight or less, and may be about 3% by weight or less. It may be about 1.5% by weight or less (for example, about 1% by weight or less).
  • a cross-linking agent may be used for the pressure-sensitive adhesive layer, if necessary.
  • the cross-linking agent is typically included in the pressure-sensitive adhesive layer in the form after the cross-linking reaction. By using a cross-linking agent, the cohesive force of the pressure-sensitive adhesive layer and the like can be appropriately adjusted.
  • a pressure-sensitive adhesive sheet containing a photoreactive monomer (B) in the pressure-sensitive adhesive layer by using a cross-linking agent and a photoreactive monomer (B) in combination, the pressure-sensitive adhesive before photocuring of the photoreactive monomer.
  • the flexibility of the layer and the deformation resistance of the pressure-sensitive adhesive layer after photocuring can be suitably compatible with each other.
  • the type of the cross-linking agent is not particularly limited, and is selected from the conventionally known cross-linking agents so that the cross-linking agent exhibits an appropriate cross-linking function in the pressure-sensitive adhesive layer, for example, depending on the composition of the pressure-sensitive adhesive composition. be able to.
  • the cross-linking agent that can be used include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, carbodiimide-based cross-linking agents, melamine-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, and metals.
  • Examples thereof include a chelate-based cross-linking agent, a metal salt-based cross-linking agent, a hydrazine-based cross-linking agent, and an amine-based cross-linking agent. These can be used alone or in combination of two or more.
  • a polyfunctional isocyanate compound having two or more functions can be used.
  • aromatic isocyanates such as tolylene diisocyanate, xylene diisocyanate, polymethylene polyphenyl diisocyanate, tris (p-isocyanatophenyl) thiophosphate, diphenylmethane diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; aliphatic isocyanates such as hexamethylene diisocyanate. Isocyanate; etc.
  • Coronate HL isocyanurate of hexamethylene diisocyanate (manufactured by Toso Co., Ltd., trade name” Coronate HX "), trimethylolpropane / xylylene diisocyanate adduct (manufactured by Mitsui Chemicals Co., Ltd., trade name” Takenate D-110N “), etc. Isocyanate adducts and the like can be exemplified.
  • epoxy-based cross-linking agent one having two or more epoxy groups in one molecule can be used without particular limitation.
  • An epoxy-based cross-linking agent having 3 to 5 epoxy groups in one molecule is preferable.
  • Specific examples of the epoxy-based cross-linking agent include N, N, N', N'-tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, and 1,6-hexane. Examples thereof include diol diglycidyl ether, polyethylene glycol diglycidyl ether, and polyglycerol polyglycidyl ether.
  • epoxy cross-linking agents include Mitsubishi Gas Chemical's product names “TETRAD-X” and “TETRAD-C”, DIC's product name “Epicron CR-5L”, and Nagase ChemteX's products. Examples thereof include the name “Denacol EX-512” and the product name "TEPIC-G” manufactured by Nissan Chemical Industries, Ltd.
  • oxazoline-based cross-linking agent those having one or more oxazoline groups in one molecule can be used without particular limitation.
  • aziridine-based cross-linking agents include trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1- (2-methyl) aziridinyl propionate)], and the like. Be done.
  • carbodiimide-based cross-linking agent a low molecular weight compound or a high molecular weight compound having two or more carbodiimide groups can be used.
  • Peroxide may be used as the cross-linking agent in some embodiments.
  • Peroxides include di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, and t-butylperoxyneodecanoate.
  • examples of peroxides having particularly excellent cross-linking reaction efficiency include di (4-t-butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide, and dibenzoyl peroxide.
  • a peroxide is used as the polymerization initiator, the peroxide remaining without being used in the polymerization reaction can be used in the crosslinking reaction.
  • the residual amount of peroxide may be quantified, and if the ratio of peroxide is less than a predetermined amount, the peroxide may be added so as to be a predetermined amount, if necessary.
  • the amount of peroxide can be quantified by the method described in Japanese Patent No. 4971517.
  • the amount used when a cross-linking agent is used is not particularly limited. From the viewpoint of realizing a pressure-sensitive adhesive that exhibits a well-balanced adhesive property such as adhesive strength and cohesive power, the amount of the cross-linking agent used should be about 5 parts by weight or less with respect to 100 parts by weight of the polymer (A). It may be 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less, or less than 1 part by weight.
  • the amount of the cross-linking agent used with respect to 100 parts by weight of the polymer (A) is, for example, from the viewpoint of facilitating the effect of the combined use. It may be 0.80 parts by weight or less, 0.60 parts by weight or less, 0.30 parts by weight or less, or 0.10 parts by weight or less.
  • the lower limit of the amount of the cross-linking agent used is not particularly limited, and it can be used in an amount larger than 0 parts by weight with respect to 100 parts by weight of the polymer (A).
  • the amount of the cross-linking agent used may be, for example, 0.001 part by weight or more, 0.01 parts by weight or more, and 0.03 parts by weight, based on 100 parts by weight of the polymer (A). It may be more than a part by weight.
  • the technique disclosed herein can be preferably carried out in a mode in which at least an isocyanate-based cross-linking agent is used as the cross-linking agent.
  • An isocyanate-based cross-linking agent and another cross-linking agent may be used in combination.
  • the amount of the isocyanate-based cross-linking agent used with respect to 100 parts by weight of the polymer (A) may be, for example, 0.005 parts by weight or more, 0.01 parts by weight or more, and 0.03. It may be more than a part by weight.
