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WO2020027038A1 - Feuille adhésive double face à feuille de protection amovible et procédé de production de ladite feuille adhésive - Google Patents

Feuille adhésive double face à feuille de protection amovible et procédé de production de ladite feuille adhésive Download PDF

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Publication number
WO2020027038A1
WO2020027038A1 PCT/JP2019/029623 JP2019029623W WO2020027038A1 WO 2020027038 A1 WO2020027038 A1 WO 2020027038A1 JP 2019029623 W JP2019029623 W JP 2019029623W WO 2020027038 A1 WO2020027038 A1 WO 2020027038A1
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Prior art keywords
sensitive adhesive
pressure
adhesive layer
sheet
release sheet
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Ceased
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PCT/JP2019/029623
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English (en)
Japanese (ja)
Inventor
滋呂 清水
信幸 岩崎
錦織　義治
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Oji Holdings Corp
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Oji Holdings Corp
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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
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners

Definitions

  • the present invention relates to a double-sided PSA sheet with a release sheet and a method for producing a double-sided PSA sheet with a release sheet.
  • LCDs liquid crystal displays
  • image display devices combining display devices such as touch panels and input devices
  • a double-sided pressure-sensitive adhesive sheet is used for bonding optical members.
  • a double-sided pressure-sensitive adhesive sheet is sometimes used for bonding different adherends.
  • the double-sided pressure-sensitive adhesive sheet is required to have an optimum pressure-sensitive adhesive force according to the adhesion characteristics 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 pressure-sensitive adhesive properties.
  • Patent Document 3 discloses a double-sided pressure-sensitive adhesive sheet that has at least two pressure-sensitive adhesive layers and is configured to be removable from a display surface of a display device.
  • the pressure-sensitive adhesive layers are formed from different types of acrylic polymers, and studies are being made to improve the durability and reworkability of the double-sided pressure-sensitive adhesive sheet.
  • the double-sided pressure-sensitive adhesive sheet of Patent Document 3 is intended for attaching a display surface and a touch panel.
  • the double-sided pressure-sensitive adhesive sheet according to the related art is peeled off from the adherend, there is a problem that the pressure-sensitive adhesive remains on the adherend during the rework operation.
  • 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 the rework operation takes time and effort.
  • a protective sheet that can be bonded and reworked by ordinary consumers who cannot use special equipment, jigs, and chemicals must be easily reworked from the display surface. The adhesion must be extremely low.
  • the double-sided pressure-sensitive adhesive sheet used for the protective sheet needs to firmly adhere to the object to be attached on the side opposite to the display surface.
  • a double-sided pressure-sensitive adhesive sheet provided with a base film between a slight pressure-sensitive adhesive layer and a strong pressure-sensitive adhesive layer is used. I have.
  • a double-sided pressure-sensitive adhesive sheet having a base film provided between a slight pressure-sensitive adhesive layer and a strong pressure-sensitive adhesive layer tends to increase in thickness, and cannot meet recent demands for thinning or has a high level of transparency. There was a problem that it could not be achieved.
  • the present inventor has proceeded with the development of a double-sided PSA sheet in which a base film is not provided between the slightly adhesive layer and the strongly adhesive layer.
  • a release sheet is provided on both surfaces of such a double-sided pressure-sensitive adhesive sheet, since the release sheet on the fine pressure-sensitive adhesive layer side peels off first, it is difficult to peel off the release sheet on the strong pressure-sensitive adhesive layer side first.
  • an object of the present invention is to provide a double-sided pressure-sensitive adhesive sheet with a release sheet that is excellent in workability of the double-sided pressure-sensitive adhesive sheet and has good air bleedability on the side of the fine pressure-sensitive adhesive layer in order to solve the above problems. That is, the present invention is a double-sided pressure-sensitive adhesive sheet with a release sheet that is easy to process because the release order of the release sheet is not limited (the release sheet on the side of the strong adhesive layer can be released first). An object of the present invention is to provide a double-sided pressure-sensitive adhesive sheet with a release sheet, which can suppress air entrapment because air is easily released when the air-permeable sheet is adhered to an adherend.
  • the present inventors have found that a first release sheet, a first pressure-sensitive adhesive layer, a second pressure-sensitive adhesive layer, and a second release sheet are laminated in this order.
  • the double-sided pressure-sensitive adhesive sheet provided with the release sheet the peeling force at the time of peeling the second release sheet from the slightly pressure-sensitive second pressure-sensitive adhesive layer, the first release sheet from the strong pressure-sensitive first pressure-sensitive adhesive layer.
  • the present invention has the following configuration.
  • the second pressure-sensitive adhesive layer is directly laminated on the first pressure-sensitive adhesive layer
  • the first pressure-sensitive adhesive layer has a glass adhesive strength of 10 to 1000 times the glass adhesive strength of the second pressure-sensitive adhesive layer
  • a double-sided pressure-sensitive adhesive sheet with a release sheet wherein the release force at the time of peeling the second release sheet from the second pressure-sensitive adhesive layer is greater than the release force at the time of peeling the first release sheet from the first pressure-sensitive adhesive layer.
  • [7] forming a first pressure-sensitive adhesive layer on the first release sheet, and forming a second pressure-sensitive adhesive layer on the second release sheet; Laminating the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer so as to be in contact with each other, a method for producing a double-sided pressure-sensitive adhesive sheet with a release sheet,
  • the first pressure-sensitive adhesive layer has a glass adhesive strength of 10 to 1000 times the glass adhesive strength of the second pressure-sensitive adhesive layer,
  • a double-sided pressure-sensitive adhesive sheet with a release sheet which is excellent in workability and has good air bleeding property on the slightly pressure-sensitive adhesive layer side.
  • FIG. 1 is a cross-sectional view illustrating a configuration of a double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention.
  • the present invention relates to a double-sided PSA sheet with a release sheet in which a first release sheet, a first PSA layer, a second PSA layer, and a second release sheet are laminated in this order.
  • the second pressure-sensitive adhesive layer is directly laminated on the first pressure-sensitive adhesive layer, and the first pressure-sensitive adhesive layer has a glass adhesive strength of the second pressure-sensitive adhesive layer with respect to glass adhesive strength. It is 10 to 1000 times.
  • the peeling force when peeling the second release sheet from the second pressure-sensitive adhesive layer is greater than the peeling force when peeling the first release sheet from the first pressure-sensitive adhesive layer. Since the double-sided pressure-sensitive adhesive sheet composed of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer has a plurality of pressure-sensitive adhesive layers, it can be called a double-sided laminated pressure-sensitive adhesive sheet.
  • the double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention has the above configuration, it is excellent in workability.
  • excellent workability means that the release order of the release sheet is not limited, that is, that the release sheet on the strong adhesive layer side can be released first, and therefore, from the double-sided adhesive sheet with a release sheet. It means that it is easy to manufacture various laminates by peeling at least one release sheet.
  • the first release sheet attached to the first pressure-sensitive adhesive layer, which is strongly adhered is in a state where it is easily released first, so the first release sheet on the first pressure-sensitive adhesive layer side.
