WO2024024829A1 - Method for peeling adhesive sheet - Google Patents

Method for peeling adhesive sheet Download PDF

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Publication number
WO2024024829A1
WO2024024829A1 PCT/JP2023/027352 JP2023027352W WO2024024829A1 WO 2024024829 A1 WO2024024829 A1 WO 2024024829A1 JP 2023027352 W JP2023027352 W JP 2023027352W WO 2024024829 A1 WO2024024829 A1 WO 2024024829A1
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WO
WIPO (PCT)
Prior art keywords
adhesive
adherend
adhesive sheet
peeling
ethanol
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PCT/JP2023/027352
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French (fr)
Japanese (ja)
Inventor
健太 熊倉
哲士 本田
廉人 太田
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日東電工株式会社
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Publication of WO2024024829A1 publication Critical patent/WO2024024829A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H41/00—Machines for separating superposed webs
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers

Definitions

  • the present invention relates to a method for peeling a pressure-sensitive adhesive sheet. Specifically, the present invention relates to a method for peeling a pressure-sensitive adhesive sheet, which includes applying an adhesive force reducing means.
  • This application claims priority based on Japanese Patent Application No. 2022-122052 filed on July 29, 2022, and the entire contents of that application are incorporated herein by reference.
  • adhesives also referred to as pressure-sensitive adhesives, hereinafter the same
  • adhesives are widely used in various fields in the form of adhesive sheets with a support, which have an adhesive layer on the support, or in the form of support-less adhesive sheets, which do not have a support. It's being used. Further, after use, the adhesive is peeled off from the adherend by appropriate means, if necessary.
  • Technical documents for peeling adhesives from adherends include Patent Documents 1 and 2.
  • display devices built into products with display functions such as smartphones, personal computers (desktops, notebooks, tablets, etc.), televisions, etc.
  • display devices built into products with display functions such as smartphones, personal computers (desktops, notebooks, tablets, etc.), televisions, etc.
  • organic EL (electroluminescence) display devices It has a multilayer structure including a plurality of different functional components, such as a PDP (plasma display panel), and each component contains a different material, so there is a great advantage in reusing it through recycling, reuse, etc.
  • surface protection sheets are adhered to the surfaces to protect them from damage and dirt. Such a surface protection sheet is removed from the adherend at an appropriate timing after the protection purpose is achieved.
  • an adhesive bonded to an adherend such as a member is usually peeled off from the adherend by utilizing the removability of the adhesive itself.
  • pressure-sensitive adhesives that are required to have high bonding reliability generally have high adhesion to adherends, and tend to have poor removability (re-peelability) from adherends.
  • the adherend may include a hard and brittle member such as glass or a thin member, and such an adherend may be damaged by the force applied when the adhesive is peeled off.
  • Patent Document 1 a technology that achieves both adhesion to adherends and removability, which can be easily peeled off using water, and We are proposing an adhesive sheet (water-releasable adhesive sheet) with improved water resistance reliability during bonding.
  • the water-releasable adhesive sheet proposed in Patent Document 1 is based on the premise that an aqueous liquid such as water is used to peel the adhesive sheet from the adherend. While it can be suitably applied to adherends with high peeling, it may not be suitably applied to adherends with low hydrophilicity.
  • a technology has been provided that achieves both adhesion and removability for adherends with relatively low hydrophilicity, such as metals and resins, in addition to highly hydrophilic adherends. This is advantageous because it broadens the range of applicable adherends.
  • the present invention was created in view of the above circumstances, and is a peeling method that can be applied even to adherends with relatively low hydrophilicity, and which improves adhesive strength and removability to the adherend.
  • An object of the present invention is to provide a method for peeling a pressure-sensitive adhesive sheet that achieves both of the following.
  • a method for peeling a pressure-sensitive adhesive sheet stuck to an adherend includes applying an adhesive force reducing means to the adhesive sheet.
  • the adhesive force reducing means includes supplying an alcohol liquid to an interface between the adherend and the adhesive sheet at a peeling front of the adhesive sheet from the adherend, and supplying the alcohol liquid to the interface. is present, the peeling front of the pressure-sensitive adhesive sheet is moved in the peeling advancing direction, and the alcohol liquid is allowed to enter the interface following the movement of the peeling front.
  • the adhesive force reducing means by applying the adhesive force reducing means, the adhesive force of the adhesive sheet can be reduced, so that the peelability (repeelability) from the adherend can be improved.
  • the adhesive strength reducing means disclosed herein uses an alcohol solution, it may be difficult to apply water to an adherend whose surface is made of a material with relatively low hydrophilicity such as metal or resin. Even when applied to adherends to which water removal is difficult, the releasability (re-peelability) from the adherend can be improved.
  • a water removal step such as drying or wiping the adherend is sometimes necessary.
  • an alcohol solution is used instead of water, the process of removing the liquid from the adherend after peeling tends to be shorter or simpler than before. Such a peeling method is also advantageous from the viewpoint of production efficiency.
  • the adhesive sheet is prepared by attaching the adhesive sheet to a stainless steel plate as an adherend and dropping 2 ⁇ L of ethanol onto the adherend one day after the adhesive sheet is attached to the adherend at room temperature. After entering one end of the interface with the adherend, according to JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, tensile at a test temperature of 23°C.
  • the ethanol peel force N1 SUS measured using a testing machine at a tensile speed of 300 mm/min and a peel angle of 180 degrees, is 0.5 N/20 mm or less.
  • a pressure-sensitive adhesive sheet having an ethanol peel force N1 SUS with respect to a stainless steel plate is equal to or lower than the above upper limit value
  • the adhesive force reduction effect due to alcohol peeling is likely to be suitably exhibited, and re-peelability from the adherend can be improved.
  • adherends having good wettability with ethanol include those having a contact angle with ethanol of 50 degrees or less.
  • the adherend include adherends whose adherend surfaces are made of a material such as glass, metal (eg, stainless steel, aluminum, etc.), resin (eg, PET, polyimide (PI), etc.).
  • the adhesive sheet is applied to a stainless steel plate as an adherend, and after one day at room temperature, the adhesive sheet cut into a rectangular shape with a width of 20 mm is attached to the adherend.
  • the adhesive force reduction distance R SUS is 30 mm or more, which is measured at a test temperature of 23° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees.
  • alcohol liquid is supplied to the interface between the adhesive sheet and the adherend (for example, an adherend whose adherend surface is made of metal, resin, etc.).
  • the effects of the adhesive force reducing means, including the above, tend to continue without deterioration.
  • a pressure-sensitive adhesive sheet that maintains the effect of reducing adhesive force is preferable from the viewpoint of reducing the amount of alcohol used in the peeling process and working efficiency.
  • the adhesive sheet has an adhesive force N0 SUS of 3.0 N/20 mm or more after one day at room temperature after attaching the adhesive sheet to a stainless steel plate as an adherend. Since the above-mentioned adhesive sheet has an adhesion force N0 SUS to a stainless steel plate that is above the lower limit value, it has excellent adhesion reliability to adherends (for example, adherends whose adherend surface is made of metal, resin, etc.). There is a tendency to show that
  • Adhesive force reduction rate S SUS [%] (1 - (ethanol peeling force N1 SUS / adhesive force N0 SUS )) x 100; S SUS is 50% or more, and adhesive force reduction distance R SUS is 30 mm or more.
  • the adhesive sheet is attached to an alkali glass plate prepared by a float method as an adherend, and after one day at room temperature, 2 ⁇ L of ethanol is dropped onto the adherend.
  • 2 ⁇ L of ethanol is dropped onto the adherend.
  • Method 1 180° peeling adhesive force to the test plate, specifically, The ethanol peel force N1 GLA is 0.5 N/20 mm or less, which is measured at a test temperature of 23° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees.
  • the adhesive sheet is attached to an alkali glass plate prepared by a float method as an adherend, and after one day at room temperature, the adhesive sheet cut into a rectangular shape with a width of 20 mm is attached.
  • JIS Z0237:2009 10.4.1 Method 1 180° pull on the test plate
  • the adhesive force reduction distance R GLA is 30 mm or more, which is measured at a test temperature of 23 ° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. .
  • an adhesive sheet whose adhesion force reduction distance R GLA to a glass plate is 30 mm or more, it is recommended to supply alcohol liquid to the interface between the adhesive sheet and the adherend (for example, an adherend whose adherend surface is made of glass).
  • the effect of the adhesive force reducing means included therein tends to be sustained without deterioration.
  • a pressure-sensitive adhesive sheet that maintains the effect of reducing adhesive force is preferable from the viewpoint of reducing the amount of alcohol used in the peeling process and working efficiency.
  • the adhesive sheet has an adhesive force N0 GLA of 3.0 N/20 mm or more after one day at room temperature after attaching the adhesive sheet to an alkali glass plate prepared by a float method as an adherend. . Since the above-mentioned adhesive sheet has an adhesion force N0 GLA to a glass plate of 3.0 N/20 mm or more, it has excellent adhesion reliability to an adherend (for example, an adherend whose surface is made of glass). There is a tendency to show
  • Adhesive force reduction rate S GLA [%] (1 - (ethanol peeling force N1 GLA / adhesive force N0 GLA )) x 100; S GLA is 50% or more, and adhesive force reduction distance R GLA is 30 mm or more.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of a pressure-sensitive adhesive sheet according to an embodiment.
  • weight may be read as “mass”.
  • % by weight may be read as “% by mass”
  • parts by weight may be read as “parts by mass”.
  • a method for peeling a pressure-sensitive adhesive sheet stuck to an adherend is provided.
  • the above peeling method is characterized in that an adhesive force reducing means is applied to the adhesive sheet.
  • the adhesive force reducing means disclosed herein supplies an alcohol liquid to an interface between the adherend and the adhesive sheet at a peeling front of the adhesive sheet from the adherend, and the alcohol liquid is present at the surface.
  • the peeling front of the pressure-sensitive adhesive sheet is moved in the peeling advancing direction, and the alcohol liquid is allowed to enter the interface in accordance with the movement of the peeling front.
  • alcohol liquid is used instead of conventional water as the liquid supplied to reduce the adhesive force of the adhesive sheet to the adherend, so it is relatively hydrophilic, making it difficult to apply water peeling.
  • the effect of reducing adhesive strength tends to be preferably exhibited even for adherends with low adhesive strength.
  • the process of removing the alcohol solution from the adherend after stripping tends to be shorter or simpler.
  • alcohols or mixed solvents containing alcohols as a main component, containing small amounts of additives as necessary, can be used.
  • a monohydric lower alcohol having 1 to 4 carbon atoms it is preferable to use a monohydric lower alcohol having 1 to 4 carbon atoms as the alcohol, and methanol, ethanol, isopropyl alcohol, etc. are particularly preferable.
  • ethanol is preferred from the viewpoints of safety, versatility, etc.
  • the solvent other than alcohols constituting the above mixed solvent water, lower ketones (eg, acetone), etc. that can be uniformly mixed with alcohols may be used.
  • the additive known surfactants and the like can be used. From the viewpoint of avoiding contamination of the adherend, in some embodiments, an alcoholic liquid containing substantially no additives may be preferably used.
  • the content of alcohol in the alcohol solution is more than 50% by weight, may be 60% by weight or more, and 70% by weight. % or more, 80 weight % or more, 90 weight % or more, 95 weight % or more, or 98 weight % or more.
  • the alcohol peeling involves supplying an alcohol solution near the outer edge of the adhesive sheet attached to the adherend, and applying the alcohol liquid from the outer edge of the adhesive sheet to the adhesive sheet and the adherend. After the adhesive sheet enters the interface, the adhesive sheet is peeled off without supplying new alcohol (that is, using only the alcohol that was supplied to the adherend before the start of peeling). Can be done.
  • the alcohol liquid that follows the movement of the peeling front and enters the interface between the adhesive sheet and the adherend runs out during the alcohol peeling process, the alcohol liquid may be removed intermittently after the start of the alcohol peeling process. Alternatively, additional alcohol liquid may be continuously supplied.
  • the amount of alcohol liquid (for example, ethanol) supplied before the start of peeling is not particularly limited, as long as it can introduce the alcohol liquid to the interface between the adhesive sheet and the adherend from outside the area where the adhesive sheet is attached.
  • the amount of the alcohol solution may be, for example, 5 ⁇ L or more, suitably 10 ⁇ L or more, and may be 20 ⁇ L or more. Further, there is no particular restriction on the upper limit of the amount of the alcohol solution.
  • the amount of the alcoholic liquid may be, for example, 10 mL or less, 5 mL or less, 1 mL or less, 0.5 mL or less, 0.1 mL or less. It may be 0.05 mL or less.
  • the operation of injecting alcohol liquid into the interface between the adhesive sheet and the adherend from the outer edge of the adhesive sheet can be performed, for example, by inserting the tip of a jig such as a cutter knife or needle into the interface at the outer edge of the adhesive sheet. Insert the adhesive sheet, scratch the outer edge of the adhesive sheet with a hook or nail, etc., and lift it up, or attach a strong adhesive tape, suction cup, etc. to the back surface near the outer edge of the adherend and lift the edge of the adhesive sheet. It can be carried out.
  • a jig such as a cutter knife or needle
  • the alcohol peeling step can be preferably carried out in such a manner that the peeling front is moved at a speed of 10 mm/min or more.
  • Moving the peeling front at a speed of 10 mm/min or more corresponds to peeling the adhesive sheet at a tensile speed of 20 mm/min or more, for example, under the condition of a peeling angle of 180 degrees.
  • the speed at which the peeling front is moved may be, for example, 50 mm/min or more, 150 mm/min or more, 300 mm/min or more, or 500 mm/min or more.
  • the upper limit of the speed at which the peeling front is moved is not particularly limited.
  • the speed at which the peeling front is moved may be, for example, 1000 mm/min or less.
  • the alcohol peeling disclosed herein is carried out, for example, in such a manner that the peeled area of the adhesive sheet per 10 ⁇ L volume of the alcohol solution (e.g. ethanol) used in the method is, for example, 50 cm 2 or more, preferably 100 cm 2 or more. be able to.
  • the alcohol solution e.g. ethanol
  • the pressure-sensitive adhesive sheet used in the peeling method disclosed herein is not particularly limited as long as it can exhibit the effect of reducing adhesive force by alcohol peeling, and various types can be used.
  • the adhesive sheet has an ethanol peel force on a stainless steel plate (hereinafter referred to as "ethanol peel force on a stainless steel plate”) measured at a temperature of 23° C., a tensile speed of 300 mm/min, and a peel angle of 180 degrees.
  • force N1 SUS or simply "ethanol peeling force N1 SUS ”
  • adherends examples include adherends whose adherend surfaces are made of a material such as glass, metal (eg, stainless steel, aluminum, etc.), resin (eg, PET, PI, etc.).
  • adherends whose adherend surfaces are made of a material such as glass, metal (eg, stainless steel, aluminum, etc.), resin (eg, PET, PI, etc.).
  • adherends with relatively low hydrophilicity for example, adherends whose adherend surface is made of metal, resin, etc.).
  • the re-peelability from the adherend can be improved.
  • the ethanol peeling force N1 SUS of the pressure-sensitive adhesive sheet to the stainless steel plate is more preferably 0.48 N/20 mm or less, still more preferably 0.45 N/20 mm or less, particularly preferably 0.4 N/20 mm or less.
  • the ethanol peeling force N1 SUS of the pressure-sensitive adhesive sheet to the stainless steel plate may be 0.35 N/20 mm or less, or 0.3 N/20 mm or less.
  • the lower limit of the ethanol peeling force N1 SUS is not particularly limited. In principle, the ethanol peeling force N1 SUS is 0 N/20 mm or more.
  • the ethanol peeling force N1 SUS of the adhesive sheet to the stainless steel plate may be 0.05 N/20 mm or more, and 0.1 N/20 mm or more. But that's fine.
  • the ethanol peel force N1 SUS of the adhesive sheet to the stainless steel plate may be 0.2 N/20 mm or less, 0.1 N/20 mm or less, or 0.05 N/20 mm or less. It may be 0.03 N/20 mm or less.
  • the lower limit of the ethanol peeling force N1 SUS of the pressure-sensitive adhesive sheet to the stainless steel plate is not particularly limited. In principle, the ethanol peeling force N1 SUS is 0 N/20 mm or more.
  • the ethanol peeling force N1 SUS against a stainless steel plate is measured in detail by the following method. A similar measurement method is used in the examples described later.
  • a test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm.
  • An evaluation sample in which the adhesive side of the test piece was bonded to a stainless steel plate (SUS304BA plate) as an adherend using a hand roller was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C. After holding the evaluation sample taken out from the autoclave in an environment of 23°C and 50% RH for one day, in the same environment, 2 ⁇ L of ethanol was applied to the surface of the adherend exposed from the end near one longitudinal end of the test piece. drip.
  • JIS Z0237:2009 10.4.1 Method 1 180° peeling adhesive force to the test plate Accordingly, specifically, the peel strength was measured using a tensile tester at a test temperature of 23° C. at a tensile speed of 300 mm/min and a peel angle of 180 degrees, and this was determined as the ethanol peel force against the stainless steel plate N1 SUS [N /20mm].
  • the contact angle of the surface of the stainless steel plate (SUS304BA plate) used as the adherend to which the adhesive sheet is bonded to ethanol is approximately 10 degrees, and the contact angle to distilled water is approximately 85 degrees.
  • the adhesive sheet has adhesive strength (hereinafter referred to as "stainless steel”) to a stainless steel plate measured at a temperature of 23° C., a tensile speed of 300 mm/min, and a peel angle of 180 degrees.
  • the adhesive force to the steel plate (also referred to as “adhesive force N0 SUS “ or simply “adhesive force N0 SUS ”) is 3.0 N/20 mm or more.
  • adherends for example, adherends whose adherend surface is made of metal, resin, etc.
  • the adhesive force N0 SUS of the adhesive sheet to the stainless steel plate is more preferably 3.5 N/20 mm or more, still more preferably 4.0 N/20 mm or more, particularly preferably 4.5 N/20 mm or more.
  • the upper limit of the adhesive force N0 SUS to the stainless steel plate is not particularly limited. From the viewpoint of balancing other adhesive properties, the adhesive force N0 SUS of the adhesive sheet to the stainless steel plate may be 15 N/20 mm or less, 10 N/20 mm or less, or 7 N/20 mm or less.
  • the adhesive force N0 SUS of the adhesive sheet to the stainless steel plate may be less than 3.0 N/20 mm, may be less than 2.5 N/20 mm, or may be less than 2.0 N/20 mm. , 1.0N/20mm or less.
  • the lower limit of the adhesive force N0 SUS of the adhesive sheet to the stainless steel plate is not particularly limited. In principle, the adhesive force N0 SUS is 0 N/20 mm or more, for example, it may be 0.1 N/20 mm or more, or it may be 0.2 N/20 mm or more.
  • the adhesive force N0 SUS to a stainless steel plate is measured by the following method. A similar measuring method is used in the examples described later.
  • a test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm.
  • An evaluation sample in which the adhesive side of the test piece was bonded to a stainless steel plate (SUS304BA plate) as an adherend using a hand roller was placed in an autoclave and treated at a pressure of 5 atm and a temperature of 50° C. for 15 minutes.
  • a cutter knife was inserted into the interface between the test piece and the adherend under the same environment to cut the longitudinal direction of the test piece.
  • the adhesive sheet has a rectangular adhesive sheet with a width of 20 mm, and is measured at a temperature of 23° C., at a tensile rate of 300 mm/min, and at a peel angle of 180 degrees, with respect to a stainless steel plate.
  • the adhesive force reduction distance (hereinafter also referred to as "adhesive force reduction distance R SUS to stainless steel plate” or simply “adhesive force reduction distance R SUS ”) is 30 mm or more.
  • an adhesive sheet whose adhesion force reduction distance R SUS to a stainless steel plate is 30 mm or more, alcohol liquid is supplied to the interface between the adhesive sheet and the adherend (for example, an adherend whose adherend surface is made of metal, resin, etc.).
  • the effects of the adhesive force reducing means tend to continue without deterioration.
  • a pressure-sensitive adhesive sheet that maintains the effect of reducing adhesive force is preferable from the viewpoint of reducing the amount of alcohol used in the peeling process and working efficiency.
  • the adhesive force reduction distance R SUS to a stainless steel plate is measured by the following method. A similar measuring method is used in the examples described later.
  • a test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm.
  • An evaluation sample in which the adhesive side of the test piece was bonded to a stainless steel plate (SUS304BA plate) as an adherend using a hand roller was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C. After holding the evaluation sample taken out from the autoclave in an environment of 23°C and 50% RH for one day, in the same environment, 2 ⁇ L of ethanol was applied to the surface of the adherend exposed from the end near one longitudinal end of the test piece. drip.
  • JIS Z0237:2009 10.4.1 Method 1 180° peeling adhesive force to the test plate Accordingly, specifically, the peel strength is continuously measured at a test temperature of 23° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. At this time, the peel strength that is continuously measured starting from the point where ethanol is dropped on the interface is 0.5 ⁇ (adhesive force N0 SUS - ethanol peel force N1) than the ethanol peel force N1 SUS [N/20 mm]. Measure the moving distance of the peeling front of the adhesive sheet from the start point to the end point when the end point is the point where the area has increased by more than SUS ) [N/20 mm], and define this as the adhesive force reduction distance R SUS [mm].
  • an adherend for example, an adherend whose adherend surface is made of metal or resin
  • the adhesive strength reduction rate S SUS is suitably 70% or more, preferably 80% or more, more preferably more than 90%, and still more preferably 92% or more, For example, it may be 95% or more, or 97% or more.
  • the upper limit of the adhesive force reduction rate S SUS is 100% in principle, and is, for example, less than 100%.
