WO2020256068A1 - Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive et corps multicouche - Google Patents

Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive et corps multicouche Download PDF

Info

Publication number
WO2020256068A1
WO2020256068A1 PCT/JP2020/023975 JP2020023975W WO2020256068A1 WO 2020256068 A1 WO2020256068 A1 WO 2020256068A1 JP 2020023975 W JP2020023975 W JP 2020023975W WO 2020256068 A1 WO2020256068 A1 WO 2020256068A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive sheet
polyrotaxane
meth
Prior art date
Application number
PCT/JP2020/023975
Other languages
English (en)
Japanese (ja)
Inventor
山本　真之
貴迪 山口
Original Assignee
王子ホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2019115661A external-priority patent/JP6699788B1/ja
Priority claimed from JP2019115662A external-priority patent/JP6696614B1/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 WO2020256068A1 publication Critical patent/WO2020256068A1/fr

Links

Images

Classifications

    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material 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
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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, an adhesive sheet with a release sheet, and a laminate.
  • a display device such as a liquid crystal display (LCD) and an input device used in combination with a display device such as a touch panel are widely used.
  • LCD liquid crystal display
  • an input device used in combination with a display device such as a touch panel.
  • transparent adhesive sheets are used for bonding optical members, and transparent adhesive sheets are also used for bonding display devices and input devices. ..
  • the pressure-sensitive adhesive sheet formed by two-stage polymerization in which polymerization is carried out by heat (or active energy ray) and then polymerization by active energy ray (or heat) is an adhesive having both thermosetting property and active energy ray curable property. It is formed from a composition (hereinafter, may be referred to as "dual curable pressure-sensitive adhesive composition").
  • the pressure-sensitive adhesive composition is thermoset before being bonded to the adherend, temporarily adhered to the adherend, and then further irradiated with active energy rays to completely cure the pressure-sensitive adhesive composition ( It is called post-curing or after-cure). As a result, the pressure-sensitive adhesive layer is firmly adhered to the adherend.
  • Patent Document 1 includes 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).
  • a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer obtained by semi-curing a pressure-sensitive adhesive composition containing the solvent (E) by heating is described.
  • Patent Document 2 describes a pressure-sensitive adhesive sheet comprising a (meth) acrylic acid ester copolymer, a heat-crosslinking agent, an active energy ray-curable component, and an active energy ray-curable pressure-sensitive adhesive containing a polyrotaxane compound.
  • the polyrotaxane compound is incorporated into the crosslinked structure of the base polymer in a semi-cured state.
  • an optical member to which an adhesive sheet is attached may be used in a harsh environment such as a high temperature or high humidity environment, and in such an environment, the optical member has dimensions as the heat or humidity changes. May make a difference. Depending on the material of the optical member, the degree of susceptibility to heat is different. Therefore, when other types of optical members are bonded together, the size of the pair of optical members differs, and the adhesive sheet becomes corresponding. It was a problem because it could curl.
  • the adhesive sheet used for bonding optical members may be required to have high transparency depending on the application.
  • the present inventors are a post-curing adhesive sheet, which is a highly transparent adhesive sheet having excellent outgas resistance and curl resistance. We proceeded with the study for the purpose of providing.
  • the present inventors have added a crosslinkable (meth) acrylic copolymer to the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer in a semi-cured state.
  • a cross-linking agent a polyrotaxane having a predetermined structure, a monomer having an alkylene glycol group in the molecule and two (meth) acryloyl groups, and a polymerization initiator, the pressure-sensitive adhesive layer after post-curing can be formed. It has been found that it can exhibit excellent outgas resistance and curl resistance. Also.
  • the present inventors have found that such an adhesive layer also has high transparency, and have completed the present invention. 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 crosslinkable (meth) acrylic copolymer, a crosslinker, a polyrotaxane, a monomer having an alkylene glycol group in the molecule and two (meth) acryloyl groups, and a polymerization initiator.
  • Polyrotaxane is an adhesive sheet having a linear portion and an annular portion that is included in a state of penetrating a part of the linear portion, and the molecule constituting the cyclic portion has a vinyl group.
  • the polyrotaxane has a first polyrotaxane and a second polyrotaxane.
  • the first polyrotaxane has a linear portion and a cyclic portion that is included in a state of penetrating a part of the linear portion, and the molecule constituting the cyclic portion has a hydroxy group.
  • the second polyrotaxane has a linear portion and a cyclic portion that is included in a state of penetrating a part of the linear portion, and the molecule constituting the cyclic portion has a vinyl group, according to [1].
  • Adhesive sheet [3] The pressure-sensitive adhesive sheet according to [1] or [2], wherein the content of polyrotaxane is 0.1 to 5 parts by mass with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer.
  • the pressure-sensitive adhesive sheet according to [9] or [10], wherein the resin plate, the resin sheet and the resin film contain at least one selected from a polycarbonate resin and a (meth) acrylic resin.
  • An adhesive sheet with a release sheet comprising a pair of release sheets having different peeling forces on both surfaces of the adhesive sheet according to any one of [1] to [11].
  • FIG. 1 is a schematic view showing a cross section of a release sheet or an adhesive sheet having a base material.
  • FIG. 2 is a schematic diagram illustrating the structure of polyrotaxane.
  • 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) acrylic represents both acrylic and methacrylic, or either of them.
  • “monomer” and “monomer” are synonymous, and “polymer” and “polymer” 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 includes a crosslinkable (meth) acrylic copolymer, a crosslinker, a polyrotaxane, a monomer having an alkylene glycol group in the molecule and two (meth) acryloyl groups, and a polymerization initiator.
  • the polyrotaxane has a linear portion and a cyclic portion that is included in a state of penetrating a part of the linear portion, and the molecule constituting the cyclic portion has a vinyl group.
  • the polyrotaxane preferably has a first polyrotaxane and a second polyrotaxane.
  • the first polyrotaxane has a linear portion and a cyclic portion that is included in a state of penetrating a part of the linear portion, and the molecule constituting the cyclic portion has a hydroxy group.
  • the second polyrotaxane has a linear portion and a cyclic portion that is included in a state of penetrating a part of the linear portion, and the molecule constituting the cyclic portion has a vinyl group.
  • the pressure-sensitive adhesive sheet of the first embodiment is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state, and the pressure-sensitive adhesive composition has a crosslinkable (meth) acrylic co-weight.
  • the pressure-sensitive adhesive sheet of the second embodiment is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state, and the pressure-sensitive adhesive composition is a crosslinkable (meth) acrylic copolymer or a cross-linking agent.
  • the polyrotaxane having a vinyl group is incorporated into a polymer having a high crosslink density composed of a polyfunctional monomer formed by post-curing during post-hardening. Therefore, an adhesive layer having both hardness and stress relaxation properties is formed. Therefore, the pressure-sensitive adhesive sheet of the present invention can exhibit excellent outgas resistance and curl resistance after post-curing.
  • the pressure-sensitive adhesive sheet of the present invention since the pressure-sensitive adhesive sheet of the present invention has an adhesive layer in a semi-cured state before post-curing, it has excellent flexibility in the semi-cured state and is adhered to an adherend in the semi-cured state.