  • a glass sheet is bonded on the first pressure-sensitive adhesive layer side, and the glass sheet, the first pressure-sensitive adhesive layer, and the second A laminate in which the pressure-sensitive adhesive layer and the second release sheet are bonded in this order can be easily manufactured.
  • Such a laminate is preferably used, for example, as a surface protection sheet for a liquid crystal display.
  • the second pressure-sensitive adhesive layer when the second pressure-sensitive adhesive layer is bonded to an adherend after the second release sheet of the double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention is peeled off, the second pressure-sensitive adhesive layer and the adherend are adhered. Air (bubbles) is prevented from being caught between them. That is, the second pressure-sensitive adhesive layer has excellent air bleeding property, and no air bubbles remain at the interface between the second pressure-sensitive adhesive layer and the adherend when the second pressure-sensitive adhesive layer is adhered to the adherend. .
  • a second release sheet is used in order to increase the peeling force between the second pressure-sensitive adhesive layer and the second release sheet (enhance the adhesion). Since the release property of the second pressure-sensitive adhesive layer is controlled, the air release property of the second pressure-sensitive adhesive layer is not impaired. That is, the present invention has succeeded in achieving two contradictory characteristics such as workability and air bleedability.
  • FIG. 1 is a cross-sectional view illustrating the configuration of the double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention.
  • the double-sided pressure-sensitive adhesive sheet 100 with a release sheet of the present invention has a first pressure-sensitive adhesive layer 10 and a second pressure-sensitive adhesive layer 12, and a first release sheet is provided on the first pressure-sensitive adhesive layer 10 side. 20 are laminated, and a second release sheet 22 is laminated on the second pressure-sensitive adhesive layer 12 side.
  • the first pressure-sensitive adhesive layer 10 and the second pressure-sensitive adhesive layer 12 are referred to as a double-sided pressure-sensitive adhesive sheet.
  • the double-sided pressure-sensitive adhesive sheet 50 preferably has a configuration in which a first pressure-sensitive adhesive layer 10 and a second pressure-sensitive adhesive layer 12 are laminated one by one, but includes two or more layers. There may be.
  • the first pressure-sensitive adhesive layer 10 shown as a one-layer configuration in FIG. 1 may have a laminated structure of two or more pressure-sensitive adhesive layers
  • the second pressure-sensitive adhesive layer 12 may have a two-layer structure. It may have a laminated structure of the above pressure-sensitive adhesive layers.
  • the double-sided pressure-sensitive adhesive sheet 50 is a double-sided pressure-sensitive adhesive sheet having no support (substrate) as shown in FIG. Therefore, in the double-sided pressure-sensitive adhesive sheet 50, the first pressure-sensitive adhesive layer 10 and the second pressure-sensitive adhesive layer 12 are laminated in a state of being in direct contact with each other. For this reason, the double-sided pressure-sensitive adhesive sheet can be made thinner as necessary.
  • the adhesive strength to glass of the first pressure-sensitive adhesive layer constituting the double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention may be at least 10 times the adhesive strength to glass of the second adhesive layer, and is 50 times or more. And more preferably 100 times or more. Further, the adhesive strength to glass of the first pressure-sensitive adhesive layer may be 1000 times or less, more preferably 600 times or less, of the second pressure-sensitive adhesive layer. Thus, it can be said that the first pressure-sensitive adhesive layer is a strong pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is a slight pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer firmly adheres to an adherend such as glass by making the above-mentioned relationship between the first pressure-sensitive adhesive layer's adhesive strength to glass and the second adhesive layer's adhesive strength to glass.
  • an adherend such as glass
  • the first pressure-sensitive adhesive layer has an adhesive strength to glass of preferably 1 N / 25 mm or more, more preferably 5 N / 25 mm or more, even more preferably 10 N / 25 mm or more. Further, the first pressure-sensitive adhesive layer preferably has an adhesive strength to glass of 50 N / 25 mm or less.
  • the second pressure-sensitive adhesive layer has a pressure-sensitive adhesive strength to glass of 0.01 N / 25 mm or more. Further, the adhesive force to glass of the second pressure-sensitive adhesive layer is preferably 1.5 / 25 mm or less, more preferably 0.5 N / 25 mm or less, and preferably 0.2 N / 25 mm or less. Particularly preferred.
  • the adhesive strength to glass of the double-sided pressure-sensitive adhesive sheet was determined by applying the pressure-sensitive adhesive layer of each pressure-sensitive adhesive layer to soda glass, and after 24 hours, a peeling rate of 300 mm / min and a peeling angle in accordance with JIS Z0237 Method 1. This is a value measured under the condition of 180 °.
  • the second PSA layer is directly laminated on the first PSA layer. It is preferable that the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are firmly adhered to each other, and the interface pressure between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is 1 N / 25 mm or more. Is preferably 5 N / 25 mm or more, and more preferably 10 N / 25 mm or more.
  • the upper limit of the interfacial adhesion between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is not particularly limited, but is preferably, for example, 100 N / 25 mm.
  • the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are firmly adhered to each other and have excellent interlayer adhesion.
  • the double-sided pressure-sensitive adhesive sheet is bonded to an adherend and then peeled off (when reworking). 4) It is possible to suppress occurrence of peeling between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer, and as a result, reworkability can be improved.
  • the interfacial adhesion between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer can be measured after preparing a sample for measuring interfacial adhesion as described in Examples.
  • the interfacial adhesive strength was obtained 24 hours after obtaining the “double-sided pressure-sensitive adhesive sheet with a double-sided backing substrate” (24 hours after the second pressure-sensitive adhesive layer surface and the first pressure-sensitive adhesive layer surface were adhered).
  • the second backing substrate is peeled off at a peeling rate of 300 mm / min and a peeling angle of 180 ° according to Method 1 of JIS Z 0237 to obtain a “first pressure-sensitive adhesive layer / second pressure-sensitive adhesive layer” interface.
  • the adhesive strength is obtained 24 hours after obtaining the “double-sided pressure-sensitive adhesive sheet with a double-sided backing substrate” (24 hours after the second pressure-sensitive adhesive layer surface and the first pressure-sensitive adhesive layer surface were adhered).
  • the second backing substrate is peeled off at a peeling rate of 300 mm / min and
  • the double-sided PSA sheet is obtained.
  • the excellent reworkability means that when the double-sided pressure-sensitive adhesive sheet is adhered to the adherend and then peeled off, part of the pressure-sensitive adhesive of the double-sided pressure-sensitive adhesive sheet does not remain on the adherend, and the rework work It means the property that the double-sided pressure-sensitive adhesive sheet does not break.
  • one surface of the double-sided pressure-sensitive adhesive sheet can exert a strong adhesive force to an adherend, and particularly can exert a strong adhesive force to a glass surface.
  • the double-sided pressure-sensitive adhesive sheet obtained by peeling the release sheet from the double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention has both strong adhesive strength and excellent reworkability.