  • the pressure-sensitive adhesive sheet has an ethanol peel force against a glass plate (hereinafter referred to as "ethanol peel force against a glass plate”) measured at a temperature of 23° C., a tensile speed of 300 mm/min, and a peel angle of 180 degrees. It is preferable that the pressure-sensitive adhesive sheet has a force N1 GLA or simply "ethanol peeling force N1 GLA " of 0.5 N/20 mm or less. If an adhesive sheet with an ethanol peeling force N1 GLA of 0.5 N/20 mm or less for the glass plate is used, re-peelability from the adherend can be improved even when the adherend surface is made of glass, for example. can be improved.
  • the ethanol peel force N1 GLA of the adhesive sheet to the glass plate is more preferably 0.45 N/20 mm or less (for example, 0.4 N/20 mm or less), and even more preferably 0.3 N/20 mm or less (for example, 0.25 N/20 mm or less). 20 mm or less), particularly preferably 0.2 N/20 mm or less.
  • the ethanol peel force N1 GLA of the adhesive sheet to the glass plate may be 0.15 N/20 mm or less, or 0.1 N/20 mm or less.
  • the lower limit of the ethanol peeling force N1 GLA is not particularly limited. In principle, the ethanol peeling force N1 GLA is 0 N/20 mm or more. From the viewpoint of balancing adhesive properties when bonding to an adherend, the ethanol peeling force N1 GLA of the adhesive sheet to the glass plate may be 0.05 N/20 mm or more, and 0.1 N/20 mm or more. But that's fine.
  • the ethanol peel force N1 GLA of the adhesive sheet to the glass plate may be 0.2 N/20 mm or less, 0.1 N/20 mm or less, or 0.05 N/20 mm or less. It may be 0.03 N/20 mm or less.
  • the lower limit of the ethanol peeling force N1 GLA of the pressure-sensitive adhesive sheet to the glass plate is not particularly limited. In principle, the ethanol peeling force N1 GLA is 0 N/20 mm or more.
  • the ethanol peeling force N1 GLA with respect to the glass plate is specifically measured by the following method. A similar measuring method is used in the examples described later.
  • a test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm.
  • An evaluation sample was prepared by pasting the adhesive side of the above test piece onto an alkali glass plate (manufactured by Matsunami Glass Industries Co., Ltd., manufactured by the float method, thickness 1.35 mm, blue plate edge polished) using a hand roller. The sample was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C.
  • the contact angle of the surface of the alkali glass plate used as the adherend to which the adhesive sheet is bonded to ethanol is about 10 degrees, and the contact angle to distilled water is 8 degrees.
  • the adherends used for measuring the adhesive force N0 GLA to the glass plate and the adhesive force reduction distance R GLA to the glass plate below is the same applies.
  • the adhesive sheet has adhesive strength (hereinafter referred to as "glass adhesive strength”) to a glass plate measured at a temperature of 23° C., a tensile speed of 300 mm/min, and a peeling angle of 180 degrees.
  • the adhesive force to the plate also referred to as “adhesive force N0 GLA “ or simply “adhesive force N0 GLA ”
  • N0 GLA adhesive force to the plate
  • it has excellent adhesion reliability to the adherend before peeling (for example, an adherend whose adherend surface is made of glass). It tends to show gender.
  • the adhesive force N0 GLA of the adhesive sheet to the glass plate is more preferably 3.5 N/20 mm or more, still more preferably 4.0 N/20 mm or more, particularly preferably 4.5 N/20 mm or more.
  • the upper limit of the adhesive force N0 GLA to the glass plate is not particularly limited. From the viewpoint of balancing other adhesive properties, the adhesive force N0 GLA of the adhesive sheet to the glass plate may be 20 N/20 mm or less, 15 N/20 mm or less, 10 N/20 mm or less, 8 It may be .5N/20mm or less.
  • the adhesive force N0 GLA of the adhesive sheet to the glass plate may be less than 3.0 N/20 mm, may be less than 2.5 N/20 mm, or may be less than 2.0 N/20 mm. , 1.0N/20mm or less.
  • the lower limit value of the adhesive force N0 GLA of the adhesive sheet to the glass plate is not particularly limited. In principle, the adhesive force N0 GLA is 0 N/20 mm or more, for example, it may be 0.1 N/20 mm or more, or it may be 0.2 N/20 mm or more.
  • the adhesive force N0 GLA to the glass plate is measured by the following method. A similar measurement method is used in the examples described later.
  • a test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm.
  • An evaluation sample was prepared by pasting the adhesive side of the above test piece onto an alkali glass plate (manufactured by Matsunami Glass Industries Co., Ltd., manufactured by the float method, thickness 1.35 mm, blue plate edge polished) using a hand roller. The sample was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C.
  • the adhesive sheet has a rectangular adhesive sheet with a width of 20 mm, and is measured at a temperature of 23° C., at a tensile rate of 300 mm/min, and at a peeling angle of 180 degrees with respect to a glass plate.
  • the adhesive force reduction distance (hereinafter also referred to as "adhesive force reduction distance RGLA “ or simply “adhesive force reduction distance RGLA ”) is 30 mm or more.
  • R GLA adhesion force reduction distance
  • R GLA adhesion force reduction distance
  • the effect of the adhesive force reducing means included therein tends to be sustained without deterioration.
  • a pressure-sensitive adhesive sheet that maintains the effect of reducing adhesive force is preferable from the viewpoint of reducing the amount of alcohol used in the peeling process and working efficiency.
  • the adhesive force reduction distance R GLA to the glass plate is specifically measured by the following method. A similar measuring method is used in the examples described later.
  • a test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm.
  • An evaluation sample was prepared by pasting the adhesive side of the above test piece onto an alkali glass plate (manufactured by Matsunami Glass Industries Co., Ltd., manufactured by the float method, thickness 1.35 mm, blue plate edge polished) using a hand roller. The sample was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C.
  • the peel strength continuously measured starting from the point where ethanol was dropped on the above interface was 0.5 ⁇ (adhesive force N0 GLA - ethanol peel force N1) than the ethanol peel force N1 GLA [N/20 mm].
  • GLA ) [N/20 mm] or more is the end point, and the moving distance of the peeling front of the adhesive sheet from the start point to the end point is measured, and this is defined as the adhesive force reduction distance R GLA [mm].
  • Adhesive force reduction rate S GLA (Adhesive force reduction rate S GLA )
  • Adhesive sheets with a high adhesive strength reduction rate S GLA have sufficient adhesive strength when attached to an adherend (for example, an adherend whose surface is made of glass), but when peeled off and removed, adhesive sheets such as ethanol etc. By peeling using an alcohol solution, the load applied to the adherend during peeling can be significantly reduced.
  • the adhesive force reduction rate S GLA is suitably more than 70%, preferably 90% or more, for example, it may be 92% or more, it may be 95% or more, it may be 97% or more. But that's fine.
  • the upper limit of the adhesive force reduction rate S GLA is 100% in principle, and is, for example, less than 100%.
  • FIG. 1 shows an example of the configuration of the adhesive sheet disclosed herein.
  • This adhesive sheet 1 is a one-sided adhesive including an adhesive layer 10 whose one surface 10A is a surface to be attached to an adherend, and a support 20 laminated on the other surface 10B of the adhesive layer 10. It is constructed as a sticky adhesive sheet.
  • the adhesive layer 10 is fixedly bonded to one surface 20A of the support 20.
  • a plastic film such as a polyester film can be used.
  • the adhesive layer 10 has a single-layer structure. That is, the entire adhesive layer 10 is constituted by the A layer that constitutes one surface (adhesive surface) 10A of the adhesive layer 10.
  • the adhesive sheet 1 before use (before being attached to an adherend) is, for example, as shown in FIG. It may be in the form of an adhesive sheet 50 with a release liner, which is protected by a release liner.
  • the second surface 20B (the surface opposite to the first surface 20A, also referred to as the back surface) of the support 20 is a release surface, and the adhesive surface 10A is in contact with the second surface 10B.
  • the adhesive surface 10A may be protected by being wound or laminated.
  • the release liner is not particularly limited, and includes, for example, a release liner in which the surface of a liner base material such as a resin film or paper has been subjected to release treatment, a fluorine-based polymer (such as polytetrafluoroethylene), or a polyolefin-based resin (such as polyethylene, polypropylene, etc.). ) can be used, such as a release liner made of a low adhesive material.
  • a silicone-based, long-chain alkyl-based, or other release agent may be used for the above-mentioned peeling treatment.
  • a release-treated resin film may be preferably employed as the release liner.
  • the adhesive sheet in the technology disclosed herein has good reworkability because it can be easily peeled off from the adherend using an alcohol solution, and has excellent adhesion reliability with the adherend during bonding.
  • fixing, bonding, molding, decoration, protection, etc. of the members in the form of attaching them to the adherends for example, members constituting various mobile devices, automobiles, home appliances, etc. It can be used for purposes such as support.
  • the material constituting at least the surface of the above member includes, for example, glass such as an alkali glass plate or non-alkali glass; metal materials such as resin film, stainless steel (SUS), and aluminum; acrylic resin, ABS resin, polycarbonate resin, and polystyrene resin. resin materials such as; etc.
  • the adhesive sheet disclosed herein has a surface coated with a paint such as acrylic, polyester, alkyd, melamine, urethane, acid-epoxy crosslinked, or a composite of these (e.g., acrylic-melamine, alkyd-melamine). Alternatively, it may be attached to a plated surface such as a galvanized steel plate.
  • the adhesive sheet disclosed herein may be, for example, a component of a member with an adhesive sheet, in which such a member (adherent) is joined to the adhesive sheet.
  • the member with the adhesive sheet will also be referred to as a "joint body".
  • the adhesive sheet peeling method disclosed herein can also be understood as a method for separating a member (joined body) with an adhesive sheet as described above.
  • the surface of the member that comes into contact with the adhesive layer (that is, the surface of the adherend to which the adhesive sheet is attached, hereinafter also referred to as the "joining surface") is
  • the surface may have an affinity for ethanol such that the contact angle with respect to ethanol is, for example, 60 degrees or less, preferably 50 degrees or less.
  • the ethanol contact angle of the bonded surface is preferably 40 degrees or less, more preferably 30 degrees or less (for example, 25 degrees or less), still more preferably 20 degrees or less, and 15 degrees or less. The following may be used.
  • the ethanol contact angle of the bonding surface becomes smaller, the alcohol liquid tends to wet and spread along the bonding surface, and the alcohol removability of the pressure-sensitive adhesive sheet tends to improve. This is preferable from the viewpoint of improving re-peelability when producing a member with a pressure-sensitive adhesive sheet by bonding the pressure-sensitive adhesive sheet to the bonding surface.
  • the contact angle of the bonding surface is at least one of the angles mentioned above at the time when the adhesive sheets are bonded together (for example, 30 minutes before bonding), then the contact angle is less than the predetermined value. The effect of improving releasability can be exhibited.
  • the lower limit of the contact angle with respect to ethanol is 0 degrees in principle. In some embodiments, the ethanol contact angle of the bonded surface may be greater than 0 degrees, greater than or equal to 1 degree, greater than or equal to 3 degrees, or greater than or equal to 5 degrees.
  • the surface (bonding surface) of the member that comes into contact with the adhesive layer may be a surface that exhibits such low hydrophilicity that the contact angle with respect to distilled water is, for example, 30 degrees or more, preferably 35 degrees or more.
  • the contact angle of the bonded surface with distilled water may be 40 degrees or more, 45 degrees or more, 50 degrees or more, or 60 degrees or more (for example, more than 60 degrees).
  • the technology disclosed herein tends to be able to achieve both adhesion to adherends and removability even on surfaces with relatively low hydrophilicity. This is significant in that it can be preferably applied to adherends to which conventional water peeling techniques are difficult to apply.
  • the bonded surface may have such hydrophilicity that the contact angle with respect to distilled water is, for example, 60 degrees or less, preferably 50 degrees or less. In some embodiments, the contact angle of the bonded surface to distilled water may be, for example, 45 degrees or less, 40 degrees or less, 35 degrees or less, or 30 degrees or less.
  • the contact angle of the bonding surface becomes smaller, the alcohol liquid tends to wet and spread along the bonding surface, and the alcohol removability of the pressure-sensitive adhesive sheet tends to improve. This is preferable from the viewpoint of improving reworkability when producing a member with a pressure-sensitive adhesive sheet by bonding the pressure-sensitive adhesive sheet to the bonding surface.
  • the contact angle of the bonded surface with distilled water is within any of the above-mentioned angle ranges at least at the time when the adhesive sheets are bonded together (for example, 30 minutes before bonding), then the contact angle is within the predetermined range.
  • the effect of improving reworkability can be exhibited by this.
  • the lower limit of the contact angle is 0 degrees in principle.
  • the contact angle of the bonded surface with distilled water may be greater than 0 degrees, may be greater than 1 degree, may be greater than 3 degrees, or may be greater than 5 degrees.
  • the contact angle of the bonded surface with respect to ethanol and with respect to distilled water is measured as follows. That is, in a measurement atmosphere of 23°C and 50% RH, a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., trade name "DMo-501 type", a control box “DMC-2", and a control/analysis software "FAMAS") was used. Measurements are performed by the droplet method using version 5.0.30). The amount of ethanol dropped when measuring the contact angle for ethanol and the amount of distilled water dropped when measuring the contact angle for distilled water are each 2 ⁇ L, and the contact angle is calculated using the ⁇ /2 method from the image 5 seconds after dropping. (Implemented on N5).
  • An example of a preferred use is optical use. More specifically, for example, as a method for peeling an optical pressure-sensitive adhesive sheet used for bonding optical members (for bonding optical members) or for manufacturing products (optical products) in which the above-mentioned optical members are used, The peeling method disclosed herein can be preferably implemented.
  • the above-mentioned optical member refers to a member having optical properties (for example, polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, optical rotation, visibility, etc.). say.
  • the above-mentioned optical member is not particularly limited as long as it has optical properties, but for example, it may be a member constituting a device (optical device) such as a display device (image display device) or an input device, or a member used in these devices.
  • Members include, for example, polarizing plates, wavelength plates, retardation plates, optical compensation films, brightness enhancement films, light guide plates, reflective films, antireflection films, hard coat (HC) films, shock absorption films, antifouling films, Photochromic films, light control films, transparent conductive films (ITO films), design films, decorative films, surface protection plates, prisms, lenses, color filters, transparent substrates, and members on which these are laminated (collectively referred to as (sometimes referred to as "functional film”).
  • plate and “film” each include forms such as plate, film, and sheet.
  • polarizing film includes “polarizing plate”, “polarizing sheet”, etc. .
  • the above-mentioned display devices include liquid crystal display devices, organic EL display devices, PDPs, electronic paper, etc.
  • the disclosed technology is preferably applied.
  • the display device includes a display device that allows input, such as a touch panel. There is a strong demand for recycling, reuse, etc. of the display device, and it is particularly meaningful to apply the technology disclosed herein.
  • optical member is not particularly limited, but includes, for example, a member (for example, a sheet-like, film-like, or plate-like member) made of glass, acrylic resin, polycarbonate, polyethylene terephthalate, metal thin film, etc.
  • a member for example, a sheet-like, film-like, or plate-like member
  • acrylic resin for example, acrylic resin, polycarbonate, polyethylene terephthalate, metal thin film, etc.
  • optical member in this specification also includes members (design films, decorative films, surface protection films, etc.) that serve to decorate and protect while maintaining the visibility of display devices and input devices.
  • the bonded body disclosed herein and the products, devices, and structures that include the bonded body require high adhesion reliability using adhesive sheets when joining members, while repairing and repairing component parts. It can be a component of an electronic device (preferably a portable electronic device) that requires smooth removal during replacement, inspection, recycling, etc.
  • an electronic device preferably a portable electronic device
  • mobile phones, smartphones, tablet computers, notebook computers, various wearable devices e.g., wristwear type that is worn on the wrist like a wristwatch, modular type that is worn on a part of the body with a clip or strap, etc.
  • glasses type e.g., glasses types including monocular and binocular types, including head-mounted types, clothing types that are attached to shirts, socks, hats, etc.
  • the display device may be a component of an electronic device such as a desktop personal computer, a display, or a television (liquid crystal, plasma, organic EL, etc.).
  • "portable” does not mean that it is simply portable; it also means that it has a level of portability that allows an individual (standard adult) to carry it relatively easily. shall mean.
  • the peeling method disclosed herein can damage or damage the surfaces of glass, metals, organic materials (e.g., PET, PI, etc.) during processing, transportation, storage, etc. It can be preferably applied to a method for peeling off a surface protection sheet that is used by adhering to the surface for the purpose of preventing staining.
  • the above-mentioned surface protection sheet requires a certain degree of adhesion reliability in order to protect the surface of the adherend, but it also needs to be removed at an appropriate time after the protective purpose is achieved. It is desired that it can be easily peeled off and removed from the body.
  • adherends including adherends with low hydrophilicity to which conventional water peeling techniques are difficult to apply, and exhibits an excellent peeling force reduction effect. It is useful as a peeling method.
  • the shape of the adhesive in the adhesive sheet disclosed herein is not particularly limited, and may be a regular or random pattern such as dots or stripes, but typically it is continuously formed. It is in the form of a layered adhesive layer.
  • the adhesive sheet disclosed herein is, for example, configured as a support-less double-sided adhesive sheet consisting of an adhesive layer, or a single-sided adhesive in which an adhesive layer is arranged on one side of a support (substrate). It may be configured as a sheet (single-sided adhesive sheet), or it may be configured as a double-sided adhesive sheet (double-sided adhesive sheet) having an intermediate layer such as a base layer.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is not limited to a single-layer structure, and may further include one or more pressure-sensitive adhesive layers having the same or different compositions.
  • the intermediate layer may be a pressure-sensitive adhesive layer, and in that case, the pressure-sensitive adhesive sheet includes first and second pressure-sensitive adhesive layers that constitute the surface of the pressure-sensitive adhesive sheet, and It may have at least three adhesive layers, including an adhesive layer as a layer.
  • the adhesive constituting the adhesive layer examples include acrylic adhesives, rubber adhesives (natural rubber, synthetic rubber, mixtures thereof, etc.), silicone adhesives, polyester adhesives, and urethane adhesives.
  • the adhesive may include one or more types of adhesives selected from various known adhesives, such as adhesives, polyether adhesives, polyamide adhesives, and fluorine adhesives.
  • the acrylic adhesive refers to an adhesive whose main component (base polymer) is an acrylic polymer. The same meaning applies to rubber adhesives and other adhesives.
  • the “base polymer” of the adhesive refers to the main component of the rubbery polymer contained in the adhesive, and is not interpreted in any limited manner other than this.
  • the above-mentioned rubbery polymer refers to a polymer that exhibits rubber elasticity in a temperature range around room temperature.
  • the term "main component” refers to the component contained in the largest proportion among the contained components on a weight basis. Therefore, for example, when the adhesive is composed of three or more components, the content of the main components in the adhesive may be 34% by weight or more.
  • the term "acrylic polymer” refers to a polymer derived from a monomer component containing more than 50% by weight of an acrylic monomer, and is also referred to as an acrylic polymer.
  • the above-mentioned acrylic monomer refers to a monomer derived from a monomer having at least one (meth)acryloyl group in one molecule.
  • (meth)acryloyl refers comprehensively to acryloyl and methacryloyl.
  • (meth)acrylate” comprehensively refers to acrylate and methacrylate
  • “(meth)acrylic” comprehensively refers to acrylic and methacrylic.
  • an acrylic adhesive may be preferably employed as a constituent material of the adhesive.
  • the adhesive disclosed herein may be an acrylic adhesive containing an acrylic polymer.
  • Acrylic adhesives tend to be superior in transparency, weather resistance, and design freedom.
  • Acrylic pressure-sensitive adhesives with high transparency are preferably used for optical applications and, ultimately, for bonding applications for display devices.
  • the adhesive disclosed herein includes, for example, a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms at the ester end in a proportion of 33% by weight or more.
  • the base polymer contains an acrylic polymer composed of monomer components.
  • a (meth)acrylic acid alkyl ester having an alkyl group having at least X and Y or less carbon atoms at the ester end may be referred to as "(meth)acrylic acid C XY alkyl ester.” Since it is easy to balance the properties, the proportion of (meth)acrylic acid C 1-20 alkyl ester in the total monomer components of the acrylic polymer according to some embodiments is, for example, 35% by weight or more, and 50% by weight. % or more is suitable, and may be 55% or more by weight.
  • the proportion of (meth)acrylic acid C 1-20 alkyl ester among the monomer components may be, for example, 99.9% by weight or less, 99% by weight or less, or 95% by weight or less.
  • the proportion of (meth)acrylic acid C 1-20 alkyl ester in the entire monomer component of the acrylic polymer according to some embodiments may be, for example, 85% by weight or less from the viewpoint of cohesive properties of the adhesive. , 75% by weight or less, or 65% by weight or less.
  • the (meth)acrylic acid C 1-20 alkyl esters can be used alone or in combination of two or more.
  • the monomer component includes at least one of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
  • BA n-butyl acrylate
  • EHA 2-ethylhexyl acrylate
  • the (meth)acrylic acid C 10-14 alkyl ester include lauryl acrylate (LA).
  • (meth)acrylic acid C 10-14 alkyl ester one type can be used alone or two or more types can be used in combination. Furthermore, (meth)acrylic acid C 4-18 alkyl esters can be used alone or in combination of two or more.
  • the proportion of (meth)acrylic acid C 10-14 alkyl ester in the entire monomer component of the acrylic polymer is 3% by weight or more (for example, 5% by weight). or more), more preferably 10% by weight or more (for example, 20% by weight or more), still more preferably 25% by weight or more, 30% by weight or more, 40% by weight or more, 45% by weight or more. It may be at least 50% by weight, or at least 50% by weight.
  • the proportion of (meth)acrylic acid C 10-14 alkyl ester in the entire monomer component of the acrylic polymer may be 95% by weight or less, or may be 90% by weight or less. , 80% by weight or less, 75% by weight or less, 70% by weight or less, or 65% by weight or less.
