WO2020054745A1 - 粘着シート、積層体及び積層体の製造方法 - Google Patents

粘着シート、積層体及び積層体の製造方法 Download PDF

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Publication number
WO2020054745A1
WO2020054745A1 PCT/JP2019/035611 JP2019035611W WO2020054745A1 WO 2020054745 A1 WO2020054745 A1 WO 2020054745A1 JP 2019035611 W JP2019035611 W JP 2019035611W WO 2020054745 A1 WO2020054745 A1 WO 2020054745A1
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pressure
sensitive adhesive
adhesive sheet
adhesive layer
meth
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PCT/JP2019/035611
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English (en)
French (fr)
Japanese (ja)
Inventor
大輔 黒田
誠司 瀬口
滋呂 清水
万智 浅尾
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王子ホールディングス株式会社
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Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Priority to KR1020217007342A priority Critical patent/KR20210057045A/ko
Priority to CN201980059239.7A priority patent/CN112703237A/zh
Publication of WO2020054745A1 publication Critical patent/WO2020054745A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet, a laminate, and a method for producing a laminate.
  • LCDs liquid crystal displays
  • touch panels display devices
  • transparent double-sided pressure-sensitive adhesive sheets are used for bonding optical members
  • transparent double-sided pressure-sensitive adhesive sheets are also used for bonding display devices and input devices. ing.
  • such a pressure-sensitive adhesive composition When the pressure-sensitive adhesive composition is cured by two-stage polymerization, such a pressure-sensitive adhesive composition has, for example, both heat curability and active energy ray curability, or has two-step active energy ray curability (hereinafter, referred to as “active energy ray curability”). Such a pressure-sensitive adhesive composition is sometimes referred to as a “dual-curable pressure-sensitive adhesive composition”).
  • the pressure-sensitive adhesive composition is a pressure-sensitive adhesive composition having both thermosetting properties and active energy ray-curing properties, it can be temporarily bonded, for example, by performing only thermosetting before bonding with the adherend. After that, it can be firmly bonded to the adherend by further curing with an active energy ray (referred to as post-curing or after-curing).
  • Patent Document 1 discloses a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer, in which a pressure-sensitive adhesive layer is obtained by partially polymerizing a monomer composition containing a (meth) acrylate and a hydroxyl group-containing (meth) acrylate by a bulk polymerization method.
  • a non-solvent type curable resin composition containing an acrylic resin composition on syrup obtained by polymerization, a polyfunctional (meth) acrylate compound, and a photopolymerization initiator was cured by irradiation with active energy rays.
  • a pressure-sensitive adhesive sheet, which is a layer is disclosed.
  • the photopolymerization initiator only a cleavage type photopolymerization initiator is used.
  • Patent Document 1 discusses improving the step followability and the like by partially leaving unreacted monomer in the pressure-sensitive adhesive layer.
  • Patent Document 2 discloses a double-sided pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive resin composition containing a (meth) acrylic copolymer, a crosslinking agent, and a photopolymerization initiator.
  • the ratio (X 1 / X 2 ) between the tensile modulus (X 1 ) before photocrosslinking and the tensile modulus (X 2 ) after photocrosslinking is set to 3 or more. It is intended to obtain sufficient hardness after photocrosslinking while improving the properties.
  • an after-cure type pressure-sensitive adhesive sheet there is a trade-off between step followability and processability, and it is difficult to achieve both. That is, in the conventional after-cure type pressure-sensitive adhesive sheet, when trying to increase the step followability, the pressure-sensitive adhesive may unintentionally spread at the time of bonding, and there is a problem that the processability at the time of bonding is poor. .
  • the present inventors in an after-cured pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in a semi-cured pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition, It contains a (meth) acrylic copolymer and a hydrogen-abstraction type photopolymerization initiator, but does not contain a thermosetting crosslinker and a polyfunctional monomer. Further, the ratio of the tensile elastic modulus of the pressure-sensitive adhesive layer before and after after cure Is set to be less than the predetermined value, a pressure-sensitive adhesive sheet having both step followability and processability can be obtained. Specifically, the present invention has the following configuration.
  • An adhesive sheet having an adhesive layer in which the adhesive composition is in a semi-cured state The pressure-sensitive adhesive composition contains a (meth) acrylic copolymer and a hydrogen abstraction type photopolymerization initiator, The content of the thermosetting crosslinking agent in the pressure-sensitive adhesive composition is 0.1% by mass or less, The content of the polyfunctional monomer in the pressure-sensitive adhesive composition is 0.1% by mass or less, When the tensile modulus of the pressure-sensitive adhesive layer is P and the tensile modulus of the pressure-sensitive adhesive layer after completely cured is Q, An adhesive sheet having a Q / P value of less than 3.0.
  • the adhesive layer has a breaking elongation of 1000% or more and a tensile stress or breaking stress at a tensile elongation of 2000% of 0.1 N / mm 2 or more and 0.6 N / mm 2 or less [1].
  • the pressure-sensitive adhesive sheet according to any one of to [8].
  • a laminate comprising an optical member on at least one surface side of the laminate.
  • a method for producing a laminate comprising the step of:
  • an adhesive sheet having both step followability and workability can be obtained.
  • FIG. 1 is a cross-sectional view illustrating an example of a configuration of a double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention.
  • FIG. 2 is a cross-sectional view illustrating an example of the configuration of the laminate.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • (meth) acryl means including both acryl and methacryl.
  • the present invention relates to a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in which a pressure-sensitive adhesive composition is in a semi-cured state.
  • the pressure-sensitive adhesive composition contains a (meth) acrylic copolymer and a hydrogen abstraction type photopolymerization initiator.