  • the double-sided pressure-sensitive adhesive sheet obtained by peeling the release sheet from the double-sided pressure-sensitive adhesive sheet with the release sheet of the present invention does not have a support (substrate) between each pressure-sensitive adhesive layer, the double-sided pressure-sensitive adhesive sheet has flexibility. have. For this reason, the double-sided pressure-sensitive adhesive sheet can exhibit excellent unevenness followability, and can be bonded to an adherend having an uneven structure (step structure).
  • the layer in contact with the uneven structure (step structure) may be the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer.
  • the total thickness of the double-sided PSA sheet with a release sheet of the present invention is preferably 100 ⁇ m or more, more preferably 150 m or more, and even more preferably 200 ⁇ m or more. Further, the thickness of the double-sided pressure-sensitive adhesive sheet with a release sheet is preferably 1200 ⁇ m or less, more preferably 800 ⁇ m or less, and even more preferably 500 ⁇ m or less.
  • the thickness of the double-sided pressure-sensitive adhesive sheet is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and further preferably 50 ⁇ m or more. Further, the thickness of the double-sided pressure-sensitive adhesive sheet is preferably 1,000 ⁇ m or less, more preferably 800 ⁇ m or less, and still more preferably 600 ⁇ m 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 pressure-sensitive adhesive strength and excellent reworkability.
  • the thickness of the first pressure-sensitive adhesive layer in the double-sided pressure-sensitive adhesive sheet is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 25 ⁇ m or more.
  • the thickness of the first 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 the second pressure-sensitive adhesive layer is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 25 ⁇ m or more.
  • the thickness of the second pressure-sensitive adhesive layer is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, and further preferably 300 ⁇ m or less.
  • P: Q 1: 10 to 10: 1. Is preferred.
  • P: Q the total thickness of the first pressure-sensitive adhesive layer when the double-sided pressure-sensitive adhesive sheet includes two or more first pressure-sensitive adhesive layers. When two or more pressure-sensitive adhesive layers are included, the total thickness of the second pressure-sensitive adhesive layer is represented.
  • the thickness of the first release sheet in the double-sided pressure-sensitive adhesive sheet with a release sheet is preferably 5 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more.
  • the thickness of the first release sheet is preferably 200 ⁇ m or less, more preferably 130 ⁇ m or less, and further preferably 100 ⁇ m or less.
  • the thickness of the second release sheet is preferably 5 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more.
  • the thickness of the second release sheet is preferably 200 ⁇ m or less, more preferably 130 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the haze of the double-sided PSA sheet 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 according to JIS K7136.
  • the first adhesive layer surface of the double-sided adhesive sheet is bonded to a slide glass (product number: S9112) manufactured by Matsunami Glass Co., Ltd., and the haze value is measured.
  • a slide glass product number: S9112
  • the haze value is measured.
  • 0.5 MPa, 40 ° C. Autoclave (pressure degassing) treatment for 30 minutes.
  • the second release sheet is peeled off, and measurement is performed using NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. with the glue surface exposed.
  • the total light transmittance of the double-sided PSA sheet is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more.
  • the double-sided pressure-sensitive adhesive sheet 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 according to JIS K7136.
  • the total light transmittance of the double-sided pressure-sensitive adhesive sheet can be measured by the same method as the above-described method for measuring the haze value.
  • the double-sided PSA sheet with a release sheet of the present invention includes a first PSA layer.
  • the first pressure-sensitive adhesive layer is not particularly limited as long as the first pressure-sensitive adhesive layer can exhibit the above-described adhesive force and peeling force.
  • the first pressure-sensitive adhesive layer is preferably an acrylic pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer
  • the first pressure-sensitive adhesive layer is a layer containing an acrylic resin as a main component.
  • the content of the acrylic resin in the first 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 first pressure-sensitive adhesive layer.
  • the content is more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the acrylic resin examples include an acrylic pressure-sensitive adhesive containing an acrylic polymer as a base polymer.
  • the acrylic polymer may contain at least one selected from a non-crosslinkable (meth) acrylate unit, an acrylic monomer unit having a crosslinkable functional group, and a bifunctional acrylic monomer unit. preferable.
  • the “monomer unit” is a repeating unit constituting a polymer.
  • “Acrylic monomer” is a compound having a (meth) acryloyl group.
  • (Meth) acryloyl group” indicates 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. Is preferred.
  • the crosslinkable group includes a carboxy group, a hydroxy group, an amino group, an epoxy group, a glycidyl group, and the like.
  • non-crosslinkable acrylic monomer unit examples include a (meth) acrylate unit in which a hydrogen atom of a carboxy group of (meth) acrylic acid is substituted with a hydrocarbon group.
  • the acrylic pressure-sensitive adhesive layer preferably contains a (meth) acrylate unit.
  • the (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate , Isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isobornyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meth)
  • n-butyl acrylate 2-ethylhexyl acrylate, and methyl acrylate from the viewpoint of adhesiveness. These may be used alone or in combination of two or more.
  • (meth) acrylic acid means to include both “acrylic acid” and “methacrylic acid”.
  • crosslinkable acrylic monomer unit examples include a carboxy group-containing copolymerizable monomer unit, a hydroxy group-containing copolymerizable monomer unit, an amino group-containing copolymerizable monomer unit, and a glycidyl group-containing copolymerizable unit.
  • the carboxy group-containing copolymerizable monomer include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and grataconic acid, and anhydrides thereof. Things.
  • Examples of the hydroxy group-containing copolymerizable monomer include (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.
  • Examples include (meth) acrylic acid [(mono, di or poly) alkylene glycol] such as hydroxyalkyl, mono (diethylene glycol) (meth) acrylate, and lactone (meth) acrylate such as monocaprolactone (meth) acrylate.
  • Examples of the amino group-containing copolymerizable monomer include (meth) acrylamide, allylamide and the like.
  • Examples of the glycidyl group-containing copolymerizable monomer include glycidyl (meth) acrylate.
  • 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, it is preferably a random copolymer of acrylic acid and at least one selected from n-butyl acrylate, 2-ethylhexyl acrylate and methyl acrylate, and an acrylate ester copolymer It is preferred that
  • the weight average molecular weight (Mw) of the acrylic polymer is preferably from 200,000 to 2.5 million, and more preferably from 300,000 to 2,000,000.
  • the weight average molecular weight (Mw) is calculated based on a calibration curve prepared by gel permeation chromatography (GPC) using a polystyrene standard substance.
  • the measurement conditions of gel permeation chromatography are as follows. Solvent: Tetrahydrofuran Column: Shodex KF801, KF803L, KF806L (Used by connecting three Showa Denko KK) Column temperature: 40 ° C Sample concentration: 0.5% by mass Detector: RI-2031plus (manufactured by JASCO) Pump: RI-2080plus (manufactured by JASCO) Flow rate (flow rate): 0.8 ml / min Injection volume: 10 ⁇ l
  • the first pressure-sensitive adhesive layer may contain a silane coupling agent.
  • the interfacial adhesion between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer can be further increased.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl) Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, Amino group-containing silane coupling agents such as 3-dimethylbutylidene) propylamine and N-phenyl- ⁇ -aminopropyltrimethoxysilane; and 3-aminoacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.
  • the silane coupling agent is preferably an epoxy group-containing silane coupling agent.