  • the monomer components constituting the acrylic polymer may include a combination of (meth)acrylic acid C 4-9 alkyl ester and (meth)acrylic acid C 10-14 alkyl ester.
  • the ratio of (meth)acrylic acid C 10-14 alkyl ester to (meth)acrylic acid C 4-9 alkyl ester in the entire monomer component of the acrylic polymer is The weight-based content ratio is preferably 0.1 or more, more preferably 0.3 or more.
  • the weight-based content ratio of (meth)acrylic acid C 10-14 alkyl ester to (meth)acrylic acid C 4-9 alkyl ester in the entire monomer component of the acrylic polymer is 0. It may be 5 or more, 0.8 or more, 1.0 or more, 1.2 or more, 1.4 or more, 1.8 or more, or 2.0 or more. From the viewpoint of balancing adhesive performance, in some embodiments, the weight of (meth)acrylic acid C 10-14 alkyl ester relative to (meth)acrylic acid C 4-9 alkyl ester in the entire monomer component of the acrylic polymer
  • the standard content ratio is preferably 10 or less, more preferably 5.0 or less, may be 4.0 or less, or may be 3.0 or less.
  • the monomer components constituting the acrylic polymer include (meth)acrylic acid alkyl ester and, if necessary, other monomers (copolymerizable monomers) that can be copolymerized with (meth)acrylic acid alkyl ester. You can stay there.
  • the copolymerizable monomer monomers having polar groups (e.g., carboxyl group, hydroxyl group, nitrogen atom-containing ring, etc.) and monomers with a relatively high homopolymer glass transition temperature (e.g., 10° C. or higher) are preferably used. can do.
  • a monomer having a polar group can be useful for introducing crosslinking points into the acrylic polymer and increasing the cohesive force of the adhesive.
  • the copolymerizable monomers can be used alone or in combination of two or more.
  • Non-limiting examples of copolymerizable monomers include carboxy group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, monomers containing sulfonic acid groups or phosphoric acid groups, epoxy group-containing monomers, and cyano group-containing monomers.
  • isocyanate group-containing monomer isocyanate group-containing monomer, amide group-containing monomer, amino group-containing monomer, monomer having a nitrogen atom-containing ring, monomer having a succinimide skeleton, maleimides, aminoalkyl (meth)acrylates, alkoxy group-containing monomer, alkoxysilyl group Containing monomers, vinyl esters, vinyl ethers, aromatic vinyl compounds, olefins, (meth)acrylic esters having an alicyclic hydrocarbon group, (meth)acrylic esters having an aromatic hydrocarbon group, others, ( Heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl meth)acrylate, halogen atom-containing (meth)acrylates such as vinyl chloride and fluorine atom-containing (meth)acrylates, and silicon-containing (meth)acrylates such as silicone (meth)acrylates.
  • Examples include acrylates and (meth)acrylic acid esters obtained from terpene compound derivative alcohols.
  • carboxy group-containing monomers, hydroxyl group-containing monomers, monomers having a nitrogen atom-containing ring, and (meth)acrylic acid esters having an alicyclic hydrocarbon group are preferred.
  • carboxyl group-containing monomers examples include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and the like.
  • hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4)
  • Examples include hydroxyalkyl (meth)acrylates such as -hydroxymethylcyclohexyl)methyl (meth)acrylate.
  • Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -vinylthiazole
  • (meth)acrylic esters having an alicyclic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate.
  • (meth)acrylic esters having an alicyclic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate.
  • the amount used is not particularly limited, and is preferably 0.01% by weight or more based on the total monomer components.
  • the amount of the copolymerizable monomer used may be 0.1% by weight or more, or 0.5% by weight or more based on the total monomer components.
  • the amount of the copolymerizable monomer used is 60% by weight or less of the entire monomer component, and it may be 50% by weight or less, and 40% by weight or less. It may be less than %.
  • the monomer component constituting the acrylic polymer may include a hydroxyl group-containing monomer.
  • the hydroxyl group-containing monomer By using the hydroxyl group-containing monomer, the cohesive force and degree of crosslinking (for example, crosslinking using an isocyanate crosslinking agent) of the adhesive can be suitably adjusted.
  • the hydroxyl group-containing monomer those exemplified above can be used, and for example, 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA) can be preferably employed.
  • the hydroxyl group-containing monomers can be used alone or in combination of two or more.
  • the amount used is not particularly limited, and in some preferred embodiments, the amount of the hydroxyl group-containing monomer used is 15% by weight or more, preferably 20% by weight or more of the entire monomer component. , preferably 25% by weight or more. Further, from the viewpoint of suppressing water absorption of the adhesive, in some embodiments, it is appropriate that the amount of the hydroxyl group-containing monomer used is, for example, 50% by weight or less (for example, 45% by weight or less) of the entire monomer component. , 40% by weight or less, 30% by weight or less, or 20% by weight or less.
  • the monomer component constituting the acrylic polymer may include an alicyclic hydrocarbon group-containing (meth)acrylate.
  • an alicyclic hydrocarbon group-containing (meth)acrylate thereby, the cohesive force of the adhesive can be increased.
  • the alicyclic hydrocarbon group-containing (meth)acrylate those exemplified above can be used, and for example, cyclohexyl acrylate (CHA) and isobornyl acrylate can be preferably employed.
  • the alicyclic hydrocarbon group-containing (meth)acrylates can be used singly or in combination of two or more.
  • the amount used is not particularly limited, and can be, for example, 1% by weight or more, or 5% by weight or more of the entire monomer component, and even 10% by weight or more. good.
  • the upper limit of the amount of the alicyclic hydrocarbon group-containing (meth)acrylate used is suitably about 40% by weight or less, and may be 25% by weight or less (for example, 15% by weight or less).
  • the monomer component constituting the acrylic polymer may include a monomer having a nitrogen atom.
  • the cohesive force of the adhesive can be increased.
  • the monomer having a nitrogen atom those exemplified above can be used.
  • Preferred examples of the monomer having a nitrogen atom include monomers having a nitrogen atom-containing ring.
  • N-vinyl cyclic amides can be mentioned, and among them, N-vinyl-2-pyrrolidone can be preferably employed.
  • Monomers having a nitrogen atom can be used alone or in combination of two or more.
  • the amount of the monomer having a nitrogen atom is not particularly limited, and may be, for example, 1% by weight or more, or 5% by weight or more of the entire monomer component, Furthermore, it can be 10% by weight or more. Further, the amount of the monomer having a nitrogen atom to be used is preferably, for example, 40% by weight or less of the entire monomer component, may be 30% by weight or less, or may be 15% by weight or less.
  • the monomer components constituting the acrylic polymer include a combination of a (meth)acrylic acid C 10-14 alkyl ester and a monomer having a nitrogen atom (preferably a monomer having a nitrogen atom-containing ring). obtain.
  • the content of (meth)acrylic acid C 10-14 alkyl ester based on the weight of the monomer having a nitrogen atom (preferably the monomer having a nitrogen atom-containing ring) in the entire monomer component of the acrylic polymer.
  • the ratio is preferably 1 or more (for example, 3 or more), may be 5 or more, or may be 10 or more.
  • the weight-based ratio of (meth)acrylic acid C 10-14 alkyl ester to the monomer having a nitrogen atom (preferably the monomer having a nitrogen atom-containing ring) in the entire monomer component of the acrylic polymer is The content ratio is preferably 10,000 or less, may be 5,000 or less, may be 3,000 or less, or may be 2,000 or less. In some embodiments, the content of (meth)acrylic acid C 10-14 alkyl ester based on the weight of the monomer having a nitrogen atom (preferably the monomer having a nitrogen atom-containing ring) in the entire monomer component of the acrylic polymer. The ratio may be 1000 or less, 500 or less, 200 or less, 80 or less, 40 or less, or 20 or less.
  • the entire monomer component constituting the acrylic polymer is
  • the total content of (meth)acrylic acid C 10-14 alkyl ester and a monomer having a nitrogen atom (preferably a monomer having a nitrogen atom-containing ring) may be 8% by weight or more (for example, 10% by weight or more). It is preferably 15% by weight or more (for example, 20% by weight or more), still more preferably 25% by weight or more, may be 30% by weight or more, or may be 35% by weight or more.
  • the total of (meth)acrylic acid C 10-14 alkyl ester and a monomer having a nitrogen atom (preferably a monomer having a nitrogen atom-containing ring) in the entire monomer components constituting the acrylic polymer The content may be 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less.
  • the proportion of the carboxy group-containing monomer in the monomer components of the acrylic polymer may be, for example, less than 10% by weight, may be less than 3% by weight, and may be less than 1% by weight (for example, 0.1% by weight). (less than %). It is not necessary to substantially use a carboxy group-containing monomer as a monomer component of the acrylic polymer.
  • substantially not using a carboxy group-containing monomer means not using a carboxy group-containing monomer at least intentionally.
  • An acrylic polymer having such a composition can have metal corrosion inhibiting properties for adherends containing metal.
  • the composition of the monomer components constituting the acrylic polymer can be set so that the glass transition temperature Tg determined by the Fox equation is -75°C or more and 10°C or less based on the composition of the monomer components.
  • the above Tg is suitably 0°C or lower, preferably -10°C or lower, and -20°C or lower or -30°C or lower, from the viewpoint of adhesive strength or the like. Good too.
  • the Tg may be, for example, -60°C or higher, -50°C or higher, -45°C or higher, or -40°C or higher.
  • Tg is the glass transition temperature of the copolymer (unit: K)
  • Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio on a weight basis)
  • Tgi is the weight fraction of monomer i in the copolymer.
  • the glass transition temperature of the homopolymer used to calculate Tg As the glass transition temperature of the homopolymer used to calculate Tg, the numerical value described in publicly known materials, specifically "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) shall be used. . If multiple types of values are listed in this document, the highest value is adopted.
  • thermal polymerization initiator In the polymerization, a known or commonly used thermal polymerization initiator or photopolymerization initiator may be used depending on the polymerization method, polymerization mode, etc.
  • the thermal polymerization initiator is not particularly limited, but includes, for example, an azo polymerization initiator, a peroxide initiator, a redox initiator based on a combination of a peroxide and a reducing agent, and a substituted ethane initiator. etc. can be used.
  • the photopolymerization initiator is not particularly limited, but includes, for example, a ketal photopolymerization initiator, an acetophenone photopolymerization initiator, a benzoin ether photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and an ⁇ - Ketol photoinitiator, aromatic sulfonyl chloride photoinitiator, photoactive oxime photoinitiator, benzoin photoinitiator, benzyl photoinitiator, benzophenone photoinitiator, thioxanthone photoinitiator A polymerization initiator or the like can be used.
  • the polymerization initiators can be used alone or in an appropriate combination of two or more.
  • the amount of such a thermal polymerization initiator or photopolymerization initiator to be used can be a normal amount depending on the polymerization method, polymerization mode, etc., and is not particularly limited.
  • approximately 0.001 to 5 parts by weight (typically approximately 0.01 to 2 parts by weight, for example approximately 0.01 to 1 part by weight) of a polymerization initiator may be used for 100 parts by weight of the monomer to be polymerized. Can be done.
  • chain transfer agents which can also be understood as molecular weight regulators or polymerization degree regulators
  • chain transfer agent mercaptans such as n-dodecylmercaptan, t-dodecylmercaptan, thioglycolic acid, and ⁇ -thioglycerol
  • a chain transfer agent that does not contain sulfur atoms non-sulfur chain transfer agent
  • One type of chain transfer agent can be used alone or two or more types can be used in combination.
  • the amount used can be, for example, approximately 0.01 to 1 part by weight per 100 parts by weight of the monomer component.
  • the technology disclosed herein can also be preferably practiced in an embodiment that does not use a chain transfer agent.
  • the molecular weight of the acrylic polymer obtained by appropriately employing the various polymerization methods described above is not particularly limited, and can be set within an appropriate range depending on the required performance.
  • the weight average molecular weight (Mw) of the acrylic polymer is, for example, approximately 10 ⁇ 10 4 or more, and from the viewpoint of achieving both cohesive force and adhesive force in a well-balanced manner, it is appropriate to set it to more than 30 ⁇ 10 4 .
  • the acrylic polymer according to some embodiments preferably has a Mw of about 50 ⁇ 10 4 or more.
  • the upper limit of Mw of the acrylic polymer may be approximately 500 ⁇ 10 4 or less (for example, approximately 150 ⁇ 10 4 or less).
  • the Mw may be approximately 75 ⁇ 10 4 or less.
  • Mw refers to a standard polystyrene equivalent value obtained by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a model name "HLC-8320GPC” columnumn: TSKgelGMH-H(S), manufactured by Tosoh Corporation
  • TSKgelGMH-H(S) manufactured by Tosoh Corporation
  • the adhesive disclosed herein includes a monomer component having the composition described above in the form of a polymerized product, an unpolymerized product (that is, a form in which the polymerizable functional group is unreacted), or a mixture thereof.
  • the above adhesive compositions include water-dispersed adhesive compositions in which the adhesive (adhesive component) is dispersed in water, solvent-based adhesive compositions in which the adhesive is contained in an organic solvent, and UV and radiation resistant adhesive compositions.
  • An active energy ray-curable adhesive composition prepared to be cured by active energy rays to form an adhesive, and a hot melt adhesive composition that is applied in a heated molten state and forms an adhesive when cooled to around room temperature. It can be in various forms such as a composition.
  • the adhesive composition is a solvent-based adhesive composition or a solvent-free adhesive composition.
  • Solvent-free adhesive compositions include active energy ray-curable adhesive compositions and hot-melt adhesive compositions.
  • the alcohol peeling disclosed herein is a solvent-based adhesive formed from a solvent-based adhesive composition, and an active energy ray-curable adhesive composition formed from an active energy ray (typically ultraviolet curing) curable adhesive composition. Effective against adhesives (typically UV-curable adhesives).
  • the adhesive composition according to some embodiments may be an active energy ray-curable adhesive composition.
  • active energy rays refer to energy rays with energy capable of causing chemical reactions such as polymerization reactions, crosslinking reactions, and decomposition of initiators.
  • Examples of active energy rays herein include light such as ultraviolet rays, visible rays, and infrared rays, and radiation such as ⁇ rays, ⁇ rays, ⁇ rays, electron rays, neutron rays, and X rays.
  • a preferred example of the active energy ray-curable adhesive composition is a photocurable adhesive composition.
  • a photocurable pressure-sensitive adhesive composition has the advantage that even a thick pressure-sensitive adhesive layer can be easily formed. Among these, UV-curable pressure-sensitive adhesive compositions are preferred.
  • a photocurable pressure-sensitive adhesive composition typically contains at least a portion of the monomer components of the composition (which may be a portion of the type of monomer or a portion of the amount). Contains in the form of polymers.
  • the polymerization method used to form the above-mentioned polymer is not particularly limited, and various conventionally known polymerization methods can be employed as appropriate.
  • thermal polymerization such as solution polymerization, emulsion polymerization, and bulk polymerization (typically carried out in the presence of a thermal polymerization initiator); photopolymerization carried out by irradiating light such as ultraviolet rays (typically carried out in the presence of a thermal polymerization initiator); (Carried out in the presence of a photopolymerization initiator); Radiation polymerization carried out by irradiation with radiation such as ⁇ rays and ⁇ rays; etc. can be employed as appropriate. Among these, photopolymerization is preferred.
  • Photocurable pressure-sensitive adhesive compositions include a partial polymer of monomer components (for example, an acrylic partial polymer).
  • a partially polymerized product is typically a mixture of a polymer derived from a monomer component and an unreacted monomer, and preferably takes the form of a syrup (viscous liquid).
  • a partially polymerized product having such properties may be referred to as "monomer syrup” or simply “syrup.”
  • the polymerization method for partially polymerizing the monomer components is not particularly limited, and various polymerization methods such as those described above can be appropriately selected and used. From the viewpoint of efficiency and convenience, a photopolymerization method can be preferably employed. According to photopolymerization, the polymerization conversion rate (monomer conversion) of monomer components can be easily controlled by controlling the polymerization conditions such as the amount of light irradiation (light amount).
  • the polymerization conversion rate of the monomer mixture in the above partially polymerized product is not particularly limited.
  • the above polymerization conversion rate can be, for example, about 70% by weight or less, and from the viewpoint of ease of preparation and coatability of the adhesive composition containing the above partially polymerized product, it is suitably about 50% by weight or less. , preferably about 40% by weight or less.
  • the lower limit of the polymerization conversion rate is not particularly limited, it is typically about 1% by weight or more, and suitably about 5% by weight or more.
  • the adhesive composition containing the above partially polymerized product may contain other components used as necessary (for example, a photopolymerization initiator, a surfactant as described below, a crosslinking agent, a polyfunctional monomer, an acrylic oligomer, etc.). , tackifier resin, silane coupling agent, etc.) may be blended.
  • the method of blending such other components is not particularly limited, and for example, they may be included in the monomer mixture in advance, or may be added to the partially polymerized product.
  • the adhesive is an adhesive formed from a water-dispersed adhesive composition.
  • a typical example of a water-dispersed adhesive composition is an emulsion-type adhesive composition.
  • An emulsion type adhesive composition typically contains a polymer of monomer components and additives used as necessary. Emulsion polymerization of monomer components is usually carried out in the presence of an emulsifier. According to emulsion polymerization, a polymerization reaction solution in the form of an emulsion in which a polymer of monomer components is dispersed in water is obtained.
  • a water-dispersed adhesive composition used for forming an adhesive can be preferably manufactured using the above polymerization reaction liquid.
  • the emulsifier for emulsion polymerization is not particularly limited, and known anionic emulsifiers, nonionic emulsifiers, etc. can be used.
  • the emulsifiers can be used alone or in combination of two or more.
  • anionic emulsifiers include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkylphenyl ether sulfate, Examples include sodium ethylene alkyl phenyl ether sulfate and sodium polyoxyethylene alkyl sulfosuccinate.
  • Non-limiting examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyoxypropylene block polymers, and the like.
  • An emulsifier having a reactive functional group may also be used.
  • the reactive emulsifier include radically polymerizable emulsifiers having a structure in which a radically polymerizable functional group such as a propenyl group or an allyl ether group is introduced into the above-mentioned anionic emulsifier or nonionic emulsifier.
  • the amount of emulsifier used in emulsion polymerization may be, for example, 0.2 parts by weight or more, 0.5 parts by weight or more, 1.0 parts by weight or more, based on 100 parts by weight of the monomer components.
  • the amount may be 5 parts by weight or more.
  • the amount of emulsifier used is 10 parts by weight or less per 100 parts by weight of the monomer component. , is preferably 5 parts by weight or less, and may be 3 parts by weight or less.
  • the emulsifier used in the emulsion polymerization here can also function as a surfactant, which will be described later.
  • the adhesive composition according to some embodiments may be a solvent-based adhesive composition.
  • a solvent-based adhesive composition typically contains a solution polymer of monomer components and additives used as necessary.
  • the solvent (polymerization solvent) used in solution polymerization can be appropriately selected from conventionally known organic solvents (for example, toluene, ethyl acetate, etc.).
  • a polymerization reaction solution is obtained in which a polymer of monomer components is dissolved in a polymerization solvent.
  • the solvent-based adhesive composition disclosed herein can be preferably manufactured using the above polymerization reaction solution.
  • the adhesive includes a surfactant.
  • a surfactant By incorporating a surfactant into the adhesive, it is possible to effectively reduce the peeling force using an alcohol solution, thereby improving the alcohol peelability.
  • the reason for this is not particularly limited, but in general, surfactants tend to be unevenly distributed on the surface of the adhesive because they have a hydrophilic region, thereby effectively increasing the water affinity of the surface of the adhesive. It is considered that this effect effectively reduces the peeling force when the adhesive comes into contact with an alcohol solution, and improves the alcohol peelability.
  • the above-mentioned surfactant is typically contained in the adhesive composition (and thus the adhesive) in a free form.
  • the surfactant one that is liquid at room temperature (about 25° C.) can be preferably used from the viewpoint of ease of preparing the adhesive composition.
  • One kind of surfactant can be used alone or two or more kinds can be used in combination.
  • nonionic surfactants known nonionic surfactants, anionic surfactants, cationic surfactants, etc. can be used. Among these, nonionic surfactants are preferred.
  • One kind of surfactant can be used alone or two or more kinds can be used in combination.
  • nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, and polyoxyethylene alkyl ether; Polyoxyethylene alkylphenyl ethers such as oxyethylene nonylphenyl ether; Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monooleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene Polyoxyethylene sorbitans such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, etc.
  • anionic surfactants include alkyl sulfates such as lauryl sulfate and octadecyl sulfate; fatty acid salts; alkylbenzenesulfonates such as nonylbenzenesulfonate and dodecylbenzenesulfonate; dodecylnaphthalenesulfonate, etc.
  • alkyl diphenyl ether disulfonate such as dodecyl diphenyl ether disulfonate
  • polyoxyethylene alkyl ether sulfate such as polyoxyethylene octadecyl ether sulfate, polyoxyethylene lauryl ether sulfate; polyoxyethylene lauryl phenyl ether
  • Polyoxyethylene alkyl phenyl ether sulfates such as sulfates; polyoxyethylene styrenated phenyl ether sulfates; sulfosuccinates such as lauryl sulfosuccinate and polyoxyethylene lauryl sulfosuccinate; polyoxyethylene alkyl ether phosphates; Examples include polyoxyethylene alkyl ether acetate; and the like.
  • the salt may be, for example, a metal salt (preferably a monovalent metal salt) such as a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an ammonium salt, an amine salt, etc. It can be.
  • a metal salt preferably a monovalent metal salt
  • anionic surfactants can be used alone or in combination of two or more.
  • the content of the surfactant in the adhesive is not particularly limited, and can be set so that the effect of using the surfactant is appropriately exhibited.
  • the content of the surfactant can be, for example, 0.001 parts by weight or more per 100 parts by weight of the polymer (for example, acrylic polymer) contained in the adhesive, and 0.01 parts by weight.