  • the content of the thermosetting crosslinking agent in the pressure-sensitive adhesive composition is 0.1% by mass or less
  • the content of the polyfunctional monomer in the pressure-sensitive adhesive composition is 0.1% by mass or less.
  • the pressure-sensitive adhesive sheet of the present invention has the above configuration, it has both step followability and workability.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having a post-curing property (photocrosslinking property), and can follow a step of an adherend without a gap before post-curing.
  • the pressure-sensitive adhesive sheet of the present invention does not contain a polyfunctional monomer, the step followability of the pressure-sensitive adhesive layer can be more effectively improved.
  • the step followability can be maintained even after the weather resistance test.
  • the pressure-sensitive adhesive sheet of the present invention can follow a step having a height of 30% of the thickness of the pressure-sensitive adhesive layer at a sticking portion without any gap.
  • the pressure-sensitive adhesive sheet of the present invention can exhibit excellent step followability even after being left standing for a long time in a high-temperature environment or an ultraviolet exposure environment.
  • the pressure-sensitive adhesive sheet of the present invention contains a hydrogen-abstraction-type photopolymerization initiator, and on the other hand, because it does not substantially contain a thermosetting cross-linking agent, the workability in a semi-cured state is also improved.
  • the processability of the pressure-sensitive adhesive sheet can be evaluated by the protrusion of the pressure-sensitive adhesive at the time of lamination (wise value). Specifically, when the temperature of the press section is set to 25 ° C. and the spread (wise value) of the pressure-sensitive adhesive sheet when pressed at a pressure of 0.2 MPa for 5 minutes is small, the workability is evaluated as good. it can. The distance (maximum distance) to the point where the pressure-sensitive adhesive layer spreads on each side of the release sheet is measured, and when the average value of the four sides is defined as the wage value, the wage value is preferably less than 1.2 mm.
  • the pressure-sensitive adhesive sheet of the present invention does not substantially contain a thermal crosslinking agent, the aging step can be omitted when forming the pressure-sensitive adhesive sheet. Thereby, the time required for manufacturing the pressure-sensitive adhesive sheet can be reduced.
  • the value of Q / P is less than 3.0. More preferably, it is less than 2.8, more preferably less than 2.6, even more preferably less than 2.4.
  • the lower limit of the value of Q / P is not particularly limited, but is preferably 1.0 or more.
  • the tensile modulus of the semi-cured pressure-sensitive adhesive layer is preferably 100 kPa or more and 200 kPa or less, more preferably 120 kPa or more and 180 kPa or less.
  • the tensile modulus of the pressure-sensitive adhesive layer in a semi-cured state is a value calculated from a stress-strain curve (SS curve) obtained in the measurement of tensile stress described later. Specifically, the gradient is calculated from the tensile elongation percentage and the stress value of 0% and 5%, and is defined as the tensile elastic modulus.
  • SS curve stress-strain curve
  • the tensile elastic modulus of the pressure-sensitive adhesive layer after post-curing is preferably from 150 kPa to 250 kPa, more preferably from 170 kPa to 230 kPa.
  • the tensile elastic modulus of the pressure-sensitive adhesive layer after post-curing (after complete curing) is determined by irradiating the semi-cured pressure-sensitive adhesive layer with ultraviolet rays so that the integrated light amount becomes 2000 mJ / cm 2. It is.
  • the stress value of the tensile elongation of 2000% is set to the tensile stress, and the elongation at break is set to 2000% or more.
  • the tensile stress or breaking stress when the tensile elongation of the pressure-sensitive adhesive layer after post-curing is 2000% is determined by irradiating the pressure-sensitive adhesive layer with ultraviolet rays so that the integrated light amount becomes 2000 mJ / cm 2. Obtain and measure by the same method.
  • the tensile elongation in this specification is a rate calculated by the following equation.
  • Tensile elongation (%) (Distance between chucks after tension ⁇ Distance between chucks before tension (30 mm)) / Distance between chucks before tension (30 mm) ⁇ 100
  • the pressure-sensitive adhesive sheet when measuring the tensile stress at a tensile elongation of 2000% before photocrosslinking of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet must have a breaking elongation before photocrosslinking of 2000% or more.
  • the pressure-sensitive adhesive sheet breaks before reaching a tensile elongation of 2000% when measuring the above-described tensile stress.
  • the stress value obtained by the above measurement is the breaking stress.
  • the breaking elongation of the pressure-sensitive adhesive layer in a semi-cured state is preferably at least 1,000%, more preferably at least 1200%, further preferably at least 1500%, particularly preferably at least 2,000%. preferable.
  • the tensile stress of the semi-cured pressure-sensitive adhesive layer at a tensile elongation of 2000% is preferably 0.1 N / mm 2 or more, and more preferably 0.2 N / mm 2 or more. Further, the tensile stress of the semi-cured pressure-sensitive adhesive layer at a tensile elongation of 2000% is preferably 0.6 N / mm 2 or less, more preferably 0.5 N / mm 2 or less. When the pressure-sensitive adhesive sheet breaks before reaching a tensile elongation of 2000%, the breaking stress is preferably at least 0.1 N / mm 2, more preferably at least 0.2 N / mm 2 . Further, the breaking stress of the pressure-sensitive adhesive layer in a semi-cured state is preferably 0.6 N / mm 2 or less, more preferably 0.5 N / mm 2 or less.
  • the post-curing (after complete curing) pressure-sensitive adhesive layer preferably has a breaking stress of 0.1 N / mm 2 or more, and more preferably 0.2 N / mm 2 or more. Further, the breaking stress of the pressure-sensitive adhesive layer after post-curing (after complete curing) is preferably 0.6 N / mm 2 or less, and more preferably 0.5 N / mm 2 or less.