  • a silane coupling agent having a plurality of alkoxysilyl groups in the molecule can be used.
  • Examples of such a silane coupling agent include X-41-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, and X-41-1053 manufactured by Shin-Etsu Chemical Co., Ltd. ⁇ 41-1810, X-40-2651 and the like.
  • the content of the silane coupling agent is preferably from 0.03% by mass to 5% by mass, and more preferably from 0.06% by mass to 1% by mass, based on the total mass of the first pressure-sensitive adhesive layer. Is more preferable.
  • the silane coupling agents may be used alone or as a mixture of two or more.
  • the first pressure-sensitive adhesive layer may contain a crosslinking agent. That is, the pressure-sensitive adhesive composition forming the first pressure-sensitive adhesive layer preferably contains a crosslinking agent.
  • the crosslinking agent can accelerate the crosslinking reaction of the crosslinkable acrylic monomer.
  • the crosslinking agent include, among 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 of a crosslinkable acrylic polymer. It can be appropriately selected 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. After the formation of the adhesive layer, a curing treatment may be performed in an environment of 23 ° C. to further increase the degree of crosslinking.
  • isocyanate compound examples include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
  • the diisocyanate may be used as it is, or may be used as a trifunctional derivative such as an adduct, a nurate, or a buret.
  • Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.
  • 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. No.
  • 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 pressure-sensitive adhesive composition forming the first pressure-sensitive adhesive layer is appropriately selected according to desired pressure-sensitive adhesive properties and the like, and is not particularly limited. It is preferable that the amount is 0.01 part by mass or more and 5 parts by mass or less with respect to parts by mass.
  • the first pressure-sensitive adhesive layer may include a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, an ultraviolet absorber, an antistatic agent, a photopolymerization initiator, and a light stabilizer such as a hindered amine compound, if necessary. May be included.
  • a plasticizer for example, a non-functional acrylic polymer can be used.
  • the non-functional acrylic polymer is a polymer consisting of only an acrylic monomer unit having no functional group other than the acrylate group, or having no functional group with an acrylic monomer unit having no functional group other than the acrylate group. It means a polymer composed of non-acrylic monomer units.
  • antioxidant examples include a phenolic antioxidant, an amine antioxidant, a lactone antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
  • metal corrosion inhibitor examples include a benzotriazole-based resin.
  • tackifier examples include a rosin resin, a terpene resin, a terpene phenol resin, a coumarone indene resin, a styrene resin, a xylene resin, a phenol resin, and a petroleum resin.
  • ultraviolet absorber examples include a benzotriazole-based compound and a benzophenone-based compound.
  • an antioxidant In order to prevent the first pressure-sensitive adhesive layer from deteriorating with time, it is preferable to add an antioxidant. By adding an antioxidant, it is possible to prevent a decrease in adhesive strength due to deterioration of the double-sided pressure-sensitive adhesive sheet.
  • the antiaging agent include general phenolic antioxidants, phosphorus-based antioxidants, UV inhibitors, HALS (hindered amine-based stabilizers), and the like.
  • the pressure-sensitive adhesive composition forming the first pressure-sensitive adhesive layer may contain a solvent. The solvent evaporates when the pressure-sensitive adhesive layer is formed, but the first 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 and diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone and cyclohexanone; methyl acetate Esters such as ethyl acetate, butyl
  • the double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention includes a second pressure-sensitive adhesive layer.
  • the second pressure-sensitive adhesive layer is not particularly limited as long as the second pressure-sensitive adhesive layer can exhibit the above-described adhesive force and peeling force.
  • an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and the like are preferable.
  • a silicone-based pressure-sensitive adhesive having good air bleeding property is particularly preferably used.
  • the second pressure-sensitive adhesive layer is a silicone-based pressure-sensitive adhesive layer
  • the second 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 second 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 second pressure-sensitive adhesive layer.
  • the content is more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • silicone resin examples include a silicone resin having a polysiloxane skeleton.
  • silicone resin examples include an addition reaction type, a condensation reaction type, an ultraviolet curing type, and an electron beam curing type. Among them, an addition-reaction type silicone resin is preferably used because of its high reactivity and excellent productivity.
  • the addition reaction type silicone resin include, for example, an organopolysiloxane having two or more alkenyl groups having 2 to 10 carbon atoms such as a vinyl group, an allyl group, a propenyl group, and a hexenyl group at the terminal and / or side chain of the molecule. Siloxane.
  • crosslinking agent When using an addition reaction type silicone resin, it is preferable to use a crosslinking agent and a catalyst together.
  • the crosslinking agent include an organopolysiloxane having a hydrogen atom bonded to at least two silicon atoms in one molecule. Specifically, a dimethylhydrogensiloxy group terminal-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, a trimethylsiloxy group terminal-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, a trimethylsiloxy group terminal-blocked methylhydrogenpolysiloxane, Poly (hydrogensilsesquioxane) and the like.
  • the catalyst examples include fine platinum particles, fine platinum particles adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, and white metal compounds such as rhodium. No.
  • silicone-based pressure-sensitive adhesives include KR-3704 and X40-3306 manufactured by Shin-Etsu Chemical Co., Ltd., DC7651ADHESIVE and SD7587LPSA manufactured by Dow Corning Toray Co., Ltd., and SE9500 manufactured by Aika Kogyo Co., Ltd. SE9600 and the like.
  • the urethane-based pressure-sensitive adhesive is a pressure-sensitive adhesive mainly composed of a reaction product of a polyol and a polyisocyanate.
  • the polyol is preferably a known polyol having two or more hydroxyl groups. Examples of the polyol include polyacryl polyol, polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, castor oil-based polyol, and the like.
  • the polyisocyanate is preferably a known aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, or alicyclic polyisocyanate.
  • a known catalyst can be used for the reaction between the polyol and the polyisocyanate. Examples of the catalyst include a tertiary amine compound and an organometallic compound.
  • the hydroxyl value of the urethane-based pressure-sensitive adhesive is preferably 1 to 30 mgKOH / g, more preferably 10 to 25 mgKOH / g.
  • the hydroxyl value can be adjusted by a known method such as adjusting the mixing ratio of the polyol and the polyisocyanate. When the hydroxyl value is within a predetermined range, a pressure-sensitive adhesive layer having a good crosslinking density is easily obtained, and wettability is further improved.
  • urethane-based pressure-sensitive adhesive can be used.
  • a urethane-based adhesive examples include SH-101, SH-101M, and SH-109 manufactured by Toyochem Corporation.
  • the acrylic pressure-sensitive adhesive examples include an acrylic fine pressure-sensitive adhesive containing an acrylic polymer as a base polymer.
  • the acrylic polymer may contain at least one selected from a non-crosslinkable (meth) acrylate unit, an acrylic monomer unit having a crosslinkable functional group, and a bifunctional acrylic monomer unit. preferable.
  • acrylic adhesive examples include Finetac CT-3088 manufactured by DIC Corporation and BPS6078TF manufactured by Toyochem Corporation.