  • the amount is suitably at least 0.05 parts by weight, preferably at least 0.05 parts by weight, and more preferably at least 0.1 parts by weight.
  • the content of the surfactant may be, for example, 1.0 parts by weight or more, or 1.5 parts by weight or more, based on 100 parts by weight of the polymer contained in the adhesive.
  • the amount of the surfactant used can be about 3 parts by weight or less, preferably about 2 parts by weight or less, based on 100 parts by weight of the polymer, Preferably it is less than 1 part by weight, more preferably less than 0.5 part by weight. By limiting the amount of surfactant used, it tends to be easier to maintain adhesive strength.
  • polyfunctional monomer A polyfunctional monomer may be used in the adhesive composition (and thus the adhesive) as necessary. Multifunctional monomers can serve for purposes such as adjusting cohesion.
  • the polyfunctional monomer forms a crosslinked structure with appropriate flexibility by reacting the above ethylenically unsaturated groups with light (e.g. ultraviolet light) irradiation when forming the adhesive layer or after pasting it on the adherend. It is possible. Therefore, in this specification, the term "polyfunctional monomer” can be interpreted as a crosslinking agent.
  • polyfunctional monomers can be preferably used in adhesives formed from photocurable adhesive compositions.
  • a compound having two or more ethylenically unsaturated groups can be used.
  • One type of polyfunctional monomer can be used alone or two or more types can be used in combination.
  • Examples of ethylenically unsaturated groups possessed by the polyfunctional monomer include, but are not limited to, acryloyl groups, methacryloyl groups, vinyl groups, and allyl groups.
  • Preferred ethylenically unsaturated groups from the viewpoint of photoreactivity include acryloyl and methacryloyl groups. Among them, an acryloyl group is preferred.
  • polyfunctional monomers examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.
  • the amount of the polyfunctional monomer used varies depending on its molecular weight, number of functional groups, etc.; ) Appropriately, the amount is in the range of about 0.01 parts by weight to 3.0 parts by weight per 100 parts by weight.
  • the adhesive composition disclosed herein may contain a crosslinking agent as necessary, mainly for the purpose of crosslinking within the adhesive (layer) or between the adhesive and its adjacent surface.
  • the type of crosslinking agent is not particularly limited, and may be selected from among conventionally known crosslinking agents so that the crosslinking agent exhibits an appropriate crosslinking function within the adhesive, depending on the composition of the adhesive composition, for example. Can be done.
  • crosslinking agents examples include isocyanate crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, carbodiimide crosslinking agents, melamine crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, and metals.
  • examples include chelate crosslinking agents, metal salt crosslinking agents, hydrazine crosslinking agents, and amine crosslinking agents. These can be used alone or in combination of two or more.
  • the content of the crosslinking agent (if two or more types of crosslinking agents are included, the total amount thereof) is not particularly limited. From the perspective of realizing a pressure-sensitive adhesive that exhibits adhesive properties such as adhesive strength and cohesive force in a well-balanced manner, the content of the crosslinking agent is determined by the amount of crosslinking agent contained in the pressure-sensitive adhesive. It is appropriate that the amount is approximately 5 parts by weight or less, preferably approximately 0.001 to 5 parts by weight, and approximately 0.001 to 4 parts by weight per 100 parts by weight of the monomer component of the polymer. More preferably, the amount is about 0.001 to 3 parts by weight. Alternatively, the pressure-sensitive adhesive composition may not contain a crosslinking agent as described above.
  • the adhesive composition may be substantially free of crosslinking agents such as isocyanate crosslinking agents.
  • crosslinking agent typically an isocyanate-based crosslinking agent
  • the amount of the crosslinking agent is less than 0.05 parts by weight (for example, 0.05 parts by weight) based on 100 parts by weight of the monomer components. 01 parts by weight).
  • a crosslinking catalyst may be used to advance the crosslinking reaction more effectively.
  • the adhesive composition used to form the adhesive may contain a crosslinking retarder (for example, a compound that causes keto-enol tautomerism), if desired.
  • the amounts of the crosslinking catalyst and crosslinking retarder to be used are not limited to a specific range, and are used in appropriate amounts depending on the purpose and the like.
  • the adhesive may contain a tackifying resin.
  • the tackifier resin include rosin-based tackifier resin, rosin derivative tackifier resin, petroleum-based tackifier resin, terpene-based tackifier resin, phenol-based tackifier resin, ketone-based tackifier resin, and the like. These can be used alone or in combination of two or more. Among these, one or more selected from rosin-based tackifier resins, rosin derivative tackifier resins, and terpene phenol resins can be preferably used.
  • a tackifying resin (preferably a rosin derivative tackifying resin) having a softening point of 80° C. or higher (for example, 120° C. or higher and 180° C. or lower) can be preferably used.
  • the amount of the tackifying resin to be used is preferably 1 part by weight or more per 100 parts by weight of the monomer component constituting the polymer contained in the adhesive, from the viewpoint of suitably exhibiting the effect of its use. It may be at least 10 parts by weight, at least 15 parts by weight, at least 20 parts by weight, or at least 25 parts by weight. Further, from the viewpoint of achieving both adhesion to the adherend and cohesiveness in a well-balanced manner, the amount of the tackifying resin used per 100 parts by weight of the monomer component may be, for example, 50 parts by weight or less, or 30 parts by weight or less. Alternatively, the content of the tackifying resin in the adhesive may be, for example, less than 1 part by weight per 100 parts by weight of the monomer component, and the adhesive may be substantially free of tackifying resin. It's okay.
  • the adhesive disclosed herein can contain an acrylic oligomer from the viewpoint of improving cohesive force and adhesion.
  • an acrylic oligomer it is preferable to use a polymer whose Tg is higher than that of the acrylic polymer.
  • acrylic oligomers are suitable because they are less likely to inhibit polymerization.
  • acrylic oligomers include dicyclopentanyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), and dicyclopentanyl acrylate (DCPA). , 1-adamantyl methacrylate (ADMA), and 1-adamantyl acrylate (ADA), as well as copolymers of DCPMA and methyl methacrylate (MMA), copolymers of DCPMA and IBXMA, and copolymers of ADA and MMA.
  • DCPMA dicyclopentanyl methacrylate
  • CHMA cyclohexyl methacrylate
  • IBXMA isobornyl methacrylate
  • IBXA isobornyl acrylate
  • DCPA dicyclopentanyl acrylate
  • ADMA 1-adamantyl methacrylate
  • ADA 1-adamantyl acrylate
  • Polymers copolymers of CHMA and isobutyl methacrylate (IBMA), copolymers of CHMA and IBXMA, copolymers of CHMA and acryloylmorpholine (ACMO), copolymers of CHMA and diethylacrylamide (DEAA) , a copolymer of CHMA and AA, and the like.
  • Acrylic oligomers can be used alone or in combination of two or more.
  • the Mw of the acrylic oligomer is typically about 1,000 or more and less than about 30,000, preferably about 1,500 or more and less than about 10,000, and more preferably about 2,000 or more and less than about 5,000. When Mw is within the above range, the effect of improving cohesion and adhesion to adjacent surfaces is likely to be suitably exhibited.
  • the Mw of the acrylic oligomer can be measured by gel permeation chromatography (GPC) and determined as a value in terms of standard polystyrene. Specifically, the measurement is performed using HPLC8020 manufactured by Tosoh Corporation with two columns of TSKgelGMH-H (20) at a flow rate of about 0.5 mL/min using tetrahydrofuran solvent.
  • the content can be, for example, 0.01 part by weight or more based on 100 parts by weight of the base polymer (typically an acrylic polymer), and more From the viewpoint of obtaining high effects, the amount may be 0.05 part by weight or more, or may be 0.1 part by weight or more. Further, from the viewpoint of compatibility with the base polymer, the content of the acrylic oligomer is preferably less than 30 parts by weight, and may be, for example, 10 parts by weight or less, or 1 part by weight or less.
  • the adhesive disclosed herein may also include a silane coupling agent.
  • the silane coupling agent is preferably contained in the adhesive composition (and thus the adhesive) in a free form.
  • the adhesive strength of the adhesive to an adherend tends to increase.
  • a silane coupling agent a silicon compound having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane; 3-chloro Propyltrimethoxysilane; acetoacetyl group-containing trimethoxysilane; (meth)acrylic group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; 3-isocyanatepropyltriethoxysilane
  • the amount of the silane coupling agent used can be set so as to obtain the desired effect of use, and is not particularly limited.
  • the amount of the silane coupling agent used may be, for example, 0.001 parts by weight or more based on 100 parts by weight of the monomer components constituting the polymer contained in the adhesive, to achieve a higher effect. From the viewpoint of obtaining, the amount may be 0.005 part by weight or more, 0.01 part by weight or more, or 0.015 part by weight or more. Further, in some embodiments, the amount of the silane coupling agent used may be, for example, 3 parts by weight or less, 1 part by weight or less, and 0.5 parts by weight or less, based on 100 parts by weight of the monomer components constituting the adhesive.
  • the technology disclosed herein can be implemented in an embodiment using an adhesive that does not substantially contain a silane coupling agent. By limiting the amount of the silane coupling agent used or not using the silane coupling agent, the releasability from the adherend tends to improve.
  • the adhesive disclosed herein may optionally contain a viscosity modifier (e.g., thickener), a pH adjuster, a leveling agent, a plasticizer, a filler, a coloring agent such as a pigment or dye, a stabilizer, and a preservative.
  • a viscosity modifier e.g., thickener
  • a pH adjuster e.g., a pH adjuster
  • a leveling agent e.g., a leveling agent
  • a plasticizer e.g., a leveling agent
  • a plasticizer e.g., ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate
  • the amount of components other than the base polymer (preferably acrylic polymer) in the adhesive may be limited.
  • the amount of components other than the base polymer in the adhesive is, for example, about 30% by weight or less, suitably about 15% by weight or less, preferably about 12% by weight or less ( For example, about 10% by weight or less).
  • a pressure-sensitive adhesive having such a composition easily satisfies predetermined optical properties (eg, transparency) and can be preferably used for optical applications.
  • the amount of components other than the base polymer in the adhesive may be about 5% by weight or less, about 3% by weight or less, about 1.5% by weight or less (e.g., about 1% by weight or less).
  • a composition in which the amount of components other than the base polymer (eg, acrylic polymer) is limited in this way can be preferably employed in a photocurable pressure-sensitive adhesive composition.
  • the adhesive layer may be a cured layer of the adhesive composition. That is, the adhesive layer can be formed by applying (for example, coating) an adhesive composition to a suitable surface and then appropriately performing a curing treatment. When performing two or more types of curing treatments (drying, crosslinking, polymerization, etc.), these can be performed simultaneously or in multiple stages. In pressure-sensitive adhesive compositions using partial polymers of monomer components (acrylic polymer syrup), a final copolymerization reaction is typically performed as the curing treatment. That is, the partially polymerized product is further subjected to a copolymerization reaction to form a complete polymerized product.
  • a photocurable adhesive composition for example, in the case of a photocurable adhesive composition, light irradiation is performed. Curing treatments such as crosslinking and drying may be performed as necessary. For example, if it is necessary to dry the photocurable adhesive composition (for example, in the case of a photocurable adhesive composition in which a partial polymer of a monomer component is dissolved in an organic solvent), dry the composition. It is preferable to perform photocuring after this. In an adhesive composition using a complete polymer, typically, as the curing treatment, treatments such as drying (heat drying) and crosslinking are performed as necessary.
  • An adhesive layer having a multilayer structure of two or more layers can be produced by bonding together adhesive layers formed in advance. Alternatively, a second adhesive layer may be formed by applying a pressure-sensitive adhesive composition onto a first pressure-sensitive adhesive layer formed in advance and curing the pressure-sensitive adhesive composition.
  • the adhesive composition can be applied using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, and a spray coater.
  • a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, and a spray coater.
  • the thickness of the adhesive layer is not particularly limited, and may be, for example, about 3 ⁇ m to 2000 ⁇ m. In some embodiments, the thickness of the adhesive layer is suitably 3 ⁇ m or more, preferably 10 ⁇ m or more, and more preferably 15 ⁇ m or more, from the viewpoint of adhesion to the adherend such as step followability. The thickness is more preferably 20 ⁇ m or more. Further, from the viewpoint of preventing adhesive residue from occurring due to cohesive failure of the adhesive layer, in some embodiments, the thickness of the adhesive layer is usually 500 ⁇ m or less, preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less. The thickness may be 50 ⁇ m or less, or even 30 ⁇ m or less.
  • the adhesive is preferably an optical adhesive.
  • the optical adhesive may be one that does not impair optical properties.
  • the haze value of the adhesive (layer) and ultimately the adhesive sheet is not particularly limited, but in some embodiments, it is appropriate that the haze value is approximately 10% or less, and approximately 5% or less (for example, approximately 3% or less). It can be.
  • the haze value is preferably 1.0% or less. Adhesives with such high transparency are suitable for optical applications that require high light transmittance.
  • the haze value may be less than 1.0%, may be less than 0.7%, and may be 0.5% or less (for example, 0 to 0.5%).
  • the haze value can be adjusted, for example, by selecting the composition and thickness of the adhesive.
  • the "haze value” refers to the ratio of diffusely transmitted light to the total transmitted light when visible light is irradiated onto the measurement target. Also called cloudiness value.
  • the haze value is determined by pasting the adhesive side of the adhesive layer or adhesive sheet on one side of alkali glass with a haze value of 0.1% to form a laminate of the adhesive layer or adhesive sheet and alkali glass, and then using a haze meter (for example, Murakami).
  • the alkali glass to which the adhesive layer or adhesive sheet is attached is placed so that the adhesive layer or adhesive sheet faces the light source side. Since the haze value of alkali glass is 0.1%, the value obtained by subtracting 0.1% from the measured value is defined as the haze value [%] of the adhesive layer or adhesive sheet.
  • the adhesive sheet includes a base layer.
  • the base layer is a support (support layer) that supports the adhesive layer.
  • the base layer may be an intermediate layer disposed between the first and second adhesive layers that constitute the surface of the adhesive sheet.
  • Examples of the base layer disclosed herein include various resin films such as polyolefin film, polyester film, and polyvinyl chloride film; foam sheets made of foams such as polyurethane foam, polyethylene foam, and polychloroprene foam; Woven fabrics and non-woven fabrics made of fibrous materials (natural fibers such as hemp and cotton, synthetic fibers such as polyester and vinylon, semi-synthetic fibers such as acetate, etc.) alone or in combination; Japanese paper, high-quality paper, and crafts. Examples include papers such as paper and crepe paper; metal foils such as aluminum foil, copper foil, and stainless steel (SUS); and the like. A layered body having a composite structure of these may also be used.
  • base material layers with such composite structures include, for example, laminated base materials with a structure in which metal foil and the above-mentioned resin film are laminated (multilayer base materials), resin sheets reinforced with inorganic fibers such as glass cloth, etc. can be mentioned.
  • the material for the base layer a material containing a base film that can independently maintain its shape (self-supporting or independent) can be preferably used.
  • the term "resin film” refers to a resin film that has a non-porous structure and typically is substantially void-free. Therefore, the resin film is a concept that is distinguished from foam films and nonwoven fabrics.
  • the resin film may have a single-layer structure or a multi-layer structure of two or more layers (for example, a three-layer structure).
  • the resin film may be a transparent film. Transparent resin films are suitable for optical applications.
  • Suitable examples of the resin material constituting the resin film include polyester resin, polyphenylene sulfide (PPS) resin, polyolefin resin, and polyimide resin.
  • resin films that can be preferably used as the base layer include polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, PPS film, polyetheretherketone (PEEK) film, transparent polyimide (CPI) film, and polypropylene.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PPS film polyetheretherketone
  • CPI transparent polyimide
  • TAC triacetyl cellulose
  • Preferred examples from the viewpoint of strength include PET film, PEN film, PPS film, PEEK film, and CPI film.
  • Preferred examples from the viewpoint of availability, dimensional stability, optical properties, etc. include PET film, CPI film, and TAC film.
  • additives such as light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, slip agents, anti-blocking agents, etc. may be added to the resin film as necessary. Can be done.
  • the amount of additives to be blended is not particularly limited, and can be appropriately set depending on the application and the like.
  • the method for producing the resin film is not particularly limited.
  • conventionally known general resin film forming methods such as extrusion molding, inflation molding, T-die casting molding, and calender roll molding can be appropriately employed.
  • the base material layer may be substantially composed of such a resin film.
  • the base layer may include an auxiliary layer in addition to the resin film.
  • auxiliary layers include surface treatment layers such as undercoat layers and release layers.
  • the surface of the base material layer on the adhesive layer side may be treated with corona treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of an undercoat (primer), antistatic treatment, peeling, etc., as necessary.
  • a conventionally known surface treatment such as a treatment may be applied.
  • the thickness of the base material layer is not particularly limited, and may be, for example, approximately 1000 ⁇ m or less, approximately 500 ⁇ m or less, and from the viewpoint of weight reduction and thinning, approximately 100 ⁇ m or less is appropriate, and may be 70 ⁇ m or less. Further, from the viewpoint of handleability, processability, etc., the thickness of the base material layer may be, for example, 1 ⁇ m or more, suitably about 20 ⁇ m or more, and preferably about 30 ⁇ m or more.
  • a method for peeling an adhesive sheet pasted on an adherend comprising: comprising applying an adhesive force reducing means to the adhesive sheet,
  • the adhesive force reducing means is supplying an alcohol solution to an interface between the adherend and the adhesive sheet at a peeling front of the adhesive sheet from the adherend;
  • a peeling method comprising moving a peeling front in a peeling advancing direction and allowing the alcohol solution to enter the interface following the movement of the peeling front.
  • the adhesive sheet is prepared by attaching the adhesive sheet to a stainless steel plate as an adherend, and after one day at room temperature, dropping 2 ⁇ L of ethanol onto the adherend, and applying the ethanol to the adhesive sheet and the adherend.
  • the adhesive sheet was prepared by pasting the adhesive sheet cut into a rectangular shape with a width of 20 mm on a stainless steel plate as an adherend, and after one day at room temperature, dropping 2 ⁇ L of ethanol onto the adherend.
  • Method 1 180° peeling adhesive force to the test plate, specifically, In (1) or (2) above, the adhesive strength reduction distance R SUS is 30 mm or more, measured at a test temperature of 23 ° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. Peeling method described.
  • the adhesive sheet described in (1) to (3) above has an adhesive force N0 SUS of 3.0 N/20 mm or more after one day at room temperature after pasting the adhesive sheet on a stainless steel plate as an adherend. The peeling method described in any of the above.
  • the adhesive sheet includes: After one day at room temperature after pasting the adhesive sheet on a stainless steel plate as an adherend, 2 ⁇ L of ethanol is dropped onto the adherend, and the ethanol is allowed to enter one end of the interface between the adhesive sheet and the adherend.
  • Method 1 180° peeling adhesive force to the test plate, specifically, at a test temperature of 23 ° C. Peeling according to any one of (1) to (4) above, wherein the adhesive force reduction distance R SUS is 30 mm or more, measured using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. Method. (6) The adhesive sheet is prepared by attaching the adhesive sheet to an alkali glass plate prepared by the float method as an adherend, and after one day at room temperature, dropping 2 ⁇ L of ethanol onto the adherend, and adding the ethanol to the adherend.
  • Method 1 180° peeling adhesive force to the test plate, specifically, test temperature 23 (1) to (5) above, where the ethanol peel force N1 GLA is 0.5 N/20 mm or less, measured using a tensile tester at °C at a tensile speed of 300 mm/min and a peel angle of 180 degrees. The peeling method described in any of the above. (7) The adhesive sheet was cut into a rectangular shape with a width of 20 mm and was pasted on an alkali glass plate made by the float method as an adherend, and after one day at room temperature, 2 ⁇ L was applied to the adherend.
  • the adhesive sheet has an adhesive force N0 GLA of 3.0 N/20 mm or more after one day at room temperature after attaching the adhesive sheet to an alkali glass plate prepared by a float method as an adherend.
  • the adhesive sheet includes: The adhesive sheet was attached to an alkali glass plate prepared by the float method as an adherend, and after one day at room temperature, 2 ⁇ L of ethanol was dropped onto the adherend, and the ethanol was applied to the adhesive sheet and the adherend.
  • the adhesive sheet includes a base layer and an adhesive layer disposed on at least one surface of the base layer, The peeling method according to any one of (1) to (9) above, wherein the adhesive layer is an acrylic adhesive layer containing an acrylic polymer as a base polymer.
  • the adhesive layer is formed from a water-dispersed adhesive composition, a solvent-based adhesive composition, an active energy ray-curable adhesive composition, or a hot-melt adhesive composition.
  • (12) The peeling method according to (10) or (11) above, wherein the base layer is composed of a resin film.
  • the adherend has a contact angle with ethanol of 50 degrees or less, 30 degrees or less, 20 degrees or less, or 15 degrees or less on the surface of the adherend to which the pressure-sensitive adhesive sheet is attached, according to (1) above.
  • the adherend has a contact angle with respect to distilled water on the surface to which the adhesive sheet is attached, of 30 degrees or more, 35 degrees or more, 40 degrees or more, 45 degrees or more, 50 degrees or more, or 60 degrees or more.
  • the peeling method according to any one of (1) to (13) above, wherein the peeling method is at least 60 degrees or more than 60 degrees.
  • Adhesive composition S-1 Into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 38.5 parts of 2-ethylhexyl acrylate (2EHA), 60 parts of lauryl acrylate (LA), and 2.5 parts of n-butyl acrylate (BA) were added. , 8 parts of 4-hydroxybutyl acrylate (4HBA), 0.05 parts of N-vinyl-2-pyrrolidone (NVP), and 0.0 parts of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator.