  • the amount of residual monomer in the pressure-sensitive adhesive layer in a semi-cured state is preferably 12% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and more preferably 5% by mass or less. It is particularly preferred that there is.
  • the amount of residual monomer in the semi-cured pressure-sensitive adhesive layer may be 0% by mass.
  • the amount of residual monomer in the pressure-sensitive adhesive layer can be calculated by a weight loss measurement method. Specifically, the pressure-sensitive adhesive layer is cut out into a 10 cm square, and attached to a 12 cm square, 12 ⁇ m thick aluminum foil. Then, it is put into an oven at 135 ° C., heated, and taken out after 10 minutes. By calculating the rate of weight loss of the pressure-sensitive adhesive sheet before and after heating, it is used as an index of the amount of residual monomer.
  • the pressure-sensitive adhesive layer in a semi-cured state has photocrosslinkability (curability by light irradiation). That is, the pressure-sensitive adhesive layer in a semi-cured state is a sheet in a soft state before light irradiation (before photocrosslinking). Specifically, in the present specification, when the gel fraction of the pressure-sensitive adhesive layer is increased by 10% by mass or more by irradiating the active energy ray so that the integrated light amount becomes 2000 mJ / cm 2 , the irradiation before irradiation is performed. It can be said that the pressure-sensitive adhesive layer is in a semi-cured state.
  • an optical transparent PET separator When irradiating an active energy ray, an optical transparent PET separator is attached to both surfaces of the pressure-sensitive adhesive layer, and an active energy ray (a high-pressure mercury lamp or a metal halide lamp) is integrated from one optical transparent PET separator side. Irradiation is performed at 2000 mJ / cm 2 .
  • the gel fraction of the pressure-sensitive adhesive layer in a semi-cured state is preferably 55% or less, more preferably 50% or less, further preferably 40% or less, and particularly preferably 30% or less. .
  • the gel fraction of the pressure-sensitive adhesive layer in a semi-cured state is preferably 1% or more.
  • the gel fraction of the pressure-sensitive adhesive layer after post-curing (after complete curing) is preferably 50% or more, and more preferably 55% or more.
  • the gel fraction of the pressure-sensitive adhesive sheet after post-curing (after complete curing) is determined based on the gel fraction of the pressure-sensitive adhesive sheet after irradiating the semi-cured pressure-sensitive adhesive layer with ultraviolet rays so that the integrated light amount becomes 2000 mJ / cm 2 or more. Rate.
  • the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer to glass after post-curing (after complete curing) is preferably 20.0 N / 25 mm or more, more preferably 24.0 N / 25 mm or more, and 25.0 N / 25 mm or more. Is more preferable, and particularly preferable is 27.0 N / 25 mm or more.
  • the adhesive strength of the pressure-sensitive adhesive layer to glass is the peel strength when the pressure-sensitive adhesive layer is peeled from glass at 180 ° at a tensile speed of 300 mm / min according to JIS Z0237.
  • the thickness of the pressure-sensitive adhesive sheet of the present invention is preferably 5 to 2000 ⁇ m, more preferably 30 to 1000 ⁇ m, further preferably 50 to 500 ⁇ m, and particularly preferably 70 to 200 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is also preferably within the above range.
  • the pressure-sensitive adhesive sheet of the present invention is preferably a double-sided pressure-sensitive adhesive sheet.
  • the double-sided pressure-sensitive adhesive sheet may be a single-layer double-sided pressure-sensitive adhesive sheet or a multilayer double-sided pressure-sensitive adhesive sheet in which a plurality of pressure-sensitive adhesive layers are laminated. Further, the double-sided pressure-sensitive adhesive sheet may be a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both sides of a substrate (preferably a transparent substrate).
  • plastic films such as polystyrene, styrene-acryl copolymer, acrylic resin, polyethylene terephthalate, polycarbonate, polyetheretherketone, and triacetylcellulose; optical materials such as antireflection films and electromagnetic wave shielding films Films and the like.
  • the pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive sheet for bonding optical members.
  • the optical member include each constituent member of an optical product such as a touch panel and an image display device, and a scattering prevention film bonded to a cover lens on the outermost layer.
  • an ITO film in which an ITO film is provided on a transparent resin film an ITO glass in which an ITO film is provided on a surface of a glass plate, a transparent conductive film in which a conductive polymer is coated on a transparent resin film, Hard coat films, fingerprint resistant films and the like can be mentioned.
  • the constituent members of the image display device include, for example, an antireflection film, an alignment film, a polarizing film, a retardation film, and a brightness enhancement film used for a liquid crystal display device.
  • materials used for these members include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymers, triacetyl cellulose, polyimide, and cellulose acylate.
  • the pressure-sensitive adhesive composition forms the pressure-sensitive adhesive layer in a semi-cured state described above.
  • the pressure-sensitive adhesive composition contains a (meth) acrylic copolymer and a hydrogen abstraction type photopolymerization initiator.
  • the pressure-sensitive adhesive composition does not substantially contain a thermosetting crosslinking agent, and its content is 0.1% by mass or less, and preferably 0.0% by mass.
  • the pressure-sensitive adhesive composition does not substantially contain a polyfunctional monomer, and its content is 0.1% by mass or less, and preferably 0.0% by mass.
  • the content of the thermosetting crosslinking agent and the content of the polyfunctional monomer with respect to the total mass of the pressure-sensitive adhesive layer are each 0.1% by mass or less.
  • the step followability of the pressure-sensitive adhesive layer can be more effectively improved.
  • the aging step can be omitted when forming the pressure-sensitive adhesive sheet, and the time required for manufacturing the pressure-sensitive adhesive sheet can be reduced.