  • the amount of the isocyanate-based cross-linking agent used with respect to 100 parts by weight of the polymer (A) may be, for example, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or less than 2 parts by weight. It may be less than 1 part by weight, less than 0.80 parts by weight, less than 0.60 parts by weight, less than 0.30 parts by weight, less than 0.10 parts by weight, less than 0.08 parts by weight. Good.
  • a cross-linking catalyst may be used to allow the cross-linking reaction to proceed more effectively.
  • the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, butyl tin oxide, and dioctyl tin dilaurate. Of these, tin-based cross-linking catalysts such as dioctyl tin dilaurate are preferable.
  • the amount of the cross-linking catalyst used is not particularly limited.
  • the amount of the cross-linking catalyst used can be, for example, about 0.0001 parts by weight or more, about 0.001 parts by weight or more, about 0.005 parts by weight or more, etc. with respect to 100 parts by weight of the polymer (A). It can be about 1 part by weight or less, about 0.1 part by weight or less, about 0.05 part by weight or less, and the like.
  • the pressure-sensitive adhesive composition used to form the pressure-sensitive adhesive layer can optionally contain a compound that causes keto-enol tautomerism as a cross-linking retarder.
  • a compound that causes keto-enol tautomerism can be preferably used in a pressure-sensitive adhesive composition containing an isocyanate-based cross-linking agent or a pressure-sensitive adhesive composition that can be used by blending an isocyanate-based cross-linking agent.
  • a compound that causes keto-enol tautomerism can be preferably used.
  • Various ⁇ -dicarbonyl compounds can be used as the compound that causes keto-enol tvariability.
  • ⁇ -diketones such as acetylacetone and 2,4-hexanedione
  • acetoacetate esters such as methyl acetoacetate and ethyl acetoacetate
  • propionyl acetates such as ethyl propionyl acetate
  • isobutylyl such as ethyl isobutylyl acetate.
  • Acetic acid esters; malonic acid esters such as methyl malonate and ethyl malonate; and the like.
  • acetylacetone and acetoacetic ester are preferable compounds.
  • the compounds that cause keto-enol tautomerism can be used alone or in combination of two or more.
  • the amount of the compound that causes keto-enol tvariability may be, for example, 0.1 part by weight or more and 20 parts by weight or less, and usually 0.5 parts by weight or more and 15 parts by weight, based on 100 parts by weight of the polymer (A). It is appropriate that the weight is 1 part by weight or less, for example, 1 part by weight or more and 10 parts by weight or less, and 1 part by weight or more and 5 parts by weight or less.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet disclosed herein may contain a silane coupling agent, if desired.
  • a silane coupling agent By using a silane coupling agent, the peel strength of the pressure-sensitive adhesive sheet from an adherend (for example, a glass plate) can be improved.
  • the pressure-sensitive adhesive layer containing the silane coupling agent can be suitably formed by using the pressure-sensitive adhesive composition containing the silane coupling agent.
  • the silane coupling agent is preferably contained in the pressure-sensitive adhesive composition in a free form from the viewpoint of suppressing gelation and the like.
  • the silane coupling agent is preferably contained in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet disclosed herein in a free form.
  • the silane coupling agent contained in the pressure-sensitive adhesive layer in such a form can effectively contribute to the improvement of the peeling force.
  • free form as used herein means that the silane coupling agent is not chemically bonded to the pressure-sensitive adhesive composition or other components contained in the pressure-sensitive adhesive layer.
  • silane coupling agent examples include silicon compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane; 3-chloro Propyltrimethoxysilane; acetoacetyl group-containing trimethoxysilane; (meth) acrylic group-containing silane coupling agent such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane; 3-isocyanatepropyltriethoxysilane Such as is
  • the above effects can be more preferably exerted by adopting a silane coupling agent having a trialkoxysilyl group.
  • a silane coupling agent having a trialkoxysilyl group 3-glycidoxypropyltrimethoxysilane and acetoacetyl group-containing trimethoxysilane are exemplified as preferable silane coupling agents.
  • the amount of the silane coupling agent used can be set so as to obtain the desired effect, and is not particularly limited.
  • the amount of the silane coupling agent used may be, for example, 0.001 part by weight or more with respect to 100 parts by weight of the polymer (A), and 0.01 part by weight from the viewpoint of obtaining a higher effect. It may be more than 0.05 parts by weight, or 0.1 parts by weight or more.
  • the amount of the silane coupling agent used with respect to 100 parts by weight of the polymer (A) is 3 parts by weight or less, and 1 part by weight or less. It may be 0.5 parts by weight or less.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet disclosed herein may contain a photopolymerization initiator, if necessary, for the purpose of improving or imparting photocurability.
  • a photopolymerization initiator include a ketal-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, and a benzoin ether-based photopolymerization initiator, as in the case of the photopolymerization initiator exemplified as being usable for the synthesis of the polymer (A).
  • Acylphosphine oxide-based photopolymerization initiator ⁇ -ketol-based photopolymerization initiator, aromatic sulfonyl chloride-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzyl-based photopolymerization initiator , Benzophenone-based photopolymerization initiator, thioxanthone-based photopolymerization initiator and the like can be used.
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • ketal-based photopolymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one and the like.
  • acetophenone-based photopolymerization initiator examples include 1-hydroxycyclohexyl-phenyl-ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- (2-hydroxyethoxy) -phenyl].
  • -2-Hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, methoxyacetophenone and the like are included.