  • 2EHA 2-ethylhexyl acrylate
  • LA lauryl acrylate
  • BA n-butyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • NDP N-vinyl-2-pyrrolidone
  • AIBN 2,2'-azobisisobutyronitrile
  • a solution containing acrylic polymer A with an Mw of 600,000 to 1,000,000 (solid content concentration 30%) was prepared by adding 2 parts of acrylic polymer A and ethyl acetate as a polymerization solvent and reacting at 60°C for 4 hours under a nitrogen gas stream. ) was obtained.
  • To 100 parts of the solid content of the solution containing acrylic polymer A 0.05 part of isocyanate crosslinking agent C1 (trade name "Takenate D101E", manufactured by Mitsui Chemicals) and 1.5 parts of acrylic oligomer A were added.
  • a solvent-based adhesive composition S-1 was prepared by uniformly stirring and mixing the following components.
  • Adhesive composition S-2 0.05 isocyanate crosslinking agent (trade name "Takenate D101E", manufactured by Mitsui Chemicals, Inc.) per 100 parts solid content of the solution containing acrylic polymer A obtained in the preparation of adhesive composition S-1. 1 part, 1.5 parts of acrylic oligomer A, and 0.5 part of nonionic surfactant A1 (polyoxyethylene lauryl ether, trade name "Emulgen 104P", manufactured by Kao Corporation) and stirred uniformly. By mixing, a solvent-based adhesive composition S-2 was prepared.
  • Adhesive composition S-3 0.1 isocyanate-based crosslinking agent (trade name "Takenate D101E", manufactured by Mitsui Chemicals, Inc.) per 100 parts of solid content of the solution containing acrylic polymer A obtained in the preparation of adhesive composition S-1. 1.5 parts of acrylic oligomer A, and 0.5 part of nonionic surfactant A2 (glycerol monooleate, trade name "Rheodol MO-60", manufactured by Kao Corporation) were mixed uniformly. By stirring and mixing, a solvent-based adhesive composition S-3 was prepared.
  • Adhesive composition S-4 0.1 isocyanate-based crosslinking agent (trade name "Takenate D101E", manufactured by Mitsui Chemicals, Inc.) per 100 parts of solid content of the solution containing acrylic polymer A obtained in the preparation of adhesive composition S-1. part, 1.5 parts of acrylic oligomer A, and 0.3 part of nonionic surfactant A4 (polyoxyethylene alkyl ether, trade name "NAROACTY ID-60", manufactured by Sanyo Chemical Co., Ltd.). , and were uniformly stirred and mixed to prepare a solvent-type adhesive composition S-4.
  • solvent-type adhesive composition S-4 0.1 isocyanate-based crosslinking agent (trade name "Takenate D101E”, manufactured by Mitsui Chemicals, Inc.) per 100 parts of solid content of the solution containing acrylic polymer A obtained in the preparation of adhesive composition S-1. part, 1.5 parts of acrylic oligomer A, and 0.3 part of nonionic surfactant A4 (polyoxyethylene alkyl ether, trade
  • Adhesive composition S-5 0.5 parts of an isocyanate-based crosslinking agent (trade name "Takenate D101E”, manufactured by Mitsui Chemicals, Inc.) per 100 parts of solid content of the solution containing acrylic polymer A obtained in the preparation of adhesive composition S-1. 1.5 parts of acrylic oligomer A, and 0.5 part of nonionic surfactant A3 (polyoxyethylene polyoxypropylene alkyl ether, trade name "Emulgen MS-110", manufactured by Kao Corporation). The mixture was stirred and mixed uniformly to prepare a solvent-based adhesive composition S-5.
  • an isocyanate-based crosslinking agent trade name "Takenate D101E”, manufactured by Mitsui Chemicals, Inc.
  • nonionic surfactant A3 polyoxyethylene polyoxypropylene alkyl ether, trade name "Emulgen MS-110", manufactured by Kao Corporation.
  • Adhesive composition U-1 Lauryl acrylate (LA), 2-ethylhexyl acrylate (2EHA), N-vinyl-2-pyrrolidone (NVP), 4-hydroxybutyl acrylate (4HBA), photoinitiator A1 (trade name “Irgacure 184", Ciba Specialty Chemicals) (manufactured by Ciba Specialty Chemicals) and photopolymerization initiator A2 (trade name "Irgacure 651", manufactured by Ciba Specialty Chemicals) in a weight ratio of 60/22/10/8/0.1/0.1.
  • the monomer mixture was placed in a flask and photopolymerized by irradiating it with ultraviolet rays under a nitrogen atmosphere until the viscosity (BH viscometer, No. 5 rotor, 10 rpm, measurement temperature 30°C) reached approximately 15 Pa ⁇ s.
  • a monomer syrup containing a partially polymerized product was prepared.
  • Adhesive composition U-2 Lauryl acrylate (LA), 2-ethylhexyl acrylate (2EHA), N-vinyl-2-pyrrolidone (NVP), 4-hydroxybutyl acrylate (4HBA), photoinitiator A1 (trade name “Irgacure 184", Ciba Specialty Chemicals) (manufactured by Ciba Specialty Chemicals) and photopolymerization initiator A2 (trade name "Irgacure 651", manufactured by Ciba Specialty Chemicals) in a weight ratio of 36.4/60/2.5/1/0.05/0.05.
  • Aligninitiator A1 (trade name "Irgacure 184", Ciba Specialty Chemicals) (manufactured by Ciba Specialty Chemicals) and photopolymerization initiator A2 (trade name "Irgacure 651", manufactured by Ciba Specialty Chemicals) in a weight ratio of 38.5/60/2.5/8/0.05/0.05.
  • Adhesive composition S-6 In a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirring device, 63 parts of 2-ethylhexyl acrylate (2EHA), 9 parts of methyl methacrylate (MMA), 13 parts of 2-hydroxyethyl acrylate (HEA), and N- 15 parts of vinyl-2-pyrrolidone (NVP) was added together with 0.2 parts of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator and ethyl acetate as a polymerization solvent, and a nitrogen gas stream was added. By reacting at 60° C.
  • 2EHA 2-ethylhexyl acrylate
  • MMA methyl methacrylate
  • HOA 2-hydroxyethyl acrylate
  • NDP vinyl-2-pyrrolidone
  • AIBN 2,2'-azobisisobutyronitrile
  • Adhesive composition S-7 In a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirring device, 72 parts of 2-ethylhexyl acrylate (2EHA), 1 part of methyl methacrylate (MMA), 13 parts of 2-hydroxyethyl acrylate (HEA), and N- 14 parts of vinyl-2-pyrrolidone (NVP), 0.2 parts of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator, and 0.2 parts of ⁇ -thioglycerol (TGR) as a chain transfer agent.
  • 2EHA 2-ethylhexyl acrylate
  • MMA methyl methacrylate
  • HOA 2-hydroxyethyl acrylate
  • NDP vinyl-2-pyrrolidone
  • AIBN 2,2'-azobisisobutyronitrile
  • TGR ⁇ -thioglycerol
  • a solution containing acrylic polymer F with an Mw of 600,000 to 1,000,000 (solid content concentration 30%) was prepared by adding 12 parts of acrylic polymer F and ethyl acetate as a polymerization solvent and reacting at 60°C for 4 hours under a nitrogen gas stream. ) was obtained.
  • Adhesive composition E-1 49 parts of 2-ethylhexyl acrylate (2EHA), 49 parts of n-butyl methacrylate (BMA), 2 parts of acrylic acid (AA), and 2 parts of an anionic emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Aqualon BC2020) as an emulsifier were subjected to ion exchange.
  • An aqueous emulsion (monomer emulsion) of the monomer mixture was prepared by mixing and emulsifying in 100 parts of water.
  • the above monomer emulsion was placed in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, and stirred at room temperature for over 1 hour while introducing nitrogen gas.
  • the temperature of the system was raised to 60°C, and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057) was added as a polymerization initiator. ) and reacted at 60° C. for 6 hours to obtain an aqueous dispersion of acrylic polymer G.
  • Adhesive composition U-4 n-butyl methacrylate (BA), cyclohexyl acrylate (CHA), 4-hydroxybutyl acrylate (4HBA), photoinitiator A1 (product name "Irgacure 184", manufactured by Ciba Specialty Chemicals), and photoinitiator A2 (product name A mixture of Irgacure 651 (manufactured by Ciba Specialty Chemicals) in a weight ratio of 67/14/19/0.09/0.09 was put into a four-necked flask, and the viscosity (BH viscosity A monomer syrup containing a partial polymer of the monomer mixture was prepared by photopolymerizing the mixture by irradiating it with ultraviolet rays until the temperature reached approximately 15 Pa ⁇ s.
  • BH viscosity A monomer syrup containing a partial polymer of the monomer mixture was prepared by photopolymerizing the mixture by irradiating it with ultraviolet rays until the
  • DPHA dipentaerythritol hexaacrylate
  • HOA 2-hydroxyethyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • acrylic oligomer A and acrylic oligomer B used in the preparation of the above adhesive composition were synthesized by the following method.
  • This acrylic oligomer A had a Tg of 67° C. and a Mw of 3,500.
  • This acrylic oligomer B had a Tg of 144° C. and a Mw of 4,300.
  • Adhesive composition S-1 was applied to a 38 ⁇ m thick release film R1 (Mitsubishi Plastics Co., Ltd., MRF#38) with one side of the polyester film serving as a release surface, and dried at 130°C for 5 minutes to reduce the thickness. An adhesive layer having a thickness of 25 ⁇ m was formed.
  • a pressure-sensitive adhesive sheet according to this example was obtained by laminating a corona-treated polyethylene terephthalate (PET) film with a thickness of 50 ⁇ m to the pressure-sensitive adhesive layer on the release film R1.
  • PET polyethylene terephthalate
  • Example 2 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-2 was used instead of pressure-sensitive adhesive composition S-1.
  • Example 3 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-3 was used instead of pressure-sensitive adhesive composition S-1.
  • Example 4 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-4 was used instead of pressure-sensitive adhesive composition S-1.
  • Example 5 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-5 was used instead of pressure-sensitive adhesive composition S-1.
  • Adhesive composition U-1 was applied to a 38 ⁇ m thick release film R1 (manufactured by Mitsubishi Plastics Co., Ltd., product name “MRF#38”), with one side of the polyester film being the release surface, and one side of the polyester film was released.
  • a 38 ⁇ m thick release film R2 manufactured by Mitsubishi Plastics Co., Ltd., product name “MRE #38”
  • the 25 ⁇ m thick adhesive is released. formed a layer.
  • the ultraviolet rays were irradiated using a black light lamp at an illuminance of 4 mW/cm 2 (measured with an industrial UV checker (manufactured by Topcon, trade name "UVR-T1") with a peak sensitivity wavelength of approximately 350 nm) for 180 seconds. I went there.
  • the release film R2 covering the adhesive layer was peeled off, and a corona-treated PET film having a thickness of 50 ⁇ m was bonded to the adhesive sheet, thereby obtaining an adhesive sheet according to this example.
  • Example 7 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 6, except that pressure-sensitive adhesive composition U-2 was used instead of pressure-sensitive adhesive composition U-1.
  • Example 8 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 6, except that pressure-sensitive adhesive composition U-3 was used instead of pressure-sensitive adhesive composition U-1.
  • Example 9 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-6 was used instead of pressure-sensitive adhesive composition S-1.
  • Example 10 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-7 was used instead of pressure-sensitive adhesive composition S-1.
  • Adhesive composition E-1 was applied to release film R1 (Mitsubishi Plastics Co., Ltd., MRF #38) and dried at 120° C. for 3 minutes to form an adhesive layer with a thickness of 25 ⁇ m.
  • a pressure-sensitive adhesive sheet according to this example was obtained by laminating a corona-treated polyethylene terephthalate (PET) film with a thickness of 50 ⁇ m to the pressure-sensitive adhesive layer on the release film R1.
  • PET polyethylene terephthalate
  • Example 12 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 6, except that pressure-sensitive adhesive composition U-4 was used instead of pressure-sensitive adhesive composition U-1.
  • the adhesive force N0 SUS to the stainless steel plate, the ethanol peeling force N1 SUS , and the adhesive force reduction distance R SUS were measured based on the measurement method described above. Further, for each example of the adhesive sheet, the adhesive force N0 GLA to the glass plate, the ethanol peeling force N1 GLA , and the adhesive force reduction distance R GLA were measured based on the measurement method described above. If the obtained adhesive strength reduction distance R SUS is 30 mm or more, the persistence of adhesive strength reduction (vs. SUS): G (good), and if the adhesive strength reduction distance R SUS is less than 30 mm, the adhesive strength is Force reduction durability (vs. SUS): Rated P (poor).
  • the adhesive sheets of Examples 1 to 8 have an ethanol peel force N1 SUS of 0.5 N/20 mm or less, an adhesive force N0 SUS of 3.0 N/20 mm or more, and a long-lasting adhesive force reduction ( SUS) was good.
  • the adhesive sheets of Examples 1 to 8 have an ethanol peeling force N1 GLA of 0.5 N/20 mm or less, an adhesive force N0 GLA of 3.0 N/20 mm or more, and a long-lasting adhesive force reduction (toward glass). ) were good. It has been confirmed that when the peeling method disclosed herein is applied to the pressure-sensitive adhesive sheets of Examples 1 to 8, it is possible to particularly suitably achieve both adhesion to the adherend and removability.
  • Adhesive sheet 20 Support 30 Release liner 50 Adhesive sheet with release liner

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Abstract

With respect to a peeling method that is applicable even to adherends that exhibit a relatively low hydrophilicity, there is provided a method for peeling an adhesive sheet that exhibits both adhesive strength to adherend and removability. This peeling method is a method for peeling an adhesive sheet is affixed to an adherend. This peeling method comprises applying an adhesive strength-reducing means to the adhesive sheet, and this adhesive strength-reducing means comprises: supplying an alcohol solution to the adherend/adhesive sheet interface at the peel front of the adhesive sheet from the adherend; and moving the peel front of the adhesive sheet in the peeling advance direction with this alcohol solution being present at the interface and advancing the introduction of the alcohol solution into the interface in compliance with the movement of the peel front.

Description

粘着シートの剥離方法How to peel off the adhesive sheet
　本発明は、粘着シートの剥離方法に関する。詳しくは粘着力低減手段を適用することを含む、粘着シートの剥離方法に関する。本出願は、２０２２年７月２９日に出願された日本国特許出願２０２２－１２２０５２号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。 The present invention relates to a method for peeling a pressure-sensitive adhesive sheet. Specifically, the present invention relates to a method for peeling a pressure-sensitive adhesive sheet, which includes applying an adhesive force reducing means. This application claims priority based on Japanese Patent Application No. 2022-122052 filed on July 29, 2022, and the entire contents of that application are incorporated herein by reference.
　一般に、粘着剤（感圧接着剤ともいう。以下同じ。）は、室温付近の温度域において柔らかい固体（粘弾性体）の状態を呈し、圧力により簡単に被着体に接着する性質を有する。このような性質を活かして、粘着剤は、支持体上に粘着剤層を有する支持体付き粘着シートの形態で、あるいは支持体を有しない支持体レス粘着シートの形態で、様々な分野において広く利用されている。また、上記粘着剤は、使用後、必要な場合には適当な手段によって被着体から剥離される。被着体から粘着剤を剥離する技術文献として、特許文献１および２が挙げられる。 In general, adhesives (also referred to as pressure-sensitive adhesives, hereinafter the same) exhibit a soft solid (viscoelastic) state in the temperature range around room temperature, and have the property of easily adhering to adherends under pressure. Taking advantage of these properties, adhesives are widely used in various fields in the form of adhesive sheets with a support, which have an adhesive layer on the support, or in the form of support-less adhesive sheets, which do not have a support. It's being used. Further, after use, the adhesive is peeled off from the adherend by appropriate means, if necessary. Technical documents for peeling adhesives from adherends include Patent Documents 1 and 2.
日本国特許出願公開２０２０－２３６５６号公報Japanese Patent Application Publication No. 2020-23656 国際公開第２０２２／０３８９２６号International Publication No. 2022/038926
　近年、環境負荷低減や省資源等の観点から、粘着剤を用いて接合された部材を、使用後に製品から分離し、再利用（リサイクル、リユース等）することが多くなってきている。例えば、スマートフォン、パソコン（デスクトップ型、ノート型、タブレット型等）、テレビ等の表示機能を有する製品に内蔵された表示装置（ディスプレイデバイス）は、液晶表示装置や有機ＥＬ（エレクトロルミネッセンス）表示装置、ＰＤＰ（プラズマディスプレイパネル）など、複数かつ異種の機能性部材を含む多層構造を有しており、部材ごとに異なる材料を含むため、リサイクルやリユース等によって再利用することの利点が大きい。また、ガラスや金属・有機材料（例えばＰＥＴ、ＰＩ等）の加工、運搬、保管等の際に、これらの表面を損傷や汚れから防止する目的で、該表面に表面保護シートを接着して保護する技術が知られており、このような表面保護シートは保護目的が達成された後、適当なタイミングで被着体から除去される。 In recent years, from the perspective of reducing environmental impact and saving resources, it has become increasingly common for members bonded using adhesives to be separated from products after use and reused (recycled, reused, etc.). For example, display devices built into products with display functions such as smartphones, personal computers (desktops, notebooks, tablets, etc.), televisions, etc. include liquid crystal display devices, organic EL (electroluminescence) display devices, It has a multilayer structure including a plurality of different functional components, such as a PDP (plasma display panel), and each component contains a different material, so there is a great advantage in reusing it through recycling, reuse, etc. In addition, when processing, transporting, storing, etc. glass, metals, and organic materials (e.g., PET, PI, etc.), surface protection sheets are adhered to the surfaces to protect them from damage and dirt. Such a surface protection sheet is removed from the adherend at an appropriate timing after the protection purpose is achieved.
　部材等の被着体に接着した粘着剤は、通常、粘着剤そのものの再剥離性を利用して被着体から剥離される。しかし、高い接合信頼性を求められる粘着剤は、概して被着体に対する接着力が高く、被着体からの剥離性（再剥離性）が低下しがちである。また、被着体には、ガラス等の硬脆性の部材や薄厚の部材が含まれることがあり、そのような被着体は、粘着剤の剥離時にかかる力によって破損する場合がある。このような事情のもと、本発明者らは、被着体に対する接着力と再剥離性とを両立する技術として、特許文献１において、水を利用して容易に剥離することができ、かつ接合時における耐水信頼性が改善された粘着シート（水剥離性粘着シート）を提案している。 An adhesive bonded to an adherend such as a member is usually peeled off from the adherend by utilizing the removability of the adhesive itself. However, pressure-sensitive adhesives that are required to have high bonding reliability generally have high adhesion to adherends, and tend to have poor removability (re-peelability) from adherends. Further, the adherend may include a hard and brittle member such as glass or a thin member, and such an adherend may be damaged by the force applied when the adhesive is peeled off. Under these circumstances, the present inventors proposed in Patent Document 1 a technology that achieves both adhesion to adherends and removability, which can be easily peeled off using water, and We are proposing an adhesive sheet (water-releasable adhesive sheet) with improved water resistance reliability during bonding.
　しかし、特許文献１で提案する水剥離性粘着シートは、粘着シートの被着体からの剥離に水等の水性液体を利用することを前提としているため、ガラスやシリコンウェーハのような親水性の高い被着体からの剥離に対しては好適に適用できる一方、親水性が低い被着体に対しては好適に適用できない場合がある。この点に関して、親水性の高い被着体に加えて、例えば金属や樹脂のような親水性の比較的低い被着体に対しても、接着力と再剥離性とが両立する技術が提供されれば、適用可能な被着体の選択の幅が広がり有利である。 However, the water-releasable adhesive sheet proposed in Patent Document 1 is based on the premise that an aqueous liquid such as water is used to peel the adhesive sheet from the adherend. While it can be suitably applied to adherends with high peeling, it may not be suitably applied to adherends with low hydrophilicity. In this regard, a technology has been provided that achieves both adhesion and removability for adherends with relatively low hydrophilicity, such as metals and resins, in addition to highly hydrophilic adherends. This is advantageous because it broadens the range of applicable adherends.
　本発明は、上記の事情に鑑みて創出されたものであり、親水性の比較的低い被着体に対しても適用可能な剥離方法であって、被着体に対する接着力と再剥離性とを両立させた粘着シートの剥離方法を提供することを目的とする。 The present invention was created in view of the above circumstances, and is a peeling method that can be applied even to adherends with relatively low hydrophilicity, and which improves adhesive strength and removability to the adherend. An object of the present invention is to provide a method for peeling a pressure-sensitive adhesive sheet that achieves both of the following.
　この明細書によると、被着体に貼り付けられた粘着シートの剥離方法が提供される。この剥離方法は、上記粘着シートに、粘着力低減手段を適用することを含む。ここで、上記粘着力低減手段は、上記粘着シートの上記被着体からの剥離前線における該被着体と該粘着シートとの界面にアルコール液を供給すること、および、上記界面に上記アルコール液が存在する状態で、該粘着シートの上記剥離前線を剥離進行方向に移動させ、該剥離前線の移動に追随して上記アルコール液の上記界面への進入を進行させることを含む。 According to this specification, a method for peeling a pressure-sensitive adhesive sheet stuck to an adherend is provided. This peeling method includes applying an adhesive force reducing means to the adhesive sheet. Here, the adhesive force reducing means includes supplying an alcohol liquid to an interface between the adherend and the adhesive sheet at a peeling front of the adhesive sheet from the adherend, and supplying the alcohol liquid to the interface. is present, the peeling front of the pressure-sensitive adhesive sheet is moved in the peeling advancing direction, and the alcohol liquid is allowed to enter the interface following the movement of the peeling front.
　上記の剥離方法によると、粘着力低減手段を適用することにより、粘着シートの粘着力を低減させることができるため、被着体からの剥離性（再剥離性）を向上させることができる。また、ここに開示される粘着力低減手段は、アルコール液を利用するため、例えば被着面が金属、樹脂等の親水性が比較的低い材料で構成された被着体など、水を利用した水剥離を適用させづらい被着体に適用しても、被着体からの剥離性（再剥離性）を向上させることができる。
　また従来の、水を利用する水剥離では、剥離後の被着体に付着した水を除去するために、被着体の乾燥や拭き取り等の水除去工程が必要となることがあった。上記の剥離方法によると、水ではなくアルコール液を利用するため、従来よりも剥離後の被着体からの液体除去工程が短時間化または簡易化できる傾向にある。このような剥離方法は、生産効率の観点からも有利である。 According to the above peeling method, by applying the adhesive force reducing means, the adhesive force of the adhesive sheet can be reduced, so that the peelability (repeelability) from the adherend can be improved. In addition, since the adhesive strength reducing means disclosed herein uses an alcohol solution, it may be difficult to apply water to an adherend whose surface is made of a material with relatively low hydrophilicity such as metal or resin. Even when applied to adherends to which water removal is difficult, the releasability (re-peelability) from the adherend can be improved.
Further, in conventional water peeling using water, in order to remove water adhering to the adherend after peeling, a water removal step such as drying or wiping the adherend is sometimes necessary. According to the above-mentioned peeling method, since an alcohol solution is used instead of water, the process of removing the liquid from the adherend after peeling tends to be shorter or simpler than before. Such a peeling method is also advantageous from the viewpoint of production efficiency.
　いくつかの態様において、上記粘着シートは、被着体としてのステンレス鋼板に上記粘着シートを貼り付けて室温１日後、上記被着体に２μＬのエタノールを滴下し、該エタノールを上記粘着シートと上記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、エタノール剥離力Ｎ１ＳＵＳが、０．５Ｎ／２０ｍｍ以下である。ステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳが上記上限値以下である粘着シートを用いると、アルコール剥離による粘着力低減効果が好適に発揮されやすく、被着体からの再剥離性を向上させることができる。特に、上記粘着シートを被着体のなかでもエタノールの濡れ性のよい被着体からの剥離に適用すると、優れた剥離低減効果が発揮されやすい。上記エタノールの濡れ性のよい被着体としては、例えばエタノールに対する接触角が５０度以下である被着体が挙げられる。上記被着体としては、被着面がガラス、金属（例えばステンレス鋼、アルミニウム等）、樹脂（例えばＰＥＴ、ポリイミド（ＰＩ）等）等の材料で構成された被着体が挙げられる。 In some embodiments, the adhesive sheet is prepared by attaching the adhesive sheet to a stainless steel plate as an adherend and dropping 2 μL of ethanol onto the adherend one day after the adhesive sheet is attached to the adherend at room temperature. After entering one end of the interface with the adherend, according to JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, tensile at a test temperature of 23°C. The ethanol peel force N1 SUS , measured using a testing machine at a tensile speed of 300 mm/min and a peel angle of 180 degrees, is 0.5 N/20 mm or less. When a pressure-sensitive adhesive sheet having an ethanol peel force N1 SUS with respect to a stainless steel plate is equal to or lower than the above upper limit value is used, the adhesive force reduction effect due to alcohol peeling is likely to be suitably exhibited, and re-peelability from the adherend can be improved. In particular, when the above-mentioned pressure-sensitive adhesive sheet is applied to peeling from an adherend that has good wettability with ethanol among adherends, an excellent peeling-reducing effect is likely to be exhibited. Examples of adherends having good wettability with ethanol include those having a contact angle with ethanol of 50 degrees or less. Examples of the adherend include adherends whose adherend surfaces are made of a material such as glass, metal (eg, stainless steel, aluminum, etc.), resin (eg, PET, polyimide (PI), etc.).
　また、粘着シートと被着体の界面に供給されたアルコール液が、粘着シートの粘着剤（層）に吸収されると、粘着シートと被着体の界面に存在していたアルコール液が消失または減少してしまい、粘着シートの剥離力低減効果が低下してしまうおそれがある。
　ここに開示されるいくつかの態様において、上記粘着シートは、被着体としてのステンレス鋼板に、幅２０ｍｍの長方形状にカットされた上記粘着シートを貼り付けて室温１日後、上記被着体に２μＬのエタノールを滴下し、該エタノールを上記粘着シートと上記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＳＵＳが３０ｍｍ以上である。ステンレス鋼板に対する粘着力低減距離ＲＳＵＳが３０ｍｍ以上である粘着シートによると、粘着シートと被着体（例えば被着面が金属、樹脂等で構成された被着体）の界面にアルコール液を供給することを含む粘着力低減手段による効果が低下することなく持続する傾向にある。粘着力低減効果が持続する粘着シートは、剥離工程におけるアルコール液の使用量削減や作業効率の観点から好ましい。 In addition, when the alcohol liquid supplied to the interface between the adhesive sheet and the adherend is absorbed by the adhesive (layer) of the adhesive sheet, the alcohol liquid that was present at the interface between the adhesive sheet and the adherend disappears or As a result, the peeling force reducing effect of the pressure-sensitive adhesive sheet may decrease.
In some embodiments disclosed herein, the adhesive sheet is applied to a stainless steel plate as an adherend, and after one day at room temperature, the adhesive sheet cut into a rectangular shape with a width of 20 mm is attached to the adherend. After dropping 2 μL of ethanol and allowing the ethanol to enter one end of the interface between the adhesive sheet and the adherend, JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesion to the test plate Specifically, the adhesive force reduction distance R SUS is 30 mm or more, which is measured at a test temperature of 23° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. According to an adhesive sheet whose adhesion force reduction distance R SUS to a stainless steel plate is 30 mm or more, alcohol liquid is supplied to the interface between the adhesive sheet and the adherend (for example, an adherend whose adherend surface is made of metal, resin, etc.). The effects of the adhesive force reducing means, including the above, tend to continue without deterioration. A pressure-sensitive adhesive sheet that maintains the effect of reducing adhesive force is preferable from the viewpoint of reducing the amount of alcohol used in the peeling process and working efficiency.
　いくつかの態様において、上記粘着シートは、被着体としてのステンレス鋼板に該粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＳＵＳが３．０Ｎ／２０ｍｍ以上である。上記粘着シートはステンレス鋼板に対する粘着力Ｎ０ＳＵＳが上記下限値以上であるため、被着体（例えば被着面が金属、樹脂等で構成された被着体）に対して、優れた粘着信頼性を示す傾向にある。 In some embodiments, the adhesive sheet has an adhesive force N0 SUS of 3.0 N/20 mm or more after one day at room temperature after attaching the adhesive sheet to a stainless steel plate as an adherend. Since the above-mentioned adhesive sheet has an adhesion force N0 SUS to a stainless steel plate that is above the lower limit value, it has excellent adhesion reliability to adherends (for example, adherends whose adherend surface is made of metal, resin, etc.). There is a tendency to show that
　いくつかの態様において、上記粘着シートは、下記式：粘着力低減率ＳＳＵＳ［％］＝（１－（エタノール剥離力Ｎ１ＳＵＳ／粘着力Ｎ０ＳＵＳ））×１００；で求められる粘着力低減率ＳＳＵＳが５０％以上であり、かつ、粘着力低減距離ＲＳＵＳが３０ｍｍ以上である。上記粘着シートを用いると、アルコール剥離による粘着力低減効果が好適に発揮されやすく、かつ該粘着力低減効果が持続する傾向にある。 In some embodiments, the adhesive sheet has an adhesive force reduction rate determined by the following formula: Adhesive force reduction rate S SUS [%] = (1 - (ethanol peeling force N1 SUS / adhesive force N0 SUS )) x 100; S SUS is 50% or more, and adhesive force reduction distance R SUS is 30 mm or more. When the above-mentioned pressure-sensitive adhesive sheet is used, the adhesive force reducing effect by alcohol peeling tends to be suitably exhibited, and the adhesive force reducing effect tends to be sustained.
　いくつかの態様において、上記粘着シートは、被着体としてのフロート法で作製されたアルカリガラス板に上記粘着シートを貼り付けて室温１日後、上記被着体に２μＬのエタノールを滴下し、該エタノールを上記粘着シートと上記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、エタノール剥離力Ｎ１ＧＬＡが、０．５Ｎ／２０ｍｍ以下である。ガラス板に対するエタノール剥離力Ｎ１ＧＬＡが上記上限値以下である粘着シートを、ここに開示される剥離方法に用いると、アルコール剥離による粘着力低減効果が好適に発揮されやすく、被着体からの再剥離性を向上させることができる。特に、上記粘着シートを被着体のなかでもエタノールの濡れ性のよい被着体からの剥離に適用すると、優れた剥離低減効果が発揮されやすい。上記エタノールの濡れ性のよい被着体としては、例えばエタノールに対する接触角が５０度以下である被着体が挙げられる。上記被着体としては、被着面がガラス、金属（例えばステンレス鋼、アルミニウム等）、樹脂（例えばＰＥＴ、ＰＩ等）等の材料で構成された被着体が挙げられる。 In some embodiments, the adhesive sheet is attached to an alkali glass plate prepared by a float method as an adherend, and after one day at room temperature, 2 μL of ethanol is dropped onto the adherend. After entering ethanol into one end of the interface between the adhesive sheet and the adherend, follow JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, The ethanol peel force N1 GLA is 0.5 N/20 mm or less, which is measured at a test temperature of 23° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. When a pressure-sensitive adhesive sheet having an ethanol peeling force N1 GLA of less than the above upper limit on a glass plate is used in the peeling method disclosed herein, the adhesive force reduction effect by alcohol peeling is likely to be suitably exhibited, and re-release from the adherend is easily achieved. Removability can be improved. In particular, when the pressure-sensitive adhesive sheet is applied to peel from an adherend that has good wettability with ethanol among adherends, an excellent peel-reducing effect is likely to be exhibited. Examples of adherends having good wettability with ethanol include those having a contact angle with ethanol of 50 degrees or less. Examples of the adherend include adherends whose adherend surfaces are made of a material such as glass, metal (for example, stainless steel, aluminum, etc.), resin (for example, PET, PI, etc.).
　いくつかの態様において、上記粘着シートは、被着体としてのフロート法で作製されたアルカリガラス板に、幅２０ｍｍの長方形状にカットされた上記粘着シートを貼り付けて室温１日後、上記被着体に２μＬのエタノールを滴下し、該エタノールを上記粘着シートと上記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＧＬＡが３０ｍｍ以上である。ガラス板に対する粘着力低減距離ＲＧＬＡが３０ｍｍ以上である粘着シートによると、粘着シートと被着体（例えば被着面がガラスで構成された被着体）の界面にアルコール液を供給することを含む粘着力低減手段による効果が低下することなく持続する傾向にある。粘着力低減効果が持続する粘着シートは、剥離工程におけるアルコール液の使用量削減や作業効率の観点から好ましい。 In some embodiments, the adhesive sheet is attached to an alkali glass plate prepared by a float method as an adherend, and after one day at room temperature, the adhesive sheet cut into a rectangular shape with a width of 20 mm is attached. After dropping 2 μL of ethanol onto the body and allowing the ethanol to enter one end of the interface between the adhesive sheet and the adherend, JIS Z0237:2009 10.4.1 Method 1: 180° pull on the test plate According to the peel adhesion force, specifically, the adhesive force reduction distance R GLA is 30 mm or more, which is measured at a test temperature of 23 ° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. . According to an adhesive sheet whose adhesion force reduction distance R GLA to a glass plate is 30 mm or more, it is recommended to supply alcohol liquid to the interface between the adhesive sheet and the adherend (for example, an adherend whose adherend surface is made of glass). The effect of the adhesive force reducing means included therein tends to be sustained without deterioration. A pressure-sensitive adhesive sheet that maintains the effect of reducing adhesive force is preferable from the viewpoint of reducing the amount of alcohol used in the peeling process and working efficiency.
　いくつかの態様において、上記粘着シートは、被着体としてのフロート法で作製されたアルカリガラス板に上記粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＧＬＡが３．０Ｎ／２０ｍｍ以上である。上記粘着シートはガラス板に対する粘着力Ｎ０ＧＬＡが３．０Ｎ／２０ｍｍ以上であるため、被着体（例えば被着面がガラスで構成された被着体）に対して、優れた粘着信頼性を示す傾向にある。 In some embodiments, the adhesive sheet has an adhesive force N0 GLA of 3.0 N/20 mm or more after one day at room temperature after attaching the adhesive sheet to an alkali glass plate prepared by a float method as an adherend. . Since the above-mentioned adhesive sheet has an adhesion force N0 GLA to a glass plate of 3.0 N/20 mm or more, it has excellent adhesion reliability to an adherend (for example, an adherend whose surface is made of glass). There is a tendency to show
　いくつかの態様において、上記粘着シートは、下記式：粘着力低減率ＳＧＬＡ［％］＝（１－（エタノール剥離力Ｎ１ＧＬＡ／粘着力Ｎ０ＧＬＡ））×１００；で求められる粘着力低減率ＳＧＬＡが５０％以上であり、かつ、粘着力低減距離ＲＧＬＡが３０ｍｍ以上である。上記粘着シートを用いると、アルコール剥離による粘着力低減効果が好適に発揮されやすく、かつ該粘着力低減効果が持続する傾向にある。 In some embodiments, the adhesive sheet has an adhesive force reduction rate determined by the following formula: Adhesive force reduction rate S GLA [%] = (1 - (ethanol peeling force N1 GLA / adhesive force N0 GLA )) x 100; S GLA is 50% or more, and adhesive force reduction distance R GLA is 30 mm or more. When the above-mentioned pressure-sensitive adhesive sheet is used, the adhesive force reducing effect by alcohol peeling tends to be suitably exhibited, and the adhesive force reducing effect tends to be sustained.
一実施形態に係る粘着シートの構成を模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically showing the configuration of a pressure-sensitive adhesive sheet according to an embodiment.
　以下、本発明の好適な実施形態を説明する。なお、本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、本明細書に記載された発明の実施についての教示と出願時の技術常識とに基づいて当業者に理解され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。また、以下の図面において、同じ作用を奏する部材・部位には同じ符号を付して説明することがあり、重複する説明は省略または簡略化することがある。また、図面に記載の実施形態は、本発明を明瞭に説明するために模式化されており、実際に提供される製品のサイズや縮尺を必ずしも正確に表したものではない。 Hereinafter, preferred embodiments of the present invention will be described. Matters other than those specifically mentioned in this specification that are necessary for carrying out the present invention are based on the teachings regarding carrying out the invention described in this specification and the common general knowledge at the time of filing. can be understood by those skilled in the art. The present invention can be implemented based on the content disclosed in this specification and the common general knowledge in the field. Furthermore, in the following drawings, members and portions that have the same function may be described with the same reference numerals, and overlapping descriptions may be omitted or simplified. Further, the embodiments shown in the drawings are schematic for clearly explaining the present invention, and do not necessarily accurately represent the size or scale of the actually provided products.
　この明細書において、「重量」は「質量」と読み替えてもよいものとする。例えば、「重量％」は「質量％」と読み替えてもよく、「重量部」は「質量部」と読み替えてもよいものとする。 In this specification, "weight" may be read as "mass". For example, "% by weight" may be read as "% by mass", and "parts by weight" may be read as "parts by mass".
　＜粘着力低減手段＞
　この明細書によると、被着体に貼り付けられた粘着シートの剥離方法が提供される。上記剥離方法は、粘着シートに粘着力低減手段を適用することを特徴とする。ここに開示される粘着力低減手段は、上記粘着シートの上記被着体からの剥離前線における上記被着体と上記粘着シートとの界面にアルコール液を供給し、記界面に上記アルコール液が存在する状態で、上記粘着シートの上記剥離前線を剥離進行方向に移動させ、該剥離前線の移動に追随して上記アルコール液の上記界面への進入を進行させることを含む。このような粘着力低減手段を用いると、被着体に対して接着力が高い粘着シートに適用されて、被着体からの再剥離性を向上させることができる。なお、上記剥離方法において、被着体と粘着シートとの接着界面の剥離に曝される箇所を「剥離前線」という。 <Adhesive force reduction means>
According to this specification, a method for peeling a pressure-sensitive adhesive sheet stuck to an adherend is provided. The above peeling method is characterized in that an adhesive force reducing means is applied to the adhesive sheet. The adhesive force reducing means disclosed herein supplies an alcohol liquid to an interface between the adherend and the adhesive sheet at a peeling front of the adhesive sheet from the adherend, and the alcohol liquid is present at the surface. In this state, the peeling front of the pressure-sensitive adhesive sheet is moved in the peeling advancing direction, and the alcohol liquid is allowed to enter the interface in accordance with the movement of the peeling front. When such an adhesive force reducing means is used, it can be applied to a pressure-sensitive adhesive sheet that has a high adhesive force to an adherend, and the re-peelability from the adherend can be improved. In addition, in the above-mentioned peeling method, the part exposed to peeling of the adhesive interface between the adherend and the adhesive sheet is referred to as the "peeling front".
　また、上記剥離方法によると、粘着シートの被着体に対する粘着力を低減させるために供給する液体として、従来の水ではなくアルコール液を利用するため、水剥離が適用されにくい親水性が比較的低い被着体に対しても粘着力低減効果が好ましく発揮される傾向にある。また、水を用いる水剥離と比較し、剥離後に被着体からアルコール液を除去する工程が短時間化または簡易化される傾向にある。 In addition, according to the above peeling method, alcohol liquid is used instead of conventional water as the liquid supplied to reduce the adhesive force of the adhesive sheet to the adherend, so it is relatively hydrophilic, making it difficult to apply water peeling. The effect of reducing adhesive strength tends to be preferably exhibited even for adherends with low adhesive strength. Furthermore, compared to water stripping using water, the process of removing the alcohol solution from the adherend after stripping tends to be shorter or simpler.
　ここに開示される粘着力低減手段に使用されるアルコール液としては、アルコール類またはアルコール類を主成分とする混合溶媒に、必要に応じて少量の添加剤を含有させたものを用いることができる。被着体との濡れ性および粘着力低減効果の観点から、上記アルコール類としては、炭素原子数１～４の一価の低級アルコールを用いることが好ましく、特にメタノール、エタノール、イソプロピルアルコール等が好ましい。なかでも安全性、汎用性等の観点から、エタノールが好ましい。 As the alcohol liquid used in the adhesive force reducing means disclosed herein, alcohols or mixed solvents containing alcohols as a main component, containing small amounts of additives as necessary, can be used. . From the viewpoint of wettability with the adherend and adhesive force reduction effect, it is preferable to use a monohydric lower alcohol having 1 to 4 carbon atoms as the alcohol, and methanol, ethanol, isopropyl alcohol, etc. are particularly preferable. . Among them, ethanol is preferred from the viewpoints of safety, versatility, etc.
　上記混合溶媒を構成するアルコール類以外の溶媒としては、アルコール類と均一に混合し得る水、低級ケトン（例えばアセトン）等を使用し得る。上記添加剤としては、公知の界面活性剤等を用いることができる。被着体の汚染を避ける観点から、いくつかの態様において、添加剤を実質的に含有しないアルコール液を好ましく使用し得る。 As the solvent other than alcohols constituting the above mixed solvent, water, lower ketones (eg, acetone), etc. that can be uniformly mixed with alcohols may be used. As the additive, known surfactants and the like can be used. From the viewpoint of avoiding contamination of the adherend, in some embodiments, an alcoholic liquid containing substantially no additives may be preferably used.
　粘着力低減および剥離後のアルコール液除去の観点から、いくつかの態様において、上記アルコール液におけるアルコール類の含有率は、５０重量％超であり、６０重量％以上であってもよく、７０重量％以上でもよく、８０重量％以上でもよく、９０重量％以上でもよく、９５重量％以上でもよく、９８重量％以上でもよい。 In some embodiments, from the viewpoint of reducing adhesive strength and removing alcohol solution after peeling, the content of alcohol in the alcohol solution is more than 50% by weight, may be 60% by weight or more, and 70% by weight. % or more, 80 weight % or more, 90 weight % or more, 95 weight % or more, or 98 weight % or more.
　いくつかの態様において、上記アルコール剥離は、被着体に貼り付けられた粘着シートの外縁付近にアルコール液を供給し、そのアルコール液を上記粘着シートの外縁から該粘着シートと上記被着体との界面に進入させた後、新たなアルコール液の供給を行うことなく（すなわち、剥離開始前に被着体に供給したアルコール液のみを利用して）粘着シートの剥離を進行させる態様で行うことができる。なお、アルコール剥離工程の途中で、剥離前線の移動に追随して粘着シートと被着体との界面に進入させるアルコール液が途中で枯渇するようであれば、該アルコール剥離工程の開始後に断続的または連続的にアルコール液を追加供給してもよい。 In some embodiments, the alcohol peeling involves supplying an alcohol solution near the outer edge of the adhesive sheet attached to the adherend, and applying the alcohol liquid from the outer edge of the adhesive sheet to the adhesive sheet and the adherend. After the adhesive sheet enters the interface, the adhesive sheet is peeled off without supplying new alcohol (that is, using only the alcohol that was supplied to the adherend before the start of peeling). Can be done. In addition, if the alcohol liquid that follows the movement of the peeling front and enters the interface between the adhesive sheet and the adherend runs out during the alcohol peeling process, the alcohol liquid may be removed intermittently after the start of the alcohol peeling process. Alternatively, additional alcohol liquid may be continuously supplied.
　剥離開始前に供給するアルコール液（例えばエタノール）の量は、粘着シートの貼付け範囲外から該粘着シートと被着体との界面に上記アルコール液を導入し得る量であればよく、特に限定されない。上記アルコール液の量は、例えば５μＬ以上であってよく、１０μＬ以上が適当であり、２０μＬ以上でもよい。また、上記アルコール液の量の上限について特に制限はない。いくつかの態様において、作業性向上等の観点から、上記アルコール液の量は、例えば１０ｍＬ以下であってよく、５ｍＬ以下でもよく、１ｍＬ以下でもよく、０．５ｍＬ以下でもよく、０．１ｍＬ以下でもよく、０．０５ｍＬ以下でもよい。 The amount of alcohol liquid (for example, ethanol) supplied before the start of peeling is not particularly limited, as long as it can introduce the alcohol liquid to the interface between the adhesive sheet and the adherend from outside the area where the adhesive sheet is attached. . The amount of the alcohol solution may be, for example, 5 μL or more, suitably 10 μL or more, and may be 20 μL or more. Further, there is no particular restriction on the upper limit of the amount of the alcohol solution. In some embodiments, from the viewpoint of improving workability, the amount of the alcoholic liquid may be, for example, 10 mL or less, 5 mL or less, 1 mL or less, 0.5 mL or less, 0.1 mL or less. It may be 0.05 mL or less.
　剥離開始時に上記粘着シートの外縁から該粘着シートと上記被着体との界面にアルコール液を進入させる操作は、例えば、粘着シートの外縁において上記界面にカッターナイフや針等の治具の先端を差し込む、粘着シートの外縁を鉤や爪等で引掻いて持ち上げる、強粘着性の粘着テープや吸盤等を被着体の外縁付近の背面に付着させて該粘着シートの端を持ち上げるなどの態様で行うことができる。 At the start of peeling, the operation of injecting alcohol liquid into the interface between the adhesive sheet and the adherend from the outer edge of the adhesive sheet can be performed, for example, by inserting the tip of a jig such as a cutter knife or needle into the interface at the outer edge of the adhesive sheet. Insert the adhesive sheet, scratch the outer edge of the adhesive sheet with a hook or nail, etc., and lift it up, or attach a strong adhesive tape, suction cup, etc. to the back surface near the outer edge of the adherend and lift the edge of the adhesive sheet. It can be carried out.
　また、アルコール剥離工程は、上記剥離前線を１０ｍｍ／分以上の速度で移動させる態様で好ましく実施され得る。剥離前線を１０ｍｍ／分以上の速度で移動させることは、例えば剥離角度１８０度の条件においては、粘着シートを２０ｍｍ／分以上の引張速度で剥離することに相当する。上記剥離前線を移動させる速度は、例えば５０ｍｍ／分以上でもよく、１５０ｍｍ／分以上でもよく、３００ｍｍ／分以上でもよく、５００ｍｍ／分以上でもよい。剥離前線を移動させる速度の上限は特に制限されない。上記剥離前線を移動させる速度は、例えば１０００ｍｍ／分以下であり得る。 Furthermore, the alcohol peeling step can be preferably carried out in such a manner that the peeling front is moved at a speed of 10 mm/min or more. Moving the peeling front at a speed of 10 mm/min or more corresponds to peeling the adhesive sheet at a tensile speed of 20 mm/min or more, for example, under the condition of a peeling angle of 180 degrees. The speed at which the peeling front is moved may be, for example, 50 mm/min or more, 150 mm/min or more, 300 mm/min or more, or 500 mm/min or more. The upper limit of the speed at which the peeling front is moved is not particularly limited. The speed at which the peeling front is moved may be, for example, 1000 mm/min or less.
　ここに開示されるアルコール剥離は、例えば、該方法に使用するアルコール液（例えばエタノール）の体積１０μＬ当たりの粘着シートの剥離面積が、例えば５０ｃｍ２以上、好ましくは１００ｃｍ２以上となる態様で実施することができる。 The alcohol peeling disclosed herein is carried out, for example, in such a manner that the peeled area of the adhesive sheet per 10 μL volume of the alcohol solution (e.g. ethanol) used in the method is, for example, 50 cm 2 or more, preferably 100 cm 2 or more. be able to.
　＜粘着シートの特性＞
　ここに開示される剥離方法に用いられる粘着シートとしては、アルコール剥離により粘着力低減効果が発揮され得るものであれば特に限定されず、種々のものを用いることができる。いくつかの態様において、上記粘着シートは、２３℃の温度条件下で、引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定されるステンレス鋼板に対するエタノール剥離力（以下、「ステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳ」または単に「エタノール剥離力Ｎ１ＳＵＳ」ともいう。）が０．５Ｎ／２０ｍｍ以下である。上記ステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳが０．５Ｎ／２０ｍｍ以下である粘着シートを用いると、アルコール剥離による粘着力低減効果が好適に発揮されやすく、被着体からの再剥離性を向上させることができる。特に、上記粘着シートを被着体のなかでもエタノールの濡れ性のよい被着体からの剥離に適用すると、優れた剥離低減効果が発揮されやすい。上記エタノールの濡れ性のよい被着体としては、例えばエタノールに対する接触角が５０度以下（好ましくは３０度以下、さらに好ましくは２０度以下）である被着体が挙げられる。上記被着体の例としては、被着面がガラス、金属（例えばステンレス鋼、アルミニウム等）、樹脂（例えばＰＥＴ、ＰＩ等）等の材料で構成された被着体が挙げられる。上記粘着シートをここに開示される技術に用いると、従来の水剥離の技術を適用しにくい親水性が比較的低い被着体（例えば被着面が金属、樹脂等で構成された被着体）に適用したとしても、被着体からの再剥離性を向上させることができる。 <Characteristics of adhesive sheet>
The pressure-sensitive adhesive sheet used in the peeling method disclosed herein is not particularly limited as long as it can exhibit the effect of reducing adhesive force by alcohol peeling, and various types can be used. In some embodiments, the adhesive sheet has an ethanol peel force on a stainless steel plate (hereinafter referred to as "ethanol peel force on a stainless steel plate") measured at a temperature of 23° C., a tensile speed of 300 mm/min, and a peel angle of 180 degrees. force N1 SUS " or simply "ethanol peeling force N1 SUS ") is 0.5 N/20 mm or less. When using a pressure-sensitive adhesive sheet whose ethanol peel force N1 SUS against the stainless steel plate is 0.5 N/20 mm or less, the effect of reducing the adhesive force by alcohol peeling is likely to be suitably exhibited, and the re-peelability from the adherend is improved. Can be done. In particular, when the above-mentioned pressure-sensitive adhesive sheet is applied to peeling from an adherend that has good wettability with ethanol among adherends, an excellent peeling-reducing effect is likely to be exhibited. Examples of adherends having good wettability with ethanol include those having a contact angle with ethanol of 50 degrees or less (preferably 30 degrees or less, more preferably 20 degrees or less). Examples of the above-mentioned adherends include adherends whose adherend surfaces are made of a material such as glass, metal (eg, stainless steel, aluminum, etc.), resin (eg, PET, PI, etc.). When the above adhesive sheet is used in the technique disclosed herein, it is difficult to apply conventional water release techniques to adherends with relatively low hydrophilicity (for example, adherends whose adherend surface is made of metal, resin, etc.). ), the re-peelability from the adherend can be improved.
　上記粘着シートのステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳは、より好ましくは０．４８Ｎ／２０ｍｍ以下であり、さらに好ましくは０．４５Ｎ／２０ｍｍ以下であり、特に好ましくは０．４Ｎ／２０ｍｍ以下である。いくつかの態様において、上記粘着シートのステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳは、０．３５Ｎ／２０ｍｍ以下であってもよく、０．３Ｎ／２０ｍｍ以下でもよい。上記エタノール剥離力Ｎ１ＳＵＳの下限値は特に限定されない。原理的には上記エタノール剥離力Ｎ１ＳＵＳは０Ｎ／２０ｍｍ以上である。被着体との接合時における接着特性のバランスをとる観点からは、上記粘着シートのステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳは、０．０５Ｎ／２０ｍｍ以上であってもよく、０．１Ｎ／２０ｍｍ以上でもよい。 The ethanol peeling force N1 SUS of the pressure-sensitive adhesive sheet to the stainless steel plate is more preferably 0.48 N/20 mm or less, still more preferably 0.45 N/20 mm or less, particularly preferably 0.4 N/20 mm or less. In some embodiments, the ethanol peeling force N1 SUS of the pressure-sensitive adhesive sheet to the stainless steel plate may be 0.35 N/20 mm or less, or 0.3 N/20 mm or less. The lower limit of the ethanol peeling force N1 SUS is not particularly limited. In principle, the ethanol peeling force N1 SUS is 0 N/20 mm or more. From the viewpoint of balancing the adhesive properties when bonding to the adherend, the ethanol peeling force N1 SUS of the adhesive sheet to the stainless steel plate may be 0.05 N/20 mm or more, and 0.1 N/20 mm or more. But that's fine.
　他のいくつかの態様において、上記粘着シートのステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳは、０．２Ｎ／２０ｍｍ以下であってもよく、０．１Ｎ／２０ｍｍ以下でもよく、０．０５Ｎ／２０ｍｍ以下でもよく、０．０３Ｎ／２０ｍｍ以下でもよい。上記粘着シートのステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳの下限値は特に限定されない。原理的にはエタノール剥離力Ｎ１ＳＵＳは０Ｎ／２０ｍｍ以上である。 In some other embodiments, the ethanol peel force N1 SUS of the adhesive sheet to the stainless steel plate may be 0.2 N/20 mm or less, 0.1 N/20 mm or less, or 0.05 N/20 mm or less. It may be 0.03 N/20 mm or less. The lower limit of the ethanol peeling force N1 SUS of the pressure-sensitive adhesive sheet to the stainless steel plate is not particularly limited. In principle, the ethanol peeling force N1 SUS is 0 N/20 mm or more.
　ステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳは、詳しくは以下の方法により測定される。後述する実施例でも同様の測定方法が用いられる。 The ethanol peeling force N1 SUS against a stainless steel plate is measured in detail by the following method. A similar measurement method is used in the examples described later.
　［エタノール剥離力Ｎ１ＳＵＳの測定］
　測定対象の粘着シートを幅２０ｍｍ、長さ１２０ｍｍの長方形状にカットして試験片を調製する。上記試験片の粘着面を被着体としてのステンレス鋼板（ＳＵＳ３０４ＢＡ板）にハンドローラーで貼り合わせた評価用サンプルを、オートクレーブに投入し、圧力５ａｔｍ、温度５０℃の条件で１５分間処理する。
　オートクレーブから取り出した評価用サンプルを２３℃、５０％ＲＨの環境に１日保持した後、同環境下において、試験片の長手方向の一端付近において該一端から露出する被着体表面に２μＬのエタノールを滴下する。そして、試験片と被着体との界面にカッターナイフを差し込んで上記エタノールを上記界面に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で剥離強度を測定し、これをステンレス鋼板に対するエタノール剥離力Ｎ１ＳＵＳ［Ｎ／２０ｍｍ］とする。 [Measurement of ethanol peeling force N1 SUS ]
A test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm. An evaluation sample in which the adhesive side of the test piece was bonded to a stainless steel plate (SUS304BA plate) as an adherend using a hand roller was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C.
After holding the evaluation sample taken out from the autoclave in an environment of 23°C and 50% RH for one day, in the same environment, 2 μL of ethanol was applied to the surface of the adherend exposed from the end near one longitudinal end of the test piece. drip. Then, after inserting a cutter knife into the interface between the test piece and the adherend to allow the ethanol to enter the interface, JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate Accordingly, specifically, the peel strength was measured using a tensile tester at a test temperature of 23° C. at a tensile speed of 300 mm/min and a peel angle of 180 degrees, and this was determined as the ethanol peel force against the stainless steel plate N1 SUS [N /20mm].
　上記エタノール剥離力Ｎ１ＳＵＳの測定において被着体として用いるステンレス鋼板（ＳＵＳ３０４ＢＡ板）の粘着シートを貼り合わせる面のエタノールに対する接触角は約１０度であり、蒸留水に対する接触角は約８５度である。以下のステンレス鋼板に対する粘着力Ｎ０ＳＵＳおよびステンレス鋼板に対する粘着力低減距離ＲＳＵＳの測定に用いられる被着体についても同様である。 In the measurement of the above ethanol peel force N1 SUS , the contact angle of the surface of the stainless steel plate (SUS304BA plate) used as the adherend to which the adhesive sheet is bonded to ethanol is approximately 10 degrees, and the contact angle to distilled water is approximately 85 degrees. . The same applies to the adherends used in the following measurements of the adhesive force N0 SUS to the stainless steel plate and the adhesive force reduction distance R SUS to the stainless steel plate.
　特に限定されないが、いくつかの態様において、上記粘着シートは、２３℃の温度条件下で、引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定されるステンレス鋼板に対する粘着力（以下、「ステンレス鋼板に対する粘着力Ｎ０ＳＵＳ」または単に「粘着力Ｎ０ＳＵＳ」ともいう。）が３．０Ｎ／２０ｍｍ以上である。ステンレス鋼板に対する粘着力Ｎ０ＳＵＳが３．０Ｎ／２０ｍｍ以上である粘着シートを用いると、剥離前の被着体（例えば被着面が金属、樹脂等で構成された被着体）に対して優れた粘着信頼性を示す傾向にある。 Although not particularly limited, in some embodiments, the adhesive sheet has adhesive strength (hereinafter referred to as "stainless steel") to a stainless steel plate measured at a temperature of 23° C., a tensile speed of 300 mm/min, and a peel angle of 180 degrees. The adhesive force to the steel plate (also referred to as "adhesive force N0 SUS " or simply "adhesive force N0 SUS ") is 3.0 N/20 mm or more. When using an adhesive sheet with an adhesion force N0 SUS of 3.0 N/20 mm or more to stainless steel plates, it has excellent adhesive properties on adherends (for example, adherends whose adherend surface is made of metal, resin, etc.) before peeling. They tend to exhibit better adhesion reliability.
　上記粘着シートのステンレス鋼板に対する粘着力Ｎ０ＳＵＳは、より好ましくは３．５Ｎ／２０ｍｍ以上であり、さらに好ましくは４．０Ｎ／２０ｍｍ以上であり、特に好ましくは４．５Ｎ／２０ｍｍ以上である。上記ステンレス鋼板に対する粘着力Ｎ０ＳＵＳの上限値は特に限定されない。他の接着特性のバランスをとる観点からは、上記粘着シートのステンレス鋼板に対する粘着力Ｎ０ＳＵＳは、１５Ｎ／２０ｍｍ以下であってもよく、１０Ｎ／２０ｍｍ以下でもよく、７Ｎ／２０ｍｍ以下でもよい。 The adhesive force N0 SUS of the adhesive sheet to the stainless steel plate is more preferably 3.5 N/20 mm or more, still more preferably 4.0 N/20 mm or more, particularly preferably 4.5 N/20 mm or more. The upper limit of the adhesive force N0 SUS to the stainless steel plate is not particularly limited. From the viewpoint of balancing other adhesive properties, the adhesive force N0 SUS of the adhesive sheet to the stainless steel plate may be 15 N/20 mm or less, 10 N/20 mm or less, or 7 N/20 mm or less.
　他のいくつかの態様において、上記粘着シートのステンレス鋼板に対する粘着力Ｎ０ＳＵＳは、３．０Ｎ／２０ｍｍ未満であってもよく、２．５Ｎ／２０ｍｍ以下でもよく、２．０Ｎ／２０ｍｍ以下でもよく、１．０Ｎ／２０ｍｍ以下でもよい。上記粘着シートのステンレス鋼板に対する粘着力Ｎ０ＳＵＳの下限値は特に限定されない。原理的には粘着力Ｎ０ＳＵＳは０Ｎ／２０ｍｍ以上であり、例えば０．１Ｎ／２０ｍｍ以上でもよく、０．２Ｎ／２０ｍｍ以上でもよい。 In some other embodiments, the adhesive force N0 SUS of the adhesive sheet to the stainless steel plate may be less than 3.0 N/20 mm, may be less than 2.5 N/20 mm, or may be less than 2.0 N/20 mm. , 1.0N/20mm or less. The lower limit of the adhesive force N0 SUS of the adhesive sheet to the stainless steel plate is not particularly limited. In principle, the adhesive force N0 SUS is 0 N/20 mm or more, for example, it may be 0.1 N/20 mm or more, or it may be 0.2 N/20 mm or more.
　ステンレス鋼板に対する粘着力Ｎ０ＳＵＳは、詳しくは以下の方法により測定される。後述する実施例でも同様の測定方法が用いられる。 In detail, the adhesive force N0 SUS to a stainless steel plate is measured by the following method. A similar measuring method is used in the examples described later.
　［粘着力Ｎ０ＳＵＳの測定］
　測定対象の粘着シートを幅２０ｍｍ、長さ１２０ｍｍの長方形状にカットして試験片を調製する。上記試験片の粘着面を被着体としてのステンレス鋼板（ＳＵＳ３０４ＢＡ板）にハンドローラーで貼り合わせた評価用サンプルを、オートクレーブに投入し、圧力５ａｔｍ、温度５０℃の条件で１５分間処理する。
　オートクレーブから取り出した評価用サンプルを２３℃、５０％ＲＨの環境に１日保持した後、同環境下において、試験片と被着体との界面にカッターナイフを差し込んで該試験片の長手方向の一端を被着体から剥離させ、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で剥離強度を測定し、これをステンレス鋼板に対する粘着力Ｎ０ＳＵＳ［Ｎ／２０ｍｍ］とする。 [Measurement of adhesive strength N0 SUS ]
A test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm. An evaluation sample in which the adhesive side of the test piece was bonded to a stainless steel plate (SUS304BA plate) as an adherend using a hand roller was placed in an autoclave and treated at a pressure of 5 atm and a temperature of 50° C. for 15 minutes.
After holding the evaluation sample taken out of the autoclave in an environment of 23°C and 50% RH for one day, a cutter knife was inserted into the interface between the test piece and the adherend under the same environment to cut the longitudinal direction of the test piece. One end was peeled off from the adherend, and according to JIS Z0237:2009 10.4.1 Method 1: 180° peel adhesion to the test plate, specifically, using a tensile tester at a test temperature of 23°C. The peel strength was measured under the conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees, and this was defined as the adhesive force to the stainless steel plate N0 SUS [N/20 mm].
　いくつかの態様において、上記粘着シートは、幅２０ｍｍの長方形状の粘着シートを用いて、２３℃の温度条件下で、引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定されるステンレス鋼板に対する粘着力低減距離（以下、「ステンレス鋼板に対する粘着力低減距離ＲＳＵＳ」または単に「粘着力低減距離ＲＳＵＳ」ともいう。）が３０ｍｍ以上である。ステンレス鋼板に対する粘着力低減距離ＲＳＵＳが３０ｍｍ以上である粘着シートによると、粘着シートと被着体（例えば被着面が金属、樹脂等で構成された被着体）の界面にアルコール液を供給することを含む粘着力低減手段による効果が低下することなく持続する傾向にある。粘着力低減効果が持続する粘着シートは、剥離工程におけるアルコール液の使用量削減や作業効率の観点から好ましい。 In some embodiments, the adhesive sheet has a rectangular adhesive sheet with a width of 20 mm, and is measured at a temperature of 23° C., at a tensile rate of 300 mm/min, and at a peel angle of 180 degrees, with respect to a stainless steel plate. The adhesive force reduction distance (hereinafter also referred to as "adhesive force reduction distance R SUS to stainless steel plate" or simply "adhesive force reduction distance R SUS ") is 30 mm or more. According to an adhesive sheet whose adhesion force reduction distance R SUS to a stainless steel plate is 30 mm or more, alcohol liquid is supplied to the interface between the adhesive sheet and the adherend (for example, an adherend whose adherend surface is made of metal, resin, etc.). The effects of the adhesive force reducing means, including the above, tend to continue without deterioration. A pressure-sensitive adhesive sheet that maintains the effect of reducing adhesive force is preferable from the viewpoint of reducing the amount of alcohol used in the peeling process and working efficiency.
　ステンレス鋼板に対する粘着力低減距離ＲＳＵＳは、詳しくは以下の方法により測定される。後述する実施例でも同様の測定方法が用いられる。 In detail, the adhesive force reduction distance R SUS to a stainless steel plate is measured by the following method. A similar measuring method is used in the examples described later.
　［粘着力低減距離ＲＳＵＳの測定］
　測定対象の粘着シートを幅２０ｍｍ、長さ１２０ｍｍの長方形状にカットして試験片を調製する。上記試験片の粘着面を被着体としてのステンレス鋼板（ＳＵＳ３０４ＢＡ板）にハンドローラーで貼り合わせた評価用サンプルを、オートクレーブに投入し、圧力５ａｔｍ、温度５０℃の条件で１５分間処理する。
　オートクレーブから取り出した評価用サンプルを２３℃、５０％ＲＨの環境に１日保持した後、同環境下において、試験片の長手方向の一端付近において該一端から露出する被着体表面に２μＬのエタノールを滴下する。そして、試験片と被着体との界面にカッターナイフを差し込んで上記エタノールを上記界面に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で継続的に剥離強度を測定する。このとき、上記界面にエタノールを滴下した箇所を始点とし、継続的に測定する剥離強度が、エタノール剥離力Ｎ１ＳＵＳ［Ｎ／２０ｍｍ］よりも０．５×（粘着力Ｎ０ＳＵＳ－エタノール剥離力Ｎ１ＳＵＳ）［Ｎ／２０ｍｍ］以上大きくなった箇所を終点とした時の、始点から終点までの粘着シートの剥離前線の移動距離を測定し、これを粘着力低減距離ＲＳＵＳ［ｍｍ］とする。 [Measurement of adhesive force reduction distance R SUS ]
A test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm. An evaluation sample in which the adhesive side of the test piece was bonded to a stainless steel plate (SUS304BA plate) as an adherend using a hand roller was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C.
After holding the evaluation sample taken out from the autoclave in an environment of 23°C and 50% RH for one day, in the same environment, 2 μL of ethanol was applied to the surface of the adherend exposed from the end near one longitudinal end of the test piece. drip. Then, after inserting a cutter knife into the interface between the test piece and the adherend to allow the ethanol to enter the interface, JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate Accordingly, specifically, the peel strength is continuously measured at a test temperature of 23° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. At this time, the peel strength that is continuously measured starting from the point where ethanol is dropped on the interface is 0.5 × (adhesive force N0 SUS - ethanol peel force N1) than the ethanol peel force N1 SUS [N/20 mm]. Measure the moving distance of the peeling front of the adhesive sheet from the start point to the end point when the end point is the point where the area has increased by more than SUS ) [N/20 mm], and define this as the adhesive force reduction distance R SUS [mm].
　（粘着力低減率ＳＳＵＳ）
　いくつかの態様において、下記式：粘着力低減率ＳＳＵＳ［％］＝（１－（エタノール剥離力Ｎ１ＳＵＳ／粘着力Ｎ０ＳＵＳ））×１００；で求められる粘着力低減率ＳＳＵＳは凡そ４０％以上（例えば凡そ５０％以上）であり得る。粘着力低減率ＳＳＵＳが大きい粘着シートは、被着体（例えば被着面が金属や樹脂で構成された被着体）に貼り付けられるときには十分な接着力を有しつつ、剥離除去時には、エタノール等のアルコール液を用いて剥離することで、剥離時に被着体に加わる負荷を顕著に軽減することができる。この性質を利用して、例えば、被着体（例えば被着面が金属や樹脂で構成された被着体）に貼り付けられた粘着シートの位置ズレや浮きを抑制する性能と、良好な剥離除去性とを両立することができる。いくつかの態様において、粘着力低減率ＳＳＵＳは７０％以上であることが適当であり、好ましくは８０％以上であり、より好ましくは９０％超であり、さらに好ましくは９２％以上であり、例えば９５％以上でもよく、９７％以上でもよい。粘着力低減率ＳＳＵＳの上限は、原理上１００％であり、例えば１００％未満である。 (Adhesive force reduction rate SSUS )
In some embodiments, the adhesive force reduction rate S SUS determined by the following formula: Adhesive force reduction rate S SUS [%] = (1 - (ethanol peeling force N1 SUS / adhesive force N0 SUS )) x 100; is approximately 40. % or more (for example, approximately 50% or more). Adhesive sheets with a high adhesive force reduction rate S SUS have sufficient adhesive force when attached to an adherend (for example, an adherend whose adherend surface is made of metal or resin), but when peeled and removed, By using an alcohol solution such as ethanol for peeling, the load applied to the adherend during peeling can be significantly reduced. Utilizing this property, for example, it is possible to suppress the positional shift or lifting of adhesive sheets attached to adherends (for example, adherends whose adherend surface is made of metal or resin), and to improve peelability. It is possible to achieve both removability and removability. In some embodiments, the adhesive strength reduction rate S SUS is suitably 70% or more, preferably 80% or more, more preferably more than 90%, and still more preferably 92% or more, For example, it may be 95% or more, or 97% or more. The upper limit of the adhesive force reduction rate S SUS is 100% in principle, and is, for example, less than 100%.
　いくつかの態様において、上記粘着シートは、２３℃の温度条件下で、引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定されるガラス板に対するエタノール剥離力（以下、「ガラス板に対するエタノール剥離力Ｎ１ＧＬＡ」または単に「エタノール剥離力Ｎ１ＧＬＡ」ともいう。）が０．５Ｎ／２０ｍｍ以下である粘着シートであることが好ましい。上記ガラス板に対するエタノール剥離力Ｎ１ＧＬＡが０．５Ｎ／２０ｍｍ以下である粘着シートを用いると、例えば被着面がガラスで構成された被着体に対しても、被着体からの再剥離性を向上させることができる。 In some embodiments, the pressure-sensitive adhesive sheet has an ethanol peel force against a glass plate (hereinafter referred to as "ethanol peel force against a glass plate") measured at a temperature of 23° C., a tensile speed of 300 mm/min, and a peel angle of 180 degrees. It is preferable that the pressure-sensitive adhesive sheet has a force N1 GLA or simply "ethanol peeling force N1 GLA " of 0.5 N/20 mm or less. If an adhesive sheet with an ethanol peeling force N1 GLA of 0.5 N/20 mm or less for the glass plate is used, re-peelability from the adherend can be improved even when the adherend surface is made of glass, for example. can be improved.
　上記粘着シートのガラス板に対するエタノール剥離力Ｎ１ＧＬＡは、より好ましくは０．４５Ｎ／２０ｍｍ以下（例えば０．４Ｎ／２０ｍｍ以下）であり、さらに好ましくは０．３Ｎ／２０ｍｍ以下（例えば０．２５Ｎ／２０ｍｍ以下）であり、特に好ましくは０．２Ｎ／２０ｍｍ以下である。いくつかの態様において、上記粘着シートのガラス板に対するエタノール剥離力Ｎ１ＧＬＡは、０．１５Ｎ／２０ｍｍ以下であってもよく、０．１Ｎ／２０ｍｍ以下でもよい。上記エタノール剥離力Ｎ１ＧＬＡの下限値は特に限定されない。原理的には上記エタノール剥離力Ｎ１ＧＬＡは０Ｎ／２０ｍｍ以上である。被着体との接合時における接着特性のバランスをとる観点からは、上記粘着シートのガラス板に対するエタノール剥離力Ｎ１ＧＬＡは、０．０５Ｎ／２０ｍｍ以上であってもよく、０．１Ｎ／２０ｍｍ以上でもよい。 The ethanol peel force N1 GLA of the adhesive sheet to the glass plate is more preferably 0.45 N/20 mm or less (for example, 0.4 N/20 mm or less), and even more preferably 0.3 N/20 mm or less (for example, 0.25 N/20 mm or less). 20 mm or less), particularly preferably 0.2 N/20 mm or less. In some embodiments, the ethanol peel force N1 GLA of the adhesive sheet to the glass plate may be 0.15 N/20 mm or less, or 0.1 N/20 mm or less. The lower limit of the ethanol peeling force N1 GLA is not particularly limited. In principle, the ethanol peeling force N1 GLA is 0 N/20 mm or more. From the viewpoint of balancing adhesive properties when bonding to an adherend, the ethanol peeling force N1 GLA of the adhesive sheet to the glass plate may be 0.05 N/20 mm or more, and 0.1 N/20 mm or more. But that's fine.
　他のいくつかの態様において、上記粘着シートのガラス板に対するエタノール剥離力Ｎ１ＧＬＡは、０．２Ｎ／２０ｍｍ以下であってもよく、０．１Ｎ／２０ｍｍ以下でもよく、０．０５Ｎ／２０ｍｍ以下でもよく、０．０３Ｎ／２０ｍｍ以下でもよい。上記粘着シートのガラス板に対するエタノール剥離力Ｎ１ＧＬＡの下限値は特に限定されない。原理的にはエタノール剥離力Ｎ１ＧＬＡは０Ｎ／２０ｍｍ以上である。 In some other embodiments, the ethanol peel force N1 GLA of the adhesive sheet to the glass plate may be 0.2 N/20 mm or less, 0.1 N/20 mm or less, or 0.05 N/20 mm or less. It may be 0.03 N/20 mm or less. The lower limit of the ethanol peeling force N1 GLA of the pressure-sensitive adhesive sheet to the glass plate is not particularly limited. In principle, the ethanol peeling force N1 GLA is 0 N/20 mm or more.
　ガラス板に対するエタノール剥離力Ｎ１ＧＬＡは、詳しくは以下の方法により測定される。後述する実施例でも同様の測定方法が用いられる。 The ethanol peeling force N1 GLA with respect to the glass plate is specifically measured by the following method. A similar measuring method is used in the examples described later.
　［エタノール剥離力Ｎ１ＧＬＡの測定］
　測定対象の粘着シートを幅２０ｍｍ、長さ１２０ｍｍの長方形状にカットして試験片を調製する。上記試験片の粘着面を被着体としてのアルカリガラス板（松浪硝子工業社製、フロート法で作製、厚さ１．３５ｍｍ、青板縁磨品）にハンドローラーで貼り合わせた評価用サンプルを、オートクレーブに投入し、圧力５ａｔｍ、温度５０℃の条件で１５分間処理する。
　オートクレーブから取り出した評価用サンプルを２３℃、５０％ＲＨの環境に１日保持した後、同環境下において、試験片の長手方向の一端付近において該一端から露出する被着体表面に２μＬのエタノールを滴下する。そして、試験片と被着体との界面にカッターナイフを差し込んで上記エタノールを上記界面に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で剥離強度を測定し、これをガラス板に対するエタノール剥離力Ｎ１ＧＬＡ［Ｎ／２０ｍｍ］とする。 [Measurement of ethanol peeling force N1 GLA ]
A test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm. An evaluation sample was prepared by pasting the adhesive side of the above test piece onto an alkali glass plate (manufactured by Matsunami Glass Industries Co., Ltd., manufactured by the float method, thickness 1.35 mm, blue plate edge polished) using a hand roller. The sample was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C.
After holding the evaluation sample taken out from the autoclave in an environment of 23°C and 50% RH for one day, in the same environment, 2 μL of ethanol was applied to the surface of the adherend exposed from the end near one longitudinal end of the test piece. drip. Then, after inserting a cutter knife into the interface between the test piece and the adherend to allow the ethanol to enter the interface, JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate Accordingly, specifically, the peel strength was measured using a tensile tester at a test temperature of 23°C at a tensile speed of 300 mm/min and a peel angle of 180 degrees, and this was calculated as the ethanol peel force against the glass plate N1 GLA [N /20mm].
　上記エタノール剥離力Ｎ１ＧＬＡの測定において被着体として用いるアルカリガラス板の粘着シートを貼り合わせる面のエタノールに対する接触角は約１０度であり、蒸留水に対する接触角は８度である。以下のガラス板に対する粘着力Ｎ０ＧＬＡおよびガラス板に対する粘着力低減距離ＲＧＬＡの測定に用いられる被着体についても同様である。 In the measurement of the ethanol peeling force N1 GLA , the contact angle of the surface of the alkali glass plate used as the adherend to which the adhesive sheet is bonded to ethanol is about 10 degrees, and the contact angle to distilled water is 8 degrees. The same applies to the adherends used for measuring the adhesive force N0 GLA to the glass plate and the adhesive force reduction distance R GLA to the glass plate below.
　特に限定されないが、いくつかの態様において、上記粘着シートは、２３℃の温度条件下で、引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定されるガラス板に対する粘着力（以下、「ガラス板に対する粘着力Ｎ０ＧＬＡ」または単に「粘着力Ｎ０ＧＬＡ」ともいう。）が３．０Ｎ／２０ｍｍ以上である。ガラス板に対する粘着力Ｎ０ＧＬＡが３．０Ｎ／２０ｍｍ以上である粘着シートを用いると、剥離前の被着体（例えば被着面がガラスで構成された被着体）に対して優れた粘着信頼性を示す傾向にある。 Although not particularly limited, in some embodiments, the adhesive sheet has adhesive strength (hereinafter referred to as "glass adhesive strength") to a glass plate measured at a temperature of 23° C., a tensile speed of 300 mm/min, and a peeling angle of 180 degrees. The adhesive force to the plate (also referred to as "adhesive force N0 GLA " or simply "adhesive force N0 GLA ") is 3.0 N/20 mm or more. When using an adhesive sheet with an adhesive force N0 GLA of 3.0 N/20 mm or more to a glass plate, it has excellent adhesion reliability to the adherend before peeling (for example, an adherend whose adherend surface is made of glass). It tends to show gender.
　上記粘着シートのガラス板に対する粘着力Ｎ０ＧＬＡは、より好ましくは３．５Ｎ／２０ｍｍ以上であり、さらに好ましくは４．０Ｎ／２０ｍｍ以上であり、特に好ましくは４．５Ｎ／２０ｍｍ以上である。上記ガラス板に対する粘着力Ｎ０ＧＬＡの上限値は特に限定されない。他の接着特性のバランスをとる観点からは、上記粘着シートのガラス板に対する粘着力Ｎ０ＧＬＡは、２０Ｎ／２０ｍｍ以下であってもよく、１５Ｎ／２０ｍｍ以下でもよく、１０Ｎ／２０ｍｍ以下でもよく、８．５Ｎ／２０ｍｍ以下でもよい。 The adhesive force N0 GLA of the adhesive sheet to the glass plate is more preferably 3.5 N/20 mm or more, still more preferably 4.0 N/20 mm or more, particularly preferably 4.5 N/20 mm or more. The upper limit of the adhesive force N0 GLA to the glass plate is not particularly limited. From the viewpoint of balancing other adhesive properties, the adhesive force N0 GLA of the adhesive sheet to the glass plate may be 20 N/20 mm or less, 15 N/20 mm or less, 10 N/20 mm or less, 8 It may be .5N/20mm or less.
　他のいくつかの態様において、上記粘着シートのガラス板に対する粘着力Ｎ０ＧＬＡは、３．０Ｎ／２０ｍｍ未満であってもよく、２．５Ｎ／２０ｍｍ以下でもよく、２．０Ｎ／２０ｍｍ以下でもよく、１．０Ｎ／２０ｍｍ以下でもよい。上記粘着シートのガラス板に対する粘着力Ｎ０ＧＬＡの下限値は特に限定されない。原理的には粘着力Ｎ０ＧＬＡは０Ｎ／２０ｍｍ以上であり、例えば０．１Ｎ／２０ｍｍ以上でもよく、０．２Ｎ／２０ｍｍ以上でもよい。 In some other embodiments, the adhesive force N0 GLA of the adhesive sheet to the glass plate may be less than 3.0 N/20 mm, may be less than 2.5 N/20 mm, or may be less than 2.0 N/20 mm. , 1.0N/20mm or less. The lower limit value of the adhesive force N0 GLA of the adhesive sheet to the glass plate is not particularly limited. In principle, the adhesive force N0 GLA is 0 N/20 mm or more, for example, it may be 0.1 N/20 mm or more, or it may be 0.2 N/20 mm or more.
　ガラス板に対する粘着力Ｎ０ＧＬＡは、詳しくは以下の方法により測定される。後述する実施例でも同様の測定方法が用いられる。 In detail, the adhesive force N0 GLA to the glass plate is measured by the following method. A similar measurement method is used in the examples described later.
　［粘着力Ｎ０ＧＬＡの測定］
　測定対象の粘着シートを幅２０ｍｍ、長さ１２０ｍｍの長方形状にカットして試験片を調製する。上記試験片の粘着面を被着体としてのアルカリガラス板（松浪硝子工業社製、フロート法で作製、厚さ１．３５ｍｍ、青板縁磨品）にハンドローラーで貼り合わせた評価用サンプルを、オートクレーブに投入し、圧力５ａｔｍ、温度５０℃の条件で１５分間処理する。
　オートクレーブから取り出した評価用サンプルを２３℃、５０％ＲＨの環境に１日保持した後、同環境下において、試験片と被着体との界面にカッターナイフを差し込んで該試験片の長手方向の一端を被着体から剥離させ、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で剥離強度を測定し、これをガラス板に対する粘着力Ｎ０ＧＬＡ［Ｎ／２０ｍｍ］とする。 [Measurement of adhesive force N0 GLA ]
A test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm. An evaluation sample was prepared by pasting the adhesive side of the above test piece onto an alkali glass plate (manufactured by Matsunami Glass Industries Co., Ltd., manufactured by the float method, thickness 1.35 mm, blue plate edge polished) using a hand roller. The sample was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C.
After holding the evaluation sample taken out of the autoclave in an environment of 23°C and 50% RH for one day, a cutter knife was inserted into the interface between the test piece and the adherend under the same environment to cut the longitudinal direction of the test piece. One end was peeled off from the adherend, and according to JIS Z0237:2009 10.4.1 Method 1: 180° peel adhesion to the test plate, specifically, using a tensile tester at a test temperature of 23°C. The peel strength was measured under the conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees, and this was defined as the adhesive force to the glass plate N0 GLA [N/20 mm].
　いくつかの態様において、上記粘着シートは、幅２０ｍｍの長方形状の粘着シートを用いて、２３℃の温度条件下で、引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定されるガラス板に対する粘着力低減距離（以下、「ガラス板に対する粘着力低減距離ＲＧＬＡ」または単に「粘着力低減距離ＲＧＬＡ」ともいう。）が３０ｍｍ以上である。ガラス板に対する粘着力低減距離ＲＧＬＡが３０ｍｍ以上である粘着シートによると、粘着シートと被着体（例えば被着面がガラスで構成された被着体）の界面にアルコール液を供給することを含む粘着力低減手段による効果が低下することなく持続する傾向にある。粘着力低減効果が持続する粘着シートは、剥離工程におけるアルコール液の使用量削減や作業効率の観点から好ましい。 In some embodiments, the adhesive sheet has a rectangular adhesive sheet with a width of 20 mm, and is measured at a temperature of 23° C., at a tensile rate of 300 mm/min, and at a peeling angle of 180 degrees with respect to a glass plate. The adhesive force reduction distance (hereinafter also referred to as "adhesive force reduction distance RGLA " or simply "adhesive force reduction distance RGLA ") is 30 mm or more. According to an adhesive sheet whose adhesion force reduction distance R GLA to a glass plate is 30 mm or more, it is recommended to supply alcohol liquid to the interface between the adhesive sheet and the adherend (for example, an adherend whose adherend surface is made of glass). The effect of the adhesive force reducing means included therein tends to be sustained without deterioration. A pressure-sensitive adhesive sheet that maintains the effect of reducing adhesive force is preferable from the viewpoint of reducing the amount of alcohol used in the peeling process and working efficiency.
　ガラス板に対する粘着力低減距離ＲＧＬＡは、詳しくは以下の方法により測定される。後述する実施例でも同様の測定方法が用いられる。 The adhesive force reduction distance R GLA to the glass plate is specifically measured by the following method. A similar measuring method is used in the examples described later.
　［粘着力低減距離ＲＧＬＡの測定］
　測定対象の粘着シートを幅２０ｍｍ、長さ１２０ｍｍの長方形状にカットして試験片を調製する。上記試験片の粘着面を被着体としてのアルカリガラス板（松浪硝子工業社製、フロート法で作製、厚さ１．３５ｍｍ、青板縁磨品）にハンドローラーで貼り合わせた評価用サンプルを、オートクレーブに投入し、圧力５ａｔｍ、温度５０℃の条件で１５分間処理する。
　オートクレーブから取り出した評価用サンプルを２３℃、５０％ＲＨの環境に１日保持した後、同環境下において、試験片の長手方向の一端付近において該一端から露出する被着体表面に２μＬのエタノールを滴下する。そして、試験片と被着体との界面にカッターナイフを差し込んで上記エタノールを上記界面に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で継続的に剥離強度を測定する。このとき、上記界面にエタノールを滴下した箇所を始点とし、継続的に測定した剥離強度が、エタノール剥離力Ｎ１ＧＬＡ［Ｎ／２０ｍｍ］よりも０．５×（粘着力Ｎ０ＧＬＡ－エタノール剥離力Ｎ１ＧＬＡ）［Ｎ／２０ｍｍ］以上大きくなった箇所を終点とした時の、始点から終点までの粘着シートの剥離前線の移動距離を測定し、これを粘着力低減距離ＲＧＬＡ［ｍｍ］とする。 [Measurement of adhesive force reduction distance R GLA ]
A test piece is prepared by cutting the adhesive sheet to be measured into a rectangular shape with a width of 20 mm and a length of 120 mm. An evaluation sample was prepared by pasting the adhesive side of the above test piece onto an alkali glass plate (manufactured by Matsunami Glass Industries Co., Ltd., manufactured by the float method, thickness 1.35 mm, blue plate edge polished) using a hand roller. The sample was placed in an autoclave and treated for 15 minutes at a pressure of 5 atm and a temperature of 50°C.
After holding the evaluation sample taken out from the autoclave in an environment of 23°C and 50% RH for one day, in the same environment, 2 μL of ethanol was applied to the surface of the adherend exposed from the end near one longitudinal end of the test piece. drip. Then, after inserting a cutter knife into the interface between the test piece and the adherend to allow the ethanol to enter the interface, JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate Accordingly, specifically, the peel strength is continuously measured at a test temperature of 23° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. At this time, the peel strength continuously measured starting from the point where ethanol was dropped on the above interface was 0.5 × (adhesive force N0 GLA - ethanol peel force N1) than the ethanol peel force N1 GLA [N/20 mm]. GLA ) [N/20 mm] or more is the end point, and the moving distance of the peeling front of the adhesive sheet from the start point to the end point is measured, and this is defined as the adhesive force reduction distance R GLA [mm].
　（粘着力低減率ＳＧＬＡ）
　いくつかの態様において、下記式：粘着力低減率ＳＧＬＡ［％］＝（１－（エタノール剥離力Ｎ１ＧＬＡ／粘着力Ｎ０ＧＬＡ））×１００；で求められる粘着力低減率ＳＧＬＡは凡そ４０％以上（例えば凡そ５０％以上）であり得る。粘着力低減率ＳＧＬＡが大きい粘着シートは、被着体（例えば被着面がガラスで構成された被着体）に貼り付けられるときには十分な接着力を有しつつ、剥離除去時には、エタノール等のアルコール液を用いて剥離することで、剥離時に被着体に加わる負荷を顕著に軽減することができる。この性質を利用して、例えば、被着体（例えば被着面がガラスで構成された被着体）に貼り付けられた粘着シートの位置ズレや浮きを抑制する性能と、良好な剥離除去性とを両立することができる。いくつかの態様において、粘着力低減率ＳＧＬＡは７０％超であることが適当であり、好ましくは９０％以上であり、例えば９２％以上であってよく、９５％以上でもよく、９７％以上でもよい。粘着力低減率ＳＧＬＡの上限は、原理上１００％であり、例えば１００％未満である。 (Adhesive force reduction rate S GLA )
In some embodiments, the adhesive force reduction rate S GLA determined by the following formula: Adhesive force reduction rate S GLA [%] = (1 - (ethