WO2020226169A1 - 粘着シート、積層体の製造方法および積層体 - Google Patents

粘着シート、積層体の製造方法および積層体 Download PDF

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Publication number
WO2020226169A1
WO2020226169A1 PCT/JP2020/018602 JP2020018602W WO2020226169A1 WO 2020226169 A1 WO2020226169 A1 WO 2020226169A1 JP 2020018602 W JP2020018602 W JP 2020018602W WO 2020226169 A1 WO2020226169 A1 WO 2020226169A1
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Prior art keywords
pressure
sensitive adhesive
adhesive layer
adhesive sheet
post
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PCT/JP2020/018602
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English (en)
French (fr)
Japanese (ja)
Inventor
山本　真之
貴迪 山口
隼介 塩田
Original Assignee
王子ホールディングス株式会社
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Priority claimed from JP2019088654A external-priority patent/JP2020183488A/ja
Priority claimed from JP2019088653A external-priority patent/JP2020183487A/ja
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
Publication of WO2020226169A1 publication Critical patent/WO2020226169A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive sheet, a method for manufacturing a laminate, and a laminate.
  • Display devices such as liquid crystal displays (LCDs) and input devices used in combination with display devices such as touch panels are widely used.
  • LCDs liquid crystal displays
  • input devices used in combination with display devices such as touch panels are widely used.
  • transparent adhesive sheets are used for bonding optical members, and transparent adhesive sheets are also used for bonding display devices and input devices. ..
  • thermosetting thermosetting property and active energy ray curable property
  • Patent Document 1 describes a base polymer (A) containing a non-crosslinkable (meth) acrylic acid ester unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group, and a lauryl acrylate (b1).
  • the solvent (E) and a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer obtained by semi-curing the pressure-sensitive adhesive composition by heating is described.
  • Patent Document 2 after bonding glass plates as plate materials, glass plates and synthetic resin plates or synthetic resin plates at least two sheets, and an adhesive sheet having at least one layer of an ultraviolet curable adhesive layer. , A method for producing a transparent laminate in which the pressure-sensitive adhesive layer is cured by ultraviolet rays by irradiating ultraviolet rays from the plate material side is described.
  • An object to be solved by the present invention is to provide an adhesive sheet having excellent processability when the pressure-sensitive adhesive layer has post-curing property and the pressure-sensitive adhesive layer is post-curing.
  • the present inventors have determined the shear storage elastic modulus G'when the pressure-sensitive adhesive layer is post-cured by using the pressure-sensitive adhesive layer having post-curing property.
  • the present invention and preferred configurations of the present invention are as follows. [1] Having a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state,
  • the pressure-sensitive adhesive composition contains a crosslinkable acrylic polymer, a crosslinker, a monomer having at least one reactive double bond in the molecule, and a polymerization initiator.
  • the pressure-sensitive adhesive layer is post-curable and An adhesive sheet that satisfies the following physical property group (1) when the adhesive layer is post-cured; Physical property group (1): Shear storage elastic modulus G'measured at 23 ° C. and frequency 1 Hz is 1 ⁇ 10 6 Pa or more, and shear storage elastic modulus G'measured at 75 ° C.
  • the probe tack value is 5 Pa or more, 23 ° C., and the probe tack value measured under the following measurement conditions is 1.5 N / 5 mm ⁇ or less.
  • Measurement conditions for probe tack value Measuring equipment: NS probe tack tester (manufactured by Nichiban Co., Ltd.) Probe diameter: 5 mm ⁇ Probe base material: Stainless steel surface finish AA # 400 Mirror surface weight by polishing: 19.6 ⁇ 0.2 g (made of brass) Probe moving speed: 1.0 cm / sec Duel time: 1 sec.
  • the pressure-sensitive adhesive composition contains less than 10 parts by mass of a monofunctional monomer having at least one reactive double bond in the molecule as a monomer with respect to 100 parts by mass of the crosslinkable acrylic polymer.
  • the gel fraction of the pressure-sensitive adhesive layer in the semi-cured state is 0% by mass or more and less than 70% by mass, and The pressure-sensitive adhesive sheet according to any one of [1] to [8], wherein when the pressure-sensitive adhesive layer is post-cured, the gel fraction after post-curing is 5% by mass or more higher than the gel fraction in the semi-cured state. ..
  • the crosslinkable functional group of the crosslinkable acrylic polymer is one or more selected from a carboxy group, a hydroxy group, an amino group, an amide group, a glycidyl group and an isocyanate group, [1] to The adhesive sheet according to any one of [9].
  • the polymerization initiator has an ability to initiate polymerization by irradiation with active energy rays.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to any one of [1] to [12] is irradiated with active energy rays and post-cured, and then has a post-cured pressure-sensitive adhesive layer and an adherend. Laminated body.
  • an adhesive sheet having excellent processability when the pressure-sensitive adhesive layer has post-curing property and the pressure-sensitive adhesive layer is post-curing.
  • FIG. 1 is a schematic view showing a cross section of an example of the pressure-sensitive adhesive sheet of the present invention.
  • FIG. 2 is a schematic view showing a cross section of an example of the laminated body of the present invention.
  • FIG. 3 is a schematic view showing a cross section of another example of the laminated body of the present invention.
  • the present invention will be described in detail below.
  • the description of the constituent elements described below may be based on typical embodiments or specific examples, but the present invention is not limited to such embodiments.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • (meth) acrylate represents both acrylate and methacrylate, or either
  • (meth) acrylic acid represents both acrylic acid and methacrylic acid, or either.
  • “monomer” and “monomer” are synonymous.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state.
  • the pressure-sensitive adhesive composition contains a crosslinkable acrylic polymer, a crosslinker, a monomer having at least one reactive double bond in the molecule, and a polymerization initiator.
  • the pressure-sensitive adhesive layer has post-curing property, and when the pressure-sensitive adhesive layer is post-cured, the pressure-sensitive adhesive sheet satisfies the following physical property group (1).