  • benzoin ether-based photopolymerization initiator examples include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether and benzoin isobutyl ether, and substituted benzoin ethers such as anisole methyl ether.
  • acylphosphine oxide-based photopolymerization initiator examples include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -2,4-di-n-butoxy.
  • phenylphosphine oxide 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like.
  • Specific examples of the ⁇ -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one, and the like. Is done.
  • aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalene sulfonyl chloride and the like.
  • the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like.
  • Specific examples of the benzoin-based photopolymerization initiator include benzoin and the like.
  • Specific examples of the benzyl-based photopolymerization initiator include benzyl and the like.
  • Specific examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone and the like.
  • thioxanthone-based photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and isopropylthioxanthone. , 2,4-Diisopropylthioxanthone, dodecylthioxanthone and the like.
  • the content of the photopolymerization initiator in the pressure-sensitive adhesive layer is not particularly limited, and can be set so that the desired effect is appropriately exhibited.
  • the content of the photopolymerization initiator can be, for example, approximately 0.005 parts by weight or more with respect to 100 parts by weight of the polymer (A) contained in the pressure-sensitive adhesive layer, and is usually 0. It is appropriate to have 0.01 parts by weight or more, preferably 0.05 parts by weight or more, 0.10 parts by weight or more, 0.15 parts by weight or more, and 0.20 parts by weight. The above may be applied. As the content of the photopolymerization initiator increases, the photocurability of the pressure-sensitive adhesive layer tends to improve.
  • the content of the photopolymerization initiator with respect to 100 parts by weight of the polymer (A) is usually preferably 10 parts by weight or less, preferably 7 parts by weight or less, and may be 5 parts by weight or less. It may be 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less. Not too much content of the photopolymerization initiator can be advantageous from the viewpoint of improving the storage stability (for example, stability against photodegradation) of the pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive layer containing the photopolymerization initiator can be typically formed by using a pressure-sensitive adhesive composition containing the photopolymerization initiator (for example, a solvent-type pressure-sensitive adhesive composition).
  • a pressure-sensitive adhesive composition containing the photopolymerization initiator for example, a solvent-type pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition containing the photopolymerization initiator can be prepared, for example, by mixing other components used in the composition with the photopolymerization initiator.
  • a pressure-sensitive adhesive composition is prepared using a polymer (A) synthesized (photopolymerized) in the presence of a photopolymerization initiator (for example, an acrylic polymer (A)), the polymer (A)
  • a photopolymerization initiator for example, an acrylic polymer (A)
  • the polymer (A) The residue (unreacted product) of the photopolymerization initiator used in synthesizing the above may be used as a part or all of the photopolymerization initiator contained in the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer disclosed herein is preferably formed by using a pressure-sensitive adhesive composition prepared by newly adding the above-mentioned amount of the photopolymerization initiator to other components. Can be done.
  • the pressure-sensitive adhesive layer in the technique disclosed herein is a leveling agent, a plasticizer, a softening agent, a colorant (dye, pigment, etc.), a filler, and an antioxidant, as long as the effects of the present invention are not significantly impaired.
  • Antioxidants, UV absorbers, Antioxidants, Light Stabilizers, Preservatives, and other known additives that can be used in adhesives may be included, if necessary. It is desirable to avoid the use of silicone-based additives (for example, silicone-based leveling agents and defoaming agents) in pressure-sensitive adhesive sheets for applications that dislike the inclusion of siloxane (for example, applications for manufacturing electronic devices).
  • the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet disclosed herein can be a cured layer of a pressure-sensitive adhesive composition containing the corresponding component. That is, the pressure-sensitive adhesive layer is subjected to drying (for example, heat-drying), cross-linking (for example, cross-linking by the reaction of the above-mentioned cross-linking agent), cooling, etc. after applying (for example, coating) the pressure-sensitive adhesive composition to an appropriate surface. It can be formed by appropriately performing a curing treatment. When performing two or more types of curing treatments, these can be performed simultaneously or in stages.
  • the pressure-sensitive adhesive composition contains at least one of the polymers (A) described above.
  • the pressure-sensitive adhesive composition according to a preferred embodiment contains an acrylic polymer (A) as the polymer (A).
  • the pressure-sensitive adhesive composition may contain the polymer (A) in the form of a precursor thereof.
  • the pressure-sensitive adhesive composition preferably contains any of the above-mentioned polymers (A) and any of the above-mentioned photoreactive monomers (B).
  • the photoreactive monomer (B) preferably contains a compound B1 having a ring structure and two or more ethylenically unsaturated groups in the molecule.
  • the compound B1 preferably has a molecular weight of 100 g / mol or more per ethylenically unsaturated group.
  • the form of the pressure-sensitive adhesive composition is not particularly limited.
  • a water-dispersed pressure-sensitive adhesive composition in which a pressure-sensitive adhesive (adhesive component) is dispersed in water, or a solvent-type pressure-sensitive adhesive in which the pressure-sensitive adhesive is contained in an organic solvent.
  • the composition may be in various conventionally known forms such as a hot melt type pressure-sensitive adhesive composition which is coated in a heat-melted state and forms a pressure-sensitive adhesive when cooled to around room temperature. From the viewpoint of ease of preparation of the pressure-sensitive adhesive composition, ease of formation of the pressure-sensitive adhesive layer, and the like, the solvent-type pressure-sensitive adhesive composition can be preferably adopted in some embodiments.