  • the pressure-sensitive adhesive composition does not substantially contain a solvent, and its content is 0.1% by mass or less, and preferably 0.0% by mass.
  • the content of the solvent with respect to the total mass of the pressure-sensitive adhesive layer is also 0.1% by mass or less.
  • the pressure-sensitive adhesive composition of the present invention is a solventless type, and it can be said that the pressure-sensitive adhesive layer formed from such a pressure-sensitive adhesive composition is a solventless pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive composition contains a (meth) acrylic copolymer.
  • the (meth) acrylic copolymer is a main polymer contained in the pressure-sensitive adhesive composition, and such a polymer is sometimes referred to as a base polymer.
  • the (meth) acrylic copolymer is also contained in the pressure-sensitive adhesive layer.
  • the (meth) acrylic copolymer is not particularly limited as long as it has an acrylic monomer unit.
  • it has a non-crosslinkable (meth) acrylate unit (a1) and a crosslinkable functional group. It is preferable that it contains an acrylic monomer unit (a2). It is preferable that the (meth) acrylic copolymer has such transparency that the visibility of the display device is not reduced.
  • the “unit” is a repeating unit (monomer unit) constituting the polymer.
  • the non-crosslinkable (meth) acrylate unit (a1) is a repeating unit derived from an alkyl (meth) acrylate.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylate.
  • Isobutyl acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, (meth) N-dodecyl acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ) Ethoxyethyl acrylate, cyclohexyl (meth) acrylate include benzyl (me
  • alkyl (meth) acrylates methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are used because of their increased tackiness. At least one kind selected from the following is preferably used. It is also preferable to use a combination of at least one selected from methyl (meth) acrylate, ethyl (meth) acrylate and n-butyl (meth) acrylate with 2-ethylhexyl (meth) acrylate. It is more preferable to use a combination of ethyl acrylate and 2-ethylhexyl (meth) acrylate.
  • the (meth) acrylic monomer unit (a2) having a crosslinkable functional group includes a hydroxy group-containing monomer unit, an amino group-containing monomer unit, a glycidyl group-containing monomer unit, and a carboxy group-containing monomer. Unit and the like. These monomer units may be used alone or in combination of two or more.
  • the hydroxy group-containing monomer unit is a repeating unit derived from the hydroxy group-containing monomer.
  • hydroxy group-containing monomer examples include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid [(mono, di or poly) alkylene glycol] such as (meth) acrylic acid mono (diethylene glycol), and (meth) acrylic acid lactone such as (meth) acrylic acid monocaprolactone.
  • the amino group-containing monomer unit include a repeating unit derived from an amino group-containing monomer such as (meth) acrylamide and allylamine.
  • Examples of the glycidyl group-containing monomer unit include a repeating unit derived from a glycidyl group-containing monomer such as glycidyl (meth) acrylate.
  • Examples of the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
  • the content of the (meth) acrylic monomer unit (a2) having a crosslinkable functional group in the (meth) acrylic copolymer is 0.01 mass with respect to the total mass of the (meth) acrylic copolymer. % Or more, more preferably 0.5% by mass or more.
  • the content of the (meth) acrylic monomer unit (a2) having a crosslinkable functional group is preferably 40% by mass or less, more preferably 35% by mass or less.
  • the (meth) acrylic copolymer may have other monomer units as needed.
  • the other monomer may be any as long as it can be copolymerized with the above-mentioned acrylic monomer.
  • the content of the other monomer units in the (meth) acrylic copolymer is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the content of the other monomer units is at least the above lower limit, the cohesive strength can be sufficiently increased, and when it is at most the above upper limit, it becomes easy to secure sufficient adhesive strength.
  • the theoretical glass transition temperature (Tg) of the (meth) acrylic copolymer is preferably -55 ° C or higher, more preferably -53 ° C or higher. Further, the theoretical glass transition temperature (Tg) of the (meth) acrylic copolymer is preferably -10 ° C or lower, more preferably -20 ° C or lower, further preferably -30 ° C or lower. -40 ° C. or lower.
  • Tg in the formula is the glass transition temperature (K: Kelvin) of the acrylic copolymer, and W1, W2. Wn is the mass fraction of each monomer constituting the acrylic copolymer, and Tg1, Tg2,... Tgn represent the glass transition temperature of the homopolymer of each monomer.)
  • the weight average molecular weight (Mw) of the (meth) acrylic copolymer is preferably 250,000 or more, more preferably 300,000 or more, further preferably 350,000 or more, and more preferably 400,000 or more. It is particularly preferred that there is. Further, the weight average molecular weight (Mw) of the (meth) acrylic copolymer is preferably 1,000,000 or less, more preferably 950,000 or less, further preferably 900,000 or less. By setting the weight average molecular weight (Mw) of the (meth) acrylic copolymer within the above range, the processability of the pressure-sensitive adhesive sheet can be further improved. Further, by setting the weight average molecular weight (Mw) of the (meth) acrylic copolymer within the above range, durability can be improved while improving step followability.
  • the weight average molecular weight of the (meth) acrylic copolymer is a value measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene.
  • the measurement conditions of gel permeation chromatography (GPC) are as follows.
  • Solvent tetrahydrofuran Column: Shodex KF801, KF803L, KF800L, KF800D (using four Showa Denko KKs connected) Column temperature: 40 ° C Sample concentration: 0.5% by mass Detector: RI-2031plus (manufactured by JASCO) Pump: RI-2080plus (manufactured by JASCO) Flow rate (flow rate): 0.8 ml / min Injection volume: 10 ⁇ l
  • the (meth) acrylic copolymer may be a commercially available product or may be produced by polymerizing an acrylic monomer.
  • the polymerization method can be appropriately selected from commonly used polymerization methods. Examples of the polymerization method include a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.