  • Physical property group (1) Shear storage elastic modulus G'measured at 23 ° C. and frequency 1 Hz is 1 ⁇ 10 6 Pa or more, and shear storage elastic modulus G'measured at 75 ° C.
  • the probe tack value is 5 Pa or more, 23 ° C., and the probe tack value measured under the following measurement conditions is 1.5 N / 5 mm ⁇ or less.
  • Measurement conditions for probe tack value Measuring equipment: NS probe tack tester (manufactured by Nichiban Co., Ltd.) Probe diameter: 5 mm ⁇ Probe base material: Stainless steel surface finish AA # 400 Mirror surface weight by polishing: 19.6 ⁇ 0.2 g (made of brass) Probe moving speed: 1.0 cm / sec Duel time: 1 sec.
  • the post-cured pressure-sensitive adhesive layer used for the measurement of the physical property group (1) is obtained by irradiating the semi-cured pressure-sensitive adhesive layer with ultraviolet rays so that the integrated light intensity is 3000 mJ / cm 2.
  • the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of the present invention has post-curability. With the above configuration, the pressure-sensitive adhesive sheet exhibits excellent processability when the pressure-sensitive adhesive layer is post-cured. By setting the shear storage elastic modulus G'at 23 ° C. and 75 ° C. when the pressure-sensitive adhesive layer is post-cured to a specific range or more, the pressure-sensitive adhesive layer becomes hard enough to exhibit excellent processability. Further, by setting the probe tack value at 23 ° C. when the pressure-sensitive adhesive layer is post-cured to a specific range or less, for example, the pressure-sensitive adhesive adheres to the punching blade during punching and the pressure-sensitive adhesive layer is deformed accordingly. It can be prevented.
  • FIG. 1 is a schematic view showing a cross section of an example of the pressure-sensitive adhesive sheet of the present invention.
  • the pressure-sensitive adhesive sheet 1 of the present invention has a pressure-sensitive adhesive layer 11.
  • the pressure-sensitive adhesive sheet 1 may be a single-layer pressure-sensitive adhesive sheet composed of only the pressure-sensitive adhesive layer 11.
  • the pressure-sensitive adhesive sheet may be a single-sided pressure-sensitive adhesive sheet having a base material (preferably a transparent base material) on one side, or a double-sided pressure-sensitive adhesive sheet.
  • a base material preferably a transparent base material
  • a transparent base material 12a may be provided on one side of the pressure-sensitive adhesive layer 11.
  • the other surface of the pressure-sensitive adhesive layer 11 is covered with the release sheet 12b.
  • the transparent base material 12a a general film used in the optical field such as a polyethylene terephthalate film, an acrylic film, a polycarbonate film, a triacetyl cellulose film, and a cycloolefin polymer film can be used. Further, an easy-adhesion layer may be provided on the pressure-sensitive adhesive layer 11 side of these transparent base materials 12a. Further, a functional layer such as a hard coat layer, an antireflection layer, an antifouling layer, and an ultraviolet absorbing layer may be provided on the opposite surface of the transparent base material 12a from the pressure-sensitive adhesive layer 11.
  • a functional layer such as a hard coat layer, an antireflection layer, an antifouling layer, and an ultraviolet absorbing layer may be provided on the opposite surface of the transparent base material 12a from the pressure-sensitive adhesive layer 11.
  • the double-sided pressure-sensitive adhesive sheet includes a single-layer pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer, a multi-layered pressure-sensitive adhesive sheet in which a plurality of pressure-sensitive adhesive layers are laminated, and between the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer.
  • Examples thereof include a multi-layered pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is laminated.
  • the double-sided adhesive sheet has a support, it is preferable to use a transparent support as the support.
  • a general film used in the optical field can be used as in the transparent base material 12a. Since such a double-sided pressure-sensitive adhesive sheet is also excellent in transparency of the pressure-sensitive adhesive sheet as a whole, it can be suitably used for bonding optical members to each other.
  • the pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet, it is preferable that the pressure-sensitive adhesive sheet has a pair of release sheets having different peeling forces on both sides of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present invention is a single-sided pressure-sensitive adhesive sheet, it may have a structure of a transparent base material / pressure-sensitive adhesive layer / release sheet.
  • the surface of the pressure-sensitive adhesive layer 11 is preferably covered with a release sheet. That is, the adhesive sheet is preferably an adhesive sheet with a release sheet.
  • the pressure-sensitive adhesive layer 11 shown in FIG. 1 has a release sheet 12b (in the case of a double-sided pressure-sensitive adhesive sheet, 12a is also a release sheet), and FIG. 1 shows an example of the configuration of the pressure-sensitive adhesive sheet 1 with the release sheet. It represents.
  • the release sheet is a removable laminated sheet having a release sheet base material and a release agent layer provided on one side of the release sheet base material, or a polyolefin film such as a polyethylene film or polypropylene film as a low-polarity base material. Can be mentioned. Papers and polymer films are used as the base material for the release sheet in the releaseable laminated sheet.
  • a general-purpose addition type or condensation type silicone type release agent or a long-chain alkyl group-containing compound is used.
  • an addition type silicone release agent having high reactivity is preferably used.
  • a commercially available product may be used as the peelable laminated sheet.
  • Examples include a heavy separator film, which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd., and a light separator film, which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd. it can.
  • the pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet
  • the peelability of the release sheet 12a and the release sheet 12b may be adjusted according to the bonding method and the bonding order.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state, the pressure-sensitive adhesive layer has post-curing property, and when the pressure-sensitive adhesive layer is post-cured, the above-mentioned physical property group ( 1) is satisfied.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is a semi-cured state of the pressure-sensitive adhesive composition and has post-curability.
  • the fact that the pressure-sensitive adhesive layer is in a semi-cured state can be confirmed from the fact that the gel fraction is 0% by mass or more and less than 70% by mass.