  • the solvent-based pressure-sensitive adhesive composition can be preferably prepared using the polymer (A), which is a polymer obtained by solution polymerization of the monomer components.
  • the pressure-sensitive adhesive composition can be applied using, for example, a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater.
  • a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater.
  • a direct method of directly applying the pressure-sensitive adhesive composition to the support to form the pressure-sensitive adhesive layer may be used, and peeling may be used.
  • a transfer method may be used in which the pressure-sensitive adhesive layer formed on the surface is transferred to the support.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be, for example, about 3 ⁇ m to 500 ⁇ m. From the viewpoint of impact resistance, in some embodiments, the thickness of the pressure-sensitive adhesive layer is preferably 5 ⁇ m or more, preferably 10 ⁇ m or more, and more preferably 15 ⁇ m or more. Further, in some embodiments, the thickness of the pressure-sensitive adhesive layer may be, for example, 200 ⁇ m or less, preferably 120 ⁇ m or less from the viewpoint of suppressing deformation of the pressure-sensitive adhesive layer, and may be 100 ⁇ m or less, or 70 ⁇ m or less. , 50 ⁇ m or less, or 35 ⁇ m or less. According to the pressure-sensitive adhesive sheet disclosed herein, a bond having high deformation resistance and high impact resistance can be formed in an embodiment including a pressure-sensitive adhesive layer having a thickness of, for example, 70 ⁇ m or less.
  • the pressure-sensitive adhesive sheet may be in the form of a pressure-sensitive adhesive sheet with a support including a support bonded to the pressure-sensitive adhesive layer.
  • the material of the support is not particularly limited, and can be appropriately selected depending on the purpose and mode of use of the adhesive sheet.
  • Non-limiting examples of supports that can be used include a polyolefin film containing a polyolefin such as polypropylene or an ethylene-propylene copolymer as a main component, a polyester film containing a polyester such as polyethylene terephthalate or polybutylene terephthalate as a main component, and the like.
  • Resin film such as polyvinyl chloride film containing polyvinyl chloride as the main component; foam sheet made of foam such as polyurethane foam, polyethylene foam, polychloroprene foam; various fibrous substances (natural fibers such as hemp and cotton, Woven fabrics and non-woven fabrics made of synthetic fibers such as polyester and vinylon, semi-synthetic fibers such as acetate, etc.) alone or by blending; papers such as Japanese paper, high-quality paper, kraft paper, crepe paper; aluminum foil, copper Metal foils such as foils; and the like.
  • the support may be a composite structure of these.
  • Examples of a support having such a composite structure include a metal layer (for example, a metal foil, a continuous or discontinuous metal sputter layer, a metal vapor deposition layer, a metal plating layer, etc.), a metal oxide layer, and the above resin film.
  • Examples thereof include a support having a structure in which and is laminated, and a resin sheet reinforced with an inorganic fiber such as a glass cloth.
  • the support may correspond to an optical member (for example, an optical film) described later, or may be a transparent member formed of a transparent material (for example, a transparent resin material or glass). Good.
  • the support film may be a porous film such as a foam film or a non-woven fabric sheet, or may be a non-porous film, and the porous layer and the non-porous layer are laminated. It may be a film having a structure.
  • a film containing an independently shape-maintainable (self-supporting or independent) resin film as a base film can be preferably used as the support film.
  • the term "resin film” means a resin film (of voidless) having a non-porous structure and typically containing substantially no bubbles. Therefore, the resin film is a concept that is distinguished from foam films and non-woven fabrics.
  • the resin film may have a single-layer structure or a multi-layer structure having two or more layers (for example, a three-layer structure).
  • Examples of the resin material constituting the resin film include polycycloolefin derived from a monomer having an aliphatic ring structure such as polyester, polyolefin, and norbornene structure, nylon 6, nylon 66, and polyamide (PA) such as partially aromatic polyamide.
  • polycycloolefin derived from a monomer having an aliphatic ring structure such as polyester, polyolefin, and norbornene structure
  • nylon 6, nylon 66 such as polyamide (PA) such as partially aromatic polyamide.
  • PA polyamide
  • PI Polyamide
  • PAI Polyamideimide
  • PEEK Polyetheretherketone
  • PES Polyethersulfone
  • PPS Polyphenylene sulfide
  • PC Polycarbonate
  • PU Polyurethane
  • EVA Ethylene-vinyl acetate copolymer
  • polystyrene polyvinyl chloride, polyvinylidene chloride, fluororesin such as polytetrafluoroethylene (PTFE), acrylic resin such as polymethylmethacrylate, cellulose-based polymer such as diacetylcellulose and triacetylcellulose, vinyl butyral polymer.
  • Arilate-based polymer, polyoxymethylene-based polymer, epoxy-based polymer and other resins can be used.
  • the resin film may be formed by using a resin material containing one kind of such a resin alone, or may be formed by using a resin material in which two or more kinds are blended. May be good.
  • the resin film may be unstretched or stretched (for example, uniaxially stretched or biaxially stretched).
  • the resin material constituting the resin film include polyester resin, PPS resin and polyolefin resin.
  • the polyester-based resin refers to a resin containing polyester in a proportion of more than 50% by weight.
  • the PPS resin refers to a resin containing PPS in a proportion of more than 50% by weight
  • the polyolefin-based resin refers to a resin containing polyolefin in a proportion of more than 50% by weight.
  • polyester resin a polyester resin containing polyester obtained by polycondensing a dicarboxylic acid and a diol as a main component is typically used.
  • the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate and the like.