  • the second pressure-sensitive adhesive layer may contain additives such as an antioxidant, a metal corrosion inhibitor, a tackifier, an ultraviolet absorber, a hindered amine compound, an antistatic agent, and a light stabilizer, if necessary.
  • additives such as an antioxidant, a metal corrosion inhibitor, a tackifier, an ultraviolet absorber, a hindered amine compound, an antistatic agent, and a light stabilizer, if necessary.
  • the antioxidant include a phenolic antioxidant, an amine antioxidant, a lactone antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
  • the metal corrosion inhibitor include a benzotriazole-based resin.
  • Examples of the tackifier include a rosin resin, a terpene resin, a terpene phenol resin, a coumarone indene resin, a styrene resin, a xylene resin, a phenol resin, and a petroleum resin.
  • Examples of the ultraviolet absorber include a benzotriazole-based compound and a benzophenone-based compound.
  • an antioxidant In order to prevent the second pressure-sensitive adhesive layer from deteriorating with time, it is preferable to add an antioxidant. By adding an antioxidant, it is possible to prevent a decrease in adhesive strength due to deterioration of the double-sided pressure-sensitive adhesive sheet.
  • the antiaging agent include general phenolic antioxidants, phosphorus-based antioxidants, UV inhibitors, HALS (hindered amine-based stabilizers), and the like.
  • the pressure-sensitive adhesive composition forming the second pressure-sensitive adhesive layer may contain a solvent.
  • the solvent evaporates when the pressure-sensitive adhesive layer is formed, but the second pressure-sensitive adhesive layer may contain the remaining solvent.
  • Examples of the solvent include the same solvents as those that can be contained in the pressure-sensitive adhesive composition that forms the first pressure-sensitive adhesive layer.
  • the double-sided PSA sheet with a release sheet of the present invention includes a first release sheet.
  • the first release sheet is preferably a release laminate sheet having a release sheet substrate and a release agent layer provided on one surface of the release sheet substrate. Paper or a polymer film is used as a release sheet substrate in the release laminate sheet.
  • the polymer film used for the release sheet substrate include a polyethylene terephthalate resin film, a polypropylene resin film, and a polyimide resin film. Among them, a polyethylene terephthalate resin film is particularly preferable in terms of economy and surface smoothness.
  • the release agent layer in the release laminate sheet is preferably composed of a release agent, and the release agent is preferably a silicone release agent. That is, the first release sheet is preferably a sheet containing a silicone-based release agent, and more preferably a sheet containing a release agent layer composed of a silicone-based release agent.
  • silicone release agent examples include an addition type silicone release agent and a condensation type silicone release agent. Among them, an addition type silicone release agent having high reactivity is preferably used. Specific examples of the silicone release agent include BY24-4527 and SD-7220 manufactured by Dow Corning Toray Silicone Co., Ltd., and KS-3600, KS-774, and X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd. Is mentioned. Further, the silicone-based release agent may contain a silicone resin which is an organosilicon compound having SiO 2 units and (CH 3 ) 3 SiO 1/2 units or CH 2 CHCH (CH 3 ) SiO 1/2 units. .
  • the silicone-based release agent may include a polyorganosiloxane and a polyorganohydrogensiloxane.
  • the polyorganosiloxane preferably has an alkenyl group directly bonded to at least two silicon atoms in one molecule, and further has an epoxy bonded to at least two silicon atoms in one molecule via a carbon atom. It is preferable to use a polyorganosiloxane having a group and having substantially no hydrogen atom directly bonded to a silicon atom.
  • the polyorganohydrogensiloxane preferably has at least three hydrogen atoms directly bonded to silicon atoms in one molecule, and has a kinematic viscosity at 25 ° C.
  • the silicone-based release agent may include a platinum-based catalyst.
  • silicone-based release agents and platinum-based catalysts containing polyorganosiloxanes and polyorganohydrogensiloxanes include KS-3800, X-62-183, X-62-2829, X-X, manufactured by Shin-Etsu Chemical Co., Ltd. -62-2853, X-62-2856, X-62-2857, PL-5000, PL-50T, LTC-856, LTC-761, SRX-212, manufactured by Toray Dow Corning Co., Ltd., Momentive Co., Ltd.
  • a release control agent may be used in combination to adjust the release property of the release agent layer.
  • the amount of the release agent applied to the first release sheet is preferably 0.05 to 0.5 g / m 2 , more preferably 0.08 to 0.3 g / m 2 , and 0.1 to 0.5 g / m 2. More preferably, it is 0.2 g / m 2 .
  • the thickness of the release agent layer of the first release sheet is preferably from 50 to 500 nm, more preferably from 80 to 300 nm, even more preferably from 100 to 200 nm.
  • a conventionally known coating method such as reverse roll coating, gravure coating, bar coating, doctor blade coating, or the like can be used.
  • the peeling force when peeling the first release sheet from the first pressure-sensitive adhesive layer is preferably 0.01 N / 50 mm or more, and more preferably 0.1 N / 50 mm or more. Further, the peeling force at the time of peeling the first release sheet from the first pressure-sensitive adhesive layer is preferably 1.0 N / 50 mm or less, more preferably 0.8 N / 50 mm or less. More preferably, it is 6 N / 50 mm or less.
  • the peeling force when peeling the first release sheet from the first pressure-sensitive adhesive layer is such that the first release sheet / the first pressure-sensitive adhesive layer / the second pressure-sensitive adhesive layer / the second release sheet is in this order.
  • the laminated double-sided pressure-sensitive adhesive sheet with a release sheet is cut out to 50 mm ⁇ 100 mm, and the first release sheet is measured by peeling at a peeling rate of 300 mm / min and a peeling angle of 180 ° according to Method 1 of JIS Z0237. .
  • the double-sided PSA sheet with a release sheet of the present invention includes a second release sheet.
  • the second release sheet may be a release laminate sheet having a release sheet substrate and a release agent layer provided on one surface of the release sheet substrate, and may be composed of only the release sheet substrate. It may be a sheet. Paper or a polymer film is used as a release sheet substrate in the release laminate sheet.
  • the release sheet substrate is preferably a polymer film substrate.
  • the polymer film used as the base material for the release sheet include a polyethylene terephthalate resin film, a polypropylene resin film, and a polyimide resin film. A polyethylene terephthalate resin film is particularly preferable in terms of economy and surface smoothness.
  • the peeling load of the second peeling sheet is preferably 70 to 20,000 mN / 50 mm.
  • the release load of the second release sheet is preferably within the above range.
  • the peeling load of the second release sheet is more preferably 100 to 18000 mN / 50 mm, and further preferably 120 to 17000 mN / 50 mm.
  • the surface of the second release sheet to which the second pressure-sensitive adhesive layer was bonded was applied to 100 pressure-sensitive adhesive layers, left at room temperature for 24 hours, and then peeled at 180 ° at a peel rate of 300 mm / min. This is the peel force when the release sheet is peeled.
  • the release layer is composed of a release agent.
  • the release agent is preferably a fluorosilicone release agent.
  • the fluorosilicone release agent contains at least one fluorine atom-containing organic group in one molecule.
  • the release agent may be a non-silicone release.
  • the non-silicone-based release agent include an aminoalkyd-based resin.
  • the second release sheet preferably contains the non-silicone release agent as described above, or the total content of the silicone release agent and the non-silicone release agent is preferably 1% by mass or less. That is, the second release sheet preferably contains either the non-silicone release agent as described above or substantially no release agent. In this specification, when the content of the release agent in the second release sheet is 1% by mass or less, it is assumed that the release agent is not substantially contained.
  • the second release sheet does not substantially contain a release agent
  • the second release sheet is preferably a substrate made of a polymer film. Examples of the polymer film include a polyester film and the like.
  • the thickness of the release agent layer is preferably from 0.03 ⁇ m to 5 ⁇ m, more preferably from 0.05 ⁇ m to 2 ⁇ m, and more preferably from 0.08 ⁇ m to 1 ⁇ m. It is more preferred that:
  • a conventionally known coating method such as reverse roll coating, gravure coating, bar coating, doctor blade coating, or the like can be used.
  • the peeling force at the time of peeling the second release sheet from the second pressure-sensitive adhesive layer is preferably 0.5 N / 50 mm or more, and more preferably 0.6 N / 50 mm or more. Further, the peeling force at the time of peeling the second release sheet from the second pressure-sensitive adhesive layer is preferably 10.0 N / 50 mm or less, more preferably 5.0 N / 50 mm or less, and 3. More preferably, it is 0 N / 50 mm or less.
  • the first release sheet / first pressure-sensitive adhesive layer / second pressure-sensitive adhesive layer / second pressure-sensitive adhesive layer Of the double-sided pressure-sensitive adhesive sheet with a release sheet laminated in this order is cut into 50 mm ⁇ 100 mm, and a PET film (A4300 # 100) with an easy-adhesion layer made by Toyobo is adhered to the first release sheet as a backing substrate. I do.
  • the second release sheet is peeled off at a peeling rate of 300 mm / min and a peeling angle of 180 ° according to Method 1 of JIS Z0237 to measure the peeling force.
  • each release sheet has a different release force, and the release force when releasing the second release sheet from the second pressure-sensitive adhesive layer is the first pressure-sensitive adhesive. It is larger than the peeling force when peeling the first release sheet from the agent layer.
  • RH peeling force at the time of peeling the second release sheet from the second pressure-sensitive adhesive layer
  • RL peeling force at the time of peeling the first release sheet from the first pressure-sensitive adhesive layer
  • the ratio of R H to R L is preferably 1.2 or more, and more preferably 1.5 or more.
  • the method for producing the double-sided pressure-sensitive adhesive sheet with a release sheet is not particularly limited, but the production process of the double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention includes forming a first pressure-sensitive adhesive layer on the first release sheet, It is preferable to include a step of forming a second pressure-sensitive adhesive layer on a release sheet, and a step of bonding the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer so as to be in contact with each other.
  • the step of forming each pressure-sensitive adhesive layer on each release sheet is preferably a step of applying each pressure-sensitive adhesive composition constituting each pressure-sensitive adhesive layer on a release sheet.
  • the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are simultaneously or sequentially formed on the first release sheet or the second release sheet, and the second release sheet or the first release sheet is bonded. May be.
  • each pressure-sensitive adhesive composition can be performed using a known coating device.
  • the coating device include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a microgravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and the like.
  • a drying step is preferably provided, and the drying step can be performed using a known heating device such as a heating furnace or an infrared lamp.
  • a heating device such as a heating furnace or an infrared lamp.
  • the step of laminating the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer so as to be in contact with each other includes a step of laminating the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer so as to be in direct contact with each other, and pressure bonding.
  • the pressing method is not particularly limited, but it is preferable to use a roll bonding machine capable of continuously pressing.
  • a double-sided PSA sheet with a release sheet in which the first release sheet, the first PSA layer, the second PSA layer, and the second release sheet are laminated in this order is obtained.
  • each pressure-sensitive adhesive layer Before the step of bonding the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer so as to be in contact with each other, each pressure-sensitive adhesive layer may be subjected to a surface activation treatment.
  • the surface activation treatment include a corona treatment and a plasma treatment.
  • the surface activation treatment is performed on the surface on the bonding surface side of each pressure-sensitive adhesive layer.
  • the surface activation treatment may be performed on one selected from the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer, or may be performed on both.
  • the surface activation treatment surface preferably has a wet tension of 70 mN / m or more, and 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 wetting tension of the first pressure-sensitive adhesive layer after the surface activation treatment is 1.1 times or more as compared with the wetting tension of the first pressure-sensitive adhesive layer before the surface activation treatment.
  • the surface activation treatment is preferably performed on the first pressure-sensitive adhesive layer.
  • the wetting tension of the surface activated surface is preferably 30 mN / m or more, more preferably 34 mN / m or more. preferable.
  • the upper limit of the wetting tension of the surface activated surface is not particularly limited, but is preferably, for example, 45 mN / m in order to prevent a decrease in transparency.
  • 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.
  • the corona treatment there is a method of discharging in a 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, more preferably 0.5 kW or more and 7.0 kW or less, and more preferably 0.5 kW or more. More preferably, it is not less than 6.0 kW.
  • the processing speed in the corona treatment is preferably from 5 m / min to 100 m / min, more preferably from 5 m / min to 90 m / min, even more preferably from 5 m / min to 80 m / min. .
  • the plasma treatment there is a method of discharging in normal pressure air by a plasma discharge machine.
  • 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, more preferably 0.5 kW or more and 3.0 kW or less, and more preferably 0.5 kW or more. More preferably, it is 1.5 kW or less.
  • the processing speed in the plasma processing is preferably from 5 m / min to 100 m / min, more preferably from 5 m / min to 90 m / min, even more preferably from 5 m / min to 80 m / min. .
  • the double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention is preferably used for bonding various members after the release sheet is released.
  • the application of the bonding is not limited, but is preferably for bonding optical members.
  • the optical member include a liquid crystal display and a touch panel.
  • the double-sided pressure-sensitive adhesive sheet after the release sheet is peeled off is preferably used for bonding glass and a liquid crystal display, or glass and a touch panel.
  • only one of the release sheets may be peeled off and bonded to various members.
  • first release sheet of the double-sided pressure-sensitive adhesive sheet with a release sheet of the present invention and bonding the first pressure-sensitive adhesive layer to glass, glass, the first pressure-sensitive adhesive layer, and the second pressure-sensitive adhesive
  • a laminate in which the layer and the second release sheet are laminated in this order may be obtained.
  • Such a laminate is preferably used, for example, as a protective film for an optical member.
  • a general consumer may peel off the second release sheet in the laminate and bond it to a liquid crystal display.
  • the double-sided pressure-sensitive adhesive sheet With a release sheet of the present invention, it is easy to process a laminated body in which glass, a first pressure-sensitive adhesive layer, a second pressure-sensitive adhesive layer, and a second release sheet are laminated in this order, and Easy to process into protective film.
  • a general consumer peels off the second release sheet in the above-mentioned laminate and pastes it on a liquid crystal display, air entrapment is small, and the protective film can be adhered neatly.
  • Adhesive composition 1A 90 parts by mass of n-butyl acrylate (BA) and 10 parts by mass of acrylic acid (AA) were copolymerized to prepare a (meth) acrylate polymer.
  • the weight average molecular weight of this (meth) acrylate polymer was 500,000.
  • silicone-based pressure-sensitive adhesive composition 2A 100 parts by mass of an addition-type organopolysiloxane (KS-847H, manufactured by Shin-Etsu Chemical Co., Ltd.) composed of an organopolysiloxane having a siloxane bond as a main skeleton and a vinyl group, and an organohydrogenpolysiloxane (solid-converted value; hereinafter the same) ) 20 parts by mass of an organopolysiloxane containing a trifunctional or tetrafunctional siloxane unit (silicone resin; SD-4584, manufactured by Toray Dow Corning Co., Ltd.), and a platinum catalyst (SRX-212 manufactured by Toray Dow Corning, Inc.) Five parts by mass were mixed, sufficiently stirred, and diluted with methyl ethyl ketone so as to have a solid content concentration of 40% by mass to obtain a silicone-based pressure-sensitive adhesive composition.
  • an addition-type organopolysiloxane (
  • the first release sheet is adhered on one side by applying evenly with an applicator so that the coating amount after drying is 50 ⁇ m on the surface of, and drying for 3 minutes in an air circulating constant temperature oven at 100 ° C.
  • the obtained acrylic pressure-sensitive adhesive layer was obtained.
  • the pressure-sensitive adhesive layer having the first release sheet adhered to one side was cured in an environment of 23 ° C. and 50% relative humidity for 7 days.
  • the coating amount of the silicone-based pressure-sensitive adhesive composition after drying on the surface of a 38 ⁇ m-thick polyethylene terephthalate film (Lumilar S-10 # 38, manufactured by Toray Industries, Inc.) (second release sheet) is 50 ⁇ m.
  • a silicone-based pressure-sensitive adhesive layer having a second release sheet adhered to one side was obtained by uniformly coating with an applicator and drying in an air-circulating constant temperature oven at 100 ° C. for 3 minutes.
  • the peeling load of Lumirror S-10 / 10 was 16000 mN / 50 mm.
  • Corona discharge treatment was performed on each surface of the acrylic pressure-sensitive adhesive layer and the silicone-based pressure-sensitive adhesive layer.
  • the corona discharge treatment was performed using a corona surface treatment device manufactured by Kasuga Electric.
  • the corona discharge treatment was performed under the condition that the wet tension of the acrylic pressure-sensitive adhesive layer was 70 mN / m or more and the wet tension of the silicone pressure-sensitive adhesive layer was 30 mN / m or more.
  • the first release sheet / first pressure-sensitive adhesive layer (acrylic pressure-sensitive adhesive layer) is formed by bonding the exposed surface of the acrylic pressure-sensitive adhesive layer subjected to the surface activation treatment and the exposed surface of the silicone-based pressure-sensitive adhesive layer to each other.
  • a double-sided pressure-sensitive adhesive sheet with a release sheet was obtained in which // second pressure-sensitive adhesive layer (silicone-based pressure-sensitive adhesive layer) / second release sheet was laminated in this order.
  • Example 2 ⁇ Preparation of a double-sided pressure-sensitive adhesive sheet with a release sheet>, except that the silicone-based pressure-sensitive adhesive composition was applied to the surface of a fluorosilicone-based release sheet (SS4C substrate thickness 75 ⁇ m, manufactured by Nipa) (second release sheet) In the same manner as in Example 1, a double-sided PSA sheet with a release sheet was obtained.
  • the peeling load of SS4C was 340 mN / 50 mm.
  • silicone-based pressure-sensitive adhesive composition 2B The silicone adhesive KR3704 manufactured by Shin-Etsu Chemical and the platinum catalyst PL50T manufactured by Shin-Etsu Chemical are sufficiently stirred at a ratio of 100 / 0.5, and diluted with toluene so that the solid content concentration becomes 40% by mass. Composition 2B was obtained.
  • Adhesive composition 2C Adhesion is achieved by mixing 6 parts by mass of T-501B (solid content: 75% by mass) as a polyisocyanate component with 100 parts by mass of urethane fine adhesive SH-101 (solid content: 60% by mass) manufactured by Toyochem Co., Ltd. Agent composition C was obtained.
  • Example 5 ⁇ Preparation of acrylic pressure-sensitive adhesive composition> (Adhesive composition 1B) 100 parts by mass of N-9369 manufactured by Nippon Synthetic Chemical Co., Ltd. and 0.9 parts by mass of curing agent L-55E are mixed, sufficiently stirred, and diluted with ethyl acetate so as to have a solid concentration of 40% by mass. By doing so, an acrylic pressure-sensitive adhesive composition 1B was obtained.
  • Adhesive composition 1B 100 parts by mass of N-9369 manufactured by Nippon Synthetic Chemical Co., Ltd. and 0.9 parts by mass of curing agent L-55E are mixed, sufficiently stirred, and diluted with ethyl acetate so as to have a solid concentration of 40% by mass.
  • silicone-based pressure-sensitive adhesive composition 2D Toray Dow Corning Co., Ltd. 100 parts by mass of a silicone-based micro-adhesive agent DOWSIL 7646 Adhesive, Toray Dow Corning Co., Ltd., silicone-based cross-linking agent 7678 1 part by mass, and Toray Dow Corning Co., Ltd., catalyst NC-25 0.3
  • the silicone adhesive composition 2D was obtained by mixing parts by mass, sufficiently stirring, and diluting with methyl ethyl ketone so that the solid content concentration became 40% by mass.
  • the silicone pressure-sensitive adhesive composition was referred to as pressure-sensitive adhesive composition 2E
  • the second release sheet was referred to as a fluorosilicone-based release sheet (manufactured by Nipah, FSC6 base material thickness 75 ⁇ m). Except for the above, a double-sided PSA sheet with a release sheet was obtained in the same manner as in Example 1.
  • the polyethylene terephthalate film with an easy-adhesion layer to which the surface-activated acrylic pressure-sensitive adhesive layer was adhered was used as an acrylic adhesive layer having a CCL / D1 / T3T3 manufactured by Shin-Tack Chemical Co., Ltd. (a PET film with an easily-adhesive layer manufactured by Toyobo). (A4300 # 100)).
  • the first release sheet of a double-sided pressure-sensitive adhesive sheet with a release sheet in which a first release sheet / first pressure-sensitive adhesive layer / second pressure-sensitive adhesive layer / second release sheet is laminated in this order is peeled off and easily adhered.
  • a polyethylene terephthalate film with a layer (A4300 # 100, manufactured by Toyobo) was adhered as a backing substrate.
  • the second release sheet was peeled off, and the adhesive surface of the second adhesive layer was adhered to soda glass. Twenty-four hours after the adhesion, the adhesive strength was measured under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 ° according to Method 1 of JIS Z 0237.