  • the gel fraction of the pressure-sensitive adhesive layer in the semi-cured state is preferably 2% by mass or more and less than 70% by mass, and particularly preferably 5 to 65% by mass. It can be confirmed that the pressure-sensitive adhesive layer is post-cured because the gel fraction is 70 to 100% by mass.
  • the gel fraction of the pressure-sensitive adhesive layer after post-curing is particularly preferably 75 to 100% by mass.
  • the fact that the pressure-sensitive adhesive layer has post-curing property means that when the pressure-sensitive adhesive layer is post-cured, the gel fraction of the pressure-sensitive adhesive layer after post-curing becomes 5% by mass or more higher than the gel fraction in the semi-cured state. It can be confirmed from that.
  • the gel fraction of the pressure-sensitive adhesive layer after post-curing is preferably 10% by mass or more higher than the gel fraction in the semi-cured state, and is 15% by mass or more higher. Is more preferable.
  • the pressure-sensitive adhesive composition In order to obtain a "semi-cured" pressure-sensitive adhesive layer, it is preferable to cure the pressure-sensitive adhesive composition only by heat. That is, the "semi-cured state” is preferably a soft pressure-sensitive adhesive layer after thermosetting and before irradiation with active energy rays. Further, in order to achieve the "post-curing state", it is preferable to irradiate the pressure-sensitive adhesive layer that has been semi-cured by heat with active energy rays to cure the pressure-sensitive adhesive layer. That is, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is preferably in a semi-cured state by thermosetting the pressure-sensitive adhesive composition, and preferably has active energy ray-curability.
  • the physical property group (1) is satisfied when the pressure-sensitive adhesive layer is post-cured.
  • the post-cured pressure-sensitive adhesive layer used for the measurement of the physical property group (1) was obtained by irradiating the semi-cured pressure-sensitive adhesive layer with ultraviolet rays so that the integrated light intensity was 3000 mJ / cm 2. It is an adhesive layer.
  • the probe tack value is 5 Pa or more, 23 ° C., and the probe tack value measured under the above-mentioned measurement conditions is 1.5 N / 5 mm ⁇ or less.
  • the shear storage elastic modulus G'measured at 23 ° C. and a frequency of 1 Hz is preferably 1.2 ⁇ 10 6 Pa or more, preferably 1.5 ⁇ 10 6 Pa or more. Is more preferable.
  • the upper limit of the shear storage modulus G 'of the adhesive layer is measured at 23 ° C. and a frequency 1Hz when it is post-cured are not particularly limited and may be below example 1.0 ⁇ 10 8 Pa.
  • the shear storage elastic modulus G'measured at 75 ° C. and a frequency of 1 Hz is preferably 1.5 ⁇ 10 5 Pa or more, preferably 2.0 ⁇ 10 5 Pa or more. Is more preferable.
  • the upper limit of the shear storage modulus G 'of the adhesive layer is measured at 23 ° C. and a frequency 1Hz when it is post-cured are not particularly limited and may be below example 1.0 ⁇ 10 8 Pa.
  • the probe tack value measured at 23 ° C. and under the above-mentioned measurement conditions is preferably 1.0 N / 5 mm ⁇ or less, and more preferably 0.5 N / 5 mm ⁇ or less.
  • the lower limit of the probe tack value measured at 23 ° C. and under the above-mentioned measurement conditions is not particularly limited, but can be, for example, 0.1 N / 5 mm ⁇ or more.
  • the pressure-sensitive adhesive layer satisfies the following physical property group (2) in a semi-cured state.
  • Physical property group (2) Shear storage elastic modulus G'measured at 23 ° C. and frequency 1 Hz is 8 ⁇ 10 5 Pa or less, and shear storage elastic modulus G'measured at 75 ° C. and frequency 1 Hz is 1 ⁇ 10
  • the probe tack value is 5 Pa or less, 23 ° C., and the probe tack value measured under the above-mentioned measurement conditions is 2.0 N / 5 mm ⁇ or more.
  • the lower limit of the shear storage elastic modulus G'measured at 23 ° C. and a frequency of 1 Hz is not particularly limited, and may be, for example, 1.0 ⁇ 10 4 Pa or more.
  • the shear storage elastic modulus G'measured at 75 ° C. and a frequency of 1 Hz is more preferably 5 ⁇ 10 4 Pa or less, and more preferably 3 ⁇ 10 4 Pa or less. Especially preferable.
  • the lower limit of the shear storage elastic modulus G'measured at 75 ° C. and a frequency of 1 Hz is not particularly limited and can be, for example, 1.0 ⁇ 10 3 Pa or more.
  • the probe tack value measured at 23 ° C. and the above-mentioned measurement conditions is more preferably 2.5 N / 5 mm ⁇ or more, and particularly preferably 3.0 N / 5 mm ⁇ or more. preferable.
  • the upper limit of the probe tack value measured at 23 ° C. and under the above-mentioned measurement conditions is not particularly limited, but can be, for example, 20.0 N / 5 mm ⁇ or less. It is preferably 0 N / 5 mm ⁇ or less.
  • the pressure-sensitive adhesive sheet of the present invention is also excellent in processability after post-curing.
  • the peeling distance is small.
  • the shear storage elastic modulus G'when the pressure-sensitive adhesive layer is post-cured is set to a specific range or more, and the probe tack value when the pressure-sensitive adhesive layer is post-cured is set to a specific range or less. By doing so, it can be improved.
  • the pressure-sensitive adhesive sheet of the present invention has less stickiness (tackiness) on the end face of the pressure-sensitive adhesive layer after post-curing.
  • the shear storage elastic modulus G'when the pressure-sensitive adhesive layer is post-cured is set to a specific range or more, and the probe tack value when the pressure-sensitive adhesive layer is post-cured is set. It can be reduced by setting it below a specific range.
  • the pressure-sensitive adhesive sheet of the present invention is also excellent in outgas resistance after post-curing.
  • the adhesive sheet is less likely to generate air bubbles and peel off after being placed in a high temperature and high humidity environment for a long time.