  • polyolefin resin one kind of polyolefin can be used alone, or two or more kinds of polyolefins can be used in combination.
  • the polyolefin can be, for example, a homopolymer of ⁇ -olefin, a copolymer of two or more kinds of ⁇ -olefins, a copolymer of one kind or two or more kinds of ⁇ -olefins and another vinyl monomer, and the like.
  • Specific examples include ethylene-propylene copolymers such as polyethylene (PE), polypropylene (PP), poly-1-butene, poly-4-methyl-1-pentene, and ethylene propylene rubber (EPR), and ethylene-propylene-.
  • Examples thereof include butene copolymers, ethylene-butene copolymers, ethylene-vinyl alcohol copolymers and ethylene-ethyl acrylate copolymers. Both low density (LD) polyolefins and high density (HD) polyolefins can be used.
  • polyolefin resin films include unstretched polypropylene (CPP) film, biaxially stretched polypropylene (OPP) film, low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, medium density polyethylene (MDPE).
  • Examples thereof include a film, a high-density polyethylene (HDPE) film, a polyethylene (PE) film in which two or more types of polyethylene (PE) are blended, and a PP / PE blend film in which polypropylene (PP) and polyethylene (PE) are blended.
  • HDPE high-density polyethylene
  • PE polyethylene
  • the resin film that can be preferably used as the support include PET film, PEN film, PPS film, PEEK film, CPP film and OPP film.
  • Preferred examples from the viewpoint of strength include PET film, PEN film, PPS film and PEEK film.
  • a PET film is mentioned as a preferable example from the viewpoint of availability, dimensional stability, optical characteristics and the like.
  • additives such as light stabilizers, antioxidants, antistatic agents, colorants (dye, pigment, etc.), fillers, slip agents, antiblocking agents, etc. shall be added to the resin film, if necessary. Can be done.
  • the blending amount of the additive is not particularly limited, and can be appropriately set according to the use of the pressure-sensitive adhesive sheet and the like.
  • the manufacturing method of the resin film is not particularly limited.
  • conventionally known general resin film molding methods such as extrusion molding, inflation molding, T-die casting molding, and calender roll molding can be appropriately adopted.
  • the support can be a support film substantially composed of such a resin film. Further, the support may be a support film including an auxiliary layer in addition to the resin film.
  • the auxiliary layer may be arranged on the pressure-sensitive adhesive layer side of the resin film, may be arranged on the side opposite to the pressure-sensitive adhesive layer, or may be arranged on both sides of the resin film.
  • the auxiliary layers include an optical property adjusting layer (eg, a tinted layer, an antireflection layer), a decorative layer that imparts the desired appearance to the support or adhesive sheet (eg, a printed layer, a laminated layer, continuous or non-continuous). (Continuous metal layer, continuous or discontinuous metal oxide layer, etc.), conductive layer, antistatic layer, undercoat layer, release layer, and the like.
  • the thickness of the support is not particularly limited and can be selected according to the purpose and mode of use of the adhesive sheet.
  • the thickness of the support may be, for example, 1000 ⁇ m or less, 500 ⁇ m or less, 100 ⁇ m or less, 70 ⁇ m or less, 50 ⁇ m or less, 25 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less.
  • the thickness of the support may be, for example, 2 ⁇ m or more, and may be 5 ⁇ m or more or 10 ⁇ m or more. In some embodiments, the thickness of the support may be, for example, 20 ⁇ m or greater, 35 ⁇ m or greater, or 55 ⁇ m or greater.
  • a surface treatment may be a treatment for improving the adhesion between the support and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer on the support.
  • the composition of the primer is not particularly limited and can be appropriately selected from known ones.
  • the thickness of the undercoat layer is not particularly limited, but is usually about 0.01 ⁇ m to 1 ⁇ m, preferably about 0.1 ⁇ m to 1 ⁇ m.
  • the side surface of the support opposite to the side bonded to the pressure-sensitive adhesive layer (hereinafter, also referred to as the back surface) is peeled, adhesively or adhesively applied as necessary.
  • Conventionally known surface treatments such as improvement treatment and antistatic treatment may be applied. For example, by surface-treating the back surface of the support with a release treatment agent, the rewinding force of the adhesive sheet in the form of being wound in a roll shape can be reduced.
  • a silicone-based stripping agent a long-chain alkyl-based stripping agent, an olefin-based stripping agent, a fluorine-based stripping agent, a fatty acid amide-based stripping agent, molybdenum sulfide, silica powder, or the like can be used. ..
  • the pressure-sensitive adhesive sheet disclosed herein can be preferably used in an embodiment in which the pressure-sensitive adhesive layer is photo-cured after being bonded to the adherend and then adhered to the adherend. By adhering the adhesive sheet to the adherend, an adherend on which the adhesive sheets are laminated is formed. By photocuring the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, a laminate containing the pressure-sensitive adhesive sheet with the cured pressure-sensitive adhesive layer and the adherend can be obtained. Therefore, according to this specification, one of the pressure-sensitive adhesive sheets disclosed herein is attached to an adherend, and the pressure-sensitive adhesive sheet is irradiated with ultraviolet rays to photo-cure the pressure-sensitive adhesive layer. A method for producing a laminate including the above is provided.
  • the pressure-sensitive adhesive sheet disclosed herein can be used for fixing, joining, molding, decorating, protecting, supporting and the like of members constituting various products.