  • the pressure-sensitive adhesive composition contains a hydrogen abstraction type photopolymerization initiator.
  • the hydrogen abstraction type photopolymerization initiator is also included in the pressure-sensitive adhesive layer.
  • the hydrogen abstraction type photopolymerization initiator initiates a polymerization reaction of the above-mentioned (meth) acrylic copolymer or a monomer constituting the (meth) acrylic copolymer by irradiation with active energy rays.
  • the hydrogen abstraction type photopolymerization initiator is a photopolymerization initiator that forms an exciplex with the photoexcited initiator and the hydrogen donor in the system, and promotes polymerization by transferring hydrogen of the hydrogen donor.
  • Examples of the hydrogen abstraction type photopolymerization initiator include, for example, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethyl Benzophenone, 4-methylbenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 3 , 3 ', 4,4'-Tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 9,10-phenanthrenequinone and the like.
  • the hydrogen abstraction type photopolymerization initiator is preferably a benzophenone-based photopolymerization initiator.
  • benzophenone-based photopolymerization initiator examples include benzophenone, 4-methylbenzophenone and 2,4,6-trimethyl. Benzophenone and the like can be mentioned.
  • the content of the hydrogen abstraction type photopolymerization initiator in the pressure-sensitive adhesive composition is preferably at least 0.1 part by mass, and more preferably 0.5 part by mass, based on 100 parts by mass of the (meth) acrylic copolymer.
  • the amount is more preferably at least 1 part by mass, and still more preferably at least 1 part by mass.
  • the content of the hydrogen abstraction type photopolymerization initiator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the (meth) acrylic copolymer.
  • a commercial product can be used as the hydrogen abstraction type photopolymerization initiator.
  • Examples of commercially available products include SPEEDCURE @ MBP and ESACURE @ TZT manufactured by Lambson.
  • the pressure-sensitive adhesive composition preferably further contains a cleavage type photopolymerization initiator.
  • the cleavage type photopolymerization initiator is a photopolymerization initiator that promotes polymerization by cleaving and decomposing a single bond of the initiator itself to generate a radical.
  • cleavage type photopolymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- ⁇ 4- (2-hydroxy- 2-methyl-propionyl) benzyl ⁇ phenyl] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxy Methyl lithate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methyl Thio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-
  • the content of the cleavage type photopolymerization initiator in the pressure-sensitive adhesive composition is preferably at least 0.01 part by mass, and preferably at least 0.1 part by mass, based on 100 parts by mass of the (meth) acrylic copolymer. Is more preferable. Further, the content of the cleavage type photopolymerization initiator is preferably at most 10 parts by mass, more preferably at most 5 parts by mass, based on 100 parts by mass of the (meth) acrylic copolymer. More preferably, the amount is not more than part by mass.
  • a commercial product can be used as the cleavage type photopolymerization initiator.
  • Examples of commercially available products include Irgacure 184 and Irgacure 819 manufactured by IGM Resin.
  • the pressure-sensitive adhesive sheet of the present invention may contain components other than those described above as long as the effects of the present invention are not impaired.
  • components known as additives for adhesives can be exemplified.
  • a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, an ultraviolet absorber, a light stabilizer such as a hindered amine compound, or the like can be selected as necessary.
  • a non-functional acrylic polymer can be used as the plasticizer.
  • the non-functional acrylic polymer is a polymer consisting of only an acrylic monomer unit having no functional group other than the acrylate group, or having no functional group with an acrylic monomer unit having no functional group other than the acrylate group. It means a polymer composed of non-acrylic monomer units. Examples of the acrylic monomer unit having no functional group other than the acrylate group include those similar to the non-crosslinkable (meth) acrylate unit.
  • non-acrylic monomer units having no functional group examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, and stearin
  • vinyl carboxylate esters such as vinyl acrylate, vinyl cyclohexanecarboxylate and vinyl benzoate, and styrene.
  • antioxidants examples include a phenolic antioxidant, an amine antioxidant, a lactone antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
  • metal corrosion inhibitor examples include a benzotriazole-based resin.
  • tackifier examples include a rosin resin, a terpene resin, a terpene phenol resin, a coumarone indene resin, a styrene resin, a xylene resin, a phenol resin, and a petroleum resin.
  • silane coupling agent examples include a mercapto silane coupling agent, a (meth) acrylic silane coupling agent, an isocyanate silane coupling agent, an epoxy silane coupling agent, and an amino silane coupling agent.
  • ultraviolet absorber examples include a benzotriazole-based compound and a benzophenone-based compound.
  • the method for producing a pressure-sensitive adhesive sheet of the present invention comprises the steps of applying the above-described pressure-sensitive adhesive composition on a release sheet to form a coating film, and irradiating the coating film with an active energy ray to cure the cured product in a semi-cured state.
  • an active energy ray the reaction between the (meth) acrylic copolymer and the hydrogen abstraction type photopolymerization initiator proceeds to form a semi-cured cured product (adhesive layer).
  • the application of the pressure-sensitive adhesive composition can be performed using a known coating device.
  • the coating device include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a microgravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and the like.
  • irradiating the coating film with an active energy ray it is preferable to irradiate the active energy ray so that the integrated light amount becomes 500 mJ / cm 2 or more, and irradiate the active energy ray so as to become 750 mJ / cm 2 or more. Is more preferable. Further, it is preferable to irradiate the active energy ray so that the integrated light amount becomes 2000 mJ / cm 2 or less, and it is more preferable to irradiate the active energy ray so that the integrated light quantity becomes 1500 mJ / cm 2 or less. In addition, when irradiating an active energy ray to a coating film, it is also preferable to irradiate an active energy ray in two steps.