  • the outgas resistance after post-curing should be improved by setting the shear storage elastic modulus G'in the semi-cured state to a specific range or less and the shear storage elastic modulus G'after post-curing to a specific range or more. Can be done.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately set according to the intended use, and is not particularly limited, but is preferably in the range of 5 to 500 ⁇ m, more preferably 10 to 300 ⁇ m, and particularly preferably 12 to 100 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately set according to the intended use, and is not particularly limited, but is preferably in the range of 5 to 500 ⁇ m, more preferably 10 to 300 ⁇ m, and particularly preferably 12 to 100 ⁇ m.
  • By setting the thickness of the pressure-sensitive adhesive layer within the above range it is possible to sufficiently suppress the generation of air bubbles from an adherend such as a base material. Further, by setting the thickness of the pressure-sensitive adhesive layer within the above range, it is possible to suppress the stickiness and stickiness of the pressure-sensitive adhesive, and as a result, the processability of the pressure-sensitive adhesive sheet can be further improved. Further, by setting the thickness of the pressure-sensitive adhesive layer within the above range, the production of a double-sided pressure-sensitive adhesive sheet becomes easy
  • the above-mentioned pressure-sensitive adhesive layer is a semi-cured state of the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition contains a crosslinkable acrylic polymer, a crosslinker, a monomer having at least one reactive double bond in the molecule, and a polymerization initiator.
  • the pressure-sensitive adhesive composition used in the present invention is preferably a dual-curable pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition contains a crosslinkable acrylic polymer.
  • the crosslinkable acrylic polymer is not particularly limited, but preferably contains a non-crosslinkable (meth) acrylic acid ester unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group.
  • the crosslinkable acrylic polymer preferably has transparency to the extent that it does not reduce the visibility of the display device.
  • a "unit" is a repeating unit (monomer unit) constituting a polymer.
  • the non-crosslinkable (meth) acrylic acid ester unit (a1) is a repeating unit derived from the (meth) acrylic acid alkyl ester.
  • the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, n-butyl (meth) acrylic acid, and (meth).
  • (meth) acrylic acid alkyl esters at least one selected from methyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate is selected because of its high adhesiveness. preferable.
  • the crosslinkable functional group of the crosslinkable acrylic polymer is preferably one or more selected from a carboxy group, a hydroxy group, an amino group, an amide group, a glycidyl group and an isocyanate group. More preferably, it is one or more selected from a carboxy group, a hydroxy group, an amino group and a glycidyl group. That is, the acrylic monomer unit (a2) having a crosslinkable functional group includes a carboxy group-containing monomer unit, a hydroxy group-containing monomer unit, an amino group-containing monomer unit, and a glycidyl group-containing monomer unit. preferable.
  • Examples of the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
  • the hydroxy group-containing monomer unit is a repeating unit derived from the hydroxy group-containing monomer.
  • Examples of the hydroxy group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.
  • Examples thereof include (meth) acrylic acid [(mono, di or poly) alkylene glycol] such as mono (meth) acrylic acid mono (diethylene glycol), and (meth) acrylic acid lactone such as (meth) acrylic acid monocaprolactone.
  • amino group-containing monomer unit examples include repeating units derived from amino group-containing monomers such as (meth) acrylamide and allylamine.
  • glycidyl group-containing monomer unit examples include repeating units derived from a glycidyl group-containing monomer such as glycidyl (meth) acrylate.
  • the content of the acrylic monomer unit (a2) having a crosslinkable functional group in the crosslinkable acrylic polymer is preferably 0.01 to 40% by mass, more preferably 0.5 to 35% by mass. ..
  • the content of the acrylic monomer unit (a2) having a crosslinkable functional group is at least the lower limit of the above range, it has sufficient crosslinkability necessary for maintaining the semi-cured state, and is in the above range. If it is below the upper limit of, it is easy to maintain the required adhesiveness.
  • the crosslinkable acrylic polymer has, if necessary, a monomer unit other than the non-crosslinkable (meth) acrylic acid ester unit (a1) and the acrylic monomer unit (a2) having a crosslinkable functional group. You may.
  • the other monomer may be copolymerizable with a non-crosslinkable (meth) acrylic acid ester and an acrylic monomer having a crosslinkable functional group, for example, (meth) acrylonitrile, vinyl acetate, styrene, chloride. Examples include vinyl, vinylpyrrolidone, vinylpyridine and the like.
  • the content of the other monomer unit in the crosslinkable acrylic polymer is preferably 0 to 20% by mass, more preferably 0 to 15% by mass.
  • the weight average molecular weight of the crosslinkable acrylic polymer is preferably 100 to 2 million, more preferably 300 to 1.5 million. When the weight average molecular weight is within the above range, the semi-cured state of the pressure-sensitive adhesive sheet can be easily maintained and the hardness after post-curing can be easily obtained. As a result, the processability of the pressure-sensitive adhesive sheet can be improved.
  • the weight average molecular weight of the crosslinkable acrylic polymer is a value before being crosslinked with a crosslinking agent.
  • the weight average molecular weight is a value measured by size exclusion chromatography (SEC) and determined based on polystyrene.
  • SEC size exclusion chromatography
  • As the crosslinkable acrylic polymer a commercially available one may be used, or one synthesized by a known method may be used.
  • the pressure-sensitive adhesive composition contains a cross-linking agent.
  • the cross-linking agent can be appropriately selected in consideration of the reactivity of the cross-linking acrylic polymer with the cross-linking functional group.
  • it can be selected from known cross-linking agents such as isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds and butylated melamine compounds.
  • an isocyanate compound and an epoxy compound are preferable because the acrylic monomer unit (a2) having a crosslinkable functional group can be easily crosslinked.
  • the cross-linking agent is one or more selected from a bifunctional or higher functional epoxy compound and a bifunctional or higher functional isocyanate compound.
  • a bifunctional or higher functional epoxy compound and a bifunctional or higher functional isocyanate compound.
  • an isocyanate compound because of the reactivity of the hydroxy group.
  • Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.
  • Examples of the epoxy compound include ethylene glycol diglycidyl ether, polytylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, openyl glycol diglycidyl ether, and 1,6-hexanediol.
  • a commercially available product can be used as the cross-linking agent.
  • Examples of commercially available products include tolylene diisocyanate compounds (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L), xylylene diisocyanate compounds (manufactured by Mitsui Chemicals, Inc., Takenate D-110N) and the like.
  • the content of the cross-linking agent in the pressure-sensitive adhesive composition is appropriately selected according to the desired adhesiveness and the like. 0.01 to 5 parts by mass is preferable, and 0.1 to 3 parts by mass is more preferable with respect to 100 parts by mass of the crosslinkable acrylic polymer.
  • the content of the cross-linking agent is at least the above lower limit value, the shear storage elastic modulus G'in the semi-cured state can be adjusted to a desired range, so that the processability is excellent.
  • the initial substrate adhesion Therefore, it does not come off even if it is rubbed by hand after post-curing, and it has excellent workability.
  • the cross-linking agent one type may be used alone or two or more types may be used in combination, and when two or more types are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition contains a monomer having at least one reactive double bond in the molecule.
  • the glass transition temperature (Tg) of the homopolymer when a monomer having at least one reactive double bond in the molecule is polymerized is preferably 30 ° C. or higher, more preferably 40 ° C. or higher. It is more preferably 45 ° C. or higher.
  • the monomer may be a monofunctional monomer having one reactive double bond in the molecule, or a polyfunctional monomer having two or more reactive double bonds in the molecule. Good. Further, as the monomer, a monofunctional monomer and a polyfunctional monomer may be used in combination.
  • Examples of the monofunctional monomer include isobolonyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, stearyl methacrylate and the like.
  • a commercially available product can be used as the monofunctional monomer. Examples of commercially available products include IBXA manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • the content of the monofunctional monomer may be 5 to 40 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer.
  • the content of the monofunctional monomer may be less than 10 parts by mass or less than 8 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer.
  • the pressure-sensitive adhesive composition may not contain a monofunctional monomer.
  • the polyfunctional monomer has two or more reactive double bonds, and among them, it is preferable that the polyfunctional monomer has 3 to 6 reactive double bonds.
  • the pressure-sensitive adhesive composition preferably contains a polyfunctional monomer containing two or more reactive double bonds in the molecule.
  • polyfunctional monomer examples include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1, (meth) acrylate. 4-butylene glycol, di (meth) acrylic acid 1,9-nonanediol, diacrylic acid 1,6-hexanediol, di (meth) acrylic acid polybutylene glycol, di (meth) acrylic acid neopentyl glycol, di (meth) ) Tetraethylene glycol acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tetra (meth) acrylic Examples thereof include (meth) acrylic acid esters of polyhydric alcohols such as pentaerythritol acid, vinyl methacrylate
  • commercially available products can be used as the polyfunctional monomer.
  • examples of commercially available products include trimethylolpropane propylene oxide-modified triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-321), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., Aronix M-405) and the like.
  • the pressure-sensitive adhesive composition preferably contains the above-mentioned monomer by 5 to 40 parts by mass, more preferably 15 to 40 parts by mass, and 25 to 40 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer. It is particularly preferable to contain 35 parts by mass.
  • the monomer may be used alone or in combination of two or more, and when two or more of them are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition preferably contains a polyfunctional monomer, and particularly preferably contains a polyfunctional monomer having 3 to 6 reactive double bonds.
  • the polyfunctional monomer having 3 to 6 reactive double bonds is preferably contained in an amount of 5 to 40 parts by mass, preferably 15 to 40 parts by mass, based on 100 parts by mass of the crosslinkable acrylic polymer. Is more preferable, and 25 to 35 parts by mass is particularly preferable.
  • the pressure-sensitive adhesive composition contains a polymerization initiator.
  • the polymerization initiator preferably has an ability to initiate polymerization by irradiation with active energy rays, and more preferably has an ability to initiate polymerization of the above-mentioned monomer.
  • the polymerization initiator for example, a known one such as a photopolymerization initiator can be used.
  • the "active energy ray” means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, electron beams, visible rays, X-rays, and ion rays. Among them, from the viewpoint of versatility, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable.
  • Examples of the polymerization initiator include acetophenone-based initiators, benzoin ether-based initiators, benzophenone-based initiators, hydroxyalkylphenone-based initiators, thioxanthone-based initiators, amine-based initiators, acylphosphine oxide-based initiators, and the like. Be done.
  • Specific examples of the acetophenone-based initiator include diethoxyacetophenone and benzyl dimethyl ketal.
  • Specific examples of the benzoin ether-based initiator include benzoin and benzoin methyl ether.
  • Specific examples of the benzophenone-based initiator include benzophenone, methyl o-benzoylbenzoate, and the like.
  • hydroxyalkylphenone-based initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Ltd., commercially available as IRGACURE184) and the like.
  • thioxanthone-based initiator examples include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone and the like.
  • amine-based initiator examples include triethanolamine, ethyl 4-dimethylbenzoate and the like.
  • acylphosphine oxide-based initiator examples include phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (manufactured by BASF Japan Ltd., commercially available as IRGACURE819) and the like.
  • the content of the polymerization initiator in the pressure-sensitive adhesive composition is appropriately selected according to the content of the monomer, the irradiation amount of active energy rays at the time of post-curing, and the like. Specifically, it is preferably 0.05 to 10% by mass, more preferably 0.1 to 5.0% by mass, based on the total mass of the monomer. If it is at least the above lower limit value, the hardness can be adjusted to a desired level by post-curing, so that workability is excellent. When it is not more than the above upper limit value, the molecular weight after post-curing is not reduced, and the workability and outgas resistance are excellent.
  • the polymerization initiator one type may be used alone or two or more types may be used in combination, and when two or more types are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition may contain a solvent.
  • the solvent is used to improve the coating suitability of the pressure-sensitive adhesive composition.
  • the solvent include hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene and dichloropropane; methanol, ethanol, Alcohols such as propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ket
  • the content of the solvent in the pressure-sensitive adhesive composition is not particularly limited, but is preferably 25 to 500 parts by mass, more preferably 30 to 400 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer.
  • the content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the pressure-sensitive adhesive composition.
  • One type of solvent may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition may further contain a plasticizer as long as the effects of the present invention are not impaired.
  • the pressure-sensitive adhesive composition contains a plasticizer, the pressure-sensitive adhesive sheet can fill the step formed on the adherend, and the unevenness-following property is enhanced.
  • the plasticizer is preferably a non-functional acrylic polymer.
  • the non-functional group acrylic polymer is a polymer consisting only of an acrylic monomer unit having no functional group other than an acrylate group, or a non-functional group having no functional group other than an acrylate group and an acrylic monomer unit having no functional group. It is a polymer composed of an acrylic monomer unit.
  • the non-functional group acrylic polymer is not crosslinked, it is possible to improve the unevenness followability without affecting the adhesiveness.
  • the acrylic monomer unit having no functional group other than the acrylate group include those similar to the non-crosslinkable (meth) acrylic acid ester unit (a1).
  • the non-acrylic monomer unit having no functional group include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, and stearer.
  • vinyl carboxylic acid esters such as vinyl acetate, vinyl cyclohexanecarboxylate, vinyl benzoate, and styrene.
  • the pressure-sensitive adhesive composition may contain components other than the above as long as the effects of the present invention are not impaired.
  • other components include components known as additives for adhesives.
  • an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, an ultraviolet absorber, a light stabilizer such as a hindered amine compound, and the like can be selected as necessary.
  • the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a lactone-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like. One type of these antioxidants may be used alone, or two or more types may be used in combination.
  • a benzodiazole-based resin can be mentioned as a preferable example because of the compatibility and high effect of the pressure-sensitive adhesive.
  • the tackifier include rosin-based resin, terpene-based resin, terpene phenol-based resin, Kumaron inden-based resin, styrene-based resin, xylene-based resin, phenol-based resin, and petroleum resin.
  • the silane coupling agent include a mercaptoalkoxysilane compound (for example, a mercapto group-substituted alkoxy oligomer).
  • the ultraviolet absorber include benzotriazole-based compounds and benzophenone-based compounds. However, when ultraviolet rays are used for the active energy rays during post-curing, it is preferable to add them within a range that does not inhibit the polymerization reaction.
  • the method for producing the adhesive sheet is not particularly limited.
  • the method for producing the pressure-sensitive adhesive sheet preferably includes a step of applying the pressure-sensitive adhesive composition on the release sheet to form a coating film and a step of heating the coating film to make a cured product in a semi-cured state.
  • the reaction between the crosslinkable acrylic polymer and the crosslinker proceeds to form a cured product (adhesive layer) in a semi-cured state. That is, during heating, the polymerization reaction of the monomer by the polymerization initiator does not proceed in the coating film, or even if it progresses, it is slight, so that the single amount contained in the pressure-sensitive adhesive composition is contained in the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present invention preferably has post-curability and active energy ray-curability.
  • an aging treatment in which the pressure-sensitive adhesive sheet is allowed to stand at a constant temperature for a certain period of time after the solvent is removed after coating.
  • the aging treatment can be performed, for example, by allowing it to stand at 23 ° C. for 7 days.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention can be post-cured by irradiating an adherend such as a base material with active energy rays.
  • the pressure-sensitive adhesive sheet of the present invention is a two-step curing pressure-sensitive adhesive sheet, and preferably has a pressure-sensitive adhesive layer semi-cured only by heat before bonding, and the pressure-sensitive adhesive layer can be post-cured by active energy rays after bonding. ..
  • the coating of the pressure-sensitive adhesive composition can be carried out 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 micro gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater and the like.
  • a known heating device such as a heating furnace or an infrared lamp can be used to heat the coating film formed by applying the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is brought into contact with the surface of the adherend.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is adhered to an adherend when it is in a semi-cured state, and the pressure-sensitive adhesive layer is post-cured by irradiating with active energy rays.
  • the pressure-sensitive adhesive sheet of the present invention is preferably used for an optical member that requires durability, particularly an application that has a complicated shape and requires punching after forming a laminated body. It is preferable that the pressure-sensitive adhesive sheet of the present invention can suppress the generation of air bubbles even when it is attached to an adherend such as a base material, post-cured, and then exposed to a high humidity and heat environment.
  • the pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive sheet used for sticking to a base material, and more preferably a pressure-sensitive adhesive sheet used for sticking to a polycarbonate base material. Examples of the polycarbonate base material include PC-1151 manufactured by Teijin Chemicals Ltd.
  • the pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive sheet used for direct bonding to a base material, but may be used for indirectly bonding to a base material.
  • a base material including a polycarbonate base material.
  • Such a multilayer base material is preferably a base material having a polycarbonate layer and a hard coat layer.
  • the composition of the hard coat layer is preferably selected from acrylic, urethane, silicone, melamine, and epoxy, and more preferably acrylic and silicone.
  • the composition of the hard coat layer is more preferably acrylic from the viewpoint of workability and hardness.
  • a multilayer base material containing a polycarbonate base material is also referred to as a polycarbonate base material.
  • the multilayer base material containing the polycarbonate base material for example, MR-58 or IMR05 manufactured by Mitsubishi Gas Chemical Company, Inc. can be used.
  • the composition of MR-58 is HC (hard coat) / PMMA (polymethyl methacrylate) / PC (polycarbonate) / HC (hard coat).
  • the overall thickness of MR-58 is preferably 0.3 mm to 1.2 mm, and the thickness of one hard coat layer is preferably 0.0005 mm to 0.02 mm.
  • the composition of IMR05 is HC (hard coat) / PC (polycarbonate).
  • the pressure-sensitive adhesive sheet of the present invention can suppress the occurrence of air bubbles and peeling even when it is attached to an optical member such as a polarizing plate, post-cured, and then exposed to a high humidity and heat environment.
  • the polarizing plate includes a polarizing element and a polarizer protective film
  • the pressure-sensitive adhesive sheet of the present invention is preferably bonded to the polarizer protective film.
  • the polarizer protective film includes a cycloolefin resin film, a cellulose acetate resin film such as triacetyl cellulose and diacetyl cellulose, a polyester resin film such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, a polycarbonate resin film, and acrylic. Examples thereof include a based resin film and a polypropylene resin film.
  • the polarizer protective film is a cellulose acetate-based resin film, the effect of suppressing the generation of bubbles is exhibited by using the pressure-sensitive adhesive sheet of the present invention.
  • the generation of air bubbles in the adherend of the adhesive sheet can be suppressed, deterioration of visibility can be prevented when the adhesive sheet is incorporated in a display device or the like.
  • the semi-cured adhesive sheet is attached to the adherend so that the unevenness can be followed. Further, the adhesive strength and the holding power can be enhanced by post-curing the pressure-sensitive adhesive layer by irradiation with active energy rays.
  • the laminate of the present invention has a pressure-sensitive adhesive layer after curing by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention with active energy rays and then curing, and an adherend.
  • the pressure-sensitive adhesive sheet contained in the laminate is post-cured by irradiating active energy rays with two adherends (for example, a base material and an optical member) bonded together with a semi-cured pressure-sensitive adhesive sheet. It is preferable to have.
  • FIG. 2 is a schematic view showing a cross section of an example of the laminated body of the present invention.
  • FIG. 2 is a cross-sectional view showing an example of the configuration of the laminated body 20 in which the pressure-sensitive adhesive sheet 21 of the present invention is bonded to the base material 22 and the optical member 24.
  • the pressure-sensitive adhesive sheet 21 in FIG. 2 corresponds to the pressure-sensitive adhesive layer 11 in FIG.
  • the pressure-sensitive adhesive sheet 21 of the present invention is preferably used for bonding to the base material 22, and may be used for bonding the base material 22 and another optical member 24. preferable.
  • the pressure-sensitive adhesive sheet 21 of the present invention may be used for bonding with a polarizing plate.
  • Examples of the optical member included in the laminate include each component in an optical product such as a touch panel and an image display device.
  • Examples of the constituent members of the touch panel include 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 the surface of a glass plate, and a transparent conductive film in which a transparent resin film is coated with a conductive polymer.
  • Examples include hard coat films and fingerprint resistant films.
  • Examples of the constituent members of the image display device include an antireflection film, an alignment film, a polarizing film, a retardation film, and a luminance improving film used in a liquid crystal display device.
  • Examples of the material used for these members include glass, polycarbonate, polyethylene terephthalate, polymethylmethacrylate, polyethylene naphthalate, cycloolefin polymer, triacetyl cellulose, polyimide, cellulose acylate and the like.
  • the adhesive sheet of the present invention is a double-sided adhesive sheet, it can be used for bonding two adherends.
  • the adhesive sheet of the present invention is used for bonding transparent optical films inside the touch panel, bonding the transparent optical film and glass, bonding the transparent optical film of the touch panel to the liquid crystal panel, and covering glass. It is used for bonding the transparent optical film and the cover glass, and it is preferable that any of the members is a polycarbonate base material.
  • the transparent optical film a general film used in the optical field such as a polyethylene terephthalate film, an acrylic film, a polycarbonate film, a triacetyl cellulose film, and a cycloolefin polymer film can be used.
  • a hard coat layer may be provided on the transparent optical film or the polycarbonate base material.
  • FIG. 3 is a schematic view showing a cross section of another example of the laminated body of the present invention.
  • the adherend may have stepped portions (27a, 27b, 27c, 27d).
  • the base material has a stepped portion (27a, 27b), and the optical member has a stepped portion (27c, 27d).
  • the thickness of the stepped portion (27a, 27b, 27c, 27d) is usually 5 to 60 ⁇ m.
  • the adhesive sheet 21 of the present invention can be attached to a member having a stepped portion, and can follow the unevenness generated from the stepped portion.
  • the method for producing a laminate of the present invention is a step of attaching the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention to an adherend in a semi-cured state, and then irradiating an active energy ray to post-cure the pressure-sensitive adhesive layer.
  • the adherend is more preferably a base material and an optical member, and particularly preferably a polycarbonate base material, a polarizing plate, a transparent film, a transparent resin or glass.
  • the adherend is a transparent film, a transparent resin or glass.
  • the active energy rays can be irradiated from either the base material side or the optical member side, but it is preferable to irradiate from the base material side. Since the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is in a semi-cured state before irradiation with the active energy rays, the pressure-sensitive adhesive layer can follow the unevenness even if the adherend has a stepped portion. In this way, the adhesive sheet is attached to each other to follow the unevenness, and then the adhesive layer is post-cured with active energy rays to increase the cohesive force of the adhesive layer and improve the adhesiveness to the adherend. To do. In addition, the post-cured pressure-sensitive adhesive layer can prevent the base material from being deformed or distorted.
  • Examples of the active energy ray include ultraviolet rays, electron beams, visible rays, X-rays, ion rays and the like, which can be appropriately selected depending on the polymerization initiator contained in the pressure-sensitive adhesive layer. Among them, from the viewpoint of versatility, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable.
  • the light source of ultraviolet rays 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, an electrodeless ultraviolet lamp and the like can be used.
  • the electron beam for example, an electron beam emitted from each type of electron beam accelerator such as Cockloft Wald type, Bandecliff type, Resonant transformer type, Insulated core transformer type, Linear type, Dynamitron type, High frequency type is used. it can.
  • Radiation output of the UV light it is preferable that the integrated quantity of light is made to be a 100 ⁇ 10000mJ / cm 2, and more preferably made to be 500 ⁇ 5000mJ / cm 2.
  • a crosslinkable acrylic polymer was prepared by solution polymerization in ethyl acetate. 2-Hydroxyethyl acrylate monomer, n-butyl acrylate monomer, and dimethylacrylamide are blended in a mass ratio of 0.5: 10: 2.5, and AIBN (azobisisobutyronitrile) is used as a radical polymerization initiator. was dissolved in the solution. The solution was heated to 60 ° C. and randomly copolymerized to obtain a crosslinkable acrylic polymer A. The solution viscosity of the 35% by mass solution of the crosslinkable acrylic polymer at 23 ° C. was 5500 mPa ⁇ s.
  • a crosslinkable acrylic polymer B was obtained in the same manner as in Production Example 1 above except that the 2-hydroxyethyl acrylate monomer was changed to acrylic acid.
  • the pressure-sensitive adhesive composition was applied onto a first release sheet (heavy separator film, Teijin DuPont Film Co., Ltd., release-treated polyethylene terephthalate film).
  • the coating was performed using a doctor blade YD type manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying was 50 ⁇ m. Then, it was dried in a hot air dryer at 100 ° C. for 3 minutes to remove the solvent, and a pressure-sensitive adhesive sheet having a semi-cured pressure-sensitive adhesive layer was formed.
  • a second release sheet (light separator film, manufactured by Teijin DuPont Film Co., Ltd.), which has been subjected to a mold release treatment higher than the first release sheet, is attached to one side of this adhesive sheet, and the adhesive with the release sheet is attached.
  • An adhesive sheet of Example 1 which is a sheet was obtained.
  • Comparative Example 2 The crosslinkable acrylic polymer A was changed to the crosslinkable acrylic polymer B, and the crosslinking agent was changed to the epoxy compounds N, N, N', N'-tetraglycidyl-m-xylene diamine (manufactured by Mitsubishi Gas Chemicals, Ltd., trade name). Tetrad X) The pressure-sensitive adhesive sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that it was changed to 0.2 parts by mass and no polyfunctional monomer, monofunctional monomer and polymerization initiator was used. It was.
  • a dynamic viscoelastic device Rheogel-E4000 manufactured by UBM Co., Ltd.
  • the temperature was 0 ° C. to 150 ° C. under the conditions of solid shear mode, frequency 1 Hz, and strain 0.1%.
  • the shear storage elastic modulus G'of the pressure-sensitive adhesive layer in the temperature range up to was measured.
  • the shear storage elastic modulus G'of the pressure-sensitive adhesive layer at 23 ° C. and 75 ° C. is shown in Table 1 below.
  • the second release sheet which is a light separator film of the adhesive sheet
  • a PET film to prepare a sample for measurement in a semi-cured state.
  • the second release sheet which is a light separator film of the adhesive sheet
  • ultraviolet rays were irradiated from the side of the first release sheet, which is a heavy separator film, so that the integrated light intensity was 3000 mJ / cm 2, and a sample for measurement after post-curing was prepared.
  • Each measurement sample was cut into 3 cm ⁇ 3 cm, and the probe tack value was measured with a probe tack tester under the following conditions.
  • Measuring equipment NS probe tack tester (manufactured by Nichiban Co., Ltd.) Probe diameter: 5 mm ⁇ Probe base material: Stainless steel surface finish AA # 400 Mirror surface weight by polishing: 19.6 g (made of brass) Probe movement speed: 1.0 cm / sec Duel time: 1 sec
  • the second release sheet which is a light separator film of the pressure-sensitive adhesive layer
  • a PET film having a thickness of 25 ⁇ m.
  • the first release sheet which is a heavy separator film, was peeled off and attached to a PC plate.
  • the sample having the composition of PET / adhesive layer / PC was autoclaved (40 ° C., 0.5 MPa, 30 min), and then ultraviolet rays were irradiated from the PET film side so that the integrated light intensity was 3000 mJ / cm 2, and the test sample was obtained.
  • Peeling distance is less than 0.05 mm ... ⁇ Peeling distance is 0.05 mm or more and less than 0.1 mm ... ⁇ Peeling distance is 0.1 mm or more ... ⁇
  • the second release sheet which is a light separator film of the pressure-sensitive adhesive layer
  • the first release sheet which is a heavy separator film
  • the sample having the composition of PET / adhesive layer / PC was autoclaved (40 ° C., 0.5 MPa, 30 min), and then ultraviolet rays were irradiated from the PET film side so that the integrated light intensity was 3000 mJ / cm 2, and the test sample was obtained.
  • Got The test sample was placed in an environment of 105 ° C. dry and 85 ° C. 85%, and bubbles and peeling were observed after 500 hours. No bubbles or peeling is observed in either environment ... ⁇ Bubbles and peeling are observed in at least one environment ... ⁇
  • the pressure-sensitive adhesive sheet of the present invention has excellent processability when the pressure-sensitive adhesive layer is post-curable and the pressure-sensitive adhesive layer is post-cured.
  • the pressure-sensitive adhesive sheet of the present invention also had good end face stickiness and outgas resistance.
  • Comparative Example 1 it was found that when the pressure-sensitive adhesive layer after post-curing is less than the lower limit of the shear storage elastic modulus specified in the present invention, the processability is inferior when the pressure-sensitive adhesive layer is post-cured.
  • Comparative Example 2 when the pressure-sensitive adhesive layer after post-curing is below the lower limit of the shear storage elastic modulus specified in the present invention and exceeds the upper limit of the probe tack value, it is processed when the pressure-sensitive adhesive layer is post-cured. It turned out to be inferior in sex.
  • Adhesive sheet 11 Adhesive layer 12a Transparent base material or release sheet 12b Release sheet 20 Laminated body 21 Adhesive sheet 22 Base material 24 Optical members 27a, 27b, 27c, 27d Steps

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