  • the material constituting at least the surface of the member is, for example, glass such as alkaline glass or non-alkali glass; metal material such as stainless steel (SUS) and aluminum; resin material such as acrylic resin, ABS resin, polycarbonate resin and polystyrene resin. It can be; etc.
  • the member may be, for example, a member constituting various portable devices (portable devices), automobiles, home appliances, and the like.
  • the surface to which the adhesive sheet is attached is acrylic, polyester, alkyd, melamine, urethane, acid-epoxy crosslinked, or a composite of these (for example, acrylic melamine, alkyd melamine). ) And the like, or a plated surface such as a zinc-plated steel plate.
  • the member is any support film exemplified as a material that can be used for the support (for example, a resin film or a continuous or discontinuous inorganic layer (metal layer, metal oxide layer, etc.) on the resin film. It may be a support film) having.
  • the pressure-sensitive adhesive sheet disclosed herein can be, for example, a component of a member with a pressure-sensitive adhesive sheet in which the member is bonded to at least one surface of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive layer.
  • An example of a preferable application is an optical application. More specifically, it is disclosed here as, for example, an optical adhesive sheet used for bonding optical members (for bonding optical members), manufacturing products using the above optical members (optical products), and the like.
  • the adhesive sheet to be used can be preferably used.
  • the optical member is a member having optical characteristics (for example, polarization, light refraction, light scattering, light reflectivity, light transmission, light absorption, light diffractivity, light turning property, visibility, etc.).
  • the optical member is not particularly limited as long as it has optical characteristics, but is used, for example, as a member constituting a device (optical device) such as a display device (image display device) or an input device, or a member thereof.
  • Members include, for example, polarizing plates, wavelength plates, retardation plates, optical compensation films, brightness improving films, light guide plates, reflective films, antireflection films, hard coat (HC) films, shock absorbing films, antifouling films, etc.
  • Photochromic film light control film, transparent conductive film (ITO film), design film, decorative film, surface protection plate, prism, lens, color filter, transparent substrate, and members in which these are laminated (collectively referred to as these). (Sometimes referred to as “functional film”) and the like.
  • the above-mentioned “plate” and “film” shall include a plate-like, a film-like, a sheet-like form, respectively, and for example, the "polarizing film” shall include a “polarizing plate”, a “polarizing sheet” 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. Further, examples of the input device include a touch panel and the like.
  • the optical member is not particularly limited, and examples thereof include members made of glass, acrylic resin, polycarbonate, polyethylene terephthalate, a metal thin film, and the like (for example, sheet-shaped, film-shaped, and plate-shaped members).
  • the "optical member” in this specification also includes a member (design film, decorative film, surface protective film, etc.) that plays a role of decoration and protection while maintaining the visibility of the display device and the input device.
  • the mode in which the optical members are bonded using the pressure-sensitive adhesive sheet disclosed herein is not particularly limited, and examples thereof include (1) a mode in which the optical members are bonded to each other via the pressure-sensitive adhesive sheet disclosed here, and (2).
  • the optical member may be attached to a member other than the optical member via the pressure-sensitive adhesive sheet disclosed herein, or (3) the pressure-sensitive adhesive sheet disclosed here includes the optical member.
  • the adhesive sheet may be attached to an optical member or a member other than the optical member.
  • the pressure-sensitive adhesive sheet including the optical member may be, for example, a pressure-sensitive adhesive sheet in which the support is an optical member (for example, an optical film).
  • the pressure-sensitive adhesive sheet including the optical member as the support can be grasped as the pressure-sensitive optical member (for example, the pressure-sensitive optical film).
  • the pressure-sensitive adhesive sheet disclosed here is a type of pressure-sensitive adhesive sheet having a support and the above-mentioned functional film is used as the above-mentioned support
  • the pressure-sensitive adhesive sheet disclosed here is a functional film. It can also be grasped as a "adhesive type functional film" having an adhesive layer disclosed here on at least one side.
  • the matters disclosed in this specification include the following.
  • the pressure-sensitive adhesive layer contains the polymer (A) and the photoreactive monomer (B).
  • the photoreactive monomer (B) contains compound B1 having two or more ethylenically unsaturated groups.
  • the compound B1 is an adhesive sheet having a molecular weight (functional group equivalent) of 100 g / mol or more per ethylenically unsaturated group.
  • the pressure-sensitive adhesive layer contains the compound B1 as the photoreactive monomer (B) and the compound B2 having two or more functional groups and having no intramolecular ring structure (2).
  • the photoreactive monomer (B) contains compound B1 having two or more ethylenically unsaturated groups.
  • the compound B1 is a pressure-sensitive adhesive composition having a molecular weight (functional group equivalent) of 100 g / mol or more per ethylenically unsaturated group.
  • (22) The pressure-sensitive adhesive sheet according to (21) above, wherein the compound B1 contains a ring structure in the molecule.
  • the pressure-sensitive adhesive layer contains the compound B1 as the photoreactive monomer (B) and the compound B2 having two or more functional groups and having no intramolecular ring structure (22).
  • the pressure-sensitive adhesive composition according to any one of (25).
  • (28) The pressure-sensitive adhesive composition according to (27), wherein the functional group equivalent of the compound B2 is smaller than the functional group equivalent of the compound B1.
  • (29) The pressure-sensitive adhesive composition according to (27) or (28) above, wherein the functional group equivalent of the compound B2 is 400 g / mol or less.
  • (30) The pressure-sensitive adhesive according to any one of (27) to (29) above, wherein the content of the compound B2 in the pressure-sensitive adhesive layer is 25 parts by weight or less with respect to 100 parts by weight of the polymer (A).