  • the integrated light amount becomes 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less, and 200 mJ / cm 2 or more and 500 mJ / cm 2 or less.
  • the accumulated light quantity is preferable to irradiate the high-pressure mercury lamp so that 300 mJ / cm 2 or more 1500 mJ / cm 2 or less, 500 mJ / cm 2 or more 1200mJ / Cm 2 or less with a high-pressure mercury lamp.
  • the present invention may relate to a pressure-sensitive adhesive sheet with a release sheet, which includes release sheets on both sides of the above-described pressure-sensitive adhesive sheet.
  • FIG. 1 is a schematic view showing a cross section of an example of the pressure-sensitive adhesive sheet with a release sheet of the present invention.
  • the pressure-sensitive adhesive sheet 1 with a release sheet includes a pressure-sensitive adhesive sheet 11, and a release sheet 12a and a release sheet 12b on both sides.
  • the pressure-sensitive adhesive sheet 11 may be a single-layer double-sided pressure-sensitive adhesive sheet as shown in FIG. 1 or a multilayer double-sided pressure-sensitive adhesive sheet in which a plurality of pressure-sensitive adhesive layers are laminated.
  • the pressure-sensitive adhesive sheet 11 may be a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both sides of a substrate (preferably a transparent substrate).
  • the surface of the adhesive sheet 11 is preferably covered with a release sheet 12a and a release sheet 12b.
  • a release sheet a release laminate sheet having a release sheet substrate and a release agent layer provided on one surface of the release sheet substrate, or a polyolefin film such as a polyethylene film or a polypropylene film as a low polarity substrate Is mentioned.
  • the release sheet base material in the release laminate sheet is used as the release sheet base material in the release laminate sheet.
  • a general-purpose addition-type or condensation-type silicone release agent or a compound having a long-chain alkyl group is used.
  • an addition type silicone release agent having high reactivity is preferably used.
  • Specific examples of the silicone release agent include BY24-4527 and SD-7220 manufactured by Dow Corning Toray Silicone Co., Ltd., and KS-3600, KS-774, and X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd. Is mentioned.
  • the silicone-based release agent may contain a silicone resin which is an organosilicon compound having SiO 2 units and (CH 3 ) 3 SiO 1/2 units or CH 2 CHCH (CH 3 ) SiO 1/2 units. preferable.
  • a silicone resin which is an organosilicon compound having SiO 2 units and (CH 3 ) 3 SiO 1/2 units or CH 2 CHCH (CH 3 ) SiO 1/2 units.
  • Specific examples of the silicone resin include BY24-843, SD-7292, and SHR-1404 manufactured by Dow Corning Toray Silicone Co., Ltd., and KS-3800 and X92-183 manufactured by Shin-Etsu Chemical Co., Ltd.
  • a commercially available product may be used as the peelable laminated sheet.
  • a heavy separator film that is a release-treated polyethylene terephthalate film manufactured by Teijin Dupont Film Co., Ltd., and a light separator film that is a release-treated polyethylene terephthalate film manufactured by Teijin Dupont Film Co., Ltd. may be mentioned. it can.
  • the pressure-sensitive adhesive sheet of the present invention preferably has a pair of release sheets having different release forces. That is, the release sheet preferably has different release properties between the release sheet 12a and the release sheet 12b in order to facilitate release. If the releasability from one side is different from the releasability from the other, it becomes easy to peel off only the release sheet having higher releasability first. In this case, the releasability of the release sheet 12a and the release sheet 12b may be adjusted according to the bonding method and the bonding order.
  • the method for manufacturing a laminate includes a step of laminating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet to the adherend in a semi-cured state, and then irradiating active energy rays to post-cure the pressure-sensitive adhesive layer. Before the irradiation with the active energy ray, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is in a semi-cured state, so that the initial adhesiveness to the substrate is improved. As described above, after the pressure-sensitive adhesive sheet is bonded to the adherend, the pressure-sensitive adhesive layer is post-cured with active energy rays, whereby the cohesive force of the pressure-sensitive adhesive layer is increased, and the adhesion to the adherend is improved.
  • the value of Q / P is less than 3.0. Therefore, it is possible to prevent the post-cured pressure-sensitive adhesive layer from being deformed or distorted.
  • the active energy ray examples include an ultraviolet ray, an electron beam, a visible ray, an X-ray, and an ion beam, and can be appropriately selected according to the photopolymerization initiator contained in the pressure-sensitive adhesive layer. Above all, from the viewpoint of versatility, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable.
  • the ultraviolet light source for example, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, and an electrodeless ultraviolet lamp can be used.
  • the electron beam for example, electron beams emitted from various types of electron beam accelerators such as Cockloft-Wald type, Bande-Crafts type, Resonant transformer type, Insulated core transformer type, Linear type, Dynamitron type and High frequency type are used. it can.
  • Radiation output of the UV light it is preferable that the integrated quantity of light is made to be a 100 ⁇ 3000mJ / cm 2, and more preferably made to be 500 ⁇ 2000mJ / cm 2.
  • the present invention also relates to a laminate having the above-mentioned pressure-sensitive adhesive sheet and an adherend.
  • the laminate is a post-cured pressure-sensitive adhesive layer obtained by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet with an active energy ray and post-curing, and an adherend on at least one surface side of the post-cured pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet
  • the laminate is formed by irradiating active energy rays in a state where the two adherends are bonded with the pressure-sensitive adhesive sheet in a semi-cured state, and post-curing the pressure-sensitive adhesive layer. Is preferred.
  • FIG. 2 is a cross-sectional view illustrating an example of the configuration of a laminate 30 in which the pressure-sensitive adhesive sheet 11 of the present invention is bonded to an adherend 31 having a step 32.