  • the first release sheet of the double-sided pressure-sensitive adhesive sheet with a release sheet is peeled from the first pressure-sensitive adhesive layer, and a polyethylene terephthalate film with an easy-adhesion layer (A4300 # 100, manufactured by Toyobo) backed on the first pressure-sensitive adhesive layer surface (First backing substrate). Subsequently, the second release sheet was released from the second pressure-sensitive adhesive layer, and the surface of the second pressure-sensitive adhesive layer was subjected to a surface activation treatment.
  • the polyethylene terephthalate film with an easy-adhesion layer to which the surface-activated acrylic pressure-sensitive adhesive layer was adhered was used as an acrylic adhesive layer having a CCL / D1 / T3T3 manufactured by Shin-Tack Chemical Co., Ltd. (a PET film with an easily-adhesive layer manufactured by Toyobo). (A4300 # 100)).
  • the double-sided pressure-sensitive adhesive sheet with a double-sided backing substrate obtained above was cut into 50 mm ⁇ 100 mm, and the surface of the first backing substrate opposite to the surface of the pressure-sensitive adhesive layer was fixed. 24 hours after adhering the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer, the second backing substrate is peeled off, so that the interfacial adhesive force between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is removed.
  • a peeling speed 300 mm / min and a peeling angle of 180 ° according to Method 1 of JIS Z 0237.
  • the adhesive force between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is defined as the peeling force or more. did.
  • a double-sided pressure-sensitive adhesive sheet with a release sheet in which a first release sheet / first pressure-sensitive adhesive layer / second pressure-sensitive adhesive layer / second release sheet is laminated in this order is cut out to 50 mm ⁇ 100 mm, and the first release sheet is cut out.
  • a PET film A4300 # 100 with an easy-adhesion layer manufactured by Toyobo was adhered to the first adhesive layer as a backing substrate.
  • the second release sheet was peeled off at a peeling rate of 300 mm / min and a peeling angle of 180 ° according to Method 1 of JIS Z 0237, and the peeling force was measured.
  • the first release sheet of the double-sided pressure-sensitive adhesive sheet with a release sheet is peeled from the first pressure-sensitive adhesive layer, and the surface of the first pressure-sensitive adhesive layer is rolled on a Matsunami glass plate (product name: S9112, 1 mmt ⁇ 76 mm ⁇ 52 mm) by 2 kg roll. And made one reciprocation.
  • the second release sheet was peeled off, gently placed on a soda glass plate so that the second pressure-sensitive adhesive layer surfaces directly overlapped, and adhered by its own weight. At this time, air bleeding was extremely good when the area of bubbles remaining at the interface between the second pressure-sensitive adhesive layer and soda glass was 2% or less of the adhered area (().
  • the double-sided pressure-sensitive adhesive sheet with a release sheet obtained in the example was capable of peeling the first release sheet first, and was excellent in workability. Further, the double-sided pressure-sensitive adhesive sheet with a release sheet obtained in the example was obtained. When the second pressure-sensitive adhesive layer was stuck to the adherend, air entrapment was suppressed. On the other hand, the double-sided PSA sheet with a release sheet obtained in Comparative Example was not compatible with both processability and air bleeding property.
  • Second pressure-sensitive adhesive layer 10 First pressure-sensitive adhesive layer 12 Second pressure-sensitive adhesive layer 20 First release sheet 22 Second release sheet 50 Double-sided pressure-sensitive adhesive sheet 100 Double-sided pressure-sensitive adhesive sheet with release sheet

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

Abstract

L'invention concerne une feuille adhésive double face à feuille de protection amovible, présentant à la fois une excellente ouvrabilité et d'excellentes propriétés d'évacuation d'air. La feuille adhésive double face selon l'invention, est obtenue par empilement séquentiel d'une première feuille de protection amovible, d'une première couche adhésive, d'une deuxième couche adhésive et d'une deuxième feuille de protection amovible, dans cet ordre, et est configurée de sorte que : la deuxième couche adhésive soit disposée directement sur la première couche adhésive ; la force d'adhérence de la première couche adhésive sur du verre soit de 10 à 1000 fois la force d'adhérence de la deuxième couche adhésive sur le verre ; et que la force de décollement au moment où la deuxième feuille de protection amovible est séparée de la deuxième couche adhésive soit supérieure à la force de décollement au moment où la première feuille de protection amovible est séparée de la première couche adhésive.
PCT/JP2019/029623 2018-07-30 2019-07-29 Feuille adhésive double face à feuille de protection amovible et procédé de production de ladite feuille adhésive Ceased WO2020027038A1 (fr)

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JP2018142268A JP7310100B2 (ja) 2018-07-30 2018-07-30 剥離シート付き両面粘着シートおよび剥離シート付き両面粘着シートの製造方法
JP2018-142268 2018-07-30

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025225331A1 (fr) * 2024-04-26 2025-10-30 ダウ・東レ株式会社 Stratifié comprenant une couche adhésive multicouche, son utilisation et procédés de production

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JPH04114535U (ja) * 1991-03-26 1992-10-08 神崎製紙株式会社 両面粘着シート
JP2003177241A (ja) * 2001-12-10 2003-06-27 Fujimori Kogyo Co Ltd 光学用積層体、粘着剤転写テープ、および光学用積層体の製造法
JP2016017119A (ja) * 2014-07-07 2016-02-01 旭硝子株式会社 両面粘着フィルム、粘着層付き透明面材、および積層体
WO2016103372A1 (fr) * 2014-12-24 2016-06-30 リンテック株式会社 Feuille adhésive double face destinée à des panneaux de protection, et un panneau de protection de surface
JP2016199619A (ja) * 2015-04-07 2016-12-01 旭化学工業株式会社 両面テープ
WO2019142905A1 (fr) * 2018-01-18 2019-07-25 王子ホールディングス株式会社 Feuille adhésive double face et feuille adhésive double face pourvue d'une feuille antiadhésive

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ATE503589T1 (de) * 2004-09-06 2011-04-15 Coloplast As Silicon-kondomurinal mit integriertem kleber

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Publication number Priority date Publication date Assignee Title
JPH04114535U (ja) * 1991-03-26 1992-10-08 神崎製紙株式会社 両面粘着シート
JP2003177241A (ja) * 2001-12-10 2003-06-27 Fujimori Kogyo Co Ltd 光学用積層体、粘着剤転写テープ、および光学用積層体の製造法
JP2016017119A (ja) * 2014-07-07 2016-02-01 旭硝子株式会社 両面粘着フィルム、粘着層付き透明面材、および積層体
WO2016103372A1 (fr) * 2014-12-24 2016-06-30 リンテック株式会社 Feuille adhésive double face destinée à des panneaux de protection, et un panneau de protection de surface
JP2016199619A (ja) * 2015-04-07 2016-12-01 旭化学工業株式会社 両面テープ
WO2019142905A1 (fr) * 2018-01-18 2019-07-25 王子ホールディングス株式会社 Feuille adhésive double face et feuille adhésive double face pourvue d'une feuille antiadhésive

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025225331A1 (fr) * 2024-04-26 2025-10-30 ダウ・東レ株式会社 Stratifié comprenant une couche adhésive multicouche, son utilisation et procédés de production

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