  • the content of the photoreactive monomer (B) in the pressure-sensitive adhesive layer is 1 part by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the polymer (A). ).
  • the pressure-sensitive adhesive composition according to any one of. (32) The pressure-sensitive adhesive composition according to any one of (21) to (31) above, wherein the polymer (A) is an acrylic polymer. (33) The pressure-sensitive adhesive composition according to (32) above, wherein the monomer component constituting the acrylic polymer contains a monomer having a nitrogen atom-containing ring. (34) The pressure-sensitive adhesive composition according to any one of (21) to (33) above, wherein the glass transition temperature of the polymer (A) is ⁇ 45 ° C.
  • An adhesive sheet containing an adhesive layer An adhesive sheet having a tensile elastic modulus of 3.0 MPa or more measured by the tensile test and an impact resistance of 2.0 J / (10 mm) 2 or more measured by the shear impact test.
  • Adhesive sheet An adhesive sheet having a tensile elastic modulus of 3.0 MPa or more measured by the tensile test and an impact resistance of 2.0 J / (10 mm) 2 or more measured by the shear
  • the pressure-sensitive adhesive composition is formed from the pressure-sensitive adhesive composition and has a thickness selected from the range of 5 ⁇ m to 200 ⁇ m (preferably in the range of 15 ⁇ m to 25 ⁇ m) (for example, a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m).
  • the pressure-sensitive adhesive composition according to any one of (21) to (37) above, wherein the tensile elastic modulus measured by the tensile test for the pressure-sensitive adhesive layer) is 3.0 MPa or more.
  • the pressure-sensitive adhesive composition has an impact resistance of 2.0 J / (10 mm) 2 or more measured by the shear impact test for a pressure-sensitive adhesive layer having the thickness formed from the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition has a peel strength of 1.0 N / 10 mm or more measured by the peel-off test for a pressure-sensitive adhesive layer having the thickness formed from the pressure-sensitive adhesive composition (44). Alternatively, the pressure-sensitive adhesive composition according to (45).
  • a film member with an adhesive sheet which comprises the adhesive sheet according to any one of (1) to (20) and (40) to (43), and a film member bonded to the adhesive layer.
  • (48) Attaching the adhesive sheet according to any one of (1) to (20) and (40) to (43) above to the adherend, and By irradiating the adhesive sheet with ultraviolet rays to photo-curing the adhesive layer, A method for producing a laminate, which comprises in this order.
  • Polymer P2 In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 64.5 parts of BA, 6 parts of CHA, 9.6 parts of NVP, 5 parts of iSTA and 14.9 parts of 4HBA as monomer components, and ⁇ -thio as a chain transfer agent.
  • a solution of the polymer P2 was obtained by charging 0.07 part of glycerol and 122 parts of ethyl acetate as a polymerization solvent and adding 0.2 part of AIBN as a thermal polymerization initiator and performing solution polymerization in a nitrogen atmosphere.
  • the Mw of the polymer P2 was 600,000.
  • the Tg of the polymer P2 calculated from the composition of the monomer component is ⁇ 39 ° C.
  • an isocyanate-based cross-linking agent X1 (trimethylolpropane / xylylene diisocyanate adduct (manufactured by Mitsui Chemicals, Inc., trade name: Takenate D)) -110N, solid content concentration 75%)) is 0.05 parts based on solid content, dioctyltin dilaurate (manufactured by Tokyo Fine Chemicals, trade name: Envirizer OL-1) 0.01 parts as a cross-linking accelerator, cross-linking retarder 4 parts of acetylacetone, 0.3 part of 3-glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shinetsu Chemical Industry Co., Ltd.) as a silane coupling agent, and dipentaerythritol hexaacryl
  • Examples 2-3, 5-12 The types and amounts of the photoreactive monomers, the amount of the cross-linking agent, and the amount of the photopolymerization initiator are as shown in Tables 1 and 2, and the same as in the preparation of the solvent-based pressure-sensitive adhesive composition according to Example 1, respectively.
  • a solvent-based pressure-sensitive adhesive composition according to an example was prepared.
  • Example 4 The solvent-based adhesive according to Example 3 except that the isocyanate-based cross-linking agent X2 (trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Tosoh Corporation, trade name: Coronate L)) was used instead of the isocyanate-based cross-linking agent X1.
  • the solvent-based pressure-sensitive adhesive composition according to this example was prepared in the same manner as in the preparation of the agent composition.
  • Example 13 The solvent-type pressure-sensitive adhesive composition according to this example was prepared in the same manner as in the preparation of the solvent-type pressure-sensitive adhesive composition according to Example 10 except that the solution of polymer P2 was used instead of the solution of polymer P1.
  • the solvent-based pressure-sensitive adhesive composition according to each example prepared above is applied to the peeling surface of a release film R1 (MRF # 38 manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 38 ⁇ m in which one side of the polyester film is a peeling surface. , It was dried at 130 ° C. for 3 minutes to form a photocurable pressure-sensitive adhesive layer (supportless double-sided pressure-sensitive adhesive sheet) having a thickness of 20 ⁇ m.
  • a peeling surface of a 38 ⁇ m-thick peeling film R2 (MRE # 38 manufactured by Mitsubishi Plastics Co., Ltd.) having one side of the polyester film as a peeling surface was attached to the surface of the pressure-sensitive adhesive layer to protect it. In this way, a laminated sheet having a structure in which the release film R1, the supportless double-sided adhesive sheet, and the release film R2 are laminated in this order was obtained.