  • the adherend 31 has a step 32.
  • the thickness of the step 32 can be 5 to 60 ⁇ m.
  • the pressure-sensitive adhesive sheet 11 of the present invention can be used for bonding an adherend having a step.
  • the pressure-sensitive adhesive sheet 11 of the present invention can be used for bonding an adherend having a step portion 32 having a thickness of 35 ⁇ m or more.
  • the adherend 31 is preferably an optical member.
  • the optical member include constituent members in optical products such as a touch panel and an image display device.
  • a constituent member of the touch panel for example, an ITO film in which an ITO film is provided on a transparent resin film, an ITO glass in which an ITO film is provided on a surface of a glass plate, a transparent conductive film in which a conductive polymer is coated on a transparent resin film, Hard coat films, fingerprint resistant films and the like can be mentioned.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is preferably for lamination of a sensor of a touch panel, and more preferably for lamination of a sensor of a touch panel using a touch pen.
  • an ITO film in which an ITO film is provided on a transparent resin film, an ITO glass in which an ITO film is provided on a surface of a glass plate, Transparent conductive films coated with a polymer are preferred.
  • the constituent members of the image display device include, for example, an antireflection film, an alignment film, a polarizing film, a retardation film, and a brightness enhancement film used for a liquid crystal display device.
  • materials used for these members include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymers, triacetyl cellulose, polyimide, and cellulose acylate.
  • Example 1 (Synthesis of acrylic copolymer) 75 parts by mass of 2-ethylhexyl acrylate, 5 parts by mass of acrylic acid, 20 parts by mass of ethyl methacrylate, 1-hydroxycyclohexyl phenyl ketone 0 0.05 parts by mass, and while irradiating ultraviolet rays with an illuminance of 3 mW / cm 2 while introducing a nitrogen gas, and performing partial polymerization, a main agent A containing an acrylic copolymer having a conversion of 21.3% was obtained. .
  • the weight average molecular weight Mw of the obtained acrylic copolymer in terms of polystyrene by GPC was 701,000, and the theoretical Tg was ⁇ 47 ° C.
  • the pressure-sensitive adhesive composition A prepared as described above was treated with a 38 ⁇ m-thick polyethylene terephthalate film (first release sheet) provided with a release agent layer treated with a silicone-based release agent (Oji F-tex: 38RL- 07 (2)) was uniformly coated with an applicator so that the coating thickness after drying was 100 ⁇ m. Thereafter, the surface of the first release sheet is adhered by irradiating black light with an integrated light amount of 240 mJ / cm 2 and then irradiating a high-pressure mercury lamp with an integrated light amount of 750 mJ / cm 2. An agent layer was formed.
  • a 38 ⁇ m-thick second release sheet (Oji F-tex: 38RL-07 (L)) is attached to the surface of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer has a pair of pressure-sensitive adhesive layers having a difference in release force.
  • a double-sided PSA sheet with a release sheet having the configuration of the first release sheet / adhesive layer / second release sheet sandwiched between the release sheets was obtained.
  • Example 2 to 5 The blending ratio of the monomer component in (Synthesis of acrylic copolymer) in Example 1 was changed as shown in Table 1, and further, the blending of the photopolymerization initiator in (Preparation of pressure-sensitive adhesive composition) A double-sided PSA sheet with a release sheet was obtained in the same manner as in Example 1 except that the ratio was changed as shown in Table 1.
  • Example 6 The blending ratio of the monomer component in (Synthesis of acrylic copolymer) of Example 1 was changed as shown in Table 1, and the blending ratio of the photopolymerization initiator in (Preparation of pressure-sensitive adhesive composition) was changed. Exfoliation was carried out in the same manner as in Example 1 except that the coating thickness was changed as shown in Table 1 and that the coating film thickness in (Preparation of pressure-sensitive adhesive sheet) was changed as shown in Table 1. A double-sided PSA sheet with a sheet was obtained.
  • Example 7 A double-sided pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 1, except that the coating thickness in (Preparation of pressure-sensitive adhesive sheet) in Example 1 was changed as shown in Table 1.
  • Example 8 The blending ratio of the photopolymerization initiator in (Preparation of pressure-sensitive adhesive composition) of Example 2 was changed so as to be as shown in Table 1, and the coating film thickness in (Preparation of pressure-sensitive adhesive sheet) was changed as shown in Table 1. Except having changed so that it may become as described in above, it carried out similarly to Example 2, and obtained the double-sided pressure sensitive adhesive sheet with a release sheet.
  • Example 9 The blending ratio of the photopolymerization initiator in (Preparation of pressure-sensitive adhesive composition) in Example 1 was changed so as to be as shown in Table 1, and the light irradiation conditions in (Preparation of pressure-sensitive adhesive sheet) were as shown in Table 1.
  • a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 1, except that the changes were as described.
  • Example 10 A double-sided PSA sheet with a release sheet was obtained in the same manner as in Example 1, except that the mixing ratio of the monomer component in (Synthesis of acrylic copolymer) in Example 1 was changed as shown in Table 1. Was.
  • Example 11 In Example 1 (Synthesis of acrylic copolymer), ultraviolet rays having an illuminance of 4 mW / cm 2 were irradiated and partially polymerized to obtain a main agent A-2 containing an acrylic copolymer having a conversion rate of 25.5%. Obtained.
  • the weight average molecular weight Mw of the obtained acrylic copolymer in terms of polystyrene measured by GPC was 344.8 million, and the theoretical Tg was ⁇ 47 ° C.
  • the main component A-2 was used in (Preparation of the adhesive composition) of Example 1 and the mixing ratio of the photopolymerization initiator was changed as shown in Table 1.
