WO2019142905A1 - Double-sided adhesive sheet and double-sided adhesive sheet with release sheet - Google Patents

Double-sided adhesive sheet and double-sided adhesive sheet with release sheet Download PDF

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Publication number
WO2019142905A1
WO2019142905A1 PCT/JP2019/001438 JP2019001438W WO2019142905A1 WO 2019142905 A1 WO2019142905 A1 WO 2019142905A1 JP 2019001438 W JP2019001438 W JP 2019001438W WO 2019142905 A1 WO2019142905 A1 WO 2019142905A1
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WO
WIPO (PCT)
Prior art keywords
sensitive adhesive
pressure
adhesive layer
acrylic
double
Prior art date
Application number
PCT/JP2019/001438
Other languages
French (fr)
Japanese (ja)
Inventor
滋呂 清水
信幸 岩崎
錦織　義治
順 塩野
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.)
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Publication date
Priority claimed from JP2018127577A external-priority patent/JP7135509B2/en
Priority claimed from JP2018169436A external-priority patent/JP7099206B2/en
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Priority to US16/963,103 priority Critical patent/US20210054243A1/en
Priority to CN201980008788.1A priority patent/CN111615543A/en
Priority to KR1020207021288A priority patent/KR20200109320A/en
Publication of WO2019142905A1 publication Critical patent/WO2019142905A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • the present invention relates to a double-sided pressure-sensitive adhesive sheet and a double-sided pressure-sensitive adhesive sheet with a release sheet.
  • LCDs liquid crystal displays
  • image display devices combining display devices such as touch panels and input devices are widely used.
  • double-sided pressure-sensitive adhesive sheets are used for the purpose of bonding optical members.
  • the double-sided pressure-sensitive adhesive sheet may be used for laminating different kinds of adherends.
  • the double-sided pressure-sensitive adhesive sheet is required to have an optimum adhesive strength in accordance with the adhesive property of each adherend.
  • Patent Documents 1 and 2 disclose a double-sided pressure-sensitive adhesive sheet provided with two or more pressure-sensitive adhesive layers having different adhesion properties.
  • Patent Documents 3 and 4 disclose a double-sided pressure-sensitive adhesive sheet having at least two pressure-sensitive adhesive layers and configured to be releasable from the display surface of a display device.
  • each adhesive layer is formed from the acrylic polymer from which a kind differs, It is examined that the durability and rework property of a double-sided adhesive sheet are improved by this.
  • the double-sided adhesive sheet of patent document 3 aims at sticking of a display surface and a touch panel.
  • Patent Document 4 discloses a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer on both surfaces of a core material, and a silicone-based pressure-sensitive adhesive layer on the first pressure-sensitive adhesive layer. In the second pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive is used.
  • the double-sided pressure-sensitive adhesive sheet in the prior art is peeled again from the adherend, there is a problem that the pressure-sensitive adhesive remains on the adherend at the time of rework.
  • the adhesive remains on the adherend, it is necessary to wipe off the adhesive with a solvent or to wash the adhesive, which is a problem because it takes time and labor for rework.
  • a protective sheet for general consumers who can not use special equipment, jigs, or chemicals to perform bonding or rework must be able to be easily reworked from the display surface. The adhesion needs to be very low.
  • the double-sided pressure-sensitive adhesive sheet used for the protective sheet needs to be in close contact with the object to be adhered opposite to the display surface.
  • the inventors of the present invention have one side of the double-sided pressure-sensitive adhesive sheet exhibiting excellent adhesion to the adherend while the other side is excellent. Investigation was advanced for the purpose of providing a double-sided pressure-sensitive adhesive sheet which can exhibit reworkability and does not contain a base film.
  • the present inventors directly laminated a silicone-based pressure-sensitive adhesive layer on an acrylic pressure-sensitive adhesive layer, and an acrylic-based pressure-sensitive adhesive layer and a silicone-based pressure-sensitive adhesive layer It was found that by setting the interfacial adhesive force of the above to a predetermined value or more, a double-sided pressure-sensitive adhesive sheet which has both strong adhesive force and excellent reworkability and which does not contain a base film can be obtained.
  • the present invention has the following configuration.
  • the double-sided pressure-sensitive adhesive sheet in which the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is 1 N / 25 mm or more.
  • the acrylic pressure-sensitive adhesive layer has an acrylic copolymer containing a unit derived from butyl acrylate, Content of the unit derived from butyl acrylate is 30 mass% or more with respect to the total mass of an acrylic copolymer, The double-sided adhesive sheet as described in [1].
  • the acrylic copolymer further includes a unit derived from 2-hydroxyethyl acrylate, and the content of the unit derived from 2-hydroxyethyl acrylate is relative to the total mass of the acrylic copolymer
  • the double-sided pressure-sensitive adhesive sheet according to [2] which is 10% by mass or more and 50% by mass or less.
  • the acrylic copolymer further includes a unit derived from 2-methoxyethyl acrylate, and the content of the unit derived from 2-methoxyethyl acrylate is relative to the total mass of the acrylic copolymer
  • the double-sided pressure-sensitive adhesive sheet according to [2] which is 10% by mass or more and 50% by mass or less.
  • the surface on the interface side of the acrylic pressure-sensitive adhesive layer is a surface activation treated surface, and the wetting tension of the surface activation treated surface is 70 mN / m or more according to any one of [1] to [6] Double-sided adhesive sheet.
  • the surface on the interface side of the silicone pressure-sensitive adhesive layer is a surface activation treated surface, and the wetting tension of the surface activation treated surface is 30 mN / m or more according to any one of [1] to [7] Double-sided adhesive sheet.
  • the acrylic pressure-sensitive adhesive layer contains a silane coupling agent, The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [8], wherein the content of the silane coupling agent is 0.03% by mass to 5% by mass with respect to the total mass of the acrylic pressure-sensitive adhesive layer.
  • the acrylic pressure-sensitive adhesive layer contains an acrylic polymer containing a unit derived from a nitrogen-containing monomer, and the content of the unit derived from a nitrogen-containing monomer is relative to the total mass of the acrylic polymer
  • the acrylic pressure-sensitive adhesive layer contains a hydrogen extraction type polymerization initiator, and the content of the hydrogen extraction type polymerization initiator is 0.05% by mass or more and 10% by mass with respect to the total mass of the acrylic pressure-sensitive adhesive layer
  • the double-sided pressure-sensitive adhesive sheet according to any one of the following [1] to [10]: [12] The double-sided pressure-sensitive adhesive sheet according to [11], wherein the hydrogen abstraction type polymerization initiator is a photopolymerization initiator.
  • one side of the double-sided pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet capable of exhibiting excellent reworkability while exhibiting strong adhesion to the adherend, and the other side is a base It is possible to obtain a double-sided pressure-sensitive adhesive sheet which does not contain a wood film.
  • FIG. 1 is a cross-sectional view for explaining the structure of the double-sided pressure-sensitive adhesive sheet of the present invention.
  • the present invention has an acrylic pressure-sensitive adhesive layer and a silicone-based pressure-sensitive adhesive layer laminated directly on the acrylic pressure-sensitive adhesive layer, and the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is 1N /.
  • the present invention relates to a double-sided pressure-sensitive adhesive sheet which is 25 mm or more. Since the double-sided pressure-sensitive adhesive sheet of the present invention thus has a plurality of pressure-sensitive adhesive layers, it can also be called a double-sided laminated pressure-sensitive adhesive sheet.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is excellent in reworkability because it has the above-described configuration.
  • the excellent reworkability means that when the double-sided pressure-sensitive adhesive sheet is attached to the adherend and peeled off, a part of the pressure-sensitive adhesive of the double-sided pressure-sensitive adhesive sheet does not remain on the adherend; It refers to the property that the double-sided pressure-sensitive adhesive sheet does not break in it.
  • one surface of the double-sided pressure-sensitive adhesive sheet of the present invention can exert strong adhesive force to an adherend.
  • the double-sided pressure-sensitive adhesive sheet of the present invention can exhibit strong adhesion to the glass surface.
  • the double-sided pressure-sensitive adhesive sheet of the present invention has strong adhesion and excellent reworkability.
  • FIG. 1 is a cross-sectional view for explaining the structure of the double-sided pressure-sensitive adhesive sheet of the present invention.
  • the double-sided pressure-sensitive adhesive sheet 100 of the present invention has an acrylic pressure-sensitive adhesive layer 10 and a silicone-based pressure-sensitive adhesive layer 12.
  • the double-sided pressure-sensitive adhesive sheet 100 preferably has a structure in which the acrylic pressure-sensitive adhesive layer 10 and the silicone-based pressure-sensitive adhesive layer 12 are laminated one by one as shown in FIG. It is also good.
  • the acrylic pressure-sensitive adhesive layer 10 shown as a single-layer structure in FIG. 1 may have a laminated structure of two or more acrylic pressure-sensitive adhesive layers, and the silicone pressure-sensitive adhesive layer 12 has two layers. It may consist of a laminated structure of the above silicone pressure sensitive adhesive layers.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet having no support (base material) as shown in FIG. For this reason, in the double-sided pressure-sensitive adhesive sheet, the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer are laminated in direct contact with each other. Therefore, the double-sided pressure-sensitive adhesive sheet of the present invention can be thinned as needed. Further, since the double-sided pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet having no support (substrate), it is excellent in curved surface followability and further excellent in step followability.
  • the layer in contact with the step structure may be an acrylic pressure-sensitive adhesive layer or a silicone-based pressure-sensitive adhesive layer.
  • the double-sided pressure-sensitive adhesive sheet of the present invention has the above-mentioned constitution, the air escapeability to the display surface is also good.
  • the air release property refers to the property that air bubbles do not remain at the interface between the pressure-sensitive adhesive layer and the adherend when the double-sided pressure-sensitive adhesive sheet is attached to the adherend.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is also excellent in unevenness followability. For this reason, the double-sided pressure-sensitive adhesive sheet of the present invention can also be bonded to an adherend having a concavo-convex structure (step structure).
  • the layer in contact with the uneven structure (step structure) may be an acrylic pressure-sensitive adhesive layer or a silicone-based pressure-sensitive adhesive layer.
  • the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is preferably 1N / 25 mm or more, more preferably 5N / 25 mm or more, and 10N / 25 mm or more. It is more preferable that the distance be 15 N / 25 mm or more.
  • the upper limit value of the interfacial adhesive strength between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is not particularly limited, but is preferably, for example, 100 N / 25 mm.
  • the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer firmly adhere to each other, and are excellent in interlayer adhesion.
  • peeling occurs between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer when reworking the double-sided pressure-sensitive adhesive sheet. It is possible to suppress the occurrence, and as a result, the reworkability can be enhanced.
  • the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be measured after preparing a sample for measuring interfacial adhesion as described in the examples.
  • the peeling speed with a backing substrate was 300 mm / min according to method 1 of JIS Z 0237, peeling angle 180 ° By peeling under the conditions of 2, the adhesive force measurement of the "acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer" interface is performed.
  • the adhesion to glass on one side of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 1 N / 25 mm or more, more preferably 5 N / 25 mm or more, and still more preferably 10 N / 25 mm or more.
  • the adhesion to glass on one side of the double-sided pressure-sensitive adhesive sheet is preferably 50 N / 25 mm or less, and more preferably 30 N / 25 mm or less. It is preferable that the said adhesive force is the adhesive force side of the acrylic adhesive layer side of a double-sided adhesive sheet, and it is preferable that the glass adhesive force of an acrylic adhesive layer is in the said range.
  • the adhesion to glass on the other side of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 0.005 N / 25 mm or more, more preferably 0.05 N / 25 mm or more.
  • the adhesion to glass on the other side of the double-sided pressure-sensitive adhesive sheet is preferably 1.0 N / 25 mm or less, more preferably 0.5 N / 25 mm or less.
  • the adhesive strength is preferably the adhesive strength on the side of the silicone-based pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive sheet, and the adhesion to glass of the silicone-based pressure-sensitive adhesive layer is preferably within the above range.
  • the adhesion to glass of the double-sided pressure-sensitive adhesive sheet is determined according to method 1 of JIS Z 0237 after 24 hours after sticking the pressure-sensitive adhesive surface of each pressure-sensitive adhesive layer to soda glass, peeling speed 300 mm / min, peeling angle It is a value measured under the condition of 180 °.
  • the total thickness of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and still more preferably 50 ⁇ m or more.
  • the total thickness of the double-sided pressure-sensitive adhesive sheet is preferably 1000 ⁇ m or less, more preferably 800 ⁇ m or less, and still more preferably 600 ⁇ m or less.
  • the thickness of one layer of the acrylic pressure-sensitive adhesive layer in the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and still more preferably 25 ⁇ m or more.
  • the thickness of the acrylic pressure-sensitive adhesive layer is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, and still more preferably 300 ⁇ m or less.
  • the thickness of one layer of the silicone-based pressure-sensitive adhesive layer in the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and still more preferably 25 ⁇ m or more.
  • the thickness of the silicone-based pressure-sensitive adhesive layer is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, and still more preferably 300 ⁇ m or less.
  • the thickness ( ⁇ m) of the acrylic pressure-sensitive adhesive layer is P and the thickness ( ⁇ m) of the silicone-based pressure-sensitive adhesive layer is Q
  • P: Q 1: 10 to 10: 1 preferable.
  • P described above represents the total thickness of the acrylic pressure-sensitive adhesive layer
  • Q mentioned above is a silicone-based pressure-sensitive adhesive in the double-sided pressure-sensitive adhesive sheet. When two or more layers are contained, it represents the total thickness of the silicone-based pressure-sensitive adhesive layer.
  • the haze of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 3% or less, more preferably 1% or less.
  • the haze of the double-sided pressure-sensitive adhesive sheet refers to a value measured by a method in accordance with JIS K 7136.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is bonded to a slide glass (product number: S9112) manufactured by Matsunami Glass Co., Ltd. to measure the haze value.
  • a slide glass product number: S9112 manufactured by Matsunami Glass Co., Ltd.
  • the total light transmittance of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is characterized in that the total light transmittance is high and the transparency is excellent.
  • the total light transmittance of the double-sided pressure-sensitive adhesive sheet refers to a value measured by a method in accordance with JIS K 7136.
  • the total light transmittance of the double-sided pressure-sensitive adhesive sheet can be measured by the same method as the method of measuring the haze value described above.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is also excellent in flexibility. For this reason, even if the adherend is a member having a curved surface or a stepped portion, it can be attached following the curved surface or the stepped portion.
  • the double-sided pressure-sensitive adhesive sheet of the present invention comprises an acrylic pressure-sensitive adhesive layer.
  • the acrylic pressure-sensitive adhesive layer is a layer containing an acrylic resin, preferably an acrylic copolymer as a main component.
  • the content of the acrylic resin (acrylic copolymer) in the acrylic pressure-sensitive adhesive layer is preferably 50% by mass or more, and 60% by mass or more based on the total mass of the acrylic pressure-sensitive adhesive layer Is more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the acrylic adhesive which contains an acrylic polymer as a base polymer can be mentioned, for example.
  • the acrylic polymer contains at least one selected from non-crosslinkable (meth) acrylic acid ester units, acrylic monomer units having a crosslinkable functional group and difunctional acrylic monomer units. preferable.
  • a "monomer unit” is a repeating unit which comprises a polymer.
  • An "acrylic monomer” is a compound having a (meth) acryloyl group.
  • (Meth) cryloyl group” indicates that it is an acryloyl group or a methacryloyl group.
  • the non-crosslinkable acrylic monomer is an acrylic monomer having no crosslinkable group
  • the crosslinkable acrylic monomer is a monomer having a crosslinkable group.
  • the crosslinkable acrylic monomer may be an acrylic monomer or a non-acrylic monomer as long as it can be polymerized with the non-crosslinkable acrylic monomer, but it is an acrylic monomer Is preferred.
  • a carboxy group, a hydroxyl group, an amino group, an epoxy group, glycidyl group etc. are mentioned as a crosslinkable group.
  • the (meth) acrylic acid ester unit which substituted the hydrogen atom of the carboxy group of (meth) acrylic acid by the hydrocarbon group is mentioned, for example.
  • the acrylic pressure-sensitive adhesive layer preferably contains (meth) acrylic acid ester units.
  • (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate ( (Meth) acrylic acid isobutyl, (meth) acrylic acid t-butyl, (meth) acrylic acid n-pentyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-octyl , (Meth) acrylate isooctyl, (meth) acrylate n-nonyl, (meth) acrylate isobornyl, (meth) acrylate isononyl, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) N-undecyl acryl
  • n-butyl acrylate, 2-ethylhexyl acrylate, and methyl acrylate are preferably used from the viewpoint of adhesiveness.
  • One of these may be used alone, or two or more may be used in combination.
  • “(meth) acrylic acid” means that both "acrylic acid” and “methacrylic acid” are included.
  • crosslinkable acrylic monomer unit a carboxy group-containing copolymerizable monomer unit, a hydroxy group-containing copolymerizable monomer unit, an amino group-containing copolymerizable monomer unit, a glycidyl group-containing copolymerizable monomer A mer unit is mentioned.
  • carboxyl group-containing copolymerizable monomer for example, ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, grataconic acid and the anhydride thereof Things etc.
  • hydroxy group-containing copolymerizable monomer for example, (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. And (meth) acrylic acid lactones such as (meth) acrylic acid [(mono, di or poly) alkylene glycols] such as hydroxyalkyl, (meth) acrylic acid mono (diethylene glycol) and the like, and (meth) acrylic acid monocaprolactone.
  • the amino group-containing copolymerizable monomer include (meth) acrylamide and allylamide.
  • glycidyl group containing copolymerizable monomer glycidyl (meth) acrylate etc. are mentioned, for example.
  • the acrylic polymer is preferably an acrylic random copolymer, and more preferably a random copolymer of a crosslinkable acrylic monomer and a non-crosslinkable acrylic monomer. More specifically, a random copolymer of acrylic acid and at least one selected from n-butyl acrylate, 2-ethylhexyl acrylate and methyl acrylate is preferable, and an acrylic ester-based copolymer Is preferred.
  • the acrylic pressure-sensitive adhesive layer preferably contains an acrylic copolymer.
  • the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer preferably contains a unit derived from butyl acrylate.
  • the content of the unit derived from butyl acrylate may be 30% by mass or more, preferably 35% by mass or more, and preferably 40% by mass or more with respect to the total mass of the acrylic copolymer. It is more preferable that The content of units derived from butyl acrylate is preferably 80% by mass or less, and more preferably 70% by mass or less, based on the total mass of the acrylic copolymer.
  • the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be effectively enhanced. Reworkability of the double-sided pressure-sensitive adhesive sheet can be enhanced.
  • the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer preferably further contains a unit derived from 2-hydroxyethyl acrylate in addition to a unit derived from butyl acrylate.
  • the content of the unit derived from 2-hydroxyethyl acrylate is preferably 10% by mass or more, and more preferably 15% by mass or more, based on the total mass of the acrylic copolymer. More preferably, it is 20% by mass or more.
  • the content of units derived from 2-hydroxyethyl acrylate is preferably 50% by mass or less, and more preferably 45% by mass or less, based on the total mass of the acrylic copolymer. More preferably, it is 40% by mass or less.
  • the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be effectively increased.
  • the reworkability of the double-sided pressure-sensitive adhesive sheet can be enhanced.
  • the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer preferably further includes a unit derived from 2-methoxyethyl acrylate.
  • the content of units derived from 2-methoxyethyl acrylate is preferably 10% by mass or more, and more preferably 15% by mass or more based on the total mass of the acrylic copolymer. More preferably, it is 20% by mass or more.
  • the content of units derived from 2-methoxyethyl acrylate is preferably 50% by mass or less, more preferably 45% by mass or less, based on the total mass of the acrylic copolymer. More preferably, it is 40% by mass or less.
  • the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be effectively increased.
  • the reworkability of the double-sided pressure-sensitive adhesive sheet can be enhanced.
  • the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer is a unit derived from 2-hydroxyethyl acrylate or derived from 2-methoxyethyl acrylate It is preferable that the acrylic copolymer has a unit derived from 2-hydroxyethyl acrylate in addition to a unit derived from butyl acrylate, and an acrylic acid-2 - May have both of the units derived from methoxyethyl.
  • the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer may further contain units derived from other acrylic monomers.
  • alkyl (meth) acrylate other than the acrylic monomer mentioned above can be mentioned.
  • alkyl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid-2 -Ethylhexyl etc.
  • the acrylic copolymer preferably contains a unit derived from 2-ethylhexyl acrylate.
  • the content of the unit derived from the alkyl (meth) acrylate is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more based on the total mass of the acrylic copolymer. It is further preferred that The content of the unit derived from the alkyl (meth) acrylate is preferably 80% by mass or less, and more preferably 70% by mass or less, based on the total mass of the acrylic copolymer.
  • the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer may contain, as another acrylic monomer, a unit derived from an acrylic monomer having a crosslinkable functional group.
  • a crosslinkable functional group a carboxy group, an amino group, an amide group, glycidyl group, an isocyanate group etc. can be mentioned, for example, Especially, it is preferable that a crosslinkable functional group is a carboxy group. That is, the acrylic copolymer preferably contains a unit derived from acrylic acid.
  • the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer preferably further contains at least one selected from a unit derived from 2-ethylhexyl acrylate and a unit derived from acrylic acid, More preferably, it further comprises both units derived from 2-ethylhexyl acrylate and units derived from acrylic acid.
  • the acrylic copolymer may have other monomer units, as required.
  • Other monomers may be used as long as they can be copolymerized with the above-mentioned acrylic monomers, and examples thereof include (meth) acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinyl pyrrolidone, vinyl pyridine and the like.
  • the acrylic copolymer may further contain units derived from nitrogen-containing monomers.
  • nitrogen-containing monomers include acryloyl morpholine, urethane acrylate, (meth) acrylamide, allylamide, dimethyl acrylamide, diethyl acrylamide, dimethylaminopropyl acrylamide, diacetone acrylamide and the like.
  • the content of the unit derived from the nitrogen-containing monomer is preferably 5% by mass or more based on the total mass of the acrylic polymer. Further, the content of the unit derived from the nitrogen-containing monomer is preferably 70% by mass or less, more preferably 50% by mass or less, with respect to the total mass of the acrylic polymer, and 20% by mass The content is more preferably 10% by mass or less.
  • the weight average molecular weight (Mw) of the acrylic copolymer is preferably 200,000 or more and 2.50 or less, and more preferably 300,000 or more and 2,000,000 or less.
  • the weight average molecular weight (Mw) is calculated based on a calibration curve prepared using a polystyrene standard substance by gel permeation chromatography (GPC) measurement.
  • the measurement conditions of gel permeation chromatography are as follows. Solvent: Tetrahydrofuran column: Shodex KF801, KF803L, KF806L (Showa Denko Co., Ltd. product three connected) Column temperature: 40 ° C Sample concentration: 0.5 mass% Detector: RI-2031 plus (made by JASCO) Pump: RI-2080plus (made by JASCO) Flow rate (flow rate): 0.8 ml / min Injection volume: 10 ⁇ l
  • the acrylic pressure-sensitive adhesive layer preferably contains a silane coupling agent.
  • the acrylic pressure-sensitive adhesive layer contains a silane coupling agent, the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be more effectively enhanced.
  • silane coupling agent for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,1 Amino group-containing silane coupling agents such as 3-dimethylbutylidene) propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane Meta) Acrylic group containing silane Coupling agent; 3- isocyan
  • silane coupling agent one having a plurality of alkoxysilyl groups in the molecule can also be used.
  • silane coupling agent for example, X-41-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1059 manufactured by Shin-Etsu Chemical Co., Ltd. And -41-1810 and X-40-2651.
  • the content of the silane coupling agent is preferably 0.03% by mass or more and 5% by mass or less with respect to the total mass of the acrylic pressure-sensitive adhesive layer. Moreover, it is preferable that content of a silane coupling agent is 0.06 mass% or more and 1 mass% or less with respect to the total mass of an acrylic adhesive layer.
  • the silane coupling agents may be used alone or in combination of two or more.
  • the acrylic pressure-sensitive adhesive layer may contain a crosslinking agent. That is, it is preferable that the acrylic adhesive composition which forms an acrylic adhesive layer contains a crosslinking agent, and, thereby, can accelerate the crosslinking reaction of the crosslinkable acrylic monomer mentioned above.
  • the crosslinking agent for example, among the known crosslinking agents such as an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound, a butylated melamine compound and a polyfunctional acrylate, the crosslinkability possessed by the crosslinkable acrylic polymer It can be selected appropriately in consideration of the reactivity with the functional group.
  • the method of crosslinking can be selected from known methods such as thermal crosslinking or ionizing radiation crosslinking.
  • curing treatment may be performed in an environment of 23 ° C. or the like in order to further increase the degree of crosslinking.
  • isocyanate compound examples include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.
  • the dicyanate may be used as it is as a bifunctional compound, or as a trifunctional derivative such as an adduct, a nurate or a burette.
  • epoxy compound for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, tetraglycidyl xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. It can be mentioned.
  • the crosslinking agent one type may be used alone, or two or more types may be used in combination.
  • the content of the crosslinking agent in the acrylic pressure-sensitive adhesive composition that forms the acrylic pressure-sensitive adhesive layer is appropriately selected according to the desired adhesive physical properties and the like, and is not particularly limited. It is preferable that it is 0.01 to 5 parts by mass.
  • the acrylic pressure-sensitive adhesive layer may contain a hydrogen abstraction type polymerization initiator.
  • the hydrogen abstraction type polymerization initiator is particularly preferably a photopolymerization initiator.
  • Examples of hydrogen abstraction type photopolymerization initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethyl Benzophenone, 4-methylbenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethyl anthraquinone, 3 And 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 9,10-phen
  • the hydrogen abstraction type photopolymerization initiator preferably contains at least one selected from benzophenone, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone.
  • examples of these commercially available products include Irgacure MBF, SpeedcureMBP, speedcureTZT, SpeedcureMBF, SpeedcureITX, SpeedcureDETX, SpeedcureCPTX, SpeedcureMBB, Speedcure PBZ and the like.
  • the content of the hydrogen extraction-type polymerization initiator is preferably 0.05% by mass or more and 10% by mass or less based on the total mass of the acrylic pressure-sensitive adhesive layer.
  • the acrylic pressure-sensitive adhesive layer is, if necessary, a light stabilizer such as a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, an ultraviolet absorber, an antistatic agent, a photopolymerization initiator, a hindered amine compound, etc. From among these, additives can be selected and blended as required.
  • a plasticizer for example, a nonfunctional acrylic polymer can be used.
  • a nonfunctional acrylic polymer is a polymer consisting only of 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 and no functional group It means a polymer consisting of non-acrylic monomer units.
  • antioxidants examples include phenol based antioxidants, amine based antioxidants, lactone based antioxidants, phosphorus based antioxidants, sulfur based antioxidants and the like. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
  • benzotriazole resin can be mentioned.
  • tackifiers include rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, styrene resins, xylene resins, phenol resins, petroleum resins and the like.
  • UV absorber examples include benzotriazole compounds and benzophenone compounds.
  • an antiaging agent in order to prevent the time-dependent deterioration of an acrylic adhesive layer, it is preferable to add an antiaging agent.
  • an anti-aging agent By adding an anti-aging agent, it is possible to prevent the decrease in adhesion due to the deterioration of the double-sided pressure-sensitive adhesive sheet.
  • anti-aging agents include general phenol-based antioxidants, phosphorus-based antioxidants, ultraviolet inhibitors, HALS (hindered amine-based stabilizers) and the like.
  • the acrylic pressure-sensitive adhesive composition forming the acrylic pressure-sensitive adhesive layer may contain a solvent.
  • the solvent evaporates when forming the pressure-sensitive adhesive layer, but the acrylic pressure-sensitive adhesive layer may contain the remaining solvent.
  • the solvent examples 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 etc.
  • hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone etc.
  • Methyl acetate Esters such as ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate and ethyl butyrate Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, polyols and derivatives thereof such as propylene glycol monomethyl ether acetate.
  • the double-sided pressure-sensitive adhesive sheet of the present invention contains a silicone-based pressure-sensitive adhesive layer.
  • the silicone-based pressure-sensitive adhesive layer is a layer containing a silicone-based resin (silicone-based pressure-sensitive adhesive) as a main component.
  • the content of the silicone-based resin in the silicone-based pressure-sensitive adhesive layer is preferably 50% by mass or more, and more preferably 60% by mass or more based on the total mass of the silicone-based pressure-sensitive adhesive layer
  • the content is more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • silicone resins examples include silicone resins having a polysiloxane skeleton.
  • Silicone resins include addition reaction type, condensation reaction type, ultraviolet ray curing type, electron beam curing type and the like. Among them, addition reaction type silicone resins are preferably used because they have high reactivity and are excellent in productivity.
  • the addition reaction type silicone resin for example, an organopoly resin having two or more alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group and hexenyl group at the terminal and / or side chain of the molecule.
  • a siloxane is mentioned.
  • crosslinking agent examples include organopolysiloxanes having hydrogen atoms bonded to at least two silicon atoms in one molecule.
  • the crosslinking agent include organopolysiloxanes having hydrogen atoms bonded to at least two silicon atoms in one molecule. Specifically, dimethylhydrogensiloxy end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy end-capped dimethylsiloxane-methyl hydrogen siloxane copolymer, trimethylsiloxy end-capped methylhydrogenpolysiloxane, Poly (hydrogen silsesquioxane) etc. are mentioned.
  • particulate platinum As the catalyst, particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, white metal compounds such as palladium and rhodium, etc. It can be mentioned.
  • the silicone-based pressure-sensitive adhesive layer contains, if necessary, additives such as an antioxidant, a metal corrosion inhibitor, a tackifier, an ultraviolet light absorber, a hindered amine compound, an antistatic agent, and a light stabilizer as needed. It can be selected and blended.
  • additives such as an antioxidant, a metal corrosion inhibitor, a tackifier, an ultraviolet light absorber, a hindered amine compound, an antistatic agent, and a light stabilizer as needed. It can be selected and blended.
  • the antioxidant include phenol based antioxidants, amine based antioxidants, lactone based antioxidants, phosphorus based antioxidants, sulfur based antioxidants and the like. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
  • benzotriazole resin can be mentioned.
  • tackifiers include rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, styrene resins, xylene resins, phenol resins, petroleum resins and the like.
  • UV absorber examples include benzotriazole compounds and benzophenone compounds.
  • an antiaging agent in order to prevent the time-dependent deterioration of a silicone type adhesive layer, it is preferable to add an antiaging agent.
  • an anti-aging agent By adding an anti-aging agent, it is possible to prevent the decrease in adhesion due to the deterioration of the double-sided pressure-sensitive adhesive sheet.
  • anti-aging agents include general phenol-based antioxidants, phosphorus-based antioxidants, ultraviolet inhibitors, HALS (hindered amine-based stabilizers) and the like.
  • the silicone-based pressure-sensitive adhesive composition forming the silicone-based pressure-sensitive adhesive layer may contain a solvent.
  • the solvent evaporates when forming the pressure-sensitive adhesive layer, but the silicone-based pressure-sensitive adhesive layer may contain the remaining solvent.
  • a solvent the thing similar to the solvent which an acrylic adhesive composition may contain is mentioned.
  • a commercial item can be used as a silicone type adhesive.
  • silicone-based pressure-sensitive adhesives for example, KR-3704, X40-3306 manufactured by Shin-Etsu Chemical Co., Ltd., DC7651ADHESIVE manufactured by Toray Dow Corning Co., Ltd., SD7587LPSA, SE9500 manufactured by Aika Kogyo Co., Ltd. SE9600 etc. are mentioned.
  • the manufacturing process of the double-sided adhesive sheet of this invention includes the process of laminating
  • Each pressure-sensitive adhesive layer is preferably a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) formed by coating, and more preferably a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) formed by sequential coating.
  • sequential application means that each pressure-sensitive adhesive layer is applied in each step and formed into a separate sheet.
  • an acrylic pressure-sensitive adhesive composition is coated on a release sheet to form an acrylic pressure-sensitive adhesive layer, and a silicone-based pressure-sensitive adhesive composition on another release sheet. And applying a silicone-based pressure-sensitive adhesive layer. Then, a step of overlapping and pressure-bonding the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer so as to be in direct contact with each other is included.
  • Coating of each pressure-sensitive adhesive composition can be carried out using a known coating apparatus.
  • a coating apparatus a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a microgravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater etc. are mentioned, for example.
  • a drying process after coating and a drying process can be implemented using well-known heating apparatuses, such as a heating furnace and an infrared lamp.
  • the manufacturing process of a double-sided adhesive sheet includes a surface activation treatment process before superposing an acrylic adhesive layer and a silicone adhesive layer.
  • the surface activation treatment include corona treatment and plasma treatment. Among them, corona treatment is preferably performed as the surface activation treatment.
  • the surface activation treatment step at least one selected from the acrylic pressure-sensitive adhesive layer and the silicone pressure-sensitive adhesive layer is preferably subjected to surface activation treatment.
  • the surface activation treatment is preferably performed on the surface on the bonding surface side of each pressure-sensitive adhesive layer. That is, at least one selected from the surface on the interface side of the acrylic pressure-sensitive adhesive layer and the surface on the interface side of the silicone-based pressure-sensitive adhesive layer is preferably a surface activation treated surface.
  • a surface activation treatment is performed on both the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer.
  • the surface on the interface side of the acrylic pressure-sensitive adhesive layer and the surface on the interface side of the silicone-based pressure-sensitive adhesive layer are preferably a surface activation treated surface.
  • the surface activation treatment is applied only to either the acrylic pressure-sensitive adhesive layer or the silicone pressure-sensitive adhesive layer, the surface activation treatment is preferably applied to the silicone pressure-sensitive adhesive layer.
  • the wetting tension of the surface activation treated surface is preferably 70 mN / m or more, more preferably 73 mN / m or more .
  • the upper limit of the wetting tension of the surface activation treated surface is not particularly limited.
  • the wet tension of the acrylic pressure-sensitive adhesive layer after the surface activation treatment is preferably 1.1 or more times the wet tension of the acrylic pressure-sensitive adhesive layer before the surface activation treatment.
  • the surface activation treatment is preferably applied to the acrylic pressure-sensitive adhesive layer.
  • the wetting tension of the surface activation treated surface is preferably 30 mN / m or more, more preferably 34 mN / m or more. And 35 mN / m or more.
  • the upper limit of the wetting tension of the surface activation treated surface is not particularly limited, it is preferably, for example, 50 mN / m or less, more preferably 45 mN / m or less, in order to prevent the decrease in transparency. preferable.
  • the wetting tension is measured by applying a wetting indication standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) to the surface of the adhesive layer according to JIS K 6768 1999.
  • corona treatment there is a method of discharging in normal pressure air by a corona treatment machine.
  • the corona output in the corona treatment is not particularly limited, but is preferably, for example, 0.5 kW or more and 8.0 kW or less, and more preferably 0.5 kW or more and 7.0 kW or less. It is more preferable that it is 6.0 kW or less.
  • the treatment speed in the corona treatment is preferably 5 m / min to 100 m / min, more preferably 5 m / min to 90 m / min, and still more preferably 5 m / min to 80 m / min. .
  • the plasma treatment there is a method of discharging in normal pressure air by a plasma discharger.
  • the plasma output in the plasma processing is not particularly limited, but is preferably, for example, 0.5 kW or more and 5.0 kW or less, and more preferably 0.5 kW or more and 3.0 kW or less. More preferably, it is 1.5 kW or less.
  • the processing speed in the plasma processing is preferably 5 m / min to 100 m / min, more preferably 5 m / min to 90 m / min, and still more preferably 5 m / min to 80 m / min. .
  • the degree of surface activation is preferably adjusted as appropriate so that the wetting tension is in the above-mentioned range.
  • the pressure-bonding method in the step of pressure-bonding the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is not particularly limited, but it is preferable to use a roll bonding machine capable of continuously pressure-bonding.
  • a release sheet is preferably laminated on at least one surface of the double-sided pressure-sensitive adhesive sheet, and more preferably, the release sheet is laminated on both sides of the double-sided pressure-sensitive adhesive sheet. That is, the double-sided pressure-sensitive adhesive sheet of the present invention is preferably a double-sided pressure-sensitive adhesive sheet with a release sheet provided with release sheets on both sides of the double-sided pressure-sensitive adhesive sheet.
  • a release sheet a peelable laminate sheet having a release sheet substrate and a release agent layer provided on one side of the release sheet substrate, or a polyolefin film such as a polyethylene film or a polypropylene film as a low polarity substrate
  • Papers and polymer films are used for the release sheet base in the release laminate sheet.
  • the release agent constituting the release agent layer for example, a general-purpose addition type or condensation type silicone release agent or a long chain alkyl group-containing compound is used. In particular, an addition-type silicone release agent having high reactivity is preferably used.
  • silicone release agents include BY24-4527 and SD-7220 manufactured by Toray Dow Corning Silicone Co., Ltd., KS-3600 manufactured by Shin-Etsu Chemical Co., Ltd., KS-774 and X62-2600, etc. Can be mentioned.
  • a silicone resin which is an organic silicon compound having a SiO 2 unit and a (CH 3 ) 3 SiO 1/2 unit or a CH 2 CHCH (CH 3 ) SiO 1/2 unit in a silicone-based release agent preferable.
  • Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404, etc. manufactured by Toray Dow Corning Silicone Co., Ltd., and KS-3800, X92-183, etc. manufactured by Shin-Etsu Chemical Co., Ltd.
  • the first release sheet (release sheet on the acrylic pressure-sensitive adhesive layer side) is preferably a release sheet on the light release force side, and the release strength at the time of releasing the first release sheet from the acrylic pressure-sensitive adhesive layer is
  • the thickness is preferably 0.01 N / 50 mm or more, more preferably 0.1 N / 50 mm or more. Moreover, it is preferable that it is 1.0 N / 50 mm or less, and, as for the peeling force at the time of peeling a 1st peeling sheet from an acrylic adhesive layer, it is more preferable that it is 0.8 N / 50 mm or less, and 0.6 N It is further more preferable that it is / 50 mm or less.
  • the second release sheet (release sheet on the silicone-based pressure-sensitive adhesive layer side) is preferably a release sheet on the heavy release force side, and the release force at the time of releasing the second release sheet from the silicone-based pressure-sensitive adhesive layer is It is preferable that it is 0.5 N / 50 mm or more, and it is more preferable that it is 0.6 N / 50 mm or more. Moreover, it is preferable that it is 10.0 N / 50 mm or less, and, as for the peeling force at the time of peeling a 2nd peeling sheet from a silicone type adhesive layer, it is more preferable that it is 5.0 N / 50 mm or less, and 3.0 N It is further more preferable that it is / 50 mm or less.
  • the release force of the second release sheet (release sheet on the side of the silicone-based pressure-sensitive adhesive layer) is R H and the release force of the first release sheet (release-side on the side of the acrylic pressure-sensitive adhesive layer) is R L
  • the value of R H / R L is preferably 1.5 or more, and more preferably 2.0 or more.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is preferably used for the application of bonding of various members.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is preferably a double-sided pressure-sensitive adhesive sheet for optical member bonding.
  • a liquid crystal display or a touch panel can be mentioned, for example.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is preferably used for bonding a glass and a liquid crystal display or a glass and a touch panel.
  • the present invention may relate to a laminate having the double-sided pressure-sensitive adhesive sheet described above and an adherend.
  • the laminate is a laminate in which the bonding surface with the first adherend is an acrylic pressure-sensitive adhesive layer and the bonding surface with the second adherend is a silicone-based pressure-sensitive adhesive layer Is preferred.
  • the first adherend is preferably glass. With such a configuration, removability from the second adherend is facilitated, while firmly adhering to the first adherend.
  • Example 1 Preparation of Acrylic Pressure-Sensitive Adhesive Composition> A (meth) acrylic acid ester polymer was prepared by copolymerizing 90 parts by mass of n-butyl acrylate (BA) and 10 parts by mass of acrylic acid (AA). The weight average molecular weight of this (meth) acrylic acid ester polymer was 500,000.
  • KS-847H consisting of an organopolysiloxane having a siloxane bond as a main skeleton and having a vinyl group and an organohydrogenpolysiloxane 20 parts by mass of an organopolysiloxane containing a trifunctional or tetrafunctional siloxane unit (silicone resin; manufactured by Toray Dow Corning, SD-4584), a platinum catalyst (manufactured by Toray Dow Corning, SRX-212).
  • the silicone-based pressure-sensitive adhesive composition was obtained by mixing 5 parts by mass, sufficiently stirring, and diluting with methyl ethyl ketone so that the solid content concentration was 40% by mass.
  • ⁇ Preparation of double-sided adhesive sheet> (Preparation of acrylic pressure-sensitive adhesive layer)
  • the first release sheet is attached to one side by uniformly coating the surface with an applicator so that the coated amount after drying is 50 ⁇ m and drying in an air circulating constant temperature oven at 100 ° C. for 3 minutes.
  • the obtained acrylic adhesive layer was obtained.
  • the pressure-sensitive adhesive layer having the first release sheet attached to one side was aged for 7 days in an environment of 23 ° C. and 50% relative humidity.
  • silicone pressure sensitive adhesive layer (Preparation of silicone pressure sensitive adhesive layer) Apply a silicone-based pressure-sensitive adhesive composition uniformly on the surface of a 38 ⁇ m-thick polyethylene terephthalate film (Lumirror S-10 # 38, manufactured by Toray Industries, Inc.) with an applicator so that the coated amount after drying is 50 ⁇ m. By drying in an air circulating constant temperature oven at 100 ° C. for 3 minutes, a silicone-based pressure-sensitive adhesive layer in which the second release sheet was attached to one side was obtained.
  • a silicone-based pressure-sensitive adhesive composition uniformly on the surface of a 38 ⁇ m-thick polyethylene terephthalate film (Lumirror S-10 # 38, manufactured by Toray Industries, Inc.) with an applicator so that the coated amount after drying is 50 ⁇ m.
  • a silicone-based pressure-sensitive adhesive layer in which the second release sheet was attached to one side was obtained.
  • the surface of each of the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer was subjected to corona discharge treatment.
  • the corona discharge treatment was performed using a corona surface treatment apparatus made by Kasuga Denki.
  • the corona discharge treatment was performed under the conditions that the wetting tension of the acrylic pressure-sensitive adhesive layer was 70 mN / m or more and the wetting tension of the silicone-based pressure-sensitive adhesive layer was 30 mN / m or more.
  • Example 2 Example 1 (surface activation treatment) except that the surface activation treatment of each of the acrylic pressure-sensitive adhesive layer and the silicone pressure-sensitive adhesive layer was changed to plasma discharge treatment (Sekisui Chemical Atmospheric Pressure Plasma Surface Treatment Device RT Series) In the same manner as in, a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained.
  • the plasma discharge treatment was performed under the conditions that the wetting tension of the acrylic pressure-sensitive adhesive layer was 70 mN / m or more and the wetting tension of the silicone-based pressure-sensitive adhesive layer was 30 mN / m or more.
  • Example 3 A release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the surface activation treatment of the silicone-based pressure-sensitive adhesive layer was not performed in (Surface activation treatment). The corona discharge treatment was performed under the condition that the wetting tension of the acrylic pressure-sensitive adhesive layer was 70 mN / m or more.
  • Example 4 A release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the surface activation treatment of the acrylic pressure-sensitive adhesive layer was not performed in (Surface activation treatment). The corona discharge treatment was performed under the condition that the wetting tension of the silicone-based pressure-sensitive adhesive layer was 30 mN / m or more.
  • Example 5 An acrylic pressure-sensitive adhesive composition (B) was obtained in the same manner as in Example 1, except that no silane coupling agent was added in ⁇ Preparation of acrylic pressure-sensitive adhesive composition>.
  • a release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive composition (B) was used instead of the acrylic pressure-sensitive adhesive composition (A).
  • Example 7 In ⁇ Preparation of Acrylic Pressure-Sensitive Adhesive Composition>, 25 parts by mass of n-butyl acrylate (BA), 55 parts by mass of 2-ethylhexyl acrylate (2EHA), 5 parts by mass of diethyl acrylamide (DEAA), and 4-acryloyl A (meth) acrylic acid ester polymer was prepared by copolymerizing 5 parts by mass of moropholin (ACMO). The weight average molecular weight of this (meth) acrylic acid ester polymer was 1,000,000.
  • An acrylic pressure-sensitive adhesive composition (D) was obtained in the same manner as in Example 5 except that this (meth) acrylic acid ester polymer was used.
  • a release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 5, except that the acrylic pressure-sensitive adhesive composition (D) was used instead of the acrylic pressure-sensitive adhesive composition (B).
  • an acrylic adhesive A composition (E) 100 parts by mass of the (meth) acrylic acid ester polymer obtained, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, TERAD-C) 0 as an epoxy crosslinking agent 05 parts by mass, 1.5 parts by mass of 4-methylbenzophenone as a hydrogen extraction photoinitiator, sufficiently stirred, and diluted with ethyl acetate so that the solid content becomes 40% by mass, an acrylic adhesive A composition (E) was obtained.
  • a release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 5, except that the acrylic pressure-sensitive adhesive composition (E) was used instead of the acrylic pressure-sensitive adhesive composition (B).
  • ultraviolet rays high pressure mercury
  • the integrated light amount was 1000 mJ / cm 2 to finally obtain a double-sided pressure-sensitive adhesive sheet with a release sheet used for evaluation.
  • the first release sheet of a double-sided pressure-sensitive adhesive sheet with a release sheet on which a first release sheet / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / second release sheet are laminated in this order is peeled off.
  • a polyethylene terephthalate film (Toyobo, A4300 # 100) was adhered as a backing substrate.
  • the second release sheet was released, and the adhesive surface of the silicone-based pressure-sensitive adhesive layer was attached to soda glass. Twenty-four hours after the application, adhesion was measured according to method 1 of JIS Z 0237 under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °.
  • the wetting tension was measured by applying a wetting indication standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) to the surface of the adhesive layer according to JIS K 6768 1999.
  • a (meth) acrylic acid ester polymer was prepared by copolymerizing 90 parts by mass of n-butyl acrylate (BA) and 10 parts by mass of acrylic acid (AA). The weight average molecular weight of this (meth) acrylic acid ester polymer was 500,000.
  • the resulting acrylic pressure-sensitive adhesive composition is uniformly coated on the surface of a polyethylene terephthalate film with an easy-adhesion layer (A4300 # 100 made by Toyobo Co., Ltd.) with an applicator so that the coated amount after drying is 25 ⁇ m, 100 By drying in an air circulating constant temperature oven for 3 minutes, an adhesive tape with a backing substrate was obtained.
  • an easy-adhesion layer A4300 # 100 made by Toyobo Co., Ltd.
  • the wet tension is
  • the surface activation treatment was performed on the surface of the silicone-based pressure-sensitive adhesive layer using a corona surface treatment apparatus manufactured by Kasuga Denki in order to achieve 34 mN / m or more. Furthermore, the surface activation treatment was performed using a corona surface treatment apparatus made by Kasuga Electric Co., Ltd. so that the wet tension of the surface of the acrylic pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape with substrate for backing was 73 mN / m or more.
  • the surface activation treatment was applied to the surface of the silicone adhesive layer that had been subjected to the surface activation treatment of “polyethylene terephthalate film with easy adhesion layer / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer”.
  • the first peelable sheet is obtained by cutting a double-sided pressure-sensitive adhesive sheet with a release sheet on which a first release sheet / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / second release sheet are laminated in this order into 25 ⁇ 50 mm square
  • the sheet was peeled off, and a slide glass (manufactured by Matsunami Glass, S9112, size 76 ⁇ 52 mm) was attached to the acrylic pressure-sensitive adhesive layer (2 kg roller, 1 reciprocation). Thereafter, the second release sheet was removed, and the silicone-based pressure-sensitive adhesive layer was attached to soda glass (manufactured by Matsunami Glass, S9112, size 76 ⁇ 52 mm).
  • the double-sided pressure-sensitive adhesive sheet with a double-sided glass plate thus obtained is set in a universal type tensile tester (Tensilon UTM-4-100, manufactured by Orientec Co., Ltd.), peeling speed 300 mm / min, peeling angle according to JIS Z 0237
  • the silicone-based pressure-sensitive adhesive layer was peeled from the slide glass under the condition of 90 ° (peeling upward) and evaluated based on the following criteria. "Excellent": After adhering the silicone-based pressure-sensitive adhesive layer to a slide glass, it is left in an environment of 40 ° C and a relative humidity of 90% for 240 hours, and when peeled off thereafter, no pressure-sensitive adhesive layer remains on the slide glass surface.
  • the acrylic pressure-sensitive adhesive layer exhibited strong adhesion to glass, and the silicone-based pressure-sensitive adhesive layer was excellent in reworkability.
  • the pressure-sensitive adhesive layer remained on the adherend when reworking.
  • Example 101 ⁇ Preparation of Acrylic Pressure-Sensitive Adhesive Composition> An acrylic copolymer was prepared by copolymerizing 40 parts by mass of n-butyl acrylate, 55 parts by mass of 2-ethylhexyl acrylate, and 5 parts by mass of acrylic acid. The weight average molecular weight of this acrylic copolymer was 1,000,000.
  • acrylic copolymer 100 parts by mass of the obtained acrylic copolymer, 0.05 parts by mass of 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, TERAD-C) as an epoxy-based crosslinking agent, As a silane coupling agent, 0.15 parts by mass of silicone alkoxy oligomer (X-41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed and sufficiently stirred to give a solid content concentration of 40% by mass. By diluting with ethyl, an acrylic pressure-sensitive adhesive composition (A) was obtained.
  • 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane manufactured by Mitsubishi Gas Chemical Company, TERAD-C
  • silane coupling agent 0.15 parts by mass of silicone alkoxy oligomer (X-41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed and sufficiently stirred
  • KS-847H consisting of an organopolysiloxane having a siloxane bond as a main skeleton and having a vinyl group and an organohydrogenpolysiloxane 20 parts by mass of an organopolysiloxane containing a trifunctional or tetrafunctional siloxane unit (silicone resin; manufactured by Toray Dow Corning, SD-4584), a platinum catalyst (manufactured by Toray Dow Corning, SRX-212).
  • the silicone-based pressure-sensitive adhesive composition was obtained by mixing 5 parts by mass, sufficiently stirring, and diluting with methyl ethyl ketone so that the solid content concentration was 40% by mass.
  • ⁇ Preparation of double-sided adhesive sheet> (Preparation of acrylic pressure-sensitive adhesive layer)
  • the first release sheet is attached to one side by uniformly coating the surface with an applicator so that the coated amount after drying is 50 ⁇ m and drying in an air circulating constant temperature oven at 100 ° C. for 3 minutes.
  • the obtained acrylic adhesive layer was obtained.
  • the pressure-sensitive adhesive layer having the first release sheet attached to one side was aged for 7 days in an environment of 23 ° C. and 50% relative humidity.
  • silicone pressure sensitive adhesive layer (Preparation of silicone pressure sensitive adhesive layer) Apply a silicone-based pressure-sensitive adhesive composition uniformly on the surface of a 38 ⁇ m-thick polyethylene terephthalate film (Lumirror S-10 # 38, manufactured by Toray Industries, Inc.) with an applicator so that the coated amount after drying is 50 ⁇ m. By drying in an air circulating constant temperature oven at 100 ° C. for 3 minutes, a silicone-based pressure-sensitive adhesive layer in which the second release sheet was attached to one side was obtained.
  • a silicone-based pressure-sensitive adhesive composition uniformly on the surface of a 38 ⁇ m-thick polyethylene terephthalate film (Lumirror S-10 # 38, manufactured by Toray Industries, Inc.) with an applicator so that the coated amount after drying is 50 ⁇ m.
  • a silicone-based pressure-sensitive adhesive layer in which the second release sheet was attached to one side was obtained.
  • the surface of the silicone pressure-sensitive adhesive layer was subjected to corona discharge treatment.
  • the corona discharge treatment was performed using a corona surface treatment apparatus made by Kasuga Denki.
  • the corona discharge treatment was performed under the condition that the wet tension of the silicone pressure-sensitive adhesive layer was 30 mN / m or more.
  • Embodiment 102 Except that 40 parts by mass of n-butyl acrylate, 30 parts by mass of 2-hydroxyethyl acrylate, 25 parts by mass of 2-ethylhexyl acrylate and 5 parts by mass of acrylic acid were copolymerized to prepare an acrylic copolymer In the same manner as in Example 101, a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained. The weight average molecular weight of the obtained acrylic copolymer was 1.5 million.
  • Embodiment 103 40 parts by mass of n-butyl acrylate, 30 parts by mass of 2-methoxyethyl acrylate, 25 parts by mass of 2-ethylhexyl acrylate and 5 parts by mass of acrylic acid were copolymerized to prepare an acrylic copolymer In the same manner as in Example 101, a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained. The weight average molecular weight of the obtained acrylic copolymer was 1.5 million.
  • a release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 101, except that the surface activation treatment applied to the silicone-based pressure-sensitive adhesive layer was changed from corona discharge treatment to plasma discharge treatment.
  • the plasma discharge treatment was performed under the condition that the wetting tension of the silicone-based pressure-sensitive adhesive layer was 30 mN / m or more.
  • the acrylic pressure-sensitive adhesive layer exhibited strong adhesion to glass, and the silicone-based pressure-sensitive adhesive layer was excellent in reworkability.
  • the pressure-sensitive adhesive layer remained on the adherend when reworking.
  • the double-sided pressure-sensitive adhesive sheet obtained in the examples was also excellent in curved surface followability and step followability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

This invention addresses the problem of providing a double-sided adhesive sheet having both strong adhesive force and excellent reworkability. This invention relates to a double-sided adhesive sheet having an acrylic adhesive agent layer and a silicone adhesive agent layer directly layered on the acrylic adhesive agent layer. The interface adhesive force between the acrylic adhesive agent layer and the silicone adhesive agent layer is 1N/25 mm or greater.

Description

両面粘着シートおよび剥離シート付き両面粘着シートDouble-sided PSA sheet and release sheet with double-sided PSA sheet
　本発明は、両面粘着シートおよび剥離シート付き両面粘着シートに関する。 The present invention relates to a double-sided pressure-sensitive adhesive sheet and a double-sided pressure-sensitive adhesive sheet with a release sheet.
　近年、様々な分野で、液晶ディスプレイ（ＬＣＤ）などの表示装置や、タッチパネルなどの表示装置及び入力装置を組み合わせた画像表示装置が広く用いられている。これらの表示装置や入力装置においては、光学部材を貼り合せる用途に両面粘着シートが用いられている。 2. Description of the Related Art In recent years, in various fields, display devices such as liquid crystal displays (LCDs) and image display devices combining display devices such as touch panels and input devices are widely used. In these display devices and input devices, double-sided pressure-sensitive adhesive sheets are used for the purpose of bonding optical members.
　両面粘着シートは異種の被着材を貼り合わせる用途に用いられる場合がある。この場合、両面粘着シートには各被着材の接着特性に応じた最適な粘着力が求められる。例えば、特許文献１および２には、粘着特性の異なる２層以上の粘着剤層を備えた両面粘着シートが開示されている。 The double-sided pressure-sensitive adhesive sheet may be used for laminating different kinds of adherends. In this case, the double-sided pressure-sensitive adhesive sheet is required to have an optimum adhesive strength in accordance with the adhesive property of each adherend. For example, Patent Documents 1 and 2 disclose a double-sided pressure-sensitive adhesive sheet provided with two or more pressure-sensitive adhesive layers having different adhesion properties.
　表示装置や入力装置においては、表示面を保護するためにその表面を保護シートで覆うことが行われている。保護シートは、例えば、粘着剤層を備えたガラスシートから構成されており、保護シートを表示面に貼合することで液晶ディスプレイの割れや傷つきを抑制する。このような保護シートを使用した場合、貼合位置の修正や保護シートの経年劣化による交換のために、保護シートをリワーク（再剥離）させることが必要になる場合がある。例えば、特許文献３および４には、少なくとも２層の粘着剤層を有しており、表示装置の表示面に対して再剥離可能となるように構成された両面粘着シートが開示されている。特許文献３の実施例では、種類の異なるアクリル系ポリマーから各粘着剤層を形成しており、これにより両面粘着シートの耐久性とリワーク性を高めることが検討されている。なお、特許文献３の両面粘着シートは、表示面とタッチパネルの貼着を目的とするものである。また、特許文献４には、芯材の両表面に第１の粘着剤層と第２の粘着剤層とを有する両面粘着シートが開示されており、第１の粘着剤層にはシリコーン系粘着剤が、第２の粘着剤層にはアクリル系粘着剤が用いられている。 In the display device and the input device, in order to protect the display surface, the surface is covered with a protective sheet. The protective sheet is made of, for example, a glass sheet provided with a pressure-sensitive adhesive layer, and bonding the protective sheet to the display surface suppresses cracking and damage of the liquid crystal display. When such a protective sheet is used, it may be necessary to rework (re-peel) the protective sheet in order to correct the bonding position and replace the protective sheet due to aging. For example, Patent Documents 3 and 4 disclose a double-sided pressure-sensitive adhesive sheet having at least two pressure-sensitive adhesive layers and configured to be releasable from the display surface of a display device. In the Example of patent document 3, each adhesive layer is formed from the acrylic polymer from which a kind differs, It is examined that the durability and rework property of a double-sided adhesive sheet are improved by this. In addition, the double-sided adhesive sheet of patent document 3 aims at sticking of a display surface and a touch panel. Patent Document 4 discloses a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer on both surfaces of a core material, and a silicone-based pressure-sensitive adhesive layer on the first pressure-sensitive adhesive layer. In the second pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive is used.
特開平５－１７７２５号公報JP-A-5-17725 特開２０１１－５７８８３号公報JP, 2011-57883, A 特開２００４－２３１７２３号公報JP, 2004-231723, A 特許第６１９７１０２号公報Patent No. 6197102
　しかしながら、従来技術における両面粘着シートを被着体から再剥離する場合、リワーク作業時に被着材に粘着剤が残るという問題があった。被着材に粘着剤が残った場合は、溶剤で粘着剤を拭き取ったり、洗浄したりする必要があり、リワーク作業に手間と時間がかかるため問題となる。特に、特別な装置、冶具、薬品を用いることの出来ない一般消費者が貼り合せやリワーク作業を行う保護シートは、表示面から容易にリワークされ得る必要があるため、保護シートの表示面への粘着力を極めて低くする必要がある。一方で、保護シートに用いられている両面粘着シートは、表示面とは反対側の被着対象には強固に密着する必要がある。一般的に、このように相反する粘着特性を有する粘着剤層同士を積層することは困難であるため、微粘着層と強粘着層の間に基材フィルムを設けた両面粘着シートが用いられている。しかし、微粘着層と強粘着層の間に基材フィルムを設けた両面粘着シートは、その厚みが増大する傾向にあり、凹凸追従性が劣ったり、近年の薄膜化の要求に応えられないという問題があった。 However, when the double-sided pressure-sensitive adhesive sheet in the prior art is peeled again from the adherend, there is a problem that the pressure-sensitive adhesive remains on the adherend at the time of rework. When the adhesive remains on the adherend, it is necessary to wipe off the adhesive with a solvent or to wash the adhesive, which is a problem because it takes time and labor for rework. In particular, a protective sheet for general consumers who can not use special equipment, jigs, or chemicals to perform bonding or rework must be able to be easily reworked from the display surface. The adhesion needs to be very low. On the other hand, the double-sided pressure-sensitive adhesive sheet used for the protective sheet needs to be in close contact with the object to be adhered opposite to the display surface. Generally, it is difficult to laminate pressure-sensitive adhesive layers having opposite adhesive properties as described above, so a double-sided pressure-sensitive adhesive sheet provided with a base film between the fine adhesive layer and the strong adhesive layer is used There is. However, the thickness of the double-sided pressure-sensitive adhesive sheet provided with a base film between the slight pressure-sensitive adhesive layer and the strong pressure-sensitive adhesive layer tends to increase, and the unevenness followability is inferior or can not meet the recent demand for thinning. There was a problem.
　そこで本発明者らは、このような従来技術の課題を解決するために、両面粘着シートの一方の面は被着材に対して強固な粘着力を発揮しつつも、他方の面は優れたリワーク性を発揮し得る両面粘着シートであって、基材フィルムを含まない両面粘着シートを提供することを目的として検討を進めた。 Therefore, in order to solve the problems of the prior art, the inventors of the present invention have one side of the double-sided pressure-sensitive adhesive sheet exhibiting excellent adhesion to the adherend while the other side is excellent. Investigation was advanced for the purpose of providing a double-sided pressure-sensitive adhesive sheet which can exhibit reworkability and does not contain a base film.
　上記の課題を解決するために鋭意検討を行った結果、本発明者らは、アクリル系粘着剤層にシリコーン系粘着剤層を直接積層し、かつ、アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力を所定値以上とすることにより、強固な粘着力と優れたリワーク性を兼ね備えた両面粘着シートであって、基材フィルムを含まない両面粘着シートが得られることを見出した。
　具体的に、本発明は、以下の構成を有する。 As a result of intensive studies to solve the above problems, the present inventors directly laminated a silicone-based pressure-sensitive adhesive layer on an acrylic pressure-sensitive adhesive layer, and an acrylic-based pressure-sensitive adhesive layer and a silicone-based pressure-sensitive adhesive layer It was found that by setting the interfacial adhesive force of the above to a predetermined value or more, a double-sided pressure-sensitive adhesive sheet which has both strong adhesive force and excellent reworkability and which does not contain a base film can be obtained.
Specifically, the present invention has the following configuration.
［１］　アクリル系粘着剤層と、
　アクリル系粘着剤層に直接積層されたシリコーン系粘着剤層と、を有し、
　アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力が１Ｎ／２５ｍｍ以上である両面粘着シート。
［２］　アクリル系粘着剤層は、アクリル酸ブチルに由来する単位を含むアクリル共重合体を有し、
　アクリル酸ブチルに由来する単位の含有量は、アクリル共重合体の全質量に対して、３０質量％以上である［１］に記載の両面粘着シート。
［３］　アクリル共重合体は、アクリル酸－２－ヒドロキシエチルに由来する単位をさらに含み、アクリル酸－２－ヒドロキシエチルに由来する単位の含有量は、アクリル共重合体の全質量に対して、１０質量％以上５０質量％以下である［２］に記載の両面粘着シート。
［４］　アクリル共重合体は、アクリル酸－２－メトキシエチルに由来する単位をさらに含み、アクリル酸－２－メトキシエチルに由来する単位の含有量は、アクリル共重合体の全質量に対して、１０質量％以上５０質量％以下である［２］に記載の両面粘着シート。
［５］　アクリル共重合体は、アクリル酸-２-エチルヘキシルに由来する単位及びアクリル酸に由来する単位から選択される少なくとも１種をさらに含む［２］～［４］のいずれかに記載の両面粘着シート。
［６］　アクリル系粘着剤層の界面側の表面及びシリコーン系粘着剤層の界面側の表面から選択される少なくとも一方は、表面活性化処理面である［１］～［５］のいずれかに記載の両面粘着シート。
［７］　アクリル系粘着剤層の界面側の表面が表面活性化処理面であり、表面活性化処理面の濡れ張力が７０ｍＮ／ｍ以上である［１］～［６］のいずれかに記載の両面粘着シート。
［８］　シリコーン系粘着剤層の界面側の表面が表面活性化処理面であり、表面活性化処理面の濡れ張力が３０ｍＮ／ｍ以上である［１］～［７］のいずれかに記載の両面粘着シート。
［９］　アクリル系粘着剤層は、シランカップリング剤を含み、
　シランカップリング剤の含有量は、アクリル系粘着剤層の全質量に対して０．０３質量％以上５質量％以下である［１］～［８］のいずれかに記載の両面粘着シート。
［１０］　アクリル系粘着剤層は、窒素含有単量体に由来する単位を含むアクリル重合体を含み、窒素含有単量体に由来する単位の含有量は、アクリル重合体の全質量に対して５質量％以上７０質量％以下である［１］～［９］のいずれかに記載の両面粘着シート。
［１１］　アクリル系粘着剤層は、水素引抜型重合開始剤を含み、水素引抜型重合開始剤の含有量は、アクリル系粘着剤層の全質量に対して０．０５質量％以上１０質量％以下である［１］～［１０］のいずれかに記載の両面粘着シート。
［１２］　水素引抜型重合開始剤が、光重合開始剤である［１１］に記載の両面粘着シート。
［１３］　アクリル系粘着剤層の対ガラス粘着力が１Ｎ／２５ｍｍ以上である［１］～［１２］のいずれかに記載の両面粘着シート。
［１４］　アクリル系粘着剤層の対ガラス粘着力が３０Ｎ／２５ｍｍ以下であるである［１３］に記載の両面粘着シート。
［１５］　シリコーン系粘着剤層の対ガラス粘着力が０．００５Ｎ／２５ｍｍ以上１Ｎ／２５ｍｍ以下である［１］～［１４］のいずれかに記載の両面粘着シート。
［１６］　［１］～［１５］のいずれかに記載の両面粘着シートの両面に剥離シートを備えた剥離シート付き両面粘着シート。 [1] with acrylic adhesive layer,
And having a silicone-based pressure-sensitive adhesive layer directly laminated on the acrylic pressure-sensitive adhesive layer,
The double-sided pressure-sensitive adhesive sheet in which the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is 1 N / 25 mm or more.
[2] The acrylic pressure-sensitive adhesive layer has an acrylic copolymer containing a unit derived from butyl acrylate,
Content of the unit derived from butyl acrylate is 30 mass% or more with respect to the total mass of an acrylic copolymer, The double-sided adhesive sheet as described in [1].
[3] The acrylic copolymer further includes a unit derived from 2-hydroxyethyl acrylate, and the content of the unit derived from 2-hydroxyethyl acrylate is relative to the total mass of the acrylic copolymer The double-sided pressure-sensitive adhesive sheet according to [2], which is 10% by mass or more and 50% by mass or less.
[4] The acrylic copolymer further includes a unit derived from 2-methoxyethyl acrylate, and the content of the unit derived from 2-methoxyethyl acrylate is relative to the total mass of the acrylic copolymer The double-sided pressure-sensitive adhesive sheet according to [2], which is 10% by mass or more and 50% by mass or less.
[5] The acrylic copolymer according to any one of [2] to [4], further including at least one selected from a unit derived from 2-ethylhexyl acrylate and a unit derived from acrylic acid. Adhesive sheet.
[6] At least one selected from the surface on the interface side of the acrylic pressure-sensitive adhesive layer and the surface on the interface side of the silicone-based pressure-sensitive adhesive layer is a surface activation treated surface according to any one of [1] to [5] Double-sided PSA sheet as described.
[7] The surface on the interface side of the acrylic pressure-sensitive adhesive layer is a surface activation treated surface, and the wetting tension of the surface activation treated surface is 70 mN / m or more according to any one of [1] to [6] Double-sided adhesive sheet.
[8] The surface on the interface side of the silicone pressure-sensitive adhesive layer is a surface activation treated surface, and the wetting tension of the surface activation treated surface is 30 mN / m or more according to any one of [1] to [7] Double-sided adhesive sheet.
[9] The acrylic pressure-sensitive adhesive layer contains a silane coupling agent,
The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [8], wherein the content of the silane coupling agent is 0.03% by mass to 5% by mass with respect to the total mass of the acrylic pressure-sensitive adhesive layer.
[10] The acrylic pressure-sensitive adhesive layer contains an acrylic polymer containing a unit derived from a nitrogen-containing monomer, and the content of the unit derived from a nitrogen-containing monomer is relative to the total mass of the acrylic polymer The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [9], which is 5% by mass or more and 70% by mass or less.
[11] The acrylic pressure-sensitive adhesive layer contains a hydrogen extraction type polymerization initiator, and the content of the hydrogen extraction type polymerization initiator is 0.05% by mass or more and 10% by mass with respect to the total mass of the acrylic pressure-sensitive adhesive layer The double-sided pressure-sensitive adhesive sheet according to any one of the following [1] to [10]:
[12] The double-sided pressure-sensitive adhesive sheet according to [11], wherein the hydrogen abstraction type polymerization initiator is a photopolymerization initiator.
[13] The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [12], wherein the adhesion of the acrylic pressure-sensitive adhesive layer to glass is 1 N / 25 mm or more.
[14] The double-sided pressure-sensitive adhesive sheet according to [13], wherein the adhesion to glass of the acrylic pressure-sensitive adhesive layer is 30 N / 25 mm or less.
[15] The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [14], wherein the adhesion to glass of the silicone-based pressure-sensitive adhesive layer is from 0.005 N / 25 mm to 1 N / 25 mm.
[16] A double-sided pressure-sensitive adhesive sheet with a release sheet comprising a release sheet on both sides of the double-sided pressure-sensitive adhesive sheet according to any one of [1] to [15].
　本発明によれば、両面粘着シートの一方の面は被着材に対して強固な粘着力を発揮しつつも、他方の面は優れたリワーク性を発揮し得る両面粘着シートであって、基材フィルムを含まない両面粘着シートを得ることができる。 According to the present invention, one side of the double-sided pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet capable of exhibiting excellent reworkability while exhibiting strong adhesion to the adherend, and the other side is a base It is possible to obtain a double-sided pressure-sensitive adhesive sheet which does not contain a wood film.
図１は、本発明の両面粘着シートの構成を説明する断面図である。FIG. 1 is a cross-sectional view for explaining the structure of the double-sided pressure-sensitive adhesive sheet of the present invention.
　以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、代表的な実施形態や具体例に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。 Hereinafter, the present invention will be described in detail. The description of the configuration requirements described below may be made based on typical embodiments and specific examples, but the present invention is not limited to such embodiments.
（両面粘着シート）
　本発明は、アクリル系粘着剤層と、アクリル系粘着剤層に直接積層されたシリコーン系粘着剤層と、を有し、アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力が１Ｎ／２５ｍｍ以上である両面粘着シートに関する。本発明の両面粘着シートは、このように複数の粘着剤層を有するものであるから、両面積層粘着シートと呼ぶこともできる。 (Double-sided adhesive sheet)
The present invention has an acrylic pressure-sensitive adhesive layer and a silicone-based pressure-sensitive adhesive layer laminated directly on the acrylic pressure-sensitive adhesive layer, and the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is 1N /. The present invention relates to a double-sided pressure-sensitive adhesive sheet which is 25 mm or more. Since the double-sided pressure-sensitive adhesive sheet of the present invention thus has a plurality of pressure-sensitive adhesive layers, it can also be called a double-sided laminated pressure-sensitive adhesive sheet.
　本発明の両面粘着シートは、上記構成を有するものであるため、リワーク性に優れている。ここで、リワーク性が優れていることは、両面粘着シートを被着材に貼着した後に剥離する際に、両面粘着シートの粘着剤の一部が被着材に残留しないこと、及びリワーク作業中に両面粘着シートが破断しない特性のことをいう。さらに、本発明の両面粘着シートの一方の面は被着材に対して強固な粘着力を発揮することができる。特に、本発明の両面粘着シートはガラス面に対して強固な粘着力を発揮することができる。このように、本発明の両面粘着シートは、強固な粘着力と優れたリワーク性を兼ね備えたものである。 The double-sided pressure-sensitive adhesive sheet of the present invention is excellent in reworkability because it has the above-described configuration. Here, the excellent reworkability means that when the double-sided pressure-sensitive adhesive sheet is attached to the adherend and peeled off, a part of the pressure-sensitive adhesive of the double-sided pressure-sensitive adhesive sheet does not remain on the adherend; It refers to the property that the double-sided pressure-sensitive adhesive sheet does not break in it. Furthermore, one surface of the double-sided pressure-sensitive adhesive sheet of the present invention can exert strong adhesive force to an adherend. In particular, the double-sided pressure-sensitive adhesive sheet of the present invention can exhibit strong adhesion to the glass surface. Thus, the double-sided pressure-sensitive adhesive sheet of the present invention has strong adhesion and excellent reworkability.
　図１は、本発明の両面粘着シートの構成を説明する断面図である。本発明の両面粘着シート１００は、アクリル系粘着剤層１０と、シリコーン系粘着剤層１２と、を有する。両面粘着シート１００は、図１に示されるようにアクリル系粘着剤層１０とシリコーン系粘着剤層１２を１層ずつ積層した構成であることが好ましいが、各層を２層以上含むものであってもよい。例えば、図１において１層構成として示されているアクリル系粘着剤層１０が２層以上のアクリル系粘着剤層の積層構造からなるものであってもよく、シリコーン系粘着剤層１２が２層以上のシリコーン系粘着剤層の積層構造からなるものであってもよい。 FIG. 1 is a cross-sectional view for explaining the structure of the double-sided pressure-sensitive adhesive sheet of the present invention. The double-sided pressure-sensitive adhesive sheet 100 of the present invention has an acrylic pressure-sensitive adhesive layer 10 and a silicone-based pressure-sensitive adhesive layer 12. The double-sided pressure-sensitive adhesive sheet 100 preferably has a structure in which the acrylic pressure-sensitive adhesive layer 10 and the silicone-based pressure-sensitive adhesive layer 12 are laminated one by one as shown in FIG. It is also good. For example, the acrylic pressure-sensitive adhesive layer 10 shown as a single-layer structure in FIG. 1 may have a laminated structure of two or more acrylic pressure-sensitive adhesive layers, and the silicone pressure-sensitive adhesive layer 12 has two layers. It may consist of a laminated structure of the above silicone pressure sensitive adhesive layers.
　本発明の両面粘着シートは、図１に示されるように支持体（基材）を有さない両面粘着シートである。このため、両面粘着シートにおいてアクリル系粘着剤層とシリコーン系粘着剤層は直接接する状態で積層されている。このため、本発明の両面粘着シートは必要に応じて薄膜化が可能となる。また、本発明の両面粘着シートは、支持体（基材）を有さない両面粘着シートであるため、曲面追従性に優れており、さらに段差追従性にも優れている。なお、段差構造に接する層はアクリル系粘着剤層であってもよく、シリコーン系粘着剤層であってもよい。 The double-sided pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet having no support (base material) as shown in FIG. For this reason, in the double-sided pressure-sensitive adhesive sheet, the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer are laminated in direct contact with each other. Therefore, the double-sided pressure-sensitive adhesive sheet of the present invention can be thinned as needed. Further, since the double-sided pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet having no support (substrate), it is excellent in curved surface followability and further excellent in step followability. The layer in contact with the step structure may be an acrylic pressure-sensitive adhesive layer or a silicone-based pressure-sensitive adhesive layer.
　本発明の両面粘着シートは上記構成を有するものであるため、表示面へのエアー抜け性も良好である。本明細書において、エアー抜け性とは、両面粘着シートを被着材に貼着する際、粘着剤層と被着材の界面に気泡が残らない特性をいう。さらに、本発明の両面粘着シートは凹凸追従性にも優れている。このため、本発明の両面粘着シートは凹凸構造（段差構造）を有する被着材にも貼合することができる。凹凸構造（段差構造）に接する層はアクリル系粘着剤層であってもよく、シリコーン系粘着剤層であってもよい。 Since the double-sided pressure-sensitive adhesive sheet of the present invention has the above-mentioned constitution, the air escapeability to the display surface is also good. In the present specification, the air release property refers to the property that air bubbles do not remain at the interface between the pressure-sensitive adhesive layer and the adherend when the double-sided pressure-sensitive adhesive sheet is attached to the adherend. Furthermore, the double-sided pressure-sensitive adhesive sheet of the present invention is also excellent in unevenness followability. For this reason, the double-sided pressure-sensitive adhesive sheet of the present invention can also be bonded to an adherend having a concavo-convex structure (step structure). The layer in contact with the uneven structure (step structure) may be an acrylic pressure-sensitive adhesive layer or a silicone-based pressure-sensitive adhesive layer.
　本発明の両面粘着シートにおいて、アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力は１Ｎ／２５ｍｍ以上であることが好ましく、５Ｎ／２５ｍｍ以上であることがより好ましく、１０Ｎ／２５ｍｍ以上であることがさらに好ましく、１５Ｎ／２５ｍｍ以上であることが特に好ましい。なお、アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力の上限値は特に限定されるものではないが、例えば、１００Ｎ／２５ｍｍであることが好ましい。このように、本発明の両面粘着シートにおいて、アクリル系粘着剤層とシリコーン系粘着剤層は強固に粘着しており、層間密着性に優れている。アクリル系粘着剤層とシリコーン系粘着剤層の間の界面粘着力を上記範囲内とすることにより、両面粘着シートをリワークする際にアクリル系粘着剤層とシリコーン系粘着剤層の間で剥離が生じることを抑制することができ、その結果リワーク性を高めることができる。 In the double-sided pressure-sensitive adhesive sheet of the present invention, the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is preferably 1N / 25 mm or more, more preferably 5N / 25 mm or more, and 10N / 25 mm or more. It is more preferable that the distance be 15 N / 25 mm or more. The upper limit value of the interfacial adhesive strength between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is not particularly limited, but is preferably, for example, 100 N / 25 mm. As described above, in the double-sided pressure-sensitive adhesive sheet of the present invention, the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer firmly adhere to each other, and are excellent in interlayer adhesion. By setting the interfacial adhesive force between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer in the above range, peeling occurs between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer when reworking the double-sided pressure-sensitive adhesive sheet. It is possible to suppress the occurrence, and as a result, the reworkability can be enhanced.
　アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力は、実施例に記載のとおり界面粘着力測定用サンプルを作製した後に測定することができる。
　界面粘着力は実施例に記載のとおり「易接着層付ポリエチレンテレフタレートフィルム／アクリル系粘着剤層／シリコーン系粘着剤層／裏打ち用基材付き粘着テープ」を得た２４時間後（表面活性化処理を行ったシリコーン粘着剤層面とアクリル粘着剤層面を貼着後２４時間後）に、裏打ち用基材付き粘着テープ側をＪＩＳ　Ｚ　０２３７の方法１に準じて剥離速度３００ｍｍ／ｍｉｎ、剥離角度１８０°の条件で剥離することで、「アクリル系粘着剤層／シリコーン系粘着剤層」界面の粘着力測定を行う。 The interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be measured after preparing a sample for measuring interfacial adhesion as described in the examples.
After 24 hours of obtaining “the polyethylene terephthalate film with easy adhesion layer / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / backing pressure-sensitive adhesive tape” as described in the examples (surface activation treatment) 24 hours after attaching the silicone pressure-sensitive adhesive layer side and the acrylic pressure-sensitive adhesive layer side, the peeling speed with a backing substrate was 300 mm / min according to method 1 of JIS Z 0237, peeling angle 180 ° By peeling under the conditions of 2, the adhesive force measurement of the "acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer" interface is performed.
　本発明の両面粘着シートの一方の面側の対ガラス粘着力は、１Ｎ／２５ｍｍ以上であることが好ましく、５Ｎ／２５ｍｍ以上であることがより好ましく、１０Ｎ／２５ｍｍ以上であることがさらに好ましい。また、両面粘着シートの一方の面側の対ガラス粘着力は、５０Ｎ／２５ｍｍ以下であることが好ましく、３０Ｎ／２５ｍｍ以下であることが好ましい。上記粘着力は、両面粘着シートのアクリル系粘着剤層側の粘着力であることが好ましく、アクリル系粘着剤層の対ガラス粘着力が上記範囲内であることが好ましい。 The adhesion to glass on one side of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 1 N / 25 mm or more, more preferably 5 N / 25 mm or more, and still more preferably 10 N / 25 mm or more. The adhesion to glass on one side of the double-sided pressure-sensitive adhesive sheet is preferably 50 N / 25 mm or less, and more preferably 30 N / 25 mm or less. It is preferable that the said adhesive force is the adhesive force side of the acrylic adhesive layer side of a double-sided adhesive sheet, and it is preferable that the glass adhesive force of an acrylic adhesive layer is in the said range.
　また、本発明の両面粘着シートの他方の面側の対ガラス粘着力は、０．００５Ｎ／２５ｍｍ以上であることが好ましく、０．０５Ｎ／２５ｍｍ以上であることがより好ましい。また、両面粘着シートの他方の面側の対ガラス粘着力は、１．０Ｎ／２５ｍｍ以下であることが好ましく０．５Ｎ／２５ｍｍ以下であることがより好ましい。上記粘着力は、両面粘着シートのシリコーン系粘着剤層側の粘着力であることが好ましく、シリコーン系粘着剤層の対ガラス粘着力が上記範囲内であることが好ましい。 The adhesion to glass on the other side of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 0.005 N / 25 mm or more, more preferably 0.05 N / 25 mm or more. The adhesion to glass on the other side of the double-sided pressure-sensitive adhesive sheet is preferably 1.0 N / 25 mm or less, more preferably 0.5 N / 25 mm or less. The adhesive strength is preferably the adhesive strength on the side of the silicone-based pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive sheet, and the adhesion to glass of the silicone-based pressure-sensitive adhesive layer is preferably within the above range.
　なお、両面粘着シートの対ガラス粘着力は、それぞれの粘着剤層の粘着面をソーダガラスに貼着した後、２４時間後にＪＩＳ　Ｚ　０２３７の方法１に準じて、剥離速度３００ｍｍ／ｍｉｎ、剥離角度１８０°の条件で測定される値である。各粘着剤層の対ガラス粘着力を上記範囲内とすることにより、強固な粘着力と優れたリワーク性を兼ね備えた両面粘着シートが得られる。 The adhesion to glass of the double-sided pressure-sensitive adhesive sheet is determined according to method 1 of JIS Z 0237 after 24 hours after sticking the pressure-sensitive adhesive surface of each pressure-sensitive adhesive layer to soda glass, peeling speed 300 mm / min, peeling angle It is a value measured under the condition of 180 °. By setting the adhesion to glass of each pressure-sensitive adhesive layer in the above range, a double-sided pressure-sensitive adhesive sheet having strong adhesion and excellent reworkability can be obtained.
　本発明の両面粘着シートの全体の厚みは、１０μｍ以上であることが好ましく、２０μｍ以上であることがより好ましく、５０μｍ以上であることがさらに好ましい。また、両面粘着シートの全体の厚みは、１０００μｍ以下であることが好ましく、８００μｍ以下であることがより好ましく、６００μｍ以下であることがさらに好ましい。両面粘着シートの全体の厚みを上記範囲内とすることにより、強固な粘着力と優れたリワーク性を両立しやすくなる。 The total thickness of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 50 μm or more. The total thickness of the double-sided pressure-sensitive adhesive sheet is preferably 1000 μm or less, more preferably 800 μm or less, and still more preferably 600 μm or less. By setting the total thickness of the double-sided pressure-sensitive adhesive sheet within the above range, it becomes easy to achieve both strong adhesive strength and excellent reworkability.
　本発明の両面粘着シートにおけるアクリル系粘着剤層の１層の厚みは、５μｍ以上であることが好ましく、１０μｍ以上であることがより好ましく、２５μｍ以上であることがさらに好ましい。また、アクリル系粘着剤層の厚みは、５００μｍ以下であることが好ましく、４００μｍ以下であることがより好ましく、３００μｍ以下であることがさらに好ましい。 The thickness of one layer of the acrylic pressure-sensitive adhesive layer in the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 25 μm or more. The thickness of the acrylic pressure-sensitive adhesive layer is preferably 500 μm or less, more preferably 400 μm or less, and still more preferably 300 μm or less.
　本発明の両面粘着シートにおけるシリコーン系粘着剤層の１層の厚みは、５μｍ以上であることが好ましく、１０μｍ以上であることがより好ましく、２５μｍ以上であることがさらに好ましい。また、シリコーン系粘着剤層の厚みは、５００μｍ以下であることが好ましく、４００μｍ以下であることがより好ましく、３００μｍ以下であることがさらに好ましい。 The thickness of one layer of the silicone-based pressure-sensitive adhesive layer in the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 25 μm or more. The thickness of the silicone-based pressure-sensitive adhesive layer is preferably 500 μm or less, more preferably 400 μm or less, and still more preferably 300 μm or less.
　本発明においては、アクリル系粘着剤層の厚み（μｍ）をＰとし、シリコーン系粘着剤層の厚み（μｍ）をＱとした場合、Ｐ：Ｑ＝１：１０～１０：１であることが好ましい。Ｐ：Ｑを上記範囲内とすることにより、両面粘着シートの一方の面は被着材に対して強固な粘着力を発揮しつつも、他方の面は優れたリワーク性を発揮し得る両面粘着シートが得られやすくなる。なお、上述したＰは、両面粘着シートにアクリル系粘着剤層が２層以上含まれる場合は、アクリル系粘着剤層の厚みの合計を表し、上述したＱは、両面粘着シートにシリコーン系粘着剤層が２層以上含まれる場合は、シリコーン系粘着剤層の厚みの合計を表す。 In the present invention, when the thickness (μm) of the acrylic pressure-sensitive adhesive layer is P and the thickness (μm) of the silicone-based pressure-sensitive adhesive layer is Q, P: Q = 1: 10 to 10: 1 preferable. P: By setting Q within the above range, one side of the double-sided pressure-sensitive adhesive sheet can exhibit strong releasability to the adherend, while the other side can exhibit excellent reworkability. It becomes easy to obtain a sheet. In the case where two or more acrylic pressure-sensitive adhesive layers are contained in the double-sided pressure-sensitive adhesive sheet, P described above represents the total thickness of the acrylic pressure-sensitive adhesive layer, and Q mentioned above is a silicone-based pressure-sensitive adhesive in the double-sided pressure-sensitive adhesive sheet. When two or more layers are contained, it represents the total thickness of the silicone-based pressure-sensitive adhesive layer.
　本発明の両面粘着シートのヘーズは３％以下であることが好ましく、１％以下であることがより好ましい。本明細書においては、両面粘着シートのヘーズは、ＪＩＳ　Ｋ　７１３６に準拠した方法で測定される値のことをいう。ヘーズを測定する際には、本発明の両面粘着シートを松浪ガラス社製のスライドガラス（品番：Ｓ９１１２）に貼合してヘーズ値を測定する。具体的には、両面粘着シートを松浪ガラス社製のスライドガラスに貼合した後、貼合時に混入した微細な空気などの影響を排除するために、積層されたサンプルに０．５ＭＰａ、４０℃の条件で３０分間オートクレーブ（加圧脱泡）処理を施す。その後、ガラス貼合面と逆面の剥離シートを剥がし、糊面がむき出しの状態で、日本電色工業（株）製のＮＤＨ４０００を用いて測定する。 The haze of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 3% or less, more preferably 1% or less. In the present specification, the haze of the double-sided pressure-sensitive adhesive sheet refers to a value measured by a method in accordance with JIS K 7136. When the haze is measured, the double-sided pressure-sensitive adhesive sheet of the present invention is bonded to a slide glass (product number: S9112) manufactured by Matsunami Glass Co., Ltd. to measure the haze value. Specifically, after bonding the double-sided pressure-sensitive adhesive sheet to slide glass made by Matsunami Glass Co., Ltd., in order to eliminate the influence of fine air etc. mixed at the time of bonding, 0.5 MPa and 40 ° C. Autoclave (pressure degassing) for 30 minutes under the following conditions. Then, the peeling sheet of a glass bonding surface and an opposite surface is peeled off, and it measures using NDH4000 made from Nippon Denshoku Kogyo Co., Ltd. in the state which an adhesive side exposed.
　本発明の両面粘着シートの全光線透過率は、８０％以上であることが好ましく、８５％以上であることがより好ましく、９０％以上であることがさらに好ましい。本発明の両面粘着シートは、全光線透過率が高く、透明性に優れている点に特徴がある。本明細書においては、両面粘着シートの全光線透過率は、ＪＩＳ　Ｋ　７１３６に準拠した方法で測定される値のことをいう。両面粘着シートの全光線透過率は、上述したヘーズ値の測定方法と同様の方法で測定することができる。 The total light transmittance of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. The double-sided pressure-sensitive adhesive sheet of the present invention is characterized in that the total light transmittance is high and the transparency is excellent. In the present specification, the total light transmittance of the double-sided pressure-sensitive adhesive sheet refers to a value measured by a method in accordance with JIS K 7136. The total light transmittance of the double-sided pressure-sensitive adhesive sheet can be measured by the same method as the method of measuring the haze value described above.
　また、本発明の両面粘着シートは、柔軟性にも優れている。このため、被着材が曲面や段差部を有する部材であってもその曲面や段差部に追従して貼着することができる。 The double-sided pressure-sensitive adhesive sheet of the present invention is also excellent in flexibility. For this reason, even if the adherend is a member having a curved surface or a stepped portion, it can be attached following the curved surface or the stepped portion.
＜アクリル系粘着剤層＞
　本発明の両面粘着シートはアクリル系粘着剤層を含む。アクリル系粘着剤層はアクリル系樹脂、好ましくはアクリル共重合体を主成分として含む層である。具体的には、アクリル系粘着剤層におけるアクリル系樹脂（アクリル共重合体）の含有量は、アクリル系粘着剤層の全質量に対して５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることがさらに好ましく、８０質量％以上であることが一層好ましく、９０質量％以上であることが特に好ましい。 <Acrylic adhesive layer>
The double-sided pressure-sensitive adhesive sheet of the present invention comprises an acrylic pressure-sensitive adhesive layer. The acrylic pressure-sensitive adhesive layer is a layer containing an acrylic resin, preferably an acrylic copolymer as a main component. Specifically, the content of the acrylic resin (acrylic copolymer) in the acrylic pressure-sensitive adhesive layer is preferably 50% by mass or more, and 60% by mass or more based on the total mass of the acrylic pressure-sensitive adhesive layer Is more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
　アクリル系樹脂としては、例えば、アクリル重合体をベースポリマーとして含有するアクリル系粘着剤を挙げることができる。アクリル重合体は、非架橋性の（メタ）アクリル酸エステル単位と、架橋性官能基を有するアクリル単量体単位及び二官能性アクリル系単量体単位から選択される少なくとも一方を含有することが好ましい。ここで、「単量体単位」は重合体を構成する繰り返し単位である。「アクリル単量体」は、（メタ）アクリロイル基を有する化合物である。「（メタ）クリロイル基」は、アクリロイル基又はメタクリロイル基であることを示す。また、非架橋性アクリル単量体は架橋性基を有さないアクリル単量体であり、架橋性アクリル単量体は架橋性基を有する単量体である。架橋性アクリル単量体は、非架橋性アクリル単量体と重合可能なものであればアクリル単量体であっても非アクリル単量体であってもよいが、アクリル単量体であることが好ましい。なお、架橋性基としては、カルボキシ基、ヒドロキシ基、アミノ基、エポキシ基、グリシジル基等が挙げられる。 As acrylic resin, the acrylic adhesive which contains an acrylic polymer as a base polymer can be mentioned, for example. The acrylic polymer contains at least one selected from non-crosslinkable (meth) acrylic acid ester units, acrylic monomer units having a crosslinkable functional group and difunctional acrylic monomer units. preferable. Here, a "monomer unit" is a repeating unit which comprises a polymer. An "acrylic monomer" is a compound having a (meth) acryloyl group. "(Meth) cryloyl group" indicates that it is an acryloyl group or a methacryloyl group. The non-crosslinkable acrylic monomer is an acrylic monomer having no crosslinkable group, and the crosslinkable acrylic monomer is a monomer having a crosslinkable group. The crosslinkable acrylic monomer may be an acrylic monomer or a non-acrylic monomer as long as it can be polymerized with the non-crosslinkable acrylic monomer, but it is an acrylic monomer Is preferred. In addition, a carboxy group, a hydroxyl group, an amino group, an epoxy group, glycidyl group etc. are mentioned as a crosslinkable group.
　非架橋性アクリル単量体単位としては、例えば、（メタ）アクリル酸のカルボキシ基の水素原子を炭化水素基で置換した（メタ）アクリル酸エステル単位が挙げられる。本発明では、アクリル系粘着剤層は、（メタ）アクリル酸エステル単位を含むことが好ましい。 As a non-crosslinkable acrylic monomer unit, the (meth) acrylic acid ester unit which substituted the hydrogen atom of the carboxy group of (meth) acrylic acid by the hydrocarbon group is mentioned, for example. In the present invention, the acrylic pressure-sensitive adhesive layer preferably contains (meth) acrylic acid ester units.
　（メタ）アクリル酸エステルとして具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ｎ－ウンデシル、（メタ）アクリル酸ｎ－ドデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジルが挙げられる。中でも、接着性の点からは、アクリル酸ｎ－ブチル、アクリル酸２－エチルヘキシル、アクリル酸メチルを用いることが好ましい。これらは１種を単独で使用してもよいし、２種以上を併用してもよい。なお、本発明において、「（メタ）アクリル酸」とは、「アクリル酸」及び「メタクリル酸」の両方を含むことを意味する。 Specific examples of (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate ( (Meth) acrylic acid isobutyl, (meth) acrylic acid t-butyl, (meth) acrylic acid n-pentyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-octyl , (Meth) acrylate isooctyl, (meth) acrylate n-nonyl, (meth) acrylate isobornyl, (meth) acrylate isononyl, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) N-undecyl acrylate, n-dodecyl (meth) acrylate, stearyl (meth) acrylate, ) Methoxyethyl acrylate, ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate include benzyl (meth) acrylate. Among them, n-butyl acrylate, 2-ethylhexyl acrylate, and methyl acrylate are preferably used from the viewpoint of adhesiveness. One of these may be used alone, or two or more may be used in combination. In the present invention, "(meth) acrylic acid" means that both "acrylic acid" and "methacrylic acid" are included.
　架橋性アクリル単量体単位としては、カルボキシ基含有共重合性単量体単位、ヒドロキシ基含有共重合性単量体単位、アミノ基含有共重合性単量体単位、グリシジル基含有共重合性単量体単位が挙げられる。
　カルボキシ基含有共重合性単量体としては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、グラタコン酸などのα，β－不飽和カルボン酸やその無水物などが挙げられる。
　ヒドロキシ基含有共重合性単量体としては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸２－ヒドロキシプロピルなどの（メタ）アクリル酸ヒドロキシアルキル、（メタ）アクリル酸モノ（ジエチレングリコール）などの（メタ）アクリル酸［（モノ、ジ又はポリ）アルキレングリコール］、（メタ）アクリル酸モノカプロラクトンなどの（メタ）アクリル酸ラクトンが挙げられる。
　アミノ基含有共重合性単量体としては、例えば、（メタ）アクリルアミド、アリルアミドなどが挙げられる。
　グリシジル基含有共重合性単量体としては、例えば、（メタ）アクリル酸グリシジルなどが挙げられる。 As the crosslinkable acrylic monomer unit, a carboxy group-containing copolymerizable monomer unit, a hydroxy group-containing copolymerizable monomer unit, an amino group-containing copolymerizable monomer unit, a glycidyl group-containing copolymerizable monomer A mer unit is mentioned.
As the carboxyl group-containing copolymerizable monomer, for example, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, grataconic acid and the anhydride thereof Things etc.
As the hydroxy group-containing copolymerizable monomer, for example, (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. And (meth) acrylic acid lactones such as (meth) acrylic acid [(mono, di or poly) alkylene glycols] such as hydroxyalkyl, (meth) acrylic acid mono (diethylene glycol) and the like, and (meth) acrylic acid monocaprolactone.
Examples of the amino group-containing copolymerizable monomer include (meth) acrylamide and allylamide.
As a glycidyl group containing copolymerizable monomer, glycidyl (meth) acrylate etc. are mentioned, for example.
　アクリル重合体は、アクリル系ランダム共重合体であることが好ましく、架橋性アクリル単量体と非架橋性アクリル単量体のランダム共重合体あることがより好ましい。より具体的には、アクリル酸ｎ－ブチル、アクリル酸２－エチルヘキシル及びアクリル酸メチルから選択される少なくとも１種と、アクリル酸のランダム共重合体であることが好ましく、アクリル酸エステル系共重合体であることが好ましい。 The acrylic polymer is preferably an acrylic random copolymer, and more preferably a random copolymer of a crosslinkable acrylic monomer and a non-crosslinkable acrylic monomer. More specifically, a random copolymer of acrylic acid and at least one selected from n-butyl acrylate, 2-ethylhexyl acrylate and methyl acrylate is preferable, and an acrylic ester-based copolymer Is preferred.
　上述したように、アクリル系粘着剤層はアクリル共重合体を含むことが好ましい。中でも、アクリル系粘着剤層に含まれるアクリル共重合体は、アクリル酸ブチルに由来する単位を含むことが好ましい。この場合、アクリル酸ブチルに由来する単位の含有量は、アクリル共重合体の全質量に対して、３０質量％以上であればよく、３５質量％以上であることが好ましく、４０質量％以上であることがより好ましい。また、アクリル酸ブチルに由来する単位の含有量は、アクリル共重合体の全質量に対して、８０質量％以下であることが好ましく、７０質量％以下であることがより好ましい。アクリル共重合体におけるアクリル酸ブチルに由来する単位の含有量を上記範囲内とすることにより、アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力を効果的に高めることができ、これにより両面粘着シートのリワーク性を高めることができる。 As described above, the acrylic pressure-sensitive adhesive layer preferably contains an acrylic copolymer. Among them, the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer preferably contains a unit derived from butyl acrylate. In this case, the content of the unit derived from butyl acrylate may be 30% by mass or more, preferably 35% by mass or more, and preferably 40% by mass or more with respect to the total mass of the acrylic copolymer. It is more preferable that The content of units derived from butyl acrylate is preferably 80% by mass or less, and more preferably 70% by mass or less, based on the total mass of the acrylic copolymer. By setting the content of the unit derived from butyl acrylate in the acrylic copolymer within the above range, the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be effectively enhanced. Reworkability of the double-sided pressure-sensitive adhesive sheet can be enhanced.
　アクリル系粘着剤層に含まれるアクリル共重合体は、アクリル酸ブチルに由来する単位に加えて、アクリル酸－２－ヒドロキシエチルに由来する単位をさらに含むことが好ましい。この場合、アクリル酸－２－ヒドロキシエチルに由来する単位の含有量は、アクリル共重合体の全質量に対して、１０質量％以上であることが好ましく、１５質量％以上であることがより好ましく、２０質量％以上であることがさらに好ましい。また、アクリル酸－２－ヒドロキシエチルに由来する単位の含有量は、アクリル共重合体の全質量に対して、５０質量％以下であることが好ましく、４５質量％以下であることがより好ましく、４０質量％以下であることがさらに好ましい。アクリル共重合体におけるアクリル酸－２－ヒドロキシエチルに由来する単位の含有量を上記範囲内とすることにより、アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力を効果的に高めることができ、これにより両面粘着シートのリワーク性を高めることができる。 The acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer preferably further contains a unit derived from 2-hydroxyethyl acrylate in addition to a unit derived from butyl acrylate. In this case, the content of the unit derived from 2-hydroxyethyl acrylate is preferably 10% by mass or more, and more preferably 15% by mass or more, based on the total mass of the acrylic copolymer. More preferably, it is 20% by mass or more. The content of units derived from 2-hydroxyethyl acrylate is preferably 50% by mass or less, and more preferably 45% by mass or less, based on the total mass of the acrylic copolymer. More preferably, it is 40% by mass or less. By setting the content of units derived from 2-hydroxyethyl acrylate in the acrylic copolymer within the above range, the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be effectively increased. Thus, the reworkability of the double-sided pressure-sensitive adhesive sheet can be enhanced.
　また、アクリル系粘着剤層に含まれるアクリル共重合体は、アクリル酸ブチルに由来する単位に加えて、アクリル酸－２－メトキシエチルに由来する単位をさらに含むことが好ましい。この場合、アクリル酸－２－メトキシエチルに由来する単位の含有量は、アクリル共重合体の全質量に対して、１０質量％以上であることが好ましく、１５質量％以上であることがより好ましく、２０質量％以上であることがさらに好ましい。また、アクリル酸－２－メトキシエチルに由来する単位の含有量は、アクリル共重合体の全質量に対して、５０質量％以下であることが好ましく、４５質量％以下であることがより好ましく、４０質量％以下であることがさらに好ましい。アクリル共重合体におけるアクリル酸－２－メトキシエチルに由来する単位の含有量を上記範囲内とすることにより、アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力を効果的に高めることができ、これにより両面粘着シートのリワーク性を高めることができる。 In addition to the unit derived from butyl acrylate, the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer preferably further includes a unit derived from 2-methoxyethyl acrylate. In this case, the content of units derived from 2-methoxyethyl acrylate is preferably 10% by mass or more, and more preferably 15% by mass or more based on the total mass of the acrylic copolymer. More preferably, it is 20% by mass or more. The content of units derived from 2-methoxyethyl acrylate is preferably 50% by mass or less, more preferably 45% by mass or less, based on the total mass of the acrylic copolymer. More preferably, it is 40% by mass or less. By setting the content of units derived from 2-methoxyethyl acrylate in the acrylic copolymer within the above range, the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be effectively increased. Thus, the reworkability of the double-sided pressure-sensitive adhesive sheet can be enhanced.
　なお、アクリル系粘着剤層に含まれるアクリル共重合体は、アクリル酸ブチルに由来する単位に加えて、アクリル酸－２－ヒドロキシエチルに由来する単位、もしくは、アクリル酸－２－メトキシエチルに由来する単位のいずれかを有していることが好ましいが、アクリル共重合体は、アクリル酸ブチルに由来する単位に加えて、アクリル酸－２－ヒドロキシエチルに由来する単位、および、アクリル酸－２－メトキシエチルに由来する単位の両方を有していてもよい。 In addition to the unit derived from butyl acrylate, the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer is a unit derived from 2-hydroxyethyl acrylate or derived from 2-methoxyethyl acrylate It is preferable that the acrylic copolymer has a unit derived from 2-hydroxyethyl acrylate in addition to a unit derived from butyl acrylate, and an acrylic acid-2 -May have both of the units derived from methoxyethyl.
　アクリル系粘着剤層に含まれるアクリル共重合体は、さらに他のアクリルモノマーに由来する単位を含んでいてもよい。他のアクリルモノマーとしては、上述したアクリルモノマー以外のアルキル（メタ）アクリレートを挙げることができる。アルキル（メタ）アクリレートとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸-２-エチルヘキシル等を挙げることができる。中でも、アクリル共重合体は、アクリル酸-２-エチルヘキシルに由来する単位を含むことが好ましい。アルキル（メタ）アクリレートに由来する単位の含有量は、アクリル共重合体の全質量に対して、１質量％以上であることが好ましく、５質量％以上であることがより好ましく、１０質量％以上であることがさらに好ましい。また、アルキル（メタ）アクリレートに由来する単位の含有量は、アクリル共重合体の全質量に対して、８０質量％以下であることが好ましく、７０質量％以下であることがより好ましい。 The acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer may further contain units derived from other acrylic monomers. As another acrylic monomer, alkyl (meth) acrylate other than the acrylic monomer mentioned above can be mentioned. As the alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid-2 -Ethylhexyl etc. can be mentioned. Among them, the acrylic copolymer preferably contains a unit derived from 2-ethylhexyl acrylate. The content of the unit derived from the alkyl (meth) acrylate is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more based on the total mass of the acrylic copolymer. It is further preferred that The content of the unit derived from the alkyl (meth) acrylate is preferably 80% by mass or less, and more preferably 70% by mass or less, based on the total mass of the acrylic copolymer.
　アクリル系粘着剤層に含まれるアクリル共重合体は、他のアクリルモノマーとして、架橋性官能基を有するアクリルモノマーに由来する単位を含んでいてもよい。架橋性官能基としては、例えば、カルボキシ基、アミノ基、アミド基、グリシジル基、イソシアネート基等を挙げることができ、中でも、架橋性官能基はカルボキシ基であることが好ましい。すなわち、アクリル共重合体は、アクリル酸に由来する単位を含むことが好ましい。 The acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer may contain, as another acrylic monomer, a unit derived from an acrylic monomer having a crosslinkable functional group. As a crosslinkable functional group, a carboxy group, an amino group, an amide group, glycidyl group, an isocyanate group etc. can be mentioned, for example, Especially, it is preferable that a crosslinkable functional group is a carboxy group. That is, the acrylic copolymer preferably contains a unit derived from acrylic acid.
　上述したように、アクリル系粘着剤層に含まれるアクリル共重合体は、アクリル酸-２-エチルヘキシルに由来する単位及びアクリル酸に由来する単位から選択される少なくとも１種をさらに含むことが好ましく、アクリル酸-２-エチルヘキシルに由来する単位及びアクリル酸に由来する単位の両方をさらに含むことがより好ましい。 As described above, the acrylic copolymer contained in the acrylic pressure-sensitive adhesive layer preferably further contains at least one selected from a unit derived from 2-ethylhexyl acrylate and a unit derived from acrylic acid, More preferably, it further comprises both units derived from 2-ethylhexyl acrylate and units derived from acrylic acid.
　アクリル共重合体は、必要に応じて、他の単量体単位を有してもよい。他の単量体は、上述したアクリルモノマーと共重合可能なものであればよく、例えば（メタ）アクリロニトリル、酢酸ビニル、スチレン、塩化ビニル、ビニルピロリドン、ビニルピリジン等が挙げられる。 The acrylic copolymer may have other monomer units, as required. Other monomers may be used as long as they can be copolymerized with the above-mentioned acrylic monomers, and examples thereof include (meth) acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinyl pyrrolidone, vinyl pyridine and the like.
　また、アクリル共重合体は、窒素含有単量体に由来する単位をさらに含んでいてもよい。窒素含有単量体としては、例えば、アクリロイルモロホリン、ウレタンアクリレート、（メタ）アクリルアミド、アリルアミド、ジメチルアクリルアミド、ジエチルアクリルアミド、ジメチルアミノプロピルアクリルアミド、ダイアセトンアクリルアミドなどが挙げられる。窒素含有単量体に由来する単位の含有量は、アクリル重合体の全質量に対して、５質量％以上であることが好ましい。また、窒素含有単量体に由来する単位の含有量は、アクリル重合体の全質量に対して、７０質量％以下であることが好ましく、５０質量％以下であることがより好ましく、２０質量％以下であることがさらに好ましく、１０質量％以下であることが特に好ましい。 The acrylic copolymer may further contain units derived from nitrogen-containing monomers. Examples of nitrogen-containing monomers include acryloyl morpholine, urethane acrylate, (meth) acrylamide, allylamide, dimethyl acrylamide, diethyl acrylamide, dimethylaminopropyl acrylamide, diacetone acrylamide and the like. The content of the unit derived from the nitrogen-containing monomer is preferably 5% by mass or more based on the total mass of the acrylic polymer. Further, the content of the unit derived from the nitrogen-containing monomer is preferably 70% by mass or less, more preferably 50% by mass or less, with respect to the total mass of the acrylic polymer, and 20% by mass The content is more preferably 10% by mass or less.
　アクリル共重合体の重量平均分子量（Ｍｗ）は、２０万以上２５０万以下であることが好ましく、３０万以上２００万以下であることがより好ましい。なお、重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によりポリスチレン標準物質を用いて作成した検量線をもとに計算されたものである。 The weight average molecular weight (Mw) of the acrylic copolymer is preferably 200,000 or more and 2.50 or less, and more preferably 300,000 or more and 2,000,000 or less. The weight average molecular weight (Mw) is calculated based on a calibration curve prepared using a polystyrene standard substance by gel permeation chromatography (GPC) measurement.
　ゲルパーミエーションクロマトグラフィー（ＧＰＣ）の測定条件は以下のとおりである。
溶媒：テトラヒドロフラン
カラム：Ｓｈｏｄｅｘ ＫＦ８０１、ＫＦ８０３Ｌ、ＫＦ８０６Ｌ（昭和電工（株）製を３本接続して使用した）
カラム温度：４０℃
試料濃度：０．５質量％
検出器：ＲＩ－２０３１ｐｌｕｓ（ＪＡＳＣＯ製）
ポンプ：ＲＩ－２０８０ｐｌｕｓ（ＪＡＳＣＯ製）
流量（流速）：０．８ｍｌ／ｍｉｎ
注入量：１０μｌ
校正曲線：標準ポリスチレンＳｈｏｄｅｘ ｓｔａｎｄａｒｄ ポリスチレン（昭和電工（株）製）Ｍｗ＝１３２０～２，５００，０００迄の１０サンプルによる校正曲線を使用した。 The measurement conditions of gel permeation chromatography (GPC) are as follows.
Solvent: Tetrahydrofuran column: Shodex KF801, KF803L, KF806L (Showa Denko Co., Ltd. product three connected)
Column temperature: 40 ° C
Sample concentration: 0.5 mass%
Detector: RI-2031 plus (made by JASCO)
Pump: RI-2080plus (made by JASCO)
Flow rate (flow rate): 0.8 ml / min
Injection volume: 10 μl
Calibration curve: Standard polystyrene Shodex standard A calibration curve of 10 samples of polystyrene (manufactured by Showa Denko KK) Mw = 1320 to 2,500,000 was used.
　アクリル系粘着剤層は、シランカップリング剤を含むものであることが好ましい。アクリル系粘着剤層がシランカップリング剤を含むことにより、アクリル系粘着剤層とシリコーン系粘着剤層の界面粘着力をより効果的に高めることができる。シランカップリング剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ基含有シランカップリング剤；３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチルブチリデン）プロピルアミン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤；３－アクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン等の（メタ）アクリル基含有シランカップリング剤；３－イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤；等が挙げられる。中でも、シランカップリング剤は、エポキシ基含有シランカップリング剤であることが好ましい。 The acrylic pressure-sensitive adhesive layer preferably contains a silane coupling agent. When the acrylic pressure-sensitive adhesive layer contains a silane coupling agent, the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer can be more effectively enhanced. As a silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,1 Amino group-containing silane coupling agents such as 3-dimethylbutylidene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane Meta) Acrylic group containing silane Coupling agent; 3- isocyanate propyl isocyanate group-containing silane coupling agents such as triethoxysilane; and the like. Among them, the silane coupling agent is preferably an epoxy group-containing silane coupling agent.
　また、シランカップリング剤として、分子内に複数のアルコキシシリル基を有するものを用いることもできる。このようなシランカップリング剤としては、たとえば、信越化学（株）製のＸ－４１－１０５３、Ｘ－４１－１０５９Ａ、Ｘ－４１－１０５６、Ｘ－４１－１８０５、Ｘ－４１－１８１８、Ｘ－４１－１８１０、Ｘ－４０－２６５１などが挙げられる。 In addition, as the silane coupling agent, one having a plurality of alkoxysilyl groups in the molecule can also be used. As such a silane coupling agent, for example, X-41-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1059 manufactured by Shin-Etsu Chemical Co., Ltd. And -41-1810 and X-40-2651.
　シランカップリング剤の含有量は、アクリル系粘着剤層の全質量に対して、０．０３質量％以上５質量％以下であることが好ましい。また、シランカップリング剤の含有量は、アクリル系粘着剤層の全質量に対して、０．０６質量％以上１質量％以下であることが好ましい。シランカップリング剤は、単独で使用してもよく、また２種以上を混合して使用してもよい。 The content of the silane coupling agent is preferably 0.03% by mass or more and 5% by mass or less with respect to the total mass of the acrylic pressure-sensitive adhesive layer. Moreover, it is preferable that content of a silane coupling agent is 0.06 mass% or more and 1 mass% or less with respect to the total mass of an acrylic adhesive layer. The silane coupling agents may be used alone or in combination of two or more.
　アクリル系粘着剤層は、架橋剤を含むものであってもよい。すなわち、アクリル系粘着剤層を形成するアクリル系粘着剤組成物は、架橋剤を含むことが好ましく、これにより上述した架橋性アクリル単量体の架橋反応を促進することができる。架橋剤としては、例えば、イソシアネート化合物、エポキシ化合物、オキサゾリン化合物、アジリジン化合物、金属キレート化合物、ブチル化メラミン化合物、多官能アクリレートなどの公知の架橋剤の中から、架橋性アクリル重合体が有する架橋性官能基との反応性を考慮して適宜選択できる。架橋の方式は、熱架橋あるいは電離放射線架橋など公知の方法より選択可能である。また、粘着層剤形成後に、さらに架橋度を高めるために２３℃の環境下などで養生処理を行ってもよい。 The acrylic pressure-sensitive adhesive layer may contain a crosslinking agent. That is, it is preferable that the acrylic adhesive composition which forms an acrylic adhesive layer contains a crosslinking agent, and, thereby, can accelerate the crosslinking reaction of the crosslinkable acrylic monomer mentioned above. As the crosslinking agent, for example, among the known crosslinking agents such as an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound, a butylated melamine compound and a polyfunctional acrylate, the crosslinkability possessed by the crosslinkable acrylic polymer It can be selected appropriately in consideration of the reactivity with the functional group. The method of crosslinking can be selected from known methods such as thermal crosslinking or ionizing radiation crosslinking. In addition, after forming the adhesive layer agent, curing treatment may be performed in an environment of 23 ° C. or the like in order to further increase the degree of crosslinking.
　イソシアネート化合物としては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート等が挙げられる。ジイシアネートは２官能のまま用いてもよいし、アダクト、ヌレート、ビュレットなどの３官能誘導体にして用いても良い。
　エポキシ化合物としては、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、テトラグリシジルキシレンジアミン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、トリメチロールプロパンポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル等が挙げられる。 Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like. The dicyanate may be used as it is as a bifunctional compound, or as a trifunctional derivative such as an adduct, a nurate or a burette.
As an epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, tetraglycidyl xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. It can be mentioned.
　架橋剤としては１種類を単独で用いても２種類以上を併用してもよい。アクリル系粘着剤層を形成するアクリル系粘着剤組成物中の架橋剤の含有量は、所望とする粘着物性等に応じて適宜選択され、特に限定されないが、アクリル重合体１００質量部に対し、０．０１質量部以上５質量部以下であることが好ましい。 As the crosslinking agent, one type may be used alone, or two or more types may be used in combination. The content of the crosslinking agent in the acrylic pressure-sensitive adhesive composition that forms the acrylic pressure-sensitive adhesive layer is appropriately selected according to the desired adhesive physical properties and the like, and is not particularly limited. It is preferable that it is 0.01 to 5 parts by mass.
　アクリル系粘着剤層は、水素引抜型重合開始剤を含むものであってもよい。水素引抜型重合開始剤は、光重合開始剤であることが特に好ましい。水素引抜型光重合開始剤としては、例えば、ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、ヒドロキシベンゾフェノン、３，３’－ジメチル－４－メトキシベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４－メチルベンゾフェノン、チオキサンソン、２－クロルチオキサンソン、２－メチルチオキサンソン、２，４－ジメチルチオキサンソン、イソプロピルチオキサンソン、カンファーキノン、ジベンゾスベロン、２－エチルアンスラキノン、３，３’，４，４’－テトラ（ｔ－ブチルパーオキシカルボニル）ベンゾフェノン、ベンジル、９，１０－フェナンスレンキノン等を挙げることができる。中でも、水素引抜型光重合開始剤は、ベンゾフェノン、４－メチルベンゾフェノン及び２，４，６－トリメチルベンゾフェノンから選択される少なくとも１種を含むものであることが好ましい。これらの市販品としては、イルガキュアＭＢＦ、ＳｐｅｅｄｃｕｒｅＭＢＰ、ｓｐｅｅｄｃｕｒｅＴＺＴ、ＳｐｅｅｄｃｕｒｅＭＢＦ、ＳｐｅｅｄｃｕｒｅＩＴＸ、ＳｐｅｅｄｃｕｒｅＤＥＴＸ、ＳｐｅｅｄｃｕｒｅＣＰＴＸ、ＳｐｅｅｄｃｕｒｅＭＢＢ、ＳｐｅｅｄｃｕｒｅＰＢＺ等が挙げられる。
　水素引抜型重合開始剤の含有量は、アクリル系粘着剤層の全質量に対して０．０５質量％以上１０質量％以下であることが好ましい。 The acrylic pressure-sensitive adhesive layer may contain a hydrogen abstraction type polymerization initiator. The hydrogen abstraction type polymerization initiator is particularly preferably a photopolymerization initiator. Examples of hydrogen abstraction type photopolymerization initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethyl Benzophenone, 4-methylbenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethyl anthraquinone, 3 And 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 9,10-phenanthrenequinone and the like. Among them, the hydrogen abstraction type photopolymerization initiator preferably contains at least one selected from benzophenone, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone. Examples of these commercially available products include Irgacure MBF, SpeedcureMBP, speedcureTZT, SpeedcureMBF, SpeedcureITX, SpeedcureDETX, SpeedcureCPTX, SpeedcureMBB, Speedcure PBZ and the like.
The content of the hydrogen extraction-type polymerization initiator is preferably 0.05% by mass or more and 10% by mass or less based on the total mass of the acrylic pressure-sensitive adhesive layer.
　アクリル系粘着剤層は、必要に応じて、可塑剤、酸化防止剤、金属腐食防止剤、粘着付与剤、紫外線吸収剤、帯電防止剤、光重合開始剤、ヒンダードアミン系化合物等の光安定剤等の中から添加剤を必要に応じて選択配合できる。
　可塑剤としては、例えば、無官能性アクリル重合体を用いることができる。無官能性アクリル重合体とは、アクリレート基以外の官能基を有しないアクリル単量体単位のみからなる重合体、又はアクリレート基以外の官能基を有しないアクリル単量体単位と官能基を有しない非アクリル単量体単位とからなる重合体を意味する。
　酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等が挙げられる。これら酸化防止剤は１種類を単独で使用してもよいし、２種類以上を併用してもよい。
　金属腐食防止剤としては、ベンゾリアゾール系樹脂を挙げることができる。
　粘着付与剤として、例えば、ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、スチレン系樹脂、キシレン系樹脂、フェノール系樹脂、石油樹脂などが挙げられる。
　紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物などが挙げられる。 The acrylic pressure-sensitive adhesive layer is, if necessary, a light stabilizer such as a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, an ultraviolet absorber, an antistatic agent, a photopolymerization initiator, a hindered amine compound, etc. From among these, additives can be selected and blended as required.
As a plasticizer, for example, a nonfunctional acrylic polymer can be used. A nonfunctional acrylic polymer is a polymer consisting only of 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 and no functional group It means a polymer consisting of non-acrylic monomer units.
Examples of the antioxidant include phenol based antioxidants, amine based antioxidants, lactone based antioxidants, phosphorus based antioxidants, sulfur based antioxidants and the like. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
As a metal corrosion inhibitor, benzotriazole resin can be mentioned.
Examples of tackifiers include rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, styrene resins, xylene resins, phenol resins, petroleum resins and the like.
Examples of the UV absorber include benzotriazole compounds and benzophenone compounds.
　また、アクリル系粘着剤層の経時劣化を防ぐためには老化防止剤を添加することが好ましい。老化防止剤を添加することで、両面粘着シートの劣化による粘着力低下を防ぐことができる。老化防止剤としては、一般的なフェノール系酸化防止剤、リン系酸化防止剤、紫外線防止剤、ＨＡＬＳ（ヒンダードアミン系安定剤）などを挙げることができる。 Moreover, in order to prevent the time-dependent deterioration of an acrylic adhesive layer, it is preferable to add an antiaging agent. By adding an anti-aging agent, it is possible to prevent the decrease in adhesion due to the deterioration of the double-sided pressure-sensitive adhesive sheet. Examples of anti-aging agents include general phenol-based antioxidants, phosphorus-based antioxidants, ultraviolet inhibitors, HALS (hindered amine-based stabilizers) and the like.
　アクリル系粘着剤層を形成するアクリル系粘着剤組成物は溶剤を含むものであってもよい。溶剤は、粘着剤層を形成する際に蒸散するものであるが、アクリル系粘着剤層には、残存した溶剤が含まれていてもよい。 The acrylic pressure-sensitive adhesive composition forming the acrylic pressure-sensitive adhesive layer may contain a solvent. The solvent evaporates when forming the pressure-sensitive adhesive layer, but the acrylic pressure-sensitive adhesive layer may contain the remaining solvent.
　溶剤としては、例えば、ヘキサン、ヘプタン、オクタン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、メチルシクロヘキサン等の炭化水素類；ジクロロメタン、トリクロロエタン、トリクロロエチレン、テトラクロロエチレン、ジクロロプロパン等のハロゲン化炭化水素類；メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノール、イソブチルアルコール、ジアセトンアルコール等のアルコール類；ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、イソホロン、シクロヘキサノン等のケトン類；酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸アミル、酪酸エチル等のエステル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテルアセタート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセタート等のポリオール及びその誘導体が挙げられる。 Examples of 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 etc. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone etc. Methyl acetate Esters such as ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate and ethyl butyrate Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, polyols and derivatives thereof such as propylene glycol monomethyl ether acetate.
＜シリコーン系粘着剤層＞
　本発明の両面粘着シートはシリコーン系粘着剤層を含む。シリコーン系粘着剤層はシリコーン系樹脂（シリコーン系粘着剤）を主成分として含む層である。具体的には、シリコーン系粘着剤層におけるシリコーン系樹脂の含有量は、シリコーン系粘着剤層の全質量に対して５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることがさらに好ましく、８０質量％以上であることが一層好ましく、９０質量％以上であることが特に好ましい。 <Silicone-based pressure-sensitive adhesive layer>
The double-sided pressure-sensitive adhesive sheet of the present invention contains a silicone-based pressure-sensitive adhesive layer. The silicone-based pressure-sensitive adhesive layer is a layer containing a silicone-based resin (silicone-based pressure-sensitive adhesive) as a main component. Specifically, the content of the silicone-based resin in the silicone-based pressure-sensitive adhesive layer is preferably 50% by mass or more, and more preferably 60% by mass or more based on the total mass of the silicone-based pressure-sensitive adhesive layer The content is more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
　シリコーン系樹脂としては、例えば、ポリシロキサン骨格を有するシリコーン系樹脂を挙げることができる。シリコーン系樹脂としては、付加反応型、縮合反応型、紫外線硬化型、電子線硬化型等がある。中でも、付加反応型シリコーン系樹脂は、反応性が高く生産性に優れているため、好ましく用いられる。付加反応型シリコーン系樹脂としては、例えば、分子の末端および／または側鎖に、ビニル基、アリル基、プロペニル基、ヘキセニル基等の炭素数２～１０のアルケニル基を２個以上備えたオルガノポリシロキサンが挙げられる。 Examples of silicone resins include silicone resins having a polysiloxane skeleton. Silicone resins include addition reaction type, condensation reaction type, ultraviolet ray curing type, electron beam curing type and the like. Among them, addition reaction type silicone resins are preferably used because they have high reactivity and are excellent in productivity. As the addition reaction type silicone resin, for example, an organopoly resin having two or more alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group and hexenyl group at the terminal and / or side chain of the molecule. A siloxane is mentioned.
　付加反応型シリコーン系樹脂を用いる際には、架橋剤および触媒を併用することが好ましい。架橋剤としては、例えば１分子中に少なくとも２個のケイ素原子に結合した水素原子を有するオルガノポリシロキサンが挙げられる。具体的には、ジメチルハイドロジェンシロキシ基末端封鎖ジメチルシロキサン－メチルハイドロジェンシロキサン共重合体、トリメチルシロキシ基末端封鎖ジメチルシロキサン－メチルハイドロジェンシロキサン共重合体、トリメチルシロキシ基末端封鎖メチルハイドロジェンポリシロキサン、ポリ（ハイドロジェンシルセスキオキサン）等が挙げられる。
　また、触媒としては、微粒子状白金、炭素粉末担体上に吸着された微粒子状白金、塩化白金酸、アルコール変性塩化白金酸、塩化白金酸のオレフィン錯体、パラジウム、ロジウム等の白金属系化合物等が挙げられる。 When using an addition reaction type silicone resin, it is preferable to use a crosslinking agent and a catalyst in combination. Examples of the crosslinking agent include organopolysiloxanes having hydrogen atoms bonded to at least two silicon atoms in one molecule. Specifically, dimethylhydrogensiloxy end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy end-capped dimethylsiloxane-methyl hydrogen siloxane copolymer, trimethylsiloxy end-capped methylhydrogenpolysiloxane, Poly (hydrogen silsesquioxane) etc. are mentioned.
As the catalyst, particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, white metal compounds such as palladium and rhodium, etc. It can be mentioned.
　シリコーン系粘着剤層は、必要に応じて、酸化防止剤、金属腐食防止剤、粘着付与剤、紫外線吸収剤、ヒンダードアミン系化合物、帯電防止剤、光安定剤等の添加剤中から必要に応じて選択配合できる。
　酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等が挙げられる。これら酸化防止剤は１種類を単独で使用してもよいし、２種類以上を併用してもよい。
　金属腐食防止剤としては、ベンゾリアゾール系樹脂を挙げることができる。
　粘着付与剤として、例えば、ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、スチレン系樹脂、キシレン系樹脂、フェノール系樹脂、石油樹脂などが挙げられる。
　紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物などが挙げられる。 The silicone-based pressure-sensitive adhesive layer contains, if necessary, additives such as an antioxidant, a metal corrosion inhibitor, a tackifier, an ultraviolet light absorber, a hindered amine compound, an antistatic agent, and a light stabilizer as needed. It can be selected and blended.
Examples of the antioxidant include phenol based antioxidants, amine based antioxidants, lactone based antioxidants, phosphorus based antioxidants, sulfur based antioxidants and the like. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
As a metal corrosion inhibitor, benzotriazole resin can be mentioned.
Examples of tackifiers include rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, styrene resins, xylene resins, phenol resins, petroleum resins and the like.
Examples of the UV absorber include benzotriazole compounds and benzophenone compounds.
　また、シリコーン系粘着剤層の経時劣化を防ぐためには老化防止剤を添加することが好ましい。老化防止剤を添加することで、両面粘着シートの劣化による粘着力低下を防ぐことができる。老化防止剤としては、一般的なフェノール系酸化防止剤、リン系酸化防止剤、紫外線防止剤、ＨＡＬＳ（ヒンダードアミン系安定剤）などを挙げることができる。 Moreover, in order to prevent the time-dependent deterioration of a silicone type adhesive layer, it is preferable to add an antiaging agent. By adding an anti-aging agent, it is possible to prevent the decrease in adhesion due to the deterioration of the double-sided pressure-sensitive adhesive sheet. Examples of anti-aging agents include general phenol-based antioxidants, phosphorus-based antioxidants, ultraviolet inhibitors, HALS (hindered amine-based stabilizers) and the like.
　シリコーン系粘着剤層を形成するシリコーン系粘着剤組成物は溶剤を含むものであってもよい。溶剤は、粘着剤層を形成する際に蒸散するものであるが、シリコーン系粘着剤層には、残存した溶剤が含まれていてもよい。溶剤としては、アクリル系粘着剤組成物が含み得る溶剤と同様のものが挙げられる。 The silicone-based pressure-sensitive adhesive composition forming the silicone-based pressure-sensitive adhesive layer may contain a solvent. The solvent evaporates when forming the pressure-sensitive adhesive layer, but the silicone-based pressure-sensitive adhesive layer may contain the remaining solvent. As a solvent, the thing similar to the solvent which an acrylic adhesive composition may contain is mentioned.
　シリコーン系粘着剤としては、市販品を用いることができる。このようなシリコーン系粘着剤としては、例えば、信越化学工業（株）製のＫＲ－３７０４、Ｘ４０－３３０６や東レ・ダウコーニング（株）製のＤＣ７６５１ＡＤＨＥＳＩＶＥ、ＳＤ７５８７ＬＰＳＡ、アイカ工業（株）製のＳＥ９５００、ＳＥ９６００などが挙げられる。 A commercial item can be used as a silicone type adhesive. As such silicone-based pressure-sensitive adhesives, for example, KR-3704, X40-3306 manufactured by Shin-Etsu Chemical Co., Ltd., DC7651ADHESIVE manufactured by Toray Dow Corning Co., Ltd., SD7587LPSA, SE9500 manufactured by Aika Kogyo Co., Ltd. SE9600 etc. are mentioned.
（両面粘着シートの製造方法）
　本発明の両面粘着シートの製造工程は、アクリル系粘着剤層とシリコーン系粘着剤層を積層する工程を含むことが好ましい。各粘着剤層は、塗工により形成された粘着剤層（粘着シート）であることが好ましく、逐次塗工により形成された粘着剤層（粘着シート）であることがより好ましい。なお、本明細書において逐次塗工とは、各粘着剤層が各々の工程で塗工され、別個のシート状に形成されることをいう。 (Manufacturing method of double-sided adhesive sheet)
It is preferable that the manufacturing process of the double-sided adhesive sheet of this invention includes the process of laminating | stacking an acrylic adhesive layer and a silicone adhesive layer. Each pressure-sensitive adhesive layer is preferably a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) formed by coating, and more preferably a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) formed by sequential coating. In the present specification, sequential application means that each pressure-sensitive adhesive layer is applied in each step and formed into a separate sheet.
　両面粘着シートの製造方法としては、例えば、剥離シート上にアクリル系粘着剤組成物を塗工し、アクリル系粘着剤層を形成する工程と、他の剥離シート上に、シリコーン系粘着剤組成物を塗工し、シリコーン系粘着剤層を形成する工程とを含む。そして、アクリル系粘着剤層とシリコーン系粘着剤層を、直接接するように重ね、圧着する工程を含む。 As a manufacturing method of a double-sided pressure-sensitive adhesive sheet, for example, an acrylic pressure-sensitive adhesive composition is coated on a release sheet to form an acrylic pressure-sensitive adhesive layer, and a silicone-based pressure-sensitive adhesive composition on another release sheet. And applying a silicone-based pressure-sensitive adhesive layer. Then, a step of overlapping and pressure-bonding the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer so as to be in direct contact with each other is included.
　各粘着剤組成物の塗工は、公知の塗工装置を用いて実施できる。塗工装置としては、例えば、ブレードコーター、エアナイフコーター、ロールコーター、バーコーター、グラビアコーター、マイクログラビアコーター、ロッドブレードコーター、リップコーター、ダイコーター、カーテンコーター等が挙げられる。
　また、塗工後は乾燥工程を設けることが好ましく、乾燥工程は、加熱炉、赤外線ランプ等の公知の加熱装置を用いて実施できる。 Coating of each pressure-sensitive adhesive composition can be carried out using a known coating apparatus. As a coating apparatus, a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a microgravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater etc. are mentioned, for example.
Moreover, it is preferable to provide a drying process after coating, and a drying process can be implemented using well-known heating apparatuses, such as a heating furnace and an infrared lamp.
　両面粘着シートの製造工程は、アクリル系粘着剤層とシリコーン系粘着剤層を重ね合わせる前に表面活性化処理工程を含むことが好ましい。ここで、表面活性化処理としては、例えば、コロナ処理やプラズマ処理を挙げることができる。中でも、表面活性化処理としては、コロナ処理を施すことが好ましい。 It is preferable that the manufacturing process of a double-sided adhesive sheet includes a surface activation treatment process before superposing an acrylic adhesive layer and a silicone adhesive layer. Here, examples of the surface activation treatment include corona treatment and plasma treatment. Among them, corona treatment is preferably performed as the surface activation treatment.
　表面活性化処理工程では、アクリル系粘着剤層及びシリコーン系粘着剤層から選択される少なくとも一方に表面活性化処理が施されることが好ましい。ここで、上記表面活性化処理は、各粘着剤層の貼合面側の面に施されることが好ましい。すなわち、アクリル系粘着剤層の界面側の表面及びシリコーン系粘着剤層の界面側の表面から選択される少なくとも一方は、表面活性化処理面であることが好ましい。なお、アクリル系粘着剤層及びシリコーン系粘着剤層の両方に表面活性化処理が施されることも好ましい。すなわち、アクリル系粘着剤層の界面側の表面及びシリコーン系粘着剤層の界面側の表面は、表面活性化処理面であることが好ましい。なお、表面活性化処理がアクリル系粘着剤層又はシリコーン系粘着剤層のいずれかの面にのみ施される場合、表面活性化処理はシリコーン系粘着剤層に施されることが好ましい。 In the surface activation treatment step, at least one selected from the acrylic pressure-sensitive adhesive layer and the silicone pressure-sensitive adhesive layer is preferably subjected to surface activation treatment. Here, the surface activation treatment is preferably performed on the surface on the bonding surface side of each pressure-sensitive adhesive layer. That is, at least one selected from the surface on the interface side of the acrylic pressure-sensitive adhesive layer and the surface on the interface side of the silicone-based pressure-sensitive adhesive layer is preferably a surface activation treated surface. In addition, it is also preferable that a surface activation treatment is performed on both the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer. That is, the surface on the interface side of the acrylic pressure-sensitive adhesive layer and the surface on the interface side of the silicone-based pressure-sensitive adhesive layer are preferably a surface activation treated surface. When the surface activation treatment is applied only to either the acrylic pressure-sensitive adhesive layer or the silicone pressure-sensitive adhesive layer, the surface activation treatment is preferably applied to the silicone pressure-sensitive adhesive layer.
　アクリル系粘着剤層の界面側の表面が表面活性化処理面である場合、該表面活性化処理面の濡れ張力は７０ｍＮ／ｍ以上であることが好ましく、７３ｍＮ／ｍ以上であることがより好ましい。なお、表面活性化処理面の濡れ張力の上限は特に限定されるものではない。また、表面活性化処理後のアクリル系粘着剤層の濡れ張力は、表面活性化処理前のアクリル系粘着剤層の濡れ張力に比べて１．１倍以上であることが好ましい。なお、表面活性化処理がアクリル系粘着剤層又はシリコーン系粘着剤層のいずれかの面にのみ施される場合、表面活性化処理はアクリル系粘着剤層に施されることが好ましい。 When the surface on the interface side of the acrylic pressure-sensitive adhesive layer is a surface activation treated surface, the wetting tension of the surface activation treated surface is preferably 70 mN / m or more, more preferably 73 mN / m or more . The upper limit of the wetting tension of the surface activation treated surface is not particularly limited. The wet tension of the acrylic pressure-sensitive adhesive layer after the surface activation treatment is preferably 1.1 or more times the wet tension of the acrylic pressure-sensitive adhesive layer before the surface activation treatment. When the surface activation treatment is applied only to either the acrylic pressure-sensitive adhesive layer or the silicone pressure-sensitive adhesive layer, the surface activation treatment is preferably applied to the acrylic pressure-sensitive adhesive layer.
　シリコーン系粘着剤層の界面側の表面が表面活性化処理面である場合、該表面活性化処理面の濡れ張力は３０ｍＮ／ｍ以上であることが好ましく、３４ｍＮ／ｍ以上であることがより好ましく、３５ｍＮ／ｍ以上であることがさらに好ましい。なお、表面活性化処理面の濡れ張力の上限は特に限定されるものではないが、透明性の低下を防ぐために、例えば５０ｍＮ／ｍ以下であることが好ましく、４５ｍＮ／ｍ以下であることがより好ましい。なお、濡れ張力は、ＪＩＳ　Ｋ　６７６８　１９９９に準じて濡れ指示標準液（和光純薬製）を粘着層表面に塗布することで測定する。 When the surface on the interface side of the silicone-based pressure-sensitive adhesive layer is a surface activation treated surface, the wetting tension of the surface activation treated surface is preferably 30 mN / m or more, more preferably 34 mN / m or more. And 35 mN / m or more. Although the upper limit of the wetting tension of the surface activation treated surface is not particularly limited, it is preferably, for example, 50 mN / m or less, more preferably 45 mN / m or less, in order to prevent the decrease in transparency. preferable. The wetting tension is measured by applying a wetting indication standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) to the surface of the adhesive layer according to JIS K 6768 1999.
　コロナ処理としては、コロナ処理機により常圧空気中で放電する方式が挙げられる。コロナ処理におけるコロナ出力は、特に限定されるものではないが、例えば、０．５ｋＷ以上８．０ｋＷ以下であることが好ましく、０．５ｋＷ以上７．０ｋＷ以下であることがより好ましく、０．５ｋＷ以上６．０ｋＷ以下であることがさらに好ましい。コロナ処理における処理速度は、５ｍ／分以上１００ｍ／分以下であることが好ましく、５ｍ／分以上９０ｍ／分以下であることがより好ましく、５ｍ／分以上８０ｍ／分以下であることがさらに好ましい。 As corona treatment, there is a method of discharging in normal pressure air by a corona treatment machine. The corona output in the corona treatment is not particularly limited, but is preferably, for example, 0.5 kW or more and 8.0 kW or less, and more preferably 0.5 kW or more and 7.0 kW or less. It is more preferable that it is 6.0 kW or less. The treatment speed in the corona treatment is preferably 5 m / min to 100 m / min, more preferably 5 m / min to 90 m / min, and still more preferably 5 m / min to 80 m / min. .
　プラズマ処理としては、プラズマ放電機により常圧空気中で放電する方式が挙げられる。プラズマ処理におけるプラズマ出力は、特に限定されるものではないが、例えば、０．５ｋＷ以上５．０ｋＷ以下であることが好ましく、０．５ｋＷ以上３．０ｋＷ以下であることがより好ましく、０．５ｋＷ以上１．５ｋＷ以下であることがさらに好ましい。プラズマ処理における処理速度は、５ｍ／分以上１００ｍ／分以下であることが好ましく、５ｍ／分以上９０ｍ／分以下であることがより好ましく、５ｍ／分以上８０ｍ／分以下であることがさらに好ましい。 As the plasma treatment, there is a method of discharging in normal pressure air by a plasma discharger. The plasma output in the plasma processing is not particularly limited, but is preferably, for example, 0.5 kW or more and 5.0 kW or less, and more preferably 0.5 kW or more and 3.0 kW or less. More preferably, it is 1.5 kW or less. The processing speed in the plasma processing is preferably 5 m / min to 100 m / min, more preferably 5 m / min to 90 m / min, and still more preferably 5 m / min to 80 m / min. .
　なお、表面活性化の程度は、濡れ張力が上述した範囲内となるように適宜調節することが好ましい。 The degree of surface activation is preferably adjusted as appropriate so that the wetting tension is in the above-mentioned range.
　アクリル系粘着剤層とシリコーン系粘着剤層を圧着する工程における圧着方法は、特に限定されないが、連続して圧着が可能であるロール貼合機を用いることが好ましい。 The pressure-bonding method in the step of pressure-bonding the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is not particularly limited, but it is preferable to use a roll bonding machine capable of continuously pressure-bonding.
（剥離シート付き両面粘着シート）
　両面粘着シートの少なくとも一方の面には、剥離シートが積層されることが好ましく、両面粘着シートの両面に剥離シートが積層されることがより好ましい。すなわち、本発明の両面粘着シートは、両面粘着シートの両面に剥離シートを備えた剥離シート付き両面粘着シートであることが好ましい。 (Double-sided adhesive sheet with release sheet)
A release sheet is preferably laminated on at least one surface of the double-sided pressure-sensitive adhesive sheet, and more preferably, the release sheet is laminated on both sides of the double-sided pressure-sensitive adhesive sheet. That is, the double-sided pressure-sensitive adhesive sheet of the present invention is preferably a double-sided pressure-sensitive adhesive sheet with a release sheet provided with release sheets on both sides of the double-sided pressure-sensitive adhesive sheet.
　剥離シートとしては、剥離シート用基材とこの剥離シート用基材の片面に設けられた剥離剤層とを有する剥離性積層シート、あるいは、低極性基材としてポリエチレンフィルムやポリプロピレンフィルム等のポリオレフィンフィルムが挙げられる。
　剥離性積層シートにおける剥離シート用基材には、紙類、高分子フィルムが使用される。剥離剤層を構成する剥離剤としては、例えば、汎用の付加型もしくは縮合型のシリコーン系剥離剤や長鎖アルキル基含有化合物が用いられる。特に、反応性が高い付加型シリコーン系剥離剤が好ましく用いられる。
　シリコーン系剥離剤としては、具体的には、東レ・ダウコーニングシリコーン社製のＢＹ２４－４５２７、ＳＤ－７２２０等や、信越化学工業（株）製のＫＳ－３６００、ＫＳ－７７４、Ｘ６２－２６００などが挙げられる。また、シリコーン系剥離剤中にＳｉＯ2単位と（ＣＨ3）3ＳｉＯ1/2単位あるいはＣＨ2＝ＣＨ（ＣＨ3）ＳｉＯ1/2単位を有する有機珪素化合物であるシリコーンレジンを含有することが好ましい。シリコーンレジンの具体例としては、東レ・ダウコーニングシリコーン社製のＢＹ２４－８４３、ＳＤ－７２９２、ＳＨＲ－１４０４等や、信越化学工業（株）製のＫＳ－３８００、Ｘ９２－１８３等が挙げられる。 As a release sheet, a peelable laminate sheet having a release sheet substrate and a release agent layer provided on one side of the release sheet substrate, or a polyolefin film such as a polyethylene film or a polypropylene film as a low polarity substrate Can be mentioned.
Papers and polymer films are used for the release sheet base in the release laminate sheet. As the release agent constituting the release agent layer, for example, a general-purpose addition type or condensation type silicone release agent or a long chain alkyl group-containing compound is used. In particular, an addition-type silicone release agent having high reactivity is preferably used.
Specific examples of silicone release agents include BY24-4527 and SD-7220 manufactured by Toray Dow Corning Silicone Co., Ltd., KS-3600 manufactured by Shin-Etsu Chemical Co., Ltd., KS-774 and X62-2600, etc. Can be mentioned. In addition, a silicone resin which is an organic silicon compound having a SiO 2 unit and a (CH 3 ) 3 SiO 1/2 unit or a CH 2 CHCH (CH 3 ) SiO 1/2 unit in a silicone-based release agent preferable. Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404, etc. manufactured by Toray Dow Corning Silicone Co., Ltd., and KS-3800, X92-183, etc. manufactured by Shin-Etsu Chemical Co., Ltd.
　両面粘着シートの両面に剥離シートを積層する場合、２枚の剥離シート（第１の剥離シート及び第２の剥離シート）は異なる剥離力を有することが好ましい。 When laminating | stacking a peeling sheet on both surfaces of a double-sided adhesive sheet, it is preferable that two peeling sheets (a 1st peeling sheet and a 2nd peeling sheet) have different peeling force.
　第１の剥離シート（アクリル系粘着剤層側の剥離シート）は、軽剥離力側の剥離シートであることが好ましく、アクリル系粘着剤層から第１の剥離シートを剥離する際の剥離力は、０．０１Ｎ／５０ｍｍ以上であることが好ましく、０．１Ｎ／５０ｍｍ以上であることがより好ましい。また、アクリル系粘着剤層から第１の剥離シートを剥離する際の剥離力は、１．０Ｎ／５０ｍｍ以下であることが好ましく、０．８Ｎ／５０ｍｍ以下であることがより好ましく、０．６Ｎ／５０ｍｍ以下であることがさらに好ましい。 The first release sheet (release sheet on the acrylic pressure-sensitive adhesive layer side) is preferably a release sheet on the light release force side, and the release strength at the time of releasing the first release sheet from the acrylic pressure-sensitive adhesive layer is The thickness is preferably 0.01 N / 50 mm or more, more preferably 0.1 N / 50 mm or more. Moreover, it is preferable that it is 1.0 N / 50 mm or less, and, as for the peeling force at the time of peeling a 1st peeling sheet from an acrylic adhesive layer, it is more preferable that it is 0.8 N / 50 mm or less, and 0.6 N It is further more preferable that it is / 50 mm or less.
　第２の剥離シート（シリコーン系粘着剤層側の剥離シート）は、重剥離力側の剥離シートであることが好ましく、シリコーン系粘着剤層から第２の剥離シートを剥離する際の剥離力は、０．５Ｎ／５０ｍｍ以上であることが好ましく、０．６Ｎ／５０ｍｍ以上であることがより好ましい。また、シリコーン系粘着剤層から第２の剥離シートを剥離する際の剥離力は、１０．０Ｎ／５０ｍｍ以下であることが好ましく、５．０Ｎ／５０ｍｍ以下であることがより好ましく、３．０Ｎ／５０ｍｍ以下であることがさらに好ましい。 The second release sheet (release sheet on the silicone-based pressure-sensitive adhesive layer side) is preferably a release sheet on the heavy release force side, and the release force at the time of releasing the second release sheet from the silicone-based pressure-sensitive adhesive layer is It is preferable that it is 0.5 N / 50 mm or more, and it is more preferable that it is 0.6 N / 50 mm or more. Moreover, it is preferable that it is 10.0 N / 50 mm or less, and, as for the peeling force at the time of peeling a 2nd peeling sheet from a silicone type adhesive layer, it is more preferable that it is 5.0 N / 50 mm or less, and 3.0 N It is further more preferable that it is / 50 mm or less.
　なお、第２の剥離シート（シリコーン系粘着剤層側の剥離シート）の剥離力をＲHとし、第１の剥離シート（アクリル系粘着剤層側の剥離シート）の剥離力をＲLとした場合、ＲH／ＲLの値は１．５以上であることが好ましく、２．０以上であることがより好ましい。 The release force of the second release sheet (release sheet on the side of the silicone-based pressure-sensitive adhesive layer) is R H and the release force of the first release sheet (release-side on the side of the acrylic pressure-sensitive adhesive layer) is R L In the case, the value of R H / R L is preferably 1.5 or more, and more preferably 2.0 or more.
（光学部材貼合用両面粘着シート）
　本発明の両面粘着シートは、各種部材の貼り合わせの用途に好ましく用いられる。貼り合わせの用途は制限されないが、本発明の両面粘着シートは、光学部材貼合用両面粘着シートであることが好ましい。光学部材としては、例えば、液晶ディスプレイ又はタッチパネルを挙げることができる。特に、本発明の両面粘着シートは、ガラスと液晶ディスプレイ、又は、ガラスとタッチパネルの貼合用に用いられることが好ましい。 (Double-sided adhesive sheet for optical member bonding)
The double-sided pressure-sensitive adhesive sheet of the present invention is preferably used for the application of bonding of various members. Although the use of bonding is not limited, the double-sided pressure-sensitive adhesive sheet of the present invention is preferably a double-sided pressure-sensitive adhesive sheet for optical member bonding. As an optical member, a liquid crystal display or a touch panel can be mentioned, for example. In particular, the double-sided pressure-sensitive adhesive sheet of the present invention is preferably used for bonding a glass and a liquid crystal display or a glass and a touch panel.
（積層体）
　本発明は、上述した両面粘着シートと被着材を有する積層体に関するものであってもよい。この場合、積層体は、第１の被着材との貼着面がアクリル系粘着剤層であり、第２の被着材との貼着面がシリコーン系粘着剤層である積層体であることが好ましい。中でも、第１の被着材はガラスであることが好ましい。このような構成とすることで、第１の被着材と強固に粘着しつつも、第２の被着材からは再剥離が容易となる。 (Laminate)
The present invention may relate to a laminate having the double-sided pressure-sensitive adhesive sheet described above and an adherend. In this case, the laminate is a laminate in which the bonding surface with the first adherend is an acrylic pressure-sensitive adhesive layer and the bonding surface with the second adherend is a silicone-based pressure-sensitive adhesive layer Is preferred. Among them, the first adherend is preferably glass. With such a configuration, removability from the second adherend is facilitated, while firmly adhering to the first adherend.
　以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 The features of the present invention will be more specifically described below with reference to examples and comparative examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.
［実施例１］
＜アクリル系粘着剤組成物の調製＞
　アクリル酸ｎ－ブチル（ＢＡ）９０質量部およびアクリル酸（ＡＡ）１０質量部を共重合させて、（メタ）アクリル酸エステル重合体を調製した。この（メタ）アクリル酸エステル重合体の重量平均分子量は５０万であった。 Example 1
<Preparation of Acrylic Pressure-Sensitive Adhesive Composition>
A (meth) acrylic acid ester polymer was prepared by copolymerizing 90 parts by mass of n-butyl acrylate (BA) and 10 parts by mass of acrylic acid (AA). The weight average molecular weight of this (meth) acrylic acid ester polymer was 500,000.
　得られた（メタ）アクリル酸エステル重合体１００質量部、エポキシ系架橋剤として１，３－ビス（Ｎ，Ｎ’－ジグリシジルアミノメチル）シクロヘキサン（三菱ガス化学社製、ＴＥＲＡＤ－Ｃ）０．０５質量部、シランカップリング剤としてシリコーンアルコキシオリゴマー（信越化学（株）社製、Ｘ－４１-１８１０）０．１５質量部を混合し、十分に撹拌して、固形分濃度が４０質量％となるように酢酸エチルで希釈することにより、アクリル系粘着剤組成物（Ａ）を得た。 100 parts by mass of the (meth) acrylic acid ester polymer obtained, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, TERAD-C) 0 as an epoxy crosslinking agent 05 parts by mass, and 0.15 parts by mass of silicone alkoxy oligomer (X-41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent are mixed and sufficiently stirred to give a solid content concentration of 40 mass%. The resulting solution was diluted with ethyl acetate to obtain an acrylic pressure-sensitive adhesive composition (A).
＜シリコーン系粘着剤組成物の調製＞
　シロキサン結合を主骨格としビニル基を有するオルガノポリシロキサン及びオルガノハイドロジェンポリシロキサンからなる付加型オルガノポリシロキサン（信越化学工業（株）製、ＫＳ－８４７Ｈ）１００質量部（固形分換算値；以下同じ）、３官能性又は４官能性のシロキサン単位を含むオルガノポリシロキサン（シリコーンレジン；東レダウコーニング社製、ＳＤ－４５８４）２０質量部、白金触媒（東レダウコーニング社製、ＳＲＸ－２１２）１．５質量部を混合し、十分に撹拌して、固形分濃度が４０質量％となるようにメチルエチルケトンで希釈することにより、シリコーン系粘着剤組成物を得た。 <Preparation of Silicone-Based Pressure-Sensitive Adhesive Composition>
100 parts by mass (solids equivalent value; the same as the solid content; the same as the addition type organopolysiloxane (Shin-Etsu Chemical Co., Ltd. product KS-847H) consisting of an organopolysiloxane having a siloxane bond as a main skeleton and having a vinyl group and an organohydrogenpolysiloxane 20 parts by mass of an organopolysiloxane containing a trifunctional or tetrafunctional siloxane unit (silicone resin; manufactured by Toray Dow Corning, SD-4584), a platinum catalyst (manufactured by Toray Dow Corning, SRX-212). The silicone-based pressure-sensitive adhesive composition was obtained by mixing 5 parts by mass, sufficiently stirring, and diluting with methyl ethyl ketone so that the solid content concentration was 40% by mass.
＜両面粘着シートの作製＞
（アクリル系粘着剤層の作製）
　アクリル系粘着剤組成物（Ａ）を、シリコーン系剥離剤で処理された剥離剤層を備えた厚さ３８μｍのポリエチレンテレフタレートフィルム（セパレータフィルム）（王子エフテックス社製、３８ＲＬ－０７（２））の表面に、乾燥後の塗工量が５０μｍになるようにアプリケーターで均一に塗工し、１００℃の空気循環式恒温オーブンで３分間乾燥することで、片面に第１の剥離シートが貼着されたアクリル系粘着剤層を得た。片面に第１の剥離シートが貼着された粘着剤層を２３℃、相対湿度５０％の環境にて７日間養生を行った。 <Preparation of double-sided adhesive sheet>
(Preparation of acrylic pressure-sensitive adhesive layer)
A 38 μm thick polyethylene terephthalate film (separator film) having a release agent layer treated with a silicone-based release agent (acrylic acid-based adhesive composition (A) (manufactured by Oji F-TEX, 38RL-07 (2)) The first release sheet is attached to one side by uniformly coating the surface with an applicator so that the coated amount after drying is 50 μm and drying in an air circulating constant temperature oven at 100 ° C. for 3 minutes. The obtained acrylic adhesive layer was obtained. The pressure-sensitive adhesive layer having the first release sheet attached to one side was aged for 7 days in an environment of 23 ° C. and 50% relative humidity.
（シリコーン系粘着剤層の作製）
　シリコーン系粘着剤組成物を、厚さ３８μｍのポリエチレンテレフタレートフィルム（東レ社製、ルミラーＳ－１０＃３８）の表面に、乾燥後の塗工量が５０μｍになるようにアプリケーターで均一に塗工し、１００℃の空気循環式恒温オーブンで３分間乾燥することで、片面に第２の剥離シートが貼着されたシリコーン系粘着剤層を得た。 (Preparation of silicone pressure sensitive adhesive layer)
Apply a silicone-based pressure-sensitive adhesive composition uniformly on the surface of a 38 μm-thick polyethylene terephthalate film (Lumirror S-10 # 38, manufactured by Toray Industries, Inc.) with an applicator so that the coated amount after drying is 50 μm. By drying in an air circulating constant temperature oven at 100 ° C. for 3 minutes, a silicone-based pressure-sensitive adhesive layer in which the second release sheet was attached to one side was obtained.
（表面活性化処理）
　アクリル系粘着剤層及びシリコーン系粘着剤層のそれぞれの表面にコロナ放電処理を施した。コロナ放電処理は、春日電機製のコロナ表面処理装置を用いて行った。コロナ放電処理はそれぞれ、アクリル系粘着剤層の濡れ張力が７０ｍＮ／ｍ以上、シリコーン系粘着剤層の濡れ張力が３０ｍＮ／ｍ以上となる条件で行った。 (Surface activation treatment)
The surface of each of the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer was subjected to corona discharge treatment. The corona discharge treatment was performed using a corona surface treatment apparatus made by Kasuga Denki. The corona discharge treatment was performed under the conditions that the wetting tension of the acrylic pressure-sensitive adhesive layer was 70 mN / m or more and the wetting tension of the silicone-based pressure-sensitive adhesive layer was 30 mN / m or more.
（剥離シート付き両面粘着シートの作製）
　表面活性化処理を行った面同士を貼り合せることで、第１の剥離シート／アクリル系粘着剤層／シリコーン系粘着剤層／第２の剥離シートがこの順で積層された剥離シート付き両面粘着シートを得た。 (Preparation of double-sided PSA sheet with release sheet)
By bonding the surfaces subjected to the surface activation treatment, a double-sided adhesive sheet with a release sheet in which the first release sheet / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / second release sheet are laminated in this order I got a sheet.
［実施例２］
　（表面活性化処理）においてアクリル系粘着剤層及びシリコーン系粘着剤層のそれぞれの表面活性化処理をプラズマ放電処理（積水化学工業常圧プラズマ表面処理装置　ＲＴ　Ｓｅｒｉｅｓ）へ変更した以外は実施例１と同様にして剥離シート付き両面粘着シートを得た。プラズマ放電処理はそれぞれ、アクリル系粘着剤層の濡れ張力が７０ｍＮ／ｍ以上、シリコーン系粘着剤層の濡れ張力が３０ｍＮ／ｍ以上となる条件で行った。 Example 2
Example 1 (surface activation treatment) except that the surface activation treatment of each of the acrylic pressure-sensitive adhesive layer and the silicone pressure-sensitive adhesive layer was changed to plasma discharge treatment (Sekisui Chemical Atmospheric Pressure Plasma Surface Treatment Device RT Series) In the same manner as in, a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained. The plasma discharge treatment was performed under the conditions that the wetting tension of the acrylic pressure-sensitive adhesive layer was 70 mN / m or more and the wetting tension of the silicone-based pressure-sensitive adhesive layer was 30 mN / m or more.
［実施例３］
　（表面活性化処理）においてシリコーン系粘着剤層の表面活性化処理を行わなかった以外は実施例１と同様にして剥離シート付き両面粘着シートを得た。コロナ放電処理は、アクリル系粘着剤層の濡れ張力が７０ｍＮ／ｍ以上となる条件で行った。 [Example 3]
A release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the surface activation treatment of the silicone-based pressure-sensitive adhesive layer was not performed in (Surface activation treatment). The corona discharge treatment was performed under the condition that the wetting tension of the acrylic pressure-sensitive adhesive layer was 70 mN / m or more.
［実施例４］
　（表面活性化処理）においてアクリル系粘着剤層の表面活性化処理を行わなかった以外は実施例１と同様にして剥離シート付き両面粘着シートを得た。コロナ放電処理は、シリコーン系粘着剤層の濡れ張力が３０ｍＮ／ｍ以上となる条件で行った。 Example 4
A release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the surface activation treatment of the acrylic pressure-sensitive adhesive layer was not performed in (Surface activation treatment). The corona discharge treatment was performed under the condition that the wetting tension of the silicone-based pressure-sensitive adhesive layer was 30 mN / m or more.
［実施例５］
　＜アクリル系粘着剤組成物の調製＞においてシランカップリング剤を配合しなかった以外は、実施例１と同様にしてアクリル系粘着剤組成物（Ｂ）を得た。また、アクリル系粘着剤組成物（Ａ）に代えてアクリル系粘着剤組成物（Ｂ）を用いた以外は実施例１と同様にして剥離シート付き両面粘着シートを得た。 [Example 5]
An acrylic pressure-sensitive adhesive composition (B) was obtained in the same manner as in Example 1, except that no silane coupling agent was added in <Preparation of acrylic pressure-sensitive adhesive composition>. A release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive composition (B) was used instead of the acrylic pressure-sensitive adhesive composition (A).
［実施例６］
　＜アクリル系粘着剤組成物の調製＞において、アクリル酸－２－エチルヘキシル（２ＥＨＡ）５５質量部、４－アクリロイルモロホリン（ＡＣＭＯ）４０質量部、及びアクリル酸（ＡＡ）５質量部を共重合させて、（メタ）アクリル酸エステル重合体を調製した。この（メタ）アクリル酸エステル重合体の重量平均分子量は７０万であった。この（メタ）アクリル酸エステル重合体を使用した以外は、実施例５と同様にしてアクリル系粘着剤組成物（Ｃ）を得た。また、アクリル系粘着剤組成物（Ｂ）に代えてアクリル系粘着剤組成物（Ｃ）を用いた以外は実施例５と同様にして剥離シート付き両面粘着シートを得た。 [Example 6]
In <Preparation of Acrylic Pressure-Sensitive Adhesive Composition>, 55 parts by mass of 2-ethylhexyl acrylate (2EHA), 40 parts by mass of 4-acryloylmorpholine (ACMO), and 5 parts by mass of acrylic acid (AA) are copolymerized. A (meth) acrylic acid ester polymer was prepared. The weight average molecular weight of this (meth) acrylic acid ester polymer was 700,000. An acrylic pressure-sensitive adhesive composition (C) was obtained in the same manner as in Example 5 except that this (meth) acrylic acid ester polymer was used. A release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 5, except that the acrylic pressure-sensitive adhesive composition (C) was used instead of the acrylic pressure-sensitive adhesive composition (B).
［実施例７］
　＜アクリル系粘着剤組成物の調製＞において、アクリル酸ｎ－ブチル（ＢＡ）２５質量部、アクリル酸－２－エチルヘキシル（２ＥＨＡ）５５質量部、ジエチルアクリルアミド（ＤＥＡＡ）５質量部、及び４－アクリロイルモロホリン（ＡＣＭＯ）５質量部を共重合させて、（メタ）アクリル酸エステル重合体を調製した。この（メタ）アクリル酸エステル重合体の重量平均分子量は１００万であった。この（メタ）アクリル酸エステル重合体を使用した以外は、実施例５と同様にしてアクリル系粘着剤組成物（Ｄ）を得た。また、アクリル系粘着剤組成物（Ｂ）に代えてアクリル系粘着剤組成物（Ｄ）を用いた以外は実施例５と同様にして剥離シート付き両面粘着シートを得た。 [Example 7]
In <Preparation of Acrylic Pressure-Sensitive Adhesive Composition>, 25 parts by mass of n-butyl acrylate (BA), 55 parts by mass of 2-ethylhexyl acrylate (2EHA), 5 parts by mass of diethyl acrylamide (DEAA), and 4-acryloyl A (meth) acrylic acid ester polymer was prepared by copolymerizing 5 parts by mass of moropholin (ACMO). The weight average molecular weight of this (meth) acrylic acid ester polymer was 1,000,000. An acrylic pressure-sensitive adhesive composition (D) was obtained in the same manner as in Example 5 except that this (meth) acrylic acid ester polymer was used. A release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 5, except that the acrylic pressure-sensitive adhesive composition (D) was used instead of the acrylic pressure-sensitive adhesive composition (B).
［実施例８］
　＜アクリル系粘着剤組成物の調製＞において、アクリル酸－２－エチルヘキシル（２ＥＨＡ）９０質量部、及びアクリル酸（ＡＡ）１０質量部を共重合させて、（メタ）アクリル酸エステル重合体を調製した。この（メタ）アクリル酸エステル重合体の重量平均分子量は５０万であった。得られた（メタ）アクリル酸エステル重合体１００質量部、エポキシ系架橋剤として１，３－ビス（Ｎ，Ｎ’－ジグリシジルアミノメチル）シクロヘキサン（三菱ガス化学社製、ＴＥＲＡＤ－Ｃ）０．０５質量部、水素引き抜き光開始剤として、４－メチルベンゾフェノン１．５質量部を混合し、十分攪拌して、固形分４０質量％となるように酢酸エチルで希釈することにより、アクリル系粘着剤組成物（Ｅ）を得た。アクリル系粘着剤組成物（Ｂ）に代えてアクリル系粘着剤組成物（Ｅ）を用いた以外は実施例５と同様にして剥離シート付き両面粘着シートを得た。その後、得られた剥離シート付き両面粘着シートに紫外線（高圧水銀）を積算光量が１０００ｍＪ／ｃｍ2となるように照射して、最終的に評価に用いる剥離シート付き両面粘着シートを得た。 [Example 8]
In <Preparation of Acrylic Pressure-Sensitive Adhesive Composition>, 90 parts by mass of 2-ethylhexyl acrylate (2EHA) and 10 parts by mass of acrylic acid (AA) are copolymerized to prepare a (meth) acrylic acid ester polymer did. The weight average molecular weight of this (meth) acrylic acid ester polymer was 500,000. 100 parts by mass of the (meth) acrylic acid ester polymer obtained, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, TERAD-C) 0 as an epoxy crosslinking agent 05 parts by mass, 1.5 parts by mass of 4-methylbenzophenone as a hydrogen extraction photoinitiator, sufficiently stirred, and diluted with ethyl acetate so that the solid content becomes 40% by mass, an acrylic adhesive A composition (E) was obtained. A release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 5, except that the acrylic pressure-sensitive adhesive composition (E) was used instead of the acrylic pressure-sensitive adhesive composition (B). Then, ultraviolet rays (high pressure mercury) were irradiated to the obtained double-sided pressure-sensitive adhesive sheet with a release sheet so that the integrated light amount was 1000 mJ / cm 2 to finally obtain a double-sided pressure-sensitive adhesive sheet with a release sheet used for evaluation.
［比較例１］
＜粘着積層体の作製＞
　（表面活性化処理）において、アクリル系粘着剤層及びシリコーン系粘着剤層のいずれにも表面活性化処理を行わなかった以外は実施例１と同様にして剥離シート付き両面粘着シートを得た。 Comparative Example 1
<Production of adhesive laminate>
In (Surface activation treatment), a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 1 except that the surface activation treatment was not performed on any of the acrylic pressure-sensitive adhesive layer and the silicone pressure-sensitive adhesive layer.
［比較例２］
＜粘着積層体の作製＞
　（表面活性化処理）において、アクリル系粘着剤層及びシリコーン系粘着剤層のいずれにも表面活性化処理を行わなかった以外は実施例５と同様にして剥離シート付き両面粘着シートを得た。 Comparative Example 2
<Production of adhesive laminate>
In (Surface activation treatment), a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 5, except that the surface activation treatment was not performed on any of the acrylic pressure-sensitive adhesive layer and the silicone pressure-sensitive adhesive layer.
（測定及び評価）
＜粘着力の測定＞
（アクリル系粘着剤層の粘着力）
　（アクリル系粘着剤層の作製）の作製で得られた片面に第１の剥離シートが貼着されたアクリル系粘着剤層の粘着面に易接着層付ポリエチレンテレフタレートフィルム（東洋紡製、Ａ４３００＃１００）を裏打ち基材として貼着した。第１の剥離シートを剥離し、アクリル系粘着剤層の粘着面をソーダガラスに貼着した。貼着後２４時間後に、ＪＩＳ　Ｚ　０２３７の方法１に準じて剥離速度３００ｍｍ／ｍｉｎ、剥離角度１８０°の条件で粘着力測定を行った。 (Measurement and evaluation)
<Measurement of adhesive strength>
(Adhesiveness of acrylic adhesive layer)
A polyethylene terephthalate film with an easy-to-adhere layer on an adhesive surface of an acrylic adhesive layer having a first release sheet attached on one side obtained in the preparation of an acrylic adhesive layer (Toyobo, A4300 # 100 ) As a backing substrate. The first release sheet was peeled off, and the pressure-sensitive adhesive surface of the acrylic pressure-sensitive adhesive layer was attached to soda glass. Twenty-four hours after the application, adhesion was measured according to method 1 of JIS Z 0237 under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °.
（シリコーン系粘着剤層の粘着力）
　第１の剥離シート／アクリル系粘着剤層／シリコーン系粘着剤層／第２の剥離シートがこの順で積層された剥離シート付き両面粘着シートの第１の剥離シートを剥離し、易接着層付ポリエチレンテレフタレートフィルム（東洋紡製、Ａ４３００＃１００）を裏打ち基材として貼着した。第２の剥離シートを剥離し、シリコーン系粘着剤層の粘着面をソーダガラスに貼着した。貼着後２４時間後に、ＪＩＳ　Ｚ　０２３７の方法１に準じて剥離速度３００ｍｍ／ｍｉｎ、剥離角度１８０°の条件で粘着力測定を行った。 (Adhesiveness of silicone pressure sensitive adhesive layer)
The first release sheet of a double-sided pressure-sensitive adhesive sheet with a release sheet on which a first release sheet / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / second release sheet are laminated in this order is peeled off. A polyethylene terephthalate film (Toyobo, A4300 # 100) was adhered as a backing substrate. The second release sheet was released, and the adhesive surface of the silicone-based pressure-sensitive adhesive layer was attached to soda glass. Twenty-four hours after the application, adhesion was measured according to method 1 of JIS Z 0237 under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °.
＜濡れ張力＞
　濡れ張力は、ＪＩＳ　Ｋ　６７６８　１９９９に準じて濡れ指示標準液（和光純薬製）を粘着層表面に塗布することで測定した。 <Wet tension>
The wetting tension was measured by applying a wetting indication standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) to the surface of the adhesive layer according to JIS K 6768 1999.
＜界面粘着力＞
［裏打ち用基材付き粘着テープの作製］
　アクリル酸ｎ－ブチル（ＢＡ）９０質量部およびアクリル酸（ＡＡ）１０質量部を共重合させて、（メタ）アクリル酸エステル重合体を調製した。この（メタ）アクリル酸エステル重合体の重量平均分子量は５０万であった。
　得られた（メタ）アクリル酸エステル重合体１００質量部、エポキシ系架橋剤として１，３－ビス（Ｎ，Ｎ’－ジグリシジルアミノメチル）シクロヘキサン（三菱ガス化学社製、ＴＥＲＡＤ－Ｃ）０．０５質量部、シランカップリング剤としてシリコーンアルコキシオリゴマー（信越化学（株）社製、Ｘ－４１-１８１０）５質量部を混合し、十分に撹拌して、固形分濃度が４０質量％となるように酢酸エチルで希釈することにより、裏打ち用基材付き粘着テープ用のアクリル系粘着剤組成物を得た。
　得られたアクリル系粘着剤組成物を、易接着層付ポリエチレンテレフタレートフィルム（東洋紡製Ａ４３００＃１００）の表面に、乾燥後の塗工量が２５μｍになるようにアプリケーターで均一に塗工し、１００℃の空気循環式恒温オーブンで３分間乾燥することで、裏打ち用基材付き粘着テープを得た。
［界面粘着力測定用サンプルの作製］
　実施例及び比較例で得た「第１の剥離シート／アクリル系粘着剤層／シリコーン系粘着剤層／第２の剥離シート」の「第１の剥離シート」を剥がし、アクリル系粘着剤層面に「易接着層付ポリエチレンテレフタレートフィルム（東洋紡製Ａ４３００＃１００）」を貼着した。このようにして得られた「易接着層付ポリエチレンテレフタレートフィルム／アクリル系粘着剤層／シリコーン系粘着剤層／第２の剥離シート」の「第２の剥離シート」を剥離して、濡れ張力が３４ｍＮ／ｍ以上となるとなるように、シリコーン系粘着層表面に春日電機製コロナ表面処理装置を用いて表面活性化処理を行った。さらに、裏打ち用基材付き粘着テープのアクリル系粘着剤層表面の濡れ張力が７３ｍＮ／ｍ以上となるとなるように春日電機製コロナ表面処理装置を用いて表面活性化処理を行った。
　次いで、「易接着層付ポリエチレンテレフタレートフィルム／アクリル系粘着剤層／シリコーン系粘着剤層」の表面活性化処理を行ったシリコーン粘着剤層面に、表面活性化処理を行った「裏打ち用基材付き粘着テープ」のアクリル粘着剤層面を貼着することで「易接着層付ポリエチレンテレフタレートフィルム／アクリル系粘着剤層／シリコーン系粘着剤層／裏打ち用基材付き粘着テープ」の構成を有する界面粘着力測定用サンプルを得た。
［界面粘着力測定］
　上記のようにして「易接着層付ポリエチレンテレフタレートフィルム／アクリル系粘着剤層／シリコーン系粘着剤層／裏打ち用基材付き粘着テープ」を得た２４時間後（表面活性化処理を行ったシリコーン粘着剤層面とアクリル粘着剤層面を貼着後２４時間後）に、裏打ち用基材付き粘着テープ側をＪＩＳ　Ｚ　０２３７の方法１に準じて剥離速度３００ｍｍ／ｍｉｎ、剥離角度１８０°の条件で剥離することで、「アクリル系粘着剤層／シリコーン系粘着剤層」界面の粘着力測定を行った。 <Interface adhesive force>
[Production of adhesive tape with backing substrate]
A (meth) acrylic acid ester polymer was prepared by copolymerizing 90 parts by mass of n-butyl acrylate (BA) and 10 parts by mass of acrylic acid (AA). The weight average molecular weight of this (meth) acrylic acid ester polymer was 500,000.
100 parts by mass of the (meth) acrylic acid ester polymer obtained, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, TERAD-C) 0 as an epoxy crosslinking agent Mix 05 parts by mass and 5 parts by mass of silicone alkoxy oligomer (X-41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and stir sufficiently to obtain a solid content concentration of 40% by mass The reaction mixture was diluted with ethyl acetate to obtain an acrylic pressure-sensitive adhesive composition for a backing-attached pressure-sensitive adhesive tape.
The resulting acrylic pressure-sensitive adhesive composition is uniformly coated on the surface of a polyethylene terephthalate film with an easy-adhesion layer (A4300 # 100 made by Toyobo Co., Ltd.) with an applicator so that the coated amount after drying is 25 μm, 100 By drying in an air circulating constant temperature oven for 3 minutes, an adhesive tape with a backing substrate was obtained.
[Preparation of sample for measuring interfacial adhesion force]
Peel off the "first release sheet" of the "first release sheet / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / second release sheet" obtained in Examples and Comparative Examples, and on the acrylic pressure-sensitive adhesive layer surface "A polyethylene terephthalate film with an easy adhesion layer (Toyobo Co., Ltd. A4300 # 100)" was attached. By peeling off the “second release sheet” of “the polyethylene terephthalate film with easy adhesion layer / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / second release sheet” obtained in this manner, the wet tension is The surface activation treatment was performed on the surface of the silicone-based pressure-sensitive adhesive layer using a corona surface treatment apparatus manufactured by Kasuga Denki in order to achieve 34 mN / m or more. Furthermore, the surface activation treatment was performed using a corona surface treatment apparatus made by Kasuga Electric Co., Ltd. so that the wet tension of the surface of the acrylic pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape with substrate for backing was 73 mN / m or more.
Next, with a backing substrate, the surface activation treatment was applied to the surface of the silicone adhesive layer that had been subjected to the surface activation treatment of “polyethylene terephthalate film with easy adhesion layer / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer”. Interfacial adhesive force with composition of “polyethylene terephthalate film with easy adhesion layer / acrylic pressure sensitive adhesive layer / silicone pressure sensitive adhesive layer / backing material with backing substrate” by sticking the acrylic pressure sensitive adhesive layer side of the pressure sensitive adhesive tape A sample for measurement was obtained.
[Interface adhesion measurement]
After 24 hours of obtaining "the polyethylene terephthalate film with an easy adhesion layer / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / backing pressure-sensitive adhesive tape" as described above (silicone adhesion subjected to surface activation treatment) On the adhesive tape side with a backing substrate on the adhesive layer side and the acrylic adhesive layer side after peeling and peeling at a peeling speed of 300 mm / min and a peeling angle of 180 ° according to method 1 of JIS Z 0237 Thus, the adhesion of the “acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer” interface was measured.
＜リワーク性の評価＞
　第１の剥離シート／アクリル系粘着剤層／シリコーン系粘着剤層／第２の剥離シートがこの順で積層された剥離シート付き両面粘着シートを２５×５０ｍｍ角に裁断した後、第１の剥離シートを剥離し、スライドガラス（松浪硝子製、Ｓ９１１２、サイズ７６×５２ｍｍ）をアクリル系粘着剤層に貼着（２ｋｇローラー１往復）した。その後、第２の剥離シートを剥離して、シリコーン系粘着剤層をソーダガラスに（松浪硝子製、Ｓ９１１２、サイズ７６×５２ｍｍ）に貼着した。このようにして得た両面ガラス板付両面粘着シートを万能型引張試験機（オリエンテック社製、テンシロンＵＴＭ－４－１００）にセットし、ＪＩＳ　Ｚ　０２３７に準じて、剥離速度３００ｍｍ／ｍｉｎ、剥離角度９０°の条件（上方への剥離）でシリコーン系粘着剤層をスライドガラスから剥離し、下記基準に基づき評価した。
「優」：シリコーン系粘着剤層をスライドガラスへ貼着後、４０℃、相対湿度９０％の環境にて２４０時間放置し、その後に剥離したときスライドガラス表面に粘着剤層が残っていない。
「良」：シリコーン系粘着剤層をスライドガラスへ貼着後、４０℃、相対湿度９０％の環境にて２４時間放置し、その後に剥離したときスライドガラス表面に粘着剤層が残っていない。但し、４０℃、相対湿度９０％の環境にて２４０時間放置し、その後に剥離したときスライドガラス表面に粘着剤層が残る。
「可」：シリコーン系粘着剤層をソーダガラスへ貼着後、２３℃、相対湿度５０％の環境にて３０分間放置し、その後に剥離したときスライドガラス表面に粘着剤層が残っていない。但し、４０℃、相対湿度９０％の環境にて２４時間放置し、その後に剥離したときスライドガラス表面に粘着剤層が残る。
「不可」：シリコーン系粘着剤層をソーダガラスへ貼着後、２３℃、相対湿度５０％の環境にて３０分間放置し、その後に剥離したときスライドガラス表面に粘着剤層が残る。 <Evaluation of reworkability>
The first peelable sheet is obtained by cutting a double-sided pressure-sensitive adhesive sheet with a release sheet on which a first release sheet / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / second release sheet are laminated in this order into 25 × 50 mm square The sheet was peeled off, and a slide glass (manufactured by Matsunami Glass, S9112, size 76 × 52 mm) was attached to the acrylic pressure-sensitive adhesive layer (2 kg roller, 1 reciprocation). Thereafter, the second release sheet was removed, and the silicone-based pressure-sensitive adhesive layer was attached to soda glass (manufactured by Matsunami Glass, S9112, size 76 × 52 mm). The double-sided pressure-sensitive adhesive sheet with a double-sided glass plate thus obtained is set in a universal type tensile tester (Tensilon UTM-4-100, manufactured by Orientec Co., Ltd.), peeling speed 300 mm / min, peeling angle according to JIS Z 0237 The silicone-based pressure-sensitive adhesive layer was peeled from the slide glass under the condition of 90 ° (peeling upward) and evaluated based on the following criteria.
"Excellent": After adhering the silicone-based pressure-sensitive adhesive layer to a slide glass, it is left in an environment of 40 ° C and a relative humidity of 90% for 240 hours, and when peeled off thereafter, no pressure-sensitive adhesive layer remains on the slide glass surface.
"Good": After adhering the silicone-based pressure-sensitive adhesive layer to a slide glass, it is left in an environment of 40 ° C and a relative humidity of 90% for 24 hours, and when peeled off thereafter, no pressure-sensitive adhesive layer remains on the slide glass surface. However, when left in an environment of 40 ° C. and relative humidity 90% for 240 hours and then peeled off, an adhesive layer remains on the surface of the slide glass.
"Poor": After adhering the silicone-based pressure-sensitive adhesive layer to soda glass, it is left in an environment of 23 ° C and a relative humidity of 50% for 30 minutes, and when peeled off thereafter, no pressure-sensitive adhesive layer remains on the slide glass surface. However, when left in an environment of 40 ° C. and relative humidity 90% for 24 hours and then peeled off, an adhesive layer remains on the surface of the slide glass.
"Poor": After adhering the silicone-based pressure-sensitive adhesive layer to soda glass, it is left for 30 minutes in an environment of 23 ° C and a relative humidity of 50%, and when peeled off thereafter, the pressure-sensitive adhesive layer remains on the slide glass surface.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例で得られた両面粘着シートにおいて、アクリル系粘着剤層はガラスに対して強固な粘着力を発揮しており、かつシリコーン系粘着剤層はリワーク性に優れていた。一方、比較例で得られた両面粘着シートにおいては、リワークする際に粘着剤層が被着材に残っていた。 In the double-sided pressure-sensitive adhesive sheet obtained in the examples, the acrylic pressure-sensitive adhesive layer exhibited strong adhesion to glass, and the silicone-based pressure-sensitive adhesive layer was excellent in reworkability. On the other hand, in the double-sided pressure-sensitive adhesive sheet obtained in the comparative example, the pressure-sensitive adhesive layer remained on the adherend when reworking.
［実施例１０１］
＜アクリル系粘着剤組成物の調製＞
　アクリル酸ｎ－ブチル４０質量部、アクリル酸-２-エチルヘキシル５５質量部、およびアクリル酸５質量部を共重合させて、アクリル共重合体を調製した。このアクリル共重合体の重量平均分子量は１００万であった。 [Example 101]
<Preparation of Acrylic Pressure-Sensitive Adhesive Composition>
An acrylic copolymer was prepared by copolymerizing 40 parts by mass of n-butyl acrylate, 55 parts by mass of 2-ethylhexyl acrylate, and 5 parts by mass of acrylic acid. The weight average molecular weight of this acrylic copolymer was 1,000,000.
　得られたアクリル共重合体１００質量部、エポキシ系架橋剤として１，３－ビス（Ｎ，Ｎ’－ジグリシジルアミノメチル）シクロヘキサン（三菱ガス化学社製、ＴＥＲＡＤ－Ｃ）０．０５質量部、シランカップリング剤としてシリコーンアルコキシオリゴマー（信越化学（株）社製、Ｘ－４１-１８１０）０．１５質量部を混合し、十分に撹拌して、固形分濃度が４０質量％となるように酢酸エチルで希釈することにより、アクリル系粘着剤組成物（Ａ）を得た。 100 parts by mass of the obtained acrylic copolymer, 0.05 parts by mass of 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, TERAD-C) as an epoxy-based crosslinking agent, As a silane coupling agent, 0.15 parts by mass of silicone alkoxy oligomer (X-41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed and sufficiently stirred to give a solid content concentration of 40% by mass. By diluting with ethyl, an acrylic pressure-sensitive adhesive composition (A) was obtained.
＜シリコーン系粘着剤組成物の調製＞
　シロキサン結合を主骨格としビニル基を有するオルガノポリシロキサン及びオルガノハイドロジェンポリシロキサンからなる付加型オルガノポリシロキサン（信越化学工業（株）製、ＫＳ－８４７Ｈ）１００質量部（固形分換算値；以下同じ）、３官能性又は４官能性のシロキサン単位を含むオルガノポリシロキサン（シリコーンレジン；東レダウコーニング社製、ＳＤ－４５８４）２０質量部、白金触媒（東レダウコーニング社製、ＳＲＸ－２１２）１．５質量部を混合し、十分に撹拌して、固形分濃度が４０質量％となるようにメチルエチルケトンで希釈することにより、シリコーン系粘着剤組成物を得た。 <Preparation of Silicone-Based Pressure-Sensitive Adhesive Composition>
100 parts by mass (solids equivalent value; the same as the solid content; the same as the addition type organopolysiloxane (Shin-Etsu Chemical Co., Ltd. product KS-847H) consisting of an organopolysiloxane having a siloxane bond as a main skeleton and having a vinyl group and an organohydrogenpolysiloxane 20 parts by mass of an organopolysiloxane containing a trifunctional or tetrafunctional siloxane unit (silicone resin; manufactured by Toray Dow Corning, SD-4584), a platinum catalyst (manufactured by Toray Dow Corning, SRX-212). The silicone-based pressure-sensitive adhesive composition was obtained by mixing 5 parts by mass, sufficiently stirring, and diluting with methyl ethyl ketone so that the solid content concentration was 40% by mass.
＜両面粘着シートの作製＞
（アクリル系粘着剤層の作製）
　アクリル系粘着剤組成物（Ａ）を、シリコーン系剥離剤で処理された剥離剤層を備えた厚さ３８μｍのポリエチレンテレフタレートフィルム（セパレータフィルム）（王子エフテックス社製、３８ＲＬ－０７（２））の表面に、乾燥後の塗工量が５０μｍになるようにアプリケーターで均一に塗工し、１００℃の空気循環式恒温オーブンで３分間乾燥することで、片面に第１の剥離シートが貼着されたアクリル系粘着剤層を得た。片面に第１の剥離シートが貼着された粘着剤層を２３℃、相対湿度５０％の環境にて７日間養生を行った。 <Preparation of double-sided adhesive sheet>
(Preparation of acrylic pressure-sensitive adhesive layer)
A 38 μm thick polyethylene terephthalate film (separator film) having a release agent layer treated with a silicone-based release agent (acrylic acid-based adhesive composition (A) (manufactured by Oji F-TEX, 38RL-07 (2)) The first release sheet is attached to one side by uniformly coating the surface with an applicator so that the coated amount after drying is 50 μm and drying in an air circulating constant temperature oven at 100 ° C. for 3 minutes. The obtained acrylic adhesive layer was obtained. The pressure-sensitive adhesive layer having the first release sheet attached to one side was aged for 7 days in an environment of 23 ° C. and 50% relative humidity.
（シリコーン系粘着剤層の作製）
　シリコーン系粘着剤組成物を、厚さ３８μｍのポリエチレンテレフタレートフィルム（東レ社製、ルミラーＳ－１０＃３８）の表面に、乾燥後の塗工量が５０μｍになるようにアプリケーターで均一に塗工し、１００℃の空気循環式恒温オーブンで３分間乾燥することで、片面に第２の剥離シートが貼着されたシリコーン系粘着剤層を得た。 (Preparation of silicone pressure sensitive adhesive layer)
Apply a silicone-based pressure-sensitive adhesive composition uniformly on the surface of a 38 μm-thick polyethylene terephthalate film (Lumirror S-10 # 38, manufactured by Toray Industries, Inc.) with an applicator so that the coated amount after drying is 50 μm. By drying in an air circulating constant temperature oven at 100 ° C. for 3 minutes, a silicone-based pressure-sensitive adhesive layer in which the second release sheet was attached to one side was obtained.
（表面活性化処理）
　シリコーン系粘着剤層の表面にコロナ放電処理を施した。コロナ放電処理は、春日電機製のコロナ表面処理装置を用いて行った。コロナ放電処理はシリコーン系粘着剤層の濡れ張力が３０ｍＮ／ｍ以上となる条件で行った。 (Surface activation treatment)
The surface of the silicone pressure-sensitive adhesive layer was subjected to corona discharge treatment. The corona discharge treatment was performed using a corona surface treatment apparatus made by Kasuga Denki. The corona discharge treatment was performed under the condition that the wet tension of the silicone pressure-sensitive adhesive layer was 30 mN / m or more.
（剥離シート付き両面粘着シートの作製）
　アクリル系粘着剤層に、表面活性化処理を行ったシリコーン系粘着剤層の表面活性化処理面を貼り合せることで、第１の剥離シート／アクリル系粘着剤層／シリコーン系粘着剤層／第２の剥離シートがこの順で積層された剥離シート付き両面粘着シートを得た。 (Preparation of double-sided PSA sheet with release sheet)
The first release sheet / acrylic pressure-sensitive adhesive layer / silicone pressure-sensitive adhesive layer / first by bonding the surface activation-treated surface of the silicone pressure-sensitive adhesive layer subjected to the surface activation treatment to the acrylic pressure-sensitive adhesive layer A two-sided pressure-sensitive adhesive sheet with a release sheet in which the two release sheets were laminated in this order was obtained.
［実施例１０２］
　アクリル酸ｎ－ブチル４０質量部、アクリル酸-２-ヒドロキシエチル３０質量部、アクリル酸-２-エチルヘキシル２５質量部、およびアクリル酸５質量部を共重合させて、アクリル共重合体を調製した以外は、実施例１０１と同様にして剥離シート付き両面粘着シートを得た。なお、得られたアクリル共重合体の重量平均分子量は１５０万であった。 [Embodiment 102]
Except that 40 parts by mass of n-butyl acrylate, 30 parts by mass of 2-hydroxyethyl acrylate, 25 parts by mass of 2-ethylhexyl acrylate and 5 parts by mass of acrylic acid were copolymerized to prepare an acrylic copolymer In the same manner as in Example 101, a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained. The weight average molecular weight of the obtained acrylic copolymer was 1.5 million.
［実施例１０３］
　アクリル酸ｎ－ブチル４０質量部、アクリル酸-２-メトキシエチル３０質量部、アクリル酸-２-エチルヘキシル２５質量部、およびアクリル酸５質量部を共重合させて、アクリル共重合体を調製した以外は、実施例１０１と同様にして剥離シート付き両面粘着シートを得た。なお、得られたアクリル共重合体の重量平均分子量は１５０万であった。 [Embodiment 103]
40 parts by mass of n-butyl acrylate, 30 parts by mass of 2-methoxyethyl acrylate, 25 parts by mass of 2-ethylhexyl acrylate and 5 parts by mass of acrylic acid were copolymerized to prepare an acrylic copolymer In the same manner as in Example 101, a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained. The weight average molecular weight of the obtained acrylic copolymer was 1.5 million.
［実施例１０４］
　シリコーン系粘着剤層に施した表面活性化処理を、コロナ放電処理からプラズマ放電処理に変更した以外は、実施例１０１と同様にして剥離シート付き両面粘着シートを得た。なお、プラズマ放電処理はシリコーン系粘着剤層の濡れ張力が３０ｍＮ／ｍ以上となる条件で行った。 [Embodiment 104]
A release sheet-included double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 101, except that the surface activation treatment applied to the silicone-based pressure-sensitive adhesive layer was changed from corona discharge treatment to plasma discharge treatment. The plasma discharge treatment was performed under the condition that the wetting tension of the silicone-based pressure-sensitive adhesive layer was 30 mN / m or more.
［比較例１０１］
　アクリル酸-２-エチルヘキシル５５質量部、メタクリル酸メチル４０質量部、およびアクリル酸５質量部を共重合させて、アクリル共重合体を調製した以外は、実施例１０１と同様にして剥離シート付き両面粘着シートを得た。なお、得られたアクリル共重合体の重量平均分子量は５０万であった。 Comparative Example 101
Both sides with a release sheet were prepared in the same manner as in Example 101 except that 55 parts by mass of 2-ethylhexyl acrylate, 40 parts by mass of methyl methacrylate and 5 parts by mass of acrylic acid were copolymerized to prepare an acrylic copolymer. An adhesive sheet was obtained. In addition, the weight average molecular weight of the obtained acrylic copolymer was 500,000.
［比較例１０２］
　アクリル酸ｎ－ブチル１０質量部、アクリル酸-２-エチルヘキシル５５質量部、メタクリル酸メチル３０質量部、およびアクリル酸５質量部を共重合させて、アクリル共重合体を調製した以外は、実施例１０１と同様にして剥離シート付き両面粘着シートを得た。なお、得られたアクリル共重合体の重量平均分子量は１００万であった。 [Comparative Example 102]
10 parts by mass of n-butyl acrylate, 55 parts by mass of 2-ethylhexyl acrylate, 30 parts by mass of methyl methacrylate and 5 parts by mass of acrylic acid were copolymerized to prepare an acrylic copolymer In the same manner as in 101, a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained. The weight average molecular weight of the obtained acrylic copolymer was 1,000,000.
（測定及び評価）
　＜粘着力の測定＞、＜濡れ張力＞、＜界面粘着力＞、＜リワーク性の評価＞について、上述した方法と同様の方法で行った。 (Measurement and evaluation)
About <measurement of adhesive force>, <wetting tension>, <interface adhesive force>, and <evaluation of rework property>, it carried out by the method similar to the method mentioned above.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例で得られた両面粘着シートにおいて、アクリル系粘着剤層はガラスに対して強固な粘着力を発揮しており、かつシリコーン系粘着剤層はリワーク性に優れていた。一方、比較例で得られた両面粘着シートにおいては、リワークする際に粘着剤層が被着材に残っていた。
　また、実施例で得られた両面粘着シートは曲面追従性や段差追従性にも優れていた。 In the double-sided pressure-sensitive adhesive sheet obtained in the examples, the acrylic pressure-sensitive adhesive layer exhibited strong adhesion to glass, and the silicone-based pressure-sensitive adhesive layer was excellent in reworkability. On the other hand, in the double-sided pressure-sensitive adhesive sheet obtained in the comparative example, the pressure-sensitive adhesive layer remained on the adherend when reworking.
In addition, the double-sided pressure-sensitive adhesive sheet obtained in the examples was also excellent in curved surface followability and step followability.
１０   アクリル系粘着剤層
１２   シリコーン系粘着剤層
１００ 両面粘着シート 10 acrylic adhesive layer 12 silicone adhesive layer 100 double-sided adhesive sheet

Claims (16)

  1. 　アクリル系粘着剤層と、
    　前記アクリル系粘着剤層に直接積層されたシリコーン系粘着剤層と、を有し、
    　前記アクリル系粘着剤層と前記シリコーン系粘着剤層の界面粘着力が１Ｎ／２５ｍｍ以上である両面粘着シート。     Acrylic adhesive layer,
    A silicone-based pressure-sensitive adhesive layer directly laminated on the acrylic pressure-sensitive adhesive layer,
    The double-sided pressure-sensitive adhesive sheet in which the interfacial adhesion between the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer is 1 N / 25 mm or more.
  2. 　前記アクリル系粘着剤層は、アクリル酸ブチルに由来する単位を含むアクリル共重合体を有し、
    　前記アクリル酸ブチルに由来する単位の含有量は、前記アクリル共重合体の全質量に対して、３０質量％以上である請求項１に記載の両面粘着シート。     The acrylic pressure-sensitive adhesive layer has an acrylic copolymer including a unit derived from butyl acrylate,
    The double-sided pressure-sensitive adhesive sheet according to claim 1, wherein the content of the unit derived from butyl acrylate is 30% by mass or more with respect to the total mass of the acrylic copolymer.
  3. 　前記アクリル共重合体は、アクリル酸－２－ヒドロキシエチルに由来する単位をさらに含み、前記アクリル酸－２－ヒドロキシエチルに由来する単位の含有量は、前記アクリル共重合体の全質量に対して、１０質量％以上５０質量％以下である請求項２に記載の両面粘着シート。 The acrylic copolymer further includes a unit derived from 2-hydroxyethyl acrylate, and the content of the unit derived from 2-hydroxyethyl acrylate is relative to the total mass of the acrylic copolymer. The double-sided pressure-sensitive adhesive sheet according to claim 2, which is 10% by mass or more and 50% by mass or less.
  4. 　前記アクリル共重合体は、アクリル酸－２－メトキシエチルに由来する単位をさらに含み、前記アクリル酸－２－メトキシエチルに由来する単位の含有量は、前記アクリル共重合体の全質量に対して、１０質量％以上５０質量％以下である請求項２に記載の両面粘着シート。 The acrylic copolymer further includes a unit derived from 2-methoxyethyl acrylate, and the content of the unit derived from 2-methoxyethyl acrylate is relative to the total mass of the acrylic copolymer. The double-sided pressure-sensitive adhesive sheet according to claim 2, which is 10% by mass or more and 50% by mass or less.
  5. 　前記アクリル共重合体は、アクリル酸-２-エチルヘキシルに由来する単位及びアクリル酸に由来する単位から選択される少なくとも１種をさらに含む請求項２～４のいずれか１項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 2 to 4, wherein the acrylic copolymer further contains at least one selected from a unit derived from 2-ethylhexyl acrylate and a unit derived from acrylic acid. .
  6. 　前記アクリル系粘着剤層の界面側の表面及び前記シリコーン系粘着剤層の界面側の表面から選択される少なくとも一方は、表面活性化処理面である請求項１～５のいずれか１項に記載の両面粘着シート。 The surface activation treatment surface according to any one of claims 1 to 5, wherein at least one selected from the surface on the interface side of the acrylic pressure-sensitive adhesive layer and the surface on the interface side of the silicone-based pressure-sensitive adhesive layer is a surface activation treated surface. Double-sided adhesive sheet.
  7. 　前記アクリル系粘着剤層の界面側の表面が表面活性化処理面であり、前記表面活性化処理面の濡れ張力が７０ｍＮ／ｍ以上である請求項１～６のいずれか１項に記載の両面粘着シート。 The surface on the interface side of the acrylic pressure-sensitive adhesive layer is a surface activation treated surface, and the wetting tension of the surface activation treated surface is 70 mN / m or more. Adhesive sheet.
  8. 　前記シリコーン系粘着剤層の界面側の表面が表面活性化処理面であり、前記表面活性化処理面の濡れ張力が３０ｍＮ／ｍ以上である請求項１～７のいずれか１項に記載の両面粘着シート。 The surface on the interface side of the silicone-based pressure-sensitive adhesive layer is a surface activation treated surface, and the wetting tension of the surface activation treated surface is 30 mN / m or more. Adhesive sheet.
  9. 　前記アクリル系粘着剤層は、シランカップリング剤を含み、
    　前記シランカップリング剤の含有量は、前記アクリル系粘着剤層の全質量に対して０．０３質量％以上５質量％以下である請求項１～８のいずれか１項に記載の両面粘着シート。     The acrylic pressure-sensitive adhesive layer contains a silane coupling agent,
    The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 8, wherein the content of the silane coupling agent is 0.03% by mass or more and 5% by mass or less based on the total mass of the acrylic pressure-sensitive adhesive layer. .
  10. 　前記アクリル系粘着剤層は、窒素含有単量体に由来する単位を含むアクリル重合体を含み、前記窒素含有単量体に由来する単位の含有量は、前記アクリル重合体の全質量に対して５質量％以上７０質量％以下である請求項１～９のいずれか１項に記載の両面粘着シート。 The acrylic pressure-sensitive adhesive layer contains an acrylic polymer containing a unit derived from a nitrogen-containing monomer, and the content of the unit derived from the nitrogen-containing monomer is relative to the total mass of the acrylic polymer The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 9, which is 5% by mass or more and 70% by mass or less.
  11. 　前記アクリル系粘着剤層は、水素引抜型重合開始剤を含み、前記水素引抜型重合開始剤の含有量は、前記アクリル系粘着剤層の全質量に対して０．０５質量％以上１０質量％以下である請求項１～１０のいずれか１項に記載の両面粘着シート。 The acrylic pressure-sensitive adhesive layer contains a hydrogen extraction-type polymerization initiator, and the content of the hydrogen extraction-type polymerization initiator is 0.05% by mass or more and 10% by mass with respect to the total mass of the acrylic pressure-sensitive adhesive layer The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 10, which is the following.
  12. 　前記水素引抜型重合開始剤が、光重合開始剤である請求項１１に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to claim 11, wherein the hydrogen extraction type polymerization initiator is a photopolymerization initiator.
  13. 　前記アクリル系粘着剤層の対ガラス粘着力が１Ｎ／２５ｍｍ以上である請求項１～１２のいずれか１項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 12, wherein the adhesion to glass of the acrylic pressure-sensitive adhesive layer is 1 N / 25 mm or more.
  14. 　前記アクリル系粘着剤層の対ガラス粘着力が３０Ｎ／２５ｍｍ以下であるである請求項１３に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to claim 13, wherein the adhesion to glass of the acrylic pressure-sensitive adhesive layer is 30 N / 25 mm or less.
  15. 　前記シリコーン系粘着剤層の対ガラス粘着力が０．００５Ｎ／２５ｍｍ以上１Ｎ／２５ｍｍ以下である請求項１～１４のいずれか１項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 14, wherein the adhesion to glass of the silicone-based pressure-sensitive adhesive layer is from 0.005 N / 25 mm to 1 N / 25 mm.
  16. 　請求項１～１５のいずれか１項に記載の両面粘着シートの両面に剥離シートを備えた剥離シート付き両面粘着シート。 A release sheet-included double-sided pressure-sensitive adhesive sheet comprising release sheets on both sides of the double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 15.
PCT/JP2019/001438 2018-01-18 2019-01-18 Double-sided adhesive sheet and double-sided adhesive sheet with release sheet WO2019142905A1 (en)

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