WO2021020280A1 - 粘着シート、剥離シート付き粘着シート及び積層体 - Google Patents

粘着シート、剥離シート付き粘着シート及び積層体 Download PDF

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Publication number
WO2021020280A1
WO2021020280A1 PCT/JP2020/028460 JP2020028460W WO2021020280A1 WO 2021020280 A1 WO2021020280 A1 WO 2021020280A1 JP 2020028460 W JP2020028460 W JP 2020028460W WO 2021020280 A1 WO2021020280 A1 WO 2021020280A1
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Prior art keywords
meth
pressure
sensitive adhesive
adhesive sheet
acrylate
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PCT/JP2020/028460
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English (en)
French (fr)
Japanese (ja)
Inventor
山本　真之
貴迪 山口
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王子ホールディングス株式会社
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Priority claimed from JP2019137562A external-priority patent/JP2021020999A/ja
Priority claimed from JP2019137561A external-priority patent/JP2021020998A/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 WO2021020280A1 publication Critical patent/WO2021020280A1/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
    • B32B27/16—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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)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
    • 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
    • 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.
  • 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 adhesive sheet may turn yellow, which is a problem. It was.
  • the present inventors have made a crosslinkable (polymer) having a predetermined structure in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer in a semi-cured state.
  • a crosslinkable (polymer) having a predetermined structure in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer in a semi-cured state.
  • the pressure-sensitive adhesive composition contains a crosslinkable (meth) acrylic copolymer, a crosslinker, a monofunctional monomer having one acryloyl group, a polyfunctional monomer having two acryloyl groups, and a photopolymerization initiator.
  • the crosslinkable (meth) acrylic copolymer has a unit derived from a (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms.
  • the monofunctional monomer is lauryl (meth) acrylate or tetrahydrofurfuryl (meth) acrylate
  • An adhesive sheet in which the polyfunctional monomer is a diacrylate having a bisphenol skeleton.
  • the unit derived from (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms is a unit derived from X, X-dimethylalkyl (meth) acrylate (where X is an integer of 1 to 5). ),
  • the adhesive sheet according to [1].
  • Units derived from (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms are t-butyl (meth) acrylate, t-pentyl (meth) acrylate, neo-pentyl (meth) acrylate, and t. -From the group consisting of hexyl (meth) acrylate, neo-hexyl (meth) acrylate, t-heptyl (meth) acrylate, neo-heptyl (meth) acrylate, t-octyl (meth) acrylate and neo-octyl (meth) acrylate.
  • the unit derived from (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms is any one of [1] to [3], which is a unit derived from t-butyl (meth) acrylate. Adhesive sheet described in.
  • the adhesive sheet according to any one of [1] to [5]. [7] The content of the monofunctional monomer is 5 to 30 parts by mass with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer, according to any one of [1] to [6]. Adhesive sheet. [8] The content of the diacrylate having a bisphenol skeleton is 1 to 10 parts by mass with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer, according to any one of [1] to [7]. Adhesive sheet.
  • the photopolymerization initiator according to any one of [1] to [8], wherein the photopolymerization initiator is 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.
  • Adhesive sheet [10] The pressure-sensitive adhesive sheet according to any one of [1] to [9], wherein the cross-linking agent is 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. ..
  • the pressure-sensitive adhesive sheet according to [11] or [12], 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 [13].
  • FIG. 1 is a schematic view showing a cross section of a release sheet or an adhesive sheet having a base material.
  • 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 monofunctional monomer having one acryloyl group, a polyfunctional monomer having two acryloyl groups, and a photopolymerization initiator. Contains.
  • the crosslinkable (meth) acrylic copolymer has a unit derived from (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms, and the monofunctional monomer is lauryl (meth) acrylate or It is a tetrahydrofurfuryl (meth) acrylate, and the polyfunctional monomer is a diacrylate having a bisphenol skeleton.
  • the pressure-sensitive adhesive sheet of the present invention can exhibit excellent outgas resistance and yellowing resistance after post-curing.
  • the adhesive sheet of the present invention since the crosslinkable (meth) acrylic copolymer contains a unit derived from t-butyl methacrylate, the adhesive sheet after post-curing is used in a harsh environment such as a high temperature or high humidity environment. Even if it is, yellowing is suppressed.