  • a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained.
  • Example 1 The blending ratio of the photopolymerization initiator in (Preparation of pressure-sensitive adhesive composition) of Example 1 was changed as shown in Table 2, and a polyfunctional monomer (A-HD-, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used. A double-sided PSA sheet with a release sheet was obtained in the same manner as in Example 1 except that N) was added.
  • a polyfunctional monomer A-HD-, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Comparative Example 2 A double-sided pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Comparative Example 1, except that the high-pressure mercury lamp was not irradiated in (Production of pressure-sensitive adhesive sheet) of Comparative Example 1.
  • Example 3 The blending ratio of the monomer component in (Synthesis of acrylic copolymer) in Example 1 was changed as shown in Table 2, and the blending ratio of the photopolymerization initiator in (Preparation of pressure-sensitive adhesive composition) was changed. A double-sided pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 1 except that the conditions were changed as shown in Table 2.
  • Example 4 A double-sided PSA sheet with a release sheet was prepared in the same manner as in Example 2 except that the mixing ratio of the photopolymerization initiator in (Preparation of PSA composition) in Example 2 was changed as shown in Table 2. Obtained.
  • Comparative Example 5 The composition ratio of the monomer component in Comparative Example 1 (Synthesis of acrylic copolymer) was changed as shown in Table 2, and in (Preparation of PSA composition), no polyfunctional monomer was added. Comparative Example 1 except that a thermal crosslinking agent (manufactured by Tosoh Corp., Coronate HX) was mixed as shown in Table 2 and further, a pressure-sensitive adhesive sheet was prepared and then cured at room temperature for 1 week. Similarly, a double-sided PSA sheet with a release sheet was obtained.
  • a thermal crosslinking agent manufactured by Tosoh Corp., Coronate HX
  • the first release sheet was peeled off, and only the pressure-sensitive adhesive sheet was rolled in the width direction to obtain a cylindrical sample having a diameter of 2.8 mm and a height of 50 mm.
  • the upper and lower regions of the cylindrical sample are sandwiched between two PET films (total of 4 films) having a thickness of 188 ⁇ m, a length of 25 mm, and a width of 50 mm. It was fixed so that the distance was 30 mm.
  • the film is stretched under an environment of a measurement temperature of 23 ° C. and a relative humidity of 50% under a condition of a tensile speed of 300 mm / min until the tensile elongation becomes 2000%.
  • the rate was defined as the breaking elongation, and the stress value at that time was defined as the breaking stress.
  • the stress value of the tensile elongation of 2000% was set to the tensile stress, and the elongation at break was set to 2000% or more.
  • the tensile stress or breaking stress of the post-cured pressure-sensitive adhesive sheet when the tensile elongation is 2000% is such that the integrated light amount from the first release sheet side of the cut double-sided pressure-sensitive adhesive sheet with a release sheet is 2000 mJ / cm 2. After irradiation, a cylindrical sample was obtained and measured in the same manner.
  • ⁇ Tensile modulus> The tensile modulus of the adhesive sheet was calculated from a stress-strain curve (SS curve) obtained in the measurement of ⁇ tensile stress (rupture stress) / elongation at break>. Specifically, the gradient was calculated from the tensile elongation percentage and the stress value of 0% and 5%, and was defined as the tensile elastic modulus.
  • the double-sided pressure-sensitive adhesive sheet with a release sheet obtained in each of Examples and Comparative Examples was cut into a shape of 90 mm in length and 50 mm in width, the first release sheet was separated, and a laminator (IKO-650EMT manufactured by Ubon Co., Ltd.) was used. Then, the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) was bonded so as to cover the entire printing surface in the frame shape of the printing step glass. Thereafter, the second release sheet was peeled off, and the exposed pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) was applied to a glass plate (vertical) using a vacuum bonding machine (manufactured by Joyo Engineering Co., Ltd .: vacuum laminating apparatus (JE2020B-MVH)).
  • the bonding conditions at this time were 40 ° C., a weak pressure of 0.6 kN, a strong pressure of 1.2 kN, a vacuum pressure of 100 Pa, and a pressure holding time of 10 seconds.
  • a defoaming treatment (autoclave treatment: 40 ° C., 0.5 MPa, 30 minutes) is performed, and then, an integrated light amount is applied from the side of the printing step glass with an ultraviolet irradiator (ECS-301G1 manufactured by Eye Graphics Co., Ltd.). Was irradiated with ultraviolet rays so as to be 2000 mJ / cm 2 to obtain a laminate.
  • the temperature of the press section was set to 25 ° C., and pressure was applied at a pressure of 2 MPa for 5 minutes. Thereafter, the maximum distance in which the pressure-sensitive adhesive layer spread outward from each side of the second release sheet of the pressure-sensitive adhesive sheet was measured, and the average value of the four sides was defined as a waze value. In practice, it can be determined that the workability is excellent when the value is ⁇ or more. :: less than 1.0 mm ⁇ : 1.0 mm or more and less than 1.2 mm x: 1.2 mm or more
  • the amount of residual monomer in the pressure-sensitive adhesive layer was calculated by a weight loss measurement method. Specifically, the pressure-sensitive adhesive layer was cut out into a 10 cm square and attached to a 12 cm square, 12 ⁇ m thick aluminum foil. Thereafter, it was put into an oven at 135 ° C., heated, and taken out after 10 minutes. By calculating the rate of decrease in the weight of the pressure-sensitive adhesive sheet before and after heating, it was used as an index of the residual monomer amount.
  • the pressure-sensitive adhesive sheet obtained in the example was excellent in step followability and workability.
  • both step followability and workability were not compatible.
  • the pressure-sensitive adhesive sheet obtained in the example was excellent in durability.

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