  • the adhesive sheet of the present invention exhibits excellent outgas resistance and curl resistance while firmly adhering to the adherend during post-curing.
  • the first polyrotaxane is incorporated into the crosslinked structure of the crosslinkable (meth) acrylic copolymer during thermosetting, and the second polyrotaxane is later. Since it is incorporated into the polymer formed by post-curing when it is hard, an adhesive layer having both hardness and stress relaxation properties is formed. Therefore, the pressure-sensitive adhesive sheet of the present invention can exhibit more excellent outgas resistance and curl resistance after post-curing.
  • the outgas resistance of the pressure-sensitive adhesive sheet after post-curing is such that the integrated light amount becomes 3000 mJ / cm 2 after the adherend is attached to both sides of the pressure-sensitive adhesive layer to prepare a laminated body. It can be evaluated by irradiating with ultraviolet rays, placing it in an environment of 85 ° C. and 85% relative humidity, and visually confirming each of the laminated bodies after 2 hours and 100 hours. Specifically, it is preferable that no bubbles, floats or peels are observed in the laminate after 2 hours, and more preferably no bubbles, floats or peels are observed in the laminate after 2 hours and 100 hours.
  • the curl resistance of the pressure-sensitive adhesive sheet after post-curing is such that the adherend is attached to both sides of the pressure-sensitive adhesive layer to prepare a laminate, and then the laminate is heated to 85 ° C. or 105 ° C. ( It can be evaluated by treating it in an oven having a relative humidity of 20% or less for 24 hours, taking it out, and allowing it to stand on a horizontal surface within 5 minutes. At this time, the laminated body is allowed to stand so that the convex surface is on the bottom, and the heights of the four corners of the sample from the waterside surface are measured to calculate the average value. When the average value is less than 5 mm, it can be determined that the curl resistance is good.
  • Polyrotaxane has a drawback that it is difficult to be compatible with other high molecular weight materials, and when it is added to a conventional pressure-sensitive adhesive composition, transparency is impaired even in a small amount and it cannot be used for bonding optical system members.
  • the pressure-sensitive adhesive sheet of the present invention can exhibit high transparency by using a monomer having an alkylene glycol group and two (meth) acryloyl groups in the molecule.
  • the transparency of the pressure-sensitive adhesive sheet after post-curing can be evaluated by measuring the haze of the pressure-sensitive adhesive layer. When measuring the haze of the pressure-sensitive adhesive layer, first, transparent glass plates are attached to both sides of the pressure-sensitive adhesive layer, treated in an autoclave at 40 ° C.
  • the haze of the pressure-sensitive adhesive layer after post-curing is preferably less than 1.0%, more preferably 0.9% or less, and even more preferably 0.8% or less. .. As described above, the adhesive layer after post-curing has a low haze value and is highly transparent.
  • the pressure-sensitive adhesive composition is blended with polyrotaxane in which the molecule constituting the cyclic portion has a vinyl group, and further, a single amount having an alkylene glycol group and two (meth) acryloyl groups in the molecule.
  • the pressure-sensitive adhesive composition is blended with two types of polyrotaxanes having different structures, and further has an alkylene glycol group in the molecule and two (meth) acryloyl groups.
  • the polyrotaxane structure is incorporated into both the crosslinkable (meth) acrylic copolymer which is the base polymer and the post-curing component, so that the hardness and transparency of the adhesive layer after post-curing can be improved. While increasing, the stress relaxation property when heated can be enhanced. This makes it possible to more effectively enhance the curl resistance of the pressure-sensitive adhesive layer after post-curing. Further, by using such a pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer after post-curing can exhibit more excellent outgas resistance.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet may be a single-layer pressure-sensitive adhesive sheet composed of only the pressure-sensitive adhesive layer. Further, 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.
  • the double-sided adhesive sheet includes a single-layer adhesive sheet composed of an adhesive layer, a multi-layer adhesive sheet in which a plurality of adhesive layers are laminated, and a multi-layer adhesive in which another adhesive layer is laminated between the adhesive layers.
  • a transparent support As the support, a general film used in the optical field can be used as in the case of the transparent substrate. 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 adhesive sheet of the present invention is preferably a double-sided adhesive sheet. Further, the present invention may relate to an adhesive sheet with a release sheet provided with release sheets on both surfaces of the adhesive sheet. When the adhesive sheet of the present invention is provided with the release sheets on both surfaces, the adhesive sheet 10 with the release sheet may have the release sheets 12a and 12b on both surfaces of the adhesive layer 11 as shown in FIG. preferable.
  • the release sheet is a releaseable 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 with a release sheet preferably has a pair of release sheets having different peeling forces on both surfaces of the pressure-sensitive adhesive sheet. That is, it is preferable that the release sheet has different peelability between the release sheet 12a and the release sheet 12b in order to facilitate the release. When the peelability from one side and the peelability from the other side are different, it becomes easy to peel off only the release sheet having the higher peelability first. In that case, 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 present invention may relate to an adhesive sheet with a transparent film having a transparent film on at least one surface of the adhesive sheet.
  • the transparent film is preferably at least one selected from a polyethylene terephthalate film, an acrylic film, a polycarbonate film, a triacetyl cellulose film and a cycloolefin polymer film.
  • the adhesive sheet with a transparent film may be a sheet in which a transparent film / adhesive sheet / release sheet are laminated in this 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, and the pressure-sensitive adhesive layer has post-curing property.
  • the pressure-sensitive adhesive sheet may be made of a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer before irradiation or heating is in a semi-cured state.
  • the pressure-sensitive adhesive layer is post-cured by irradiating it with active energy rays
  • the optical transparent PET separators are attached to both sides of the pressure-sensitive adhesive layer, and the active energy rays (high-pressure mercury lamp or high-pressure mercury lamp or) are attached from the optical transparent PET separator side. (Metal halide lamp) is irradiated so that the integrated light amount is 3000 mJ / cm 2 .
  • the gel fraction of the pressure-sensitive adhesive layer in the semi-cured state is preferably 10% by mass or more and less than 70% by mass, and more preferably 20% by mass or more and less than 60% by mass.
  • the gel fraction of the pressure-sensitive adhesive layer after post-curing is preferably 60 to 100% by mass, more preferably 70 to 100% by mass.
  • the "semi-cured state” is preferably a state after thermosetting. Then, it is preferable to "post-cure” by irradiating with active energy rays after that. That is, the "semi-cured state” is preferably a state after thermosetting and is a soft pressure-sensitive adhesive layer before irradiation with active energy rays.
  • the "post-curing” is preferably a step of completely curing the pressure-sensitive adhesive layer with heat or active energy rays, and more preferably a step of completely curing the pressure-sensitive adhesive layer with active energy rays. 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 thickness of the pressure-sensitive adhesive layer can be appropriately set according to the intended use, and is not particularly limited, but is preferably 5 to 1000 ⁇ m, more preferably 8 to 500 ⁇ m, and particularly preferably 10 to 300 ⁇ 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 5 to 1000 ⁇ m, more preferably 8 to 500 ⁇ m, and particularly preferably 10 to 300 ⁇ m.
  • the adhesive force against glass with a peeling speed of 300 mm / min measured by a method according to JIS Z 0237 of the pressure-sensitive adhesive layer is preferably 10 to 50 N / 25 mm in both the semi-cured state and after post-curing, and is preferably 15 to 45 N / min. It is more preferably 25 mm.
  • the above-mentioned pressure-sensitive adhesive layer is a semi-cured state of the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition used in the present invention is a dual-curable pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition has a crosslinkable (meth) acrylic copolymer, a crosslinker, a polyrotaxane (second polyrotaxane), an alkylene glycol group in the molecule, and two (meth) acryloyl groups. Contains a monomer and a polymerization initiator.
  • the pressure-sensitive adhesive composition has a crosslinkable (meth) acrylic copolymer, a crosslinker, a first polyrotaxane, a second polyrotaxane, and an alkylene glycol group in the molecule (meth). It contains a monomer having two acryloyl groups and a polymerization initiator.
  • the crosslinkable (meth) acrylic copolymer is not particularly limited as long as it has an acrylic monomer unit, and for example, a non-crosslinkable (meth) acrylic acid ester unit (a1) and a crosslinkable functional group can be used. It may contain the acrylic monomer unit (a2) having.
  • the crosslinkable (meth) acrylic copolymer 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 (meth) acrylic copolymer 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. It is preferable, and more preferably one or more selected from a carboxy group, a hydroxy group, an amino group and a glycidyl group.
  • the acrylic monomer unit (a2) having a crosslinkable functional group is preferably a carboxy group-containing monomer unit, a hydroxy group-containing monomer unit, an amino group-containing monomer unit, or a glycidyl group-containing monomer unit.
  • 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 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate. , 4-Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate and the like.
  • 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 (meth) acrylic copolymer is preferably 0.5 to 50% by mass, preferably 1.0 to 40% by mass. Is more preferable.
  • 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 acrylic monomer unit having a crosslinkable functional group in the crosslinkable (meth) acrylic copolymer is a unit derived from a hydroxy group-containing (meth) acrylate, a unit derived from the hydroxy group-containing (meth) acrylate.
  • the content is preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total mass of the crosslinkable (meth) acrylic copolymer.
  • the content of the unit derived from the hydroxy group-containing (meth) acrylate is preferably 50% by mass or less, preferably 40% by mass or less, based on the total mass of the crosslinkable (meth) acrylic copolymer. Is more preferable.
  • the content of the carboxy group-containing monomer unit may be 1% by mass or less with respect to the total mass of the crosslinkable (meth) acrylic copolymer. Preferably, it may be 0% by mass.
  • the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
  • the crosslinkable (meth) acrylic copolymer may further contain units derived from nitrogen-containing monomers.
  • the nitrogen-containing monomer is a monomer containing a nitrogen element in one molecule.
  • Examples of the nitrogen-containing monomer include dimethylacrylamide, diethylacrylamide, acryloylmorpholine, hydroxyethylacrylamide, methylolacrylamide, methoxymethylacrylamide, ethoxymethylacrylamide, dimethylaminoethylacrylamide, N-vinylcaprolactam, and N-vinyl-2-. Examples thereof include pyrrolidone, dimethylaminoethyl (meth) acrylate, and N-vinylformamide.
  • the nitrogen-containing monomer is preferably at least one selected from an acrylamide derivative, an amino group-containing monomer and a nitrogen-containing heterocyclic ring-containing monomer, and more preferably an acrylamide derivative.
  • the acrylamide derivative is more preferably at least one selected from dimethylacrylamide, diethylacrylamide and acryloylmorpholine, and particularly preferably dimethylacrylamide. Since the crosslinkable (meth) acrylic copolymer contains a unit derived from the nitrogen-containing monomer as described above, the semi-cured pressure-sensitive adhesive layer is easily adhered to the substrate, while being easily adhered to the substrate. The pressure-sensitive adhesive layer after post-curing becomes high in hardness, and outgas resistance can be further enhanced.
  • the content of the units derived from the nitrogen-containing monomer is the total mass of the crosslinkable (meth) acrylic copolymer. On the other hand, it is preferably 1% by mass or more, and more preferably 3% by mass or more.
  • the content of the unit derived from the nitrogen-containing monomer is preferably 20% by mass or less with respect to the total mass of the crosslinkable (meth) acrylic copolymer.
  • the crosslinkable (meth) acrylic copolymer may have other monomer units, if necessary.
  • the other monomer may be a monomer copolymerizable with the above-mentioned acrylic monomer, and examples thereof include (meth) acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinylpyrrolidone, and vinylpyridine.
  • the content of the other monomer unit in the crosslinkable (meth) acrylic copolymer is preferably 20% by mass or less, and more preferably 15% by mass or less.
  • the weight average molecular weight of the crosslinkable (meth) acrylic copolymer is preferably 100,000 to 2 million, more preferably 200,000 to 1.5 million. When the weight average molecular weight is within the above range, it is easy to maintain the semi-cured state of the pressure-sensitive adhesive sheet, and it is easy to obtain the hardness after post-curing, and the processability is excellent.
  • the weight average molecular weight of the crosslinkable (meth) acrylic copolymer is a value before cross-linking with a cross-linking agent.
  • the weight average molecular weight is a value measured by size exclusion chromatography (SEC) and determined based on polystyrene.
  • SEC size exclusion chromatography
  • 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 (meth) acrylic copolymer 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.
  • it is preferable to use an isocyanate compound or an epoxy compound because the hydroxy group-containing (meth) acrylate can be easily crosslinked.
  • the cross-linking agent is preferably at least one selected from a 2- to 4-functional isocyanate-based cross-linking agent and a 2- to 4-functional epoxy-based cross-linking agent.
  • Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.
  • 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.
  • Examples of the epoxy compound include TETRAD-C (manufactured by Mitsubishi Gas Chemical Company) and TETRAD-X manufactured by Mitsubishi Gas Chemical Company).
  • the content of the cross-linking agent in the pressure-sensitive adhesive composition is appropriately selected according to the desired adhesiveness and the like, but is 0.01 to 5 parts by mass with respect to 100 parts by mass of the cross-linking (meth) acrylic copolymer. Is preferable, and 0.1 to 3 parts by mass is more preferable.
  • the content of the cross-linking agent within the above range, the workability can be further improved.
  • 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 polyrotaxane.
  • the polyrotaxane molecule has a linear portion and a cyclic portion that penetrates and encapsulates a part of the linear portion.
  • the polyrotaxane molecule has at least two cyclic portions, and the linear portion penetrates through the opening of the annular portion. Since the linear portion has block groups at both ends, the above configuration can be maintained without the linear portion being separated from the cyclic portion.
  • FIG. 2 is a schematic diagram illustrating the structure of polyrotaxane.
  • the polylotaxane molecule 1 has at least two cyclic portions (cyclic molecules) 3 as "rotors".
  • a linear portion (linear molecule) 2 penetrates through the openings of these annular portions 3 as a "axis", and block groups 5 are provided at both ends of the linear portion 2.
  • the linear portion 2 of the polyrotaxane is a molecule or substance that is encapsulated in the cyclic portion 3 and can be integrated by a mechanical bond rather than a chemical bond such as a covalent bond, and may be linear.
  • “straight line” of "linear part” means that it is substantially “straight line”. That is, the linear portion 2 may have a branched chain as long as the annular portion 3 is movable on the linear portion 2.
  • the polyrotaxane is preferably a main chain-bound polyrotaxane.
  • the linear portion (linear molecule) as the above-mentioned "axis" is the main chain.
  • the cyclic portion of the polyrotaxane since the cyclic portion of the polyrotaxane has high mobility, it is possible to increase the flexibility as a molecule when incorporated into the crosslinked structure of a crosslinkable (meth) acrylic copolymer, and after post-curing. The outgas resistance and curl resistance of the adhesive sheet can be improved more effectively.
  • linear portion 2 of polyrotaxane for example, polyethylene glycol, polypropylene glycol, polyisoprene, polyisobutylene, polybutadiene, polytetrahydrofuran, polyacrylic acid ester, polydimethylsiloxane, polyethylene, polypropylene and the like are preferable, and these linear portions are used.
  • Part 2 may be mixed in two or more types in the pressure-sensitive adhesive composition.
  • the weight average molecular weight of the linear portion 2 of the polyrotaxane is preferably 1,000 or more and 300,000 or less, more preferably 3,000 or more and 100,000 or less, and further preferably 5,000 or more and 50,000 or less.
  • the weight average molecular weight of the linear portion 2 is preferably 1,000 or more and 300,000 or less, more preferably 3,000 or more and 100,000 or less, and further preferably 5,000 or more and 50,000 or less.
  • the cyclic portion 3 of polyrotaxane is a molecule capable of inclusion in the linear portion 2, and is not particularly limited as long as it can move on the linear portion 2.
  • annular of “annular part” means substantially “annular”. That is, the annular portion 3 does not have to be completely ring-closed, and may have a spiral structure, for example, as long as it can move on the linear portion 2.
  • cyclic polymers such as cyclic polyethers, cyclic polyesters, cyclic polyether amines, and cyclic polyamines, or cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin are preferably mentioned. Be done.
  • Specific examples of the cyclic polymer include crown ether or a derivative thereof, calixarene or a derivative thereof, cyclophane or a derivative thereof, cryptond or a derivative thereof, and the like.
  • cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin are preferable, and ⁇ -cyclodextrin is more preferable.
  • Two or more of these cyclic portions 3 may be mixed in polyrotaxane or in the pressure-sensitive adhesive composition.
  • the annular portion 3 is preferably used because it is relatively easy to obtain and a large number of types of block groups 5 can be selected.
  • At least one of the molecules constituting the cyclic portion 3 has a reactive group R1.
  • the reactive group R1 may be a group capable of reacting with the cross-linking agent or a group not reacting with the cross-linking agent. It is preferable that each of the plurality of cyclic portions 3 has at least one reactive group R1.
  • the reactive group R1 of the cyclic portion 3 of the first polyrotaxane is a hydroxy group. That is, in the first polyrotaxane, the molecule constituting the cyclic portion 3 has a hydroxy group. Further, the reactive group R1 of the cyclic portion 3 of the second polyrotaxane is a vinyl group. That is, in the second polyrotaxane, the molecule constituting the cyclic portion 3 has a vinyl group.
  • the pressure-sensitive adhesive composition has at least a second polyrotaxane as a polyrotaxane
  • the pressure-sensitive adhesive composition has a first polyrotaxane and a second polyrotaxane as a polyrotaxane.
  • Polyrotaxane may have other substituents in addition to the above-mentioned reactive group.
  • substituents include an acetyl group, an alkyl group, a trityl group, a tosyl group, a trimethylsilane group, a phenyl group, a carboxy group, an amino group and the like.
  • the molecular weight of the substituent is preferably 10,000 or less, and more preferably 2000 or less.
  • the vinyl group or hydroxy group contained in the cyclic portion 3 of the polyrotaxane may be directly bonded to the cyclic portion 3, but may be bonded via another substituent as described above.
  • the hydroxyl value of the first polyrotaxane is preferably 10 to 90 mgKOH / g.
  • the hydroxyl value of the second polyrotaxane is preferably less than 10 mgKOH / g.
  • the amount of the polymerization group in the second polyrotaxane is preferably 0.01 to 2 mmol / g, and the amount of the polymerization group in the first polyrotaxane is preferably less than 0.01 mmol / g.
  • the block group 5 of polyrotaxane is not particularly limited as long as it can retain the shape in which the cyclic portion 3 is skewered by the linear portion 2.
  • Examples of such a group include a bulky group and an ionic group.
  • Examples of the block group 5 of polyrotaxane include dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, anthracenes, etc., or polymers having a weight average molecular weight of 1000 or more and 1 million or less.
  • the main chain or side chain of the above can be mentioned. Two or more of these block groups 5 may be mixed in polyrotaxane.
  • polystyrene resin examples include polyamide, polyimide, polyurethane, polydimethylsiloxane, and polyacrylic acid ester.
  • the inclusion amount is 0.1% or more and 60. % Or less, more preferably 1% or more and 50% or less, and even more preferably 5% or more and 40% or less.
  • the maximum inclusion amount of the annular portion 3 can be determined by the length of the linear portion and the thickness of the annular portion. For example, when the linear part is polyethylene glycol and the cyclic part is an ⁇ -cyclodextrin molecule, the maximum inclusion amount can be determined experimentally (see Macromolecules 1993, 26, 5698-5703).
  • the weight average molecular weight of polyrotaxane is preferably 1000 or more, more preferably 5000 or more, and even more preferably 10000 or more.
  • the weight average molecular weight of polyrotaxane is preferably 2 million or less, more preferably 1 million or less, further preferably 500,000 or less, and particularly preferably 100,000 or less.
  • the weight average molecular weight of polyrotaxane is a styrene-equivalent molecular weight measured by gel permeation chromatography.
  • the measurement conditions are as follows. Solvent: tetrahydrofuran (THF) Column: Shodex K806, K805, K803G (Use by connecting 3 pieces manufactured by Showa Denko KK) Column temperature: 40 ° C Sample concentration: 0.1% by mass Detector: RI Model 504 (manufactured by GL Science) Pump: L6000 (manufactured by Hitachi, Ltd.) Flow rate (flow velocity): 1.0 ml / min Injection volume: 10 ⁇ L
  • the content of polyrotaxane is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the crosslinkable (meth) acrylic copolymer. It is more preferably 3 to 2 parts by mass.
  • the content of the first polyrotaxane is preferably 0.1 to 3 parts by mass and 0.3 to 2 parts by mass with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer. More preferred.
  • the content of the second polyrotaxane is preferably 0.1 to 3 parts by mass, and more preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer. ..
  • the pressure-sensitive adhesive layer after post-curing can exhibit sufficient stress relaxation property and can exhibit excellent curl resistance. Further, by setting the content of polyrotaxane within the above range, outgas resistance and transparency can be improved.
  • the pressure-sensitive adhesive composition contains a monomer (polyfunctional monomer) having an alkylene glycol group and two (meth) acryloyl groups in the molecule.
  • the polyfunctional monomer having an alkylene glycol group in one molecule also serves as a compatibilizer between the polyrotaxane and the crosslinkable (meth) acrylic copolymer, and therefore the pressure-sensitive adhesive layer after post-curing. Since stress relaxation property can be imparted at the same time as increasing the hardness and transparency of the adhesive layer, the adhesive layer after post-curing can exhibit excellent curl resistance.
  • the alkylene glycol group contained in the polyfunctional monomer preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. That is, the polyfunctional monomer preferably has at least one selected from an ethylene glycol group and a propylene glycol group.
  • the ethylene glycol group is -CH 2 CH 2 O-
  • the propylene glycol group is -CH 2 CH 2 CH 2 O-.
  • the polyfunctional monomer may have one alkylene glycol group in one molecule, or may have two or more alkylene glycol groups.
  • the number of alkylene glycol groups in one molecule of the polyfunctional monomer is preferably 1 to 20, and more preferably 1 to 10.
  • polyfunctional monomer examples include polyethylene glycol diacrylate, trimethylolpropane propylene oxide-modified triacrylate, and the like.
  • a commercially available product can be used as the polyfunctional monomer.
  • examples of commercially available products include trifunctional monomer M321 (trimethylolpropane propylene oxide modified triacrylate, Tg50 ° C.) and bifunctional monomer M240 (polyethylene glycol diacrylate, Tg50 ° C.) manufactured by Toagosei Co., Ltd.
  • the content of the polyfunctional monomer is preferably 1 to 20 parts by mass and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer.
  • the polyfunctional monomer may be used alone or in combination of two or more, and when two or more are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition may contain a monofunctional monomer having one reactive double bond in the molecule.
  • the monofunctional monomer examples include isobornyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, tetrahydrofurfuryl acrylate, benzyl methacrylate, N-acryloyloxyethyl hexahydrophthalimide, acrylamide, N, N. -Dimethylacrylamide, N, N-diethylacrylamide, acryloylmorpholin, vinylpyrrolidone and the like can be mentioned.
  • the monofunctional monomer is preferably tetrahydrofurfuryl acrylate.
  • the content of such a monofunctional monomer is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, based on 100 parts by mass of the crosslinkable (meth) acrylic copolymer.
  • the pressure-sensitive adhesive composition contains a polymerization initiator.
  • the polymerization initiator is preferably one that initiates the polymerization of the polyfunctional monomer or polyrotaxane (second polyrotaxane) by irradiation with active energy rays, and the polyfunctional monomer and polyrotaxane (second polyrotaxane) by irradiation with active energy rays. It is more preferable that the polymerization of the polyrotaxane (2) is initiated.
  • 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.
  • the polymerization initiator is preferably a photopolymerization initiator having an absorbance of 0.2 or more at a wavelength of 380 nm in an acetonitrile solution having a concentration of 0.1% by mass.
  • a polymerization initiator By using such a polymerization initiator, the polymerization reaction of the polyfunctional monomer and polyrotaxane (second polyrotaxane) can easily proceed by irradiation with active energy rays.
  • the photopolymerization initiator is not particularly limited, but for example, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-henylpropanol, 1- [4-( 2-Hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanone, 2-hydroxy-1-(4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methyl-1- Alkylphenone-based photopolymerization initiators such as propanone, acylphosphine oxide-based polymerization initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,4,6-trimethylbenzoyl) phenylphosphine oxide, Examples thereof include intramolecular hydrogen abstraction type photopolymerization initiators such as methyl benzoylate and 4-methylbenzophenone, as well as oil-soluble polymerization initiators such
  • the acylphosphine oxide-based photopolymerization initiator has an absorbance of 0.2 or more at a wavelength of 380 nm in an acetonitrile solution having a concentration of 0.1% by mass, so that polymerization starts even through a film or a resin plate having an ultraviolet absorbing performance. Therefore, it is preferable.
  • Commercially available products of such an acylphosphine oxide-based photopolymerization initiator include IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide BASF) and IRGACURE TPO (2,4,6-trimethyl). Benzoyludiphenylphosphine oxide (manufactured by BASF) and the like can be mentioned.
  • 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 the active energy ray at the time of post-curing, and the like, but specifically, the crosslinkability (meth).
  • the crosslinkability (meth).
  • 100 parts by mass of the acrylic copolymer 0.01 to 5 parts by mass is preferable, and 0.1 to 3 parts by mass is more preferable.
  • the pressure-sensitive adhesive composition may contain a solvent.
  • the solvent is used to improve the coating suitability of the pressure-sensitive adhesive composition.
  • Solvents include, for example, 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 isobuty
  • 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 (meth) acrylic copolymer.
  • 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 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.
  • 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, and the like can be selected as necessary.
  • dyes and pigments may be added for the purpose of coloring.
  • a non-functional group acrylic polymer may be used as the plasticizer.
  • the non-functional group acrylic polymer does not have a functional group such as a polymer consisting of only an acrylic monomer unit having no functional group other than an acrylate group or an acrylic monomer unit having no functional group other than an acrylate group.
  • examples thereof include polymers composed of non-acrylic monomer units. Since the non-functional group acrylic polymer is not crosslinked, it is possible to improve the step followability without affecting the adhesiveness.
  • the antioxidant include phenol-based antioxidants, amine-based antioxidants, lactone-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, 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, benzophenone-based compounds, and triazine-based compounds.
  • the method for producing an adhesive sheet of the present invention includes a step of applying the above-mentioned pressure-sensitive adhesive composition on a 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. Is preferable. By heating the coating film, the reaction between the crosslinkable (meth) acrylic copolymer and the crosslinker proceeds to form a cured product (adhesive layer) in a semi-cured state.
  • the polymerization reaction of the polyfunctional monomer or polyrotaxane by the polymerization initiator does not proceed in the coating film, or even if it progresses, it is slight, so that the pressure-sensitive adhesive composition is contained in the pressure-sensitive adhesive layer.
  • the polyfunctional monomer and polyrotaxane contained, and at least a part of the polymerization initiator are contained in an unreacted state.
  • the reaction of the crosslinkable (meth) acrylic copolymer, the crosslinking agent and the first polyrotaxane proceeds by heating the coating film to crosslink the crosslinkable (meth) acrylic copolymer.
  • a semi-cured cured product (adhesive layer) in which the polyrotaxane is incorporated is formed in the structure. That is, during heating, the polymerization reaction of the polyfunctional monomer or the second polyrotaxane by the polymerization initiator does not proceed in the coating film, or even if it progresses, it is slight. Therefore, the pressure-sensitive adhesive composition is contained in the pressure-sensitive adhesive layer.
  • the polyfunctional monomer and the second polyrotaxane contained in the product, and at least a part of the polymerization initiator are contained in an unreacted state.
  • the pressure-sensitive adhesive sheet of the present invention preferably has post-curability and active energy ray-curability.
  • the pressure-sensitive adhesive composition In order to make the pressure-sensitive adhesive composition semi-cured, it is preferable to perform 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 semi-cured pressure-sensitive adhesive layer can be post-cured by irradiating an adherend such as a base material with active energy rays. That is, the pressure-sensitive adhesive sheet of the present invention is a two-step curing type pressure-sensitive adhesive sheet, has a pressure-sensitive adhesive layer semi-cured only by heat before bonding, and the pressure-sensitive adhesive layer is post-cured by active energy rays after bonding. Will be done.
  • 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 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 bonding to a base material, and is a pressure-sensitive adhesive sheet used for bonding to at least one selected from a resin plate, a resin sheet, and a resin film. Is more preferable.
  • the adhesive sheet of the present invention is a double-sided adhesive sheet
  • the adhesive sheet is attached to the first member and the second member.
  • the first member is at least one selected from a resin plate, a resin sheet and a resin film
  • the second member is at least one selected from a glass plate, a resin plate, a resin sheet and a resin film. It is preferable to have.
  • these members are preferably members containing at least one selected from polycarbonate resin and (meth) acrylic resin.
  • the resin plate, the resin sheet or the resin film may be a resin plate made of polycarbonate, a resin sheet or a resin film, or may be a resin plate made of (meth) acrylic resin, a resin sheet or a resin film.
  • the resin plate, the resin sheet or the resin film may be a member containing both a polycarbonate resin and a (meth) acrylic resin, and may be, for example, a laminate of a polycarbonate resin layer and a (meth) acrylic resin. ..
  • the polycarbonate base material examples include PC-1151 manufactured by Teijin Chemicals Ltd.
  • the multilayer base material containing the polycarbonate base material for example, MR-58U or IMR05 manufactured by Mitsubishi Gas Chemical Company, Inc. can be used.
  • the composition of MR-58U is HC (hard coat) / PMMA (polymethyl methacrylate) / PC (polycarbonate) / HC (hard coat).
  • the overall thickness of MR-58U 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 suppresses the generation of bubbles and peeling even when exposed to a high humidity and heat environment after being bonded to an optical member such as a polarizing plate and post-cured.
  • 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 present invention also relates to a laminate having the above-mentioned adhesive sheet and adherend.
  • the pressure-sensitive adhesive layer of the above-mentioned pressure-sensitive adhesive sheet is irradiated with active energy rays and post-cured, and then the first member is provided on one surface side of the post-cured pressure-sensitive adhesive layer and the post-cured pressure-sensitive adhesive layer. It is preferable that the second member is provided on the other surface side of the pressure-sensitive adhesive layer after post-curing.
  • the first member is at least one selected from a resin plate, a resin sheet and a resin film
  • the second member is at least one selected from a glass plate, a resin plate, a resin sheet and a resin film. It is preferable to have. It is preferable that all the members are optical members. Examples of the optical member include each component in an optical product such as a touch panel and an image display device, a cover lens on the outermost layer, and the like.
  • the adhesive sheet of the present invention is a double-sided adhesive sheet
  • the adhesive sheet is used for bonding transparent optical films inside the touch panel, bonding the transparent optical film and glass, and bonding the transparent optical film and the liquid crystal panel of the touch panel. It may be used for bonding with a resin cover lens and a touch panel, and any member may be a member containing at least one selected from polycarbonate resin and (meth) acrylic resin.
  • a hard coat layer may be provided on the transparent optical film or the polycarbonate base material.
  • the method for producing a laminated body includes a step of attaching the pressure-sensitive adhesive layer of the above-mentioned pressure-sensitive adhesive sheet to an adherend in a semi-cured state and then irradiating an active energy ray to post-cure the pressure-sensitive adhesive layer. Before the irradiation with the active energy rays, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is in a semi-cured state, so that the initial adhesion to the substrate is good. In this way, after the pressure-sensitive adhesive sheet is attached to the adherend, the pressure-sensitive adhesive layer is post-cured with active energy rays, so that the cohesive force of the pressure-sensitive adhesive layer is increased and the adhesiveness to the adherend is improved. 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.
  • Example 1 Polyrotaxane (advanced) having 0.1 parts by mass of a cross-linking agent (Coronate L-55, manufactured by Toso Co., Ltd.) and a vinyl group as polyrotaxane with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-1.
  • a cross-linking agent Coronate L-55, manufactured by Toso Co., Ltd.
  • vinyl group as polyrotaxane with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-1.
  • Soft Materials Co., Ltd., Selm Superpolymer SA1303P 1 part by mass, bifunctional monomer (tripropylene glycol diacrylate) having an alkylene glycol group in the molecule (Toa Synthetic Co., Ltd., M220) 5 parts by mass, photopolymerization started 0.7 parts by mass of the agent (Irgacure819 manufactured by BASF) was added, and the mixture was diluted and stirred with ethyl acetate so as to have a solid content concentration of 40% by mass to prepare a pressure-sensitive adhesive composition.
  • the agent Irgacure819 manufactured by BASF
  • a 38 ⁇ m-thick polyethylene terephthalate film (first release sheet) (manufactured by Oji F-Tex Co., Ltd., 38RL-07) having a release agent layer treated with a silicone-based release agent on the pressure-sensitive adhesive composition prepared as described above.
  • the surface of (2)) is uniformly coated with an applicator so that the coating thickness after drying is 150 ⁇ m, dried in an air circulation type constant temperature oven at 100 ° C. for 3 minutes, and then on the surface of the first release sheet.
  • a pressure-sensitive adhesive layer was formed.
  • a second release sheet (manufactured by Oji F-Tex Co., Ltd., 38RL-07 (L)) having a thickness of 38 ⁇ m was attached to the surface of the pressure-sensitive adhesive layer.
  • an adhesive sheet with a release sheet having a structure of a first release sheet / an adhesive layer / a second release sheet in which the adhesive layer is sandwiched between a pair of release sheets having a difference in release force was obtained. ..
  • the adhesive sheet was cured at 23 ° C. and a relative humidity of 50% for 7 days.
  • Example 2 Polyrotaxane (containing vinyl group) was changed to SA2403P (manufactured by Advanced Soft Materials), and bifunctional monomer having an alkylene glycol group in the molecule was changed to polyethylene glycol diacrylate (manufactured by Toa Synthetic Co., Ltd., M240).
  • SA2403P manufactured by Advanced Soft Materials
  • bifunctional monomer having an alkylene glycol group in the molecule was changed to polyethylene glycol diacrylate (manufactured by Toa Synthetic Co., Ltd., M240).
  • a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 1.
  • Example 3 Polyrotaxane (advanced) having 0.05 parts by mass of a cross-linking agent (Tetrad C, manufactured by Mitsubishi Gas Chemicals, Inc.) and a vinyl group as the polyrotaxane with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-2.
  • a cross-linking agent Tetrad C, manufactured by Mitsubishi Gas Chemicals, Inc.
  • a vinyl group as the polyrotaxane with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-2.
  • Soft Materials Co., Ltd., Selm Superpolymer SA1303P 3 parts by mass, bifunctional monomer (tripropylene glycol diacrylate) having an alkylene glycol group in the molecule (Toa Synthetic Co., Ltd., M220) 10 parts by mass, photopolymerization started 1 part by mass of an agent (IrgacureTPO manufactured by BASF) was added, and the mixture was diluted and stirred with ethyl acetate so as to have a solid content concentration of 40% by mass to prepare a pressure-sensitive adhesive composition.
  • a pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition prepared as described above was used.
  • Example 4 Polyrotaxane (containing vinyl group) was changed to SA2403P (manufactured by Advanced Soft Materials), and bifunctional monomer having an alkylene glycol group in the molecule was changed to polyethylene glycol diacrylate (manufactured by Toa Synthetic Co., Ltd., M240). A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 3.
  • Example 2 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 3 except that polyrotaxane was not added.
  • Selm Superpolymer SH3400P manufactured by Materials, 7.5 parts by mass, polyfunctional monomer without alkylene glycol group in the molecule ( ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate) (new Nakamura Chemical Co., Ltd., A-9300-1CL) 5.13 parts by mass, photopolymerization initiator (BASF, manufactured by Irgacure TPO) 0.57 parts by mass, 3-glycidoxypropyltrimethoxysilane as a silane coupling agent 0.28 parts by mass was added, and the mixture was diluted and stirred with ethyl acetate so as to have a solid content concentration of 40% by mass to prepare a pressure-sensitive adhesive composition.
  • a pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition prepared as described above was used.
  • the outgas resistance evaluation was performed as follows using the pressure-sensitive adhesive sheet with a release sheet prepared in Examples and Comparative Examples.
  • the second release sheet which is a light separator film, is peeled off to expose the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is attached to a glass plate having a size of 100 mm ⁇ 200 mm as a first member. I matched it.
  • the first release sheet which is a heavy separator film
  • the exposed adhesive layer is a polycarbonate resin plate (Teijin Co., Ltd.) having a size of 120 mm ⁇ 220 mm and a thickness of 1 mm, which is one size larger than the above glass as a second member. It was affixed to the entire surface in the center of the panlight sheet PC-1151) made of the same product. As a result, a laminate sample composed of a polycarbonate resin plate / adhesive layer / glass plate was obtained. After treating the laminated sample in an autoclave at 40 ° C.
  • the second member has a size of 120 mm ⁇ 220 mm and a thickness of 1 mm instead of a polycarbonate resin plate (Panlite sheet PC-1151 manufactured by Teijin Corporation) having a size of 120 mm ⁇ 220 mm and a thickness of 1 mm. Evaluation was carried out in the same manner as in Test Example 1 except that the polycarbonate side of a polycarbonate resin plate (Iupilon sheet MR-58U manufactured by Mitsubishi Gas Chemical Company, Inc.) in which PMMA was laminated on one side was attached.
  • a polycarbonate resin plate Iupilon sheet MR-58U manufactured by Mitsubishi Gas Chemical Company, Inc.
  • ⁇ Curl resistance> A sample prepared in the same manner as in Test Example 2 of outgas resistance described above is treated in an oven at 85 ° C. (relative humidity is 20% or less) for 24 hours, and then taken out and the convex surface curled into a horizontal plane is turned down within 5 minutes. The sample was allowed to stand as described above, and the heights of the four corners of the sample from the waterside surface were measured to obtain an average value, which was evaluated according to the following criteria. ⁇ : Less than 5 mm ⁇ : 5 mm or more
  • SH3400P Overall weight average molecular weight 700,000, Linear part weight average molecular weight 35,000 SA1303: Overall weight average molecular weight 180,000, Linear part weight average molecular weight 11,000 SA2403: Overall weight average molecular weight 600,000 , Weight average molecular weight of linear part 20,000
  • Example 11 With respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-1, 0.1 part by mass of a crosslinking agent (Coronate L-55 manufactured by Toso Co., Ltd.) and polyrotaxane having a hydroxyl group as the first polyrotaxane ( Advanced Soft Materials, Selm Superpolymer SH1300P) 0.5 parts by mass, Polyrotaxan having a vinyl group as the second polyrotaxan (Advanced Soft Materials, Selm Superpolymer SA1303P) 0.5 parts by mass, molecule 5 parts by mass of a bifunctional monomer (tripropylene glycol diacrylate) (manufactured by Toa Synthetic Co., Ltd., M220) having an alkylene glycol group and 0.7 parts by mass of a photopolymerization initiator (manufactured by BASF Co., Ltd., Crosslink 819) were added therein.
  • a pressure-sensitive adhesive composition was prepared by di
  • a 38 ⁇ m-thick polyethylene terephthalate film (first release sheet) (manufactured by Oji F-Tex Co., Ltd., 38RL-07) having a release agent layer treated with a silicone-based release agent on the pressure-sensitive adhesive composition prepared as described above.
  • the surface of (2)) is uniformly coated with an applicator so that the coating thickness after drying is 150 ⁇ m, dried in an air circulation type constant temperature oven at 100 ° C. for 3 minutes, and then on the surface of the first release sheet.
  • a pressure-sensitive adhesive layer was formed.
  • a second release sheet (manufactured by Oji F-Tex Co., Ltd., 38RL-07 (L)) having a thickness of 38 ⁇ m was attached to the surface of the pressure-sensitive adhesive layer.
  • an adhesive sheet with a release sheet having a structure of a first release sheet / an adhesive layer / a second release sheet in which the adhesive layer is sandwiched between a pair of release sheets having a difference in release force was obtained. ..
  • the adhesive sheet was cured at 23 ° C. and a relative humidity of 50% for 7 days.
  • Example 12 The second polyrotaxane (containing vinyl group) was changed to SA2403P (manufactured by Advanced Soft Materials), and the bifunctional monomer having an alkylene glycol group in the molecule was changed to polyethylene glycol diacrylate (manufactured by Toa Synthetic Co., Ltd., M240). ) was obtained in the same manner as in Example 11 to obtain an adhesive composition and an adhesive sheet with a release sheet.
  • SA2403P manufactured by Advanced Soft Materials
  • polyethylene glycol diacrylate manufactured by Toa Synthetic Co., Ltd., M240
  • Example 13 With respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-2, 0.05 parts by mass of a crosslinking agent (Tetrad C, manufactured by Mitsubishi Gas Chemicals, Inc.) and polyrotaxane having a hydroxyl group as the first polyrotaxane ( 1 part by mass of Selm Superpolymer SH2400P, manufactured by Advanced Soft Materials, 2 parts by mass of polyrotaxan (Selm Superpolymer SA1303P, manufactured by Advanced Soft Materials) having a vinyl group as the second polyrotaxan, alkylene glycol in the molecule.
  • a crosslinking agent Tetrad C, manufactured by Mitsubishi Gas Chemicals, Inc.
  • polyrotaxane having a hydroxyl group as the first polyrotaxane
  • 1 part by mass of Selm Superpolymer SH2400P manufactured by Advanced Soft Materials
  • a pressure-sensitive adhesive composition was prepared by diluting and stirring so that the solution had a concentration of 40% by mass.
  • a pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 11 except that the pressure-sensitive adhesive composition prepared as described above was used.
  • Example 14 The second polyrotaxane (containing vinyl group) was changed to SA2403P (manufactured by Advanced Soft Materials), and the bifunctional monomer having an alkylene glycol group in the molecule was changed to polyethylene glycol diacrylate (manufactured by Toa Synthetic Co., Ltd., M240). ) was obtained, and the pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet with the release sheet were obtained in the same manner as in Example 13.
  • Example 12 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 13 except that the first polyrotaxane was not added and the amount of the second polyrotaxane added was changed to 3 parts by mass.
  • A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.
  • 0.28 parts by mass of trimethoxysilane was added, and the mixture was diluted and stirred with ethyl acetate so as to have a solid content concentration of 40% by mass to prepare a pressure-sensitive adhesive composition.
  • a pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 11 except that the pressure-sensitive adhesive composition prepared as described above was used.
  • ⁇ Curl resistance> A sample prepared in the same manner as in Test Example 2 of outgas resistance described above is treated in an oven at 105 ° C. (relative humidity is 20% or less) for 24 hours, and then taken out and the convex surface curled into a horizontal plane is turned down within 5 minutes. The sample was allowed to stand as described above, and the heights of the four corners of the sample from the waterside surface were measured to obtain an average value, which was evaluated according to the following criteria. ⁇ : Less than 5 mm ⁇ : 5 mm or more
  • ⁇ Haze> The haze (%) of the laminated sample was measured in the same manner as the above-mentioned ⁇ haze> measuring method, and evaluated by the same evaluation criteria as described above.
  • SH1300P Overall weight average molecular weight 180,000, Linear part weight average molecular weight 11,000
  • SH2400P Overall weight average molecular weight 400,000, Linear part weight average molecular weight 20,000
  • SH3400P Overall weight average molecular weight 700,000 , Linear part weight average molecular weight 35,000 SA1303: Overall weight average molecular weight 180,000, Linear part weight average molecular weight 11,000 SA2403: Overall weight average molecular weight 600,000, Linear part weight average Molecular weight 20,000
  • the adhesive sheet of the example was excellent in outgas resistance and curl resistance, and also had high transparency.
  • the adhesive sheet of the comparative example both outgas resistance, curl resistance, and high transparency were not achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'une feuille adhésive présentant une excellente résistance à la libération de gaz ainsi qu'une remarquable résistance à l'enroulement suite au post-durcissement. La présente invention concerne une feuille adhésive qui a une couche adhésive obtenue par semi-durcissement d'une composition adhésive qui contient un copolymère (méth)acrylique réticulable, un agent de réticulation, un polyrotaxane, un monomère qui a un groupe alkylène glycol dans chaque molécule, tout en ayant deux groupes (méth)acryloyle, et un initiateur de polymérisation.
PCT/JP2020/023975 2019-06-21 2020-06-18 Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive et corps multicouche WO2020256068A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019115661A JP6699788B1 (ja) 2019-06-21 2019-06-21 粘着シート、剥離シート付き粘着シート及び積層体
JP2019-115662 2019-06-21
JP2019-115661 2019-06-21
JP2019115662A JP6696614B1 (ja) 2019-06-21 2019-06-21 粘着シート、剥離シート付き粘着シート及び積層体

Publications (1)

Publication Number Publication Date
WO2020256068A1 true WO2020256068A1 (fr) 2020-12-24

Family

ID=74040847

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/023975 WO2020256068A1 (fr) 2019-06-21 2020-06-18 Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive et corps multicouche

Country Status (2)

Country Link
TW (1) TW202108721A (fr)
WO (1) WO2020256068A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011046917A (ja) * 2010-02-26 2011-03-10 Advanced Softmaterials Inc 光架橋性ポリロタキサン、該光架橋性ポリロタキサンを有する組成物、及び該組成物由来の架橋体、並びにこれらの製造方法
JP2015155530A (ja) * 2014-01-14 2015-08-27 日東電工株式会社 接着剤、偏光フィルム、液晶パネル、光学フィルム、および画像表示装置
JP2017110050A (ja) * 2015-12-14 2017-06-22 王子ホールディングス株式会社 粘着剤組成物及び粘着シート
JP2018044134A (ja) * 2016-09-16 2018-03-22 リンテック株式会社 粘着シート、表示体およびそれらの製造方法
JP2019085330A (ja) * 2017-11-01 2019-06-06 Ｋｊケミカルズ株式会社 光硬化性爪化粧料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011046917A (ja) * 2010-02-26 2011-03-10 Advanced Softmaterials Inc 光架橋性ポリロタキサン、該光架橋性ポリロタキサンを有する組成物、及び該組成物由来の架橋体、並びにこれらの製造方法
JP2015155530A (ja) * 2014-01-14 2015-08-27 日東電工株式会社 接着剤、偏光フィルム、液晶パネル、光学フィルム、および画像表示装置
JP2017110050A (ja) * 2015-12-14 2017-06-22 王子ホールディングス株式会社 粘着剤組成物及び粘着シート
JP2018044134A (ja) * 2016-09-16 2018-03-22 リンテック株式会社 粘着シート、表示体およびそれらの製造方法
JP2019085330A (ja) * 2017-11-01 2019-06-06 Ｋｊケミカルズ株式会社 光硬化性爪化粧料

Also Published As

Publication number Publication date
TW202108721A (zh) 2021-03-01

Similar Documents

Publication Publication Date Title
JP6693490B2 (ja) 粘着シート、積層体の製造方法および積層体
WO2020017555A1 (fr) Feuille adhésive sensible à la pression, feuille adhésive sensible à la pression comportant une feuille antiadhésive, feuille adhésive sensible à la pression comportant un film transparent, stratifié, et procédé de production d'un stratifié
JP2019077748A (ja) 粘着シート、積層体の製造方法および積層体
JP2019077747A (ja) 粘着シート、積層体の製造方法および積層体
JP6693491B2 (ja) 粘着シート、積層体の製造方法および積層体
JP6699788B1 (ja) 粘着シート、剥離シート付き粘着シート及び積層体
JP6724946B2 (ja) 粘着シート、剥離シート付き粘着シート、透明フィルム付き粘着シート、積層体および積層体の製造方法
JP6699787B1 (ja) 粘着シート、剥離シート付き粘着シート及び積層体
JP2021143251A (ja) 粘着シート、剥離シート付き粘着シート及び積層体
WO2020256068A1 (fr) Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive et corps multicouche
WO2020256067A1 (fr) Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive et corps multicouche
JP2021020999A (ja) 粘着シート、剥離シート付き粘着シート及び積層体
JP7095713B2 (ja) 粘着シート、積層体の製造方法および積層体
JP6696614B1 (ja) 粘着シート、剥離シート付き粘着シート及び積層体
JP7251073B2 (ja) 粘着シート、剥離シート付き粘着シート、積層体及び積層体の製造方法
JP6769461B2 (ja) 粘着シート、剥離シート付き粘着シート、透明フィルム付き粘着シート、積層体及び積層体の製造方法
JP6699786B1 (ja) 粘着シート、剥離シート付き粘着シート及び積層体
WO2021020280A1 (fr) Feuille adhésive, feuille adhésive pourvue d'une feuille antiadhésive et produit stratifié
JP2021143252A (ja) 粘着シート、剥離シート付き粘着シート及び積層体
JP2021143253A (ja) 粘着シート、剥離シート付き粘着シート及び積層体
JP2021143250A (ja) 粘着シート、剥離シート付き粘着シート及び積層体
JP2020193278A (ja) 粘着シート、積層体の製造方法および積層体
JP2021059617A (ja) 粘着シート
JP2021020998A (ja) 粘着シート、剥離シート付き粘着シート及び積層体
WO2020226169A1 (fr) Feuille adhésive, procédé de production d'un corps multicouche, et corps multicouche

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20826217

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20826217

Country of ref document: EP

Kind code of ref document: A1