  • outgas resistance is improved by using lauryl (meth) acrylate or tetrahydrofurfuryl (meth) acrylate as a monofunctional monomer and diacrylate having a bisphenol skeleton as a polyfunctional single amount in combination. It can be enhanced more effectively.
  • the adhesive sheet of the present invention has both excellent outgas resistance and yellowing resistance.
  • 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 the adherend in the semi-cured state. Excellent adhesion to the adherend, for example, even when the adherend has a curved surface or a stepped portion, it follows the shape of the adherend and exhibits excellent adhesion. Then, since post-curing is performed in such a state, the pressure-sensitive adhesive layer can be firmly adhered to the adherend. As described above, the adhesive sheet of the present invention exhibits excellent outgas resistance and yellowing resistance while firmly adhering to the adherend during 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 105 ° C. and a relative humidity of 10% or less, and visually checking the laminated body after 500 hours. Specifically, it is preferable that no bubbles, floats or peeling are observed in the laminate.
  • the yellowing resistance of the adhesive sheet after post-curing is calculated by calculating the amount of change in the b value ( ⁇ b * ) in the L * a * b * color space and the color difference ( ⁇ E * ab value). Can be evaluated. Specifically, when the pressure-sensitive adhesive sheet of the present invention is irradiated with active energy rays so that the integrated light amount becomes 3000 mJ / cm 2 to form a post-cured pressure-sensitive adhesive sheet, and then the post-cured pressure-sensitive adhesive sheet is treated at 105 ° C. for 500 hours.
  • L * 0 is the L * value before the post-cured adhesive sheet is treated at 105 ° C. for 500 hours
  • a * 0 is the a * value before the post-cured adhesive sheet is treated at 105 ° C. for 500 hours.
  • B * 0 are b * values before the post-curing adhesive sheet is treated at 105 ° C. for 500 hours.
  • L * 1 is the L * value after treating the post-curing adhesive sheet at 105 ° C. for 500 hours
  • a * 1 is the a * value after treating the post-curing adhesive sheet at 105 ° C. for 500 hours.
  • b * 1 is the b * value after the post-cured adhesive sheet is treated at 105 ° C. for 500 hours.
  • the value of ⁇ b * is preferably less than 0.5, more preferably 0.4 or less.
  • the value of ⁇ E * ab is preferably less than 1, more preferably 0.9 or less, further preferably 0.8 or less, still more preferably 0.7 or less. It is particularly preferably 0.6 or less.
  • 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 having 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-based 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.
  • a heavy separator film which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd.
  • a light separator film which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd., can be mentioned. 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.
  • an optical transparent PET separator is attached to both sides of the pressure-sensitive adhesive layer, and active energy rays (high-pressure mercury lamp or high-pressure mercury lamp or) are applied 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 65% by mass.
  • the gel fraction of the pressure-sensitive adhesive layer after post-curing is preferably 65 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 1 to 25 N / 25 mm in a semi-cured state, and is preferably 3 to 20 N / 25 mm. Is more preferable, and after post-curing, it is preferably 10 to 50 N / 25 mm, and more preferably 15 to 45 N / 25 mm.
  • the pressure-sensitive adhesive layer described above 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 contains a crosslinkable (meth) acrylic copolymer, a crosslinker, a monofunctional monomer having one acryloyl group, a polyfunctional monomer having two acryloyl groups, and a photopolymerization initiator.
  • the crosslinkable (meth) acrylic copolymer has a unit derived from a (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms.
  • the crosslinkable (meth) acrylic copolymer may further have a non-crosslinkable (meth) acrylic acid ester unit (a1) in addition to the above-mentioned units, and is a simple acrylic having a crosslinkable functional group. It may further contain a polymer unit (a2).
  • a "unit” is a repeating unit (monomer unit) constituting a polymer.
  • the crosslinkable (meth) acrylic copolymer has a unit derived from (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms.
  • the unit derived from the (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms is the unit derived from X, X-dimethylalkyl (meth) acrylate (where X is an integer of 1 to 5).
  • T-butyl (meth) acrylate, t-pentyl (meth) acrylate, neo-pentyl (meth) acrylate, t-hexyl (meth) acrylate, neo-hexyl (meth) acrylate, t-heptyl It is preferably a unit derived from at least one selected from the group consisting of meta) acrylate, neo-heptyl (meth) acrylate, t-octyl (meth) acrylate and neo-octyl (meth) acrylate, and is preferably t-butyl. It is particularly preferable that the unit is derived from (meth) acrylate.
  • the crosslinkable (meth) acrylic copolymer has a unit derived from a (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms, so that the obtained pressure-sensitive adhesive sheet is obtained after post-curing. It can exhibit excellent outgas resistance and yellowing resistance.
  • the degree of entanglement of the main chains affects various physical properties such as durability.
  • the crosslinkable (meth) acrylic copolymer has a unit derived from the (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms, the main chain of the crosslinkable (meth) acrylic copolymer. Due to the moderate molecular size of the branched alkyl group having 4 to 8 carbon atoms branched from, steric damage is unlikely to occur, not only does not hinder the entanglement of the main chains (polymer chains), but also the ester portions are due to the branched structure. It is presumed that the polymer contributes to the entanglement and a strong physical bond is developed to improve the durability.
  • the content of the unit derived from the (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms in the crosslinkable (meth) acrylic copolymer is based on the total mass of the crosslinkable (meth) acrylic copolymer. It is preferably 15% by mass or more, more preferably 18% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more. Further, the content of the unit derived from the (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms is 40% by mass or less with respect to the total mass of the crosslinkable (meth) acrylic copolymer. preferable.
  • the pressure-sensitive adhesive sheet of the present invention exhibits more excellent yellowing resistance after post-curing. It is possible to improve the workability.
  • the content of the unit derived from t-butyl methacrylate in the crosslinkable (meth) acrylic copolymer is preferably 15% by mass or more with respect to the total mass of the crosslinkable (meth) acrylic copolymer. , 18% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more.
  • the content of the unit derived from t-butyl methacrylate is preferably 40% by mass or less with respect to the total mass of the crosslinkable (meth) acrylic copolymer.
  • Crosslinkable (meth) acrylic copolymers include units derived from (meth) acrylates having a branched alkyl group having 4 to 8 carbon atoms, as well as other non-crosslinkable (meth) acrylic copolymers as long as they do not interfere with yellowing resistance. ) It may further have an acrylic ester unit (a1).
  • the non-crosslinkable (meth) acrylic acid ester unit (a1) is a repeating unit derived from the (meth) acrylic acid alkyl ester.
  • Examples of 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).
  • At least one selected from methyl (meth) acrylate and n-butyl (meth) acrylate is preferable because of its high adhesiveness.
  • the crosslinkable (meth) acrylic copolymer contains an acrylic monomer unit (a2) having a crosslinkable functional group in addition to a unit derived from a (meth) acrylate having a branched alkyl group having 4 to 8 carbon atoms. It may be further contained.
  • the acrylic monomer unit (a2) having a crosslinkable functional group is 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. Is preferable.
  • 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.
  • 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 crosslinkable (meth) acrylic copolymer further contains an acrylic monomer unit (a2) having a crosslinkable functional group
  • the acrylic monomer unit (a2) having a crosslinkable functional group is a hydroxy group-containing simple substance. It is preferably a monomer unit.
  • the crosslinkable (meth) acrylic copolymer has a hydroxy group-containing monomer unit, yellowing of the pressure-sensitive adhesive sheet can be suppressed more effectively.
  • the crosslinkable (meth) acrylic copolymer has a hydroxy group-containing monomer unit, it is possible to exhibit better adhesiveness to an adherend such as a resin plate.
  • 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 a monofunctional monomer having one acryloyl group.
  • the monofunctional monomer is lauryl (meth) acrylate or tetrahydrofurfuryl (meth) acrylate, and lauryl acrylate or tetrahydrofurfuryl acrylate is particularly preferable. Since the pressure-sensitive adhesive composition contains lauryl (meth) acrylate, the semi-cured pressure-sensitive adhesive sheet is excellent because it has high wettability to adherends such as resin plates and glass, but does not have high adhesive strength. Demonstrates reworkability. Further, after the adhesive sheet is completely cured, the outgas resistance of the adhesive sheet can be more effectively enhanced.
  • the pressure-sensitive adhesive composition contains tetrahydrofurfuryl (meth) acrylate
  • the semi-cured pressure-sensitive adhesive sheet has high wettability to adherends such as resin plates and glass, and the pressure-sensitive adhesive sheet is completely complete. After curing, the outgas resistance of the pressure-sensitive adhesive sheet can be enhanced more effectively.
  • the pressure-sensitive adhesive composition contains tetrahydrofurfuryl (meth) acrylate
  • the adhesiveness of the pressure-sensitive adhesive sheet can be further enhanced, and the processability of the pressure-sensitive adhesive sheet in a semi-cured state can be further enhanced.
  • the content of the monofunctional monomer described above is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 10 parts by mass with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer. It is more preferably parts by mass or more, and particularly preferably 15 parts by mass or more.
  • the content of the monofunctional monomer is preferably 30 parts by mass or less with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer.
  • the pressure-sensitive adhesive composition contains a monomer (polyfunctional monomer) having a bisphenol skeleton in the molecule and having two (meth) acryloyl groups. That is, the pressure-sensitive adhesive composition contains a diacrylate having a bisphenol skeleton as a polyfunctional monomer.
  • a polyfunctional monomer having a bisphenol skeleton in one molecule it is possible to increase the hardness of the pressure-sensitive adhesive layer after post-curing and at the same time impart stress relaxation property.
  • Examples of such a polyfunctional monomer include diacrylate of bisphenol A diglycidyl ether, diacrylate of propoxylated bisphenol A, and diacrylate of bisphenol F diglycidyl ether.
  • a commercially available product can be used as the polyfunctional monomer.
  • Examples of commercially available products include bifunctional monomer M211B (bisphenol A ethylene oxide-modified diacrylate) manufactured by Toa Synthetic Co., Ltd., bifunctional monomer M208 (bisphenol F ethylene oxide-modified diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. , Bifunctional monomer A-BPP-3 (propoxylated bisphenol A diacrylate) and the like.
  • the content of the diacrylate having a bisphenol skeleton is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 3 parts by mass with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer.
  • the above is more preferable, and 5 parts by mass or more is particularly preferable.
  • the content of the diacrylate having a bisphenol skeleton is preferably 10 parts by mass or less with respect to 100 parts by mass of the crosslinkable (meth) acrylic copolymer.
  • the pressure-sensitive adhesive composition contains a photopolymerization initiator.
  • the photopolymerization initiator is preferably one that initiates the polymerization of a polyfunctional monomer or a monofunctional monomer by irradiation with active energy rays.
  • 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 beams. Among them, from the viewpoint of versatility, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable.
  • the photopolymerization 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 photopolymerization initiator By using such a photopolymerization initiator, the polymerization reaction between the polyfunctional monomer and the monofunctional monomer 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 resin plate having 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 photopolymerization 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. Meta) With respect to 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.
  • 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 (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, the step followability can be improved 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) and the like.
  • 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 pressure-sensitive adhesive layer contains The polyfunctional monomer and monofunctional monomer contained in the pressure-sensitive adhesive composition, and at least a part of the photopolymerization 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 irradiated with active energy rays to post-cure the pressure-sensitive adhesive layer.
  • 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 pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet
  • the pressure-sensitive adhesive sheet can be used for bonding transparent optical films inside a touch panel, bonding a transparent optical film and glass, and bonding a transparent optical film and a liquid crystal panel for a touch panel. It is used for bonding with, bonding of cover glass and transparent optical film, bonding of resin cover lens and touch panel, etc., and one of the members is selected from polycarbonate resin and (meth) acrylic resin. It may be a member containing at least one kind.
  • 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 0.15 parts by mass of a cross-linking agent (Coronate L-55 manufactured by Toso Co., Ltd.) and lauryl acrylate (Osaka) as a monofunctional monomer 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.
  • lauryl acrylate Osaka
  • 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 200 ⁇ m, dried in an air circulation type constant temperature oven at 100 ° C. for 3 minutes, and then applied to 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 for 7 days under the conditions of 23 ° C. and 50% relative humidity.
  • 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 1 except that the polyfunctional monomer was changed to M211B manufactured by Toagosei Co., Ltd.
  • Example 3 0.15 parts by mass of a cross-linking agent (Coronate L-55 manufactured by Toso Co., Ltd.) and lauryl acrylate (Osaka) as a monofunctional monomer with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-2.
  • a cross-linking agent Coronate L-55 manufactured by Toso Co., Ltd.
  • lauryl acrylate Osaka
  • Example 4 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 the polyfunctional monomer was changed to M211B manufactured by Toagosei Co., Ltd.
  • Example 5 0.15 parts by mass of a cross-linking agent (Coronate L-55 manufactured by Toso Co., Ltd.) and lauryl acrylate (Osaka) as a monofunctional monomer with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-3.
  • a cross-linking agent Coronate L-55 manufactured by Toso Co., Ltd.
  • lauryl acrylate Osaka
  • Example 6 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 5 except that the polyfunctional monomer was changed to M211B manufactured by Toagosei Co., Ltd.
  • Example 7 0.15 parts by mass of a cross-linking agent (Coronate L-55 manufactured by Toso Co., Ltd.) and tetrahydrofurfuryl acrylate as a monofunctional monomer 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.
  • tetrahydrofurfuryl acrylate as a monofunctional monomer with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-1.
  • 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 200 ⁇ m, dried in an air circulation type constant temperature oven at 100 ° C. for 3 minutes, and then applied to 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 for 7 days under the conditions of 23 ° C. and 50% relative humidity.
  • Example 8 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 7 except that the polyfunctional monomer was changed to M211B manufactured by Toagosei Co., Ltd.
  • Example 9 0.15 parts by mass of a cross-linking agent (Coronate L-55 manufactured by Toso Co., Ltd.) and tetrahydrofurfuryl acrylate as a monofunctional monomer with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-2.
  • a cross-linking agent Coronate L-55 manufactured by Toso Co., Ltd.
  • tetrahydrofurfuryl acrylate as a monofunctional monomer with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-2.
  • Example 10 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 9 except that the polyfunctional monomer was changed to M211B manufactured by Toagosei Co., Ltd.
  • Example 11 0.15 parts by mass of a cross-linking agent (Coronate L-55, manufactured by Toso Co., Ltd.) and tetrahydrofurfuryl acrylate as a monofunctional monomer with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-3.
  • a cross-linking agent Coronate L-55, manufactured by Toso Co., Ltd.
  • tetrahydrofurfuryl acrylate as a monofunctional monomer with respect to 100 parts by mass of the solid content of the crosslinkable (meth) acrylic copolymer A-3.
  • 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 11 except that the polyfunctional monomer was changed to M211B manufactured by Toagosei Co., Ltd.
  • Comparative 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 Comparative Example 1 except that the monofunctional monomer was changed to ISTA manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • Comparative Example 3 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Comparative Example 1 except that the polyfunctional monomer was changed to M360 manufactured by Toagosei Co., Ltd.
  • Example 4 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 except that the monofunctional monomer was changed to ISTA manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • 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.
  • Panlight sheet PC-1151) made of the same product was attached so that the central portions of the sheets overlap each other. 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 release sheet (light release separator) of the adhesive sheet is peeled off and attached to a transparent glass plate (manufactured by Matsunami Glass Industry Co., Ltd., S9112) having a thickness of 1.2 mm, and then the first release sheet (heavy release separator) is attached.
  • a transparent glass plate manufactured by Matsunami Glass Industry Co., Ltd., S9112
  • the first release sheet herein, the first release separator
  • the adhesive sheet of the example was excellent in outgas resistance, and yellowing was suppressed even when it was left under high temperature conditions for a long time.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2020/028460 2019-07-26 2020-07-22 粘着シート、剥離シート付き粘着シート及び積層体 WO2021020280A1 (ja)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015110763A (ja) * 2013-10-31 2015-06-18 三菱レイヨン株式会社 活性エネルギー線硬化性接着剤組成物、接着層、積層体及び偏光板
JP2016084391A (ja) * 2014-10-24 2016-05-19 王子ホールディングス株式会社 粘着シート、積層体及び積層体の製造方法
JP2017179096A (ja) * 2016-03-30 2017-10-05 日本カーバイド工業株式会社 粘着剤組成物および粘着シート

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015110763A (ja) * 2013-10-31 2015-06-18 三菱レイヨン株式会社 活性エネルギー線硬化性接着剤組成物、接着層、積層体及び偏光板
JP2016084391A (ja) * 2014-10-24 2016-05-19 王子ホールディングス株式会社 粘着シート、積層体及び積層体の製造方法
JP2017179096A (ja) * 2016-03-30 2017-10-05 日本カーバイド工業株式会社 粘着剤組成物および粘着シート

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