  • the obtained adhesive sheet was measured and evaluated as follows.
  • (1) Measurement of tensile elastic modulus A high-pressure mercury lamp is used on a laminated sheet (a laminated sheet having a support-less adhesive layer sandwiched between two transparent release films) according to each example, and an illuminance of 300 mW. After irradiating with ultraviolet rays under the conditions of / cm 2 and an integrated light intensity of 3000 mJ / cm 2 and aging at 50 ° C. for 48 hours, the laminated sheet was cut into a size of 10 mm in width and 150 mm in length. In an environment of 23 ° C.
  • the impact resistance [J / (10 mm) 2 ] was determined by measuring the absorbed energy [J] when a hammer was applied under the condition of 5 m / sec. The measurements were performed three times, and Tables 1 and 2 show their arithmetic mean values.
  • a test piece is prepared by cutting the laminated sheet according to each example into a size of 10 mm in width and 150 mm in length, and the first surface of the pressure-sensitive adhesive layer in the test piece is reciprocated once with a 2 kg rubber roller. Then, it is pressure-bonded to a glass plate (alkaline glass plate manufactured by Matsunami Glass Industry Co., Ltd., manufactured by the float method, thickness 1.35 mm, blue plate edge polished product), and autoclaved (50 ° C, 0.5 MPa, 15 minutes).
  • a glass plate alkaline glass plate manufactured by Matsunami Glass Industry Co., Ltd., manufactured by the float method, thickness 1.35 mm, blue plate edge polished product
  • the haze value of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to Examples 1, 6, 8 and 11 was measured by the above-mentioned method and found to be 0.5% or less.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheets of Examples 6 and 8 showed particularly good transparency.
  • the photoreactive monomers used in Examples 1 to 13 are as follows. In Tables 1 and 2, each photoreactive monomer is indicated by an abbreviation.
  • DPHA Dipentaerythritol hexaacrylate (Shin Nakamura Chemical Industry, trade name "A-DPH", functional group equivalent 96)
  • A-DCP Tricyclodecanedimethanol diacrylate (Shin Nakamura Chemical Industry Co., Ltd., trade name "A-DCP”, functional group equivalent 152)
  • # 540 Bisphenol A diglycidyl ether acrylic acid adduct (Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 540", functional group equivalent 250)
  • R115F Bisphenol A diglycidyl ether acrylic adduct (Nippon Kayaku, trade name "KAYARAD R-115F", functional group equivalent 450)
  • # 700HV bisphenol A ethylene oxide 3.8 mol adduct diacrylate (Osaka Organic Chemical Industry, trade name "
  • the adhesive sheets of Examples 1 to 9 shown in Table 1 were excellent in deformation resistance due to their high tensile elastic modulus and exhibited high impact resistance.
  • the pressure-sensitive adhesive sheets of Examples 10, 12, and 13 shown in Table 2 had low deformation resistance, and the pressure-sensitive adhesive sheets of Example 11 had low peel strength.
  • Adhesive sheet 10 Adhesive layer 10A One surface (adhesive surface) 10B Other surface 20 Support 20A First surface 20B Second surface (back surface) 30, 31, 32 Release liner 50 Adhesive sheet with release liner 70 Film member 100 Member with adhesive sheet

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une feuille adhésive qui a une couche adhésive. Cette feuille adhésive a la caractéristique (a) et la caractéristique (b) décrites ci-après :　(a) le module élastique tel que déterminé par un essai de traction est supérieur ou égal à 3,0 MPa,　(b) la résistance aux chocs telle que déterminée par un test d'impact de cisaillement est supérieure ou égale à 2,0 J/(10 mm)2.
PCT/JP2020/024499 2019-06-28 2020-06-23 Feuille adhésive et son utilisation Ceased WO2020262340A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010073649A1 (fr) * 2008-12-26 2010-07-01 日本化薬株式会社 Composition adhésive autocollante, stratifié et dispositif d'affichage d'image
JP2013040256A (ja) * 2011-08-12 2013-02-28 Three M Innovative Properties Co 放射線硬化性粘着シート
WO2018101252A1 (fr) * 2016-12-02 2018-06-07 三菱ケミカル株式会社 Composition photodurcissable, feuille d'adhésif sensible à la pression, stratifié de feuilles d'adhésif sensible à la pression, produit durci, stratifié pour former un dispositif d'affichage d'image et dispositif d'affichage d'image

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5577074B2 (ja) * 2009-11-09 2014-08-20 日東電工株式会社 光学用粘着シート
JP6513347B2 (ja) 2014-07-07 2019-05-15 日東電工株式会社 粘着シート
JP6807234B2 (ja) * 2017-01-10 2021-01-06 日東電工株式会社 粘着シート

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010073649A1 (fr) * 2008-12-26 2010-07-01 日本化薬株式会社 Composition adhésive autocollante, stratifié et dispositif d'affichage d'image
JP2013040256A (ja) * 2011-08-12 2013-02-28 Three M Innovative Properties Co 放射線硬化性粘着シート
WO2018101252A1 (fr) * 2016-12-02 2018-06-07 三菱ケミカル株式会社 Composition photodurcissable, feuille d'adhésif sensible à la pression, stratifié de feuilles d'adhésif sensible à la pression, produit durci, stratifié pour former un dispositif d'affichage d'image et dispositif d'affichage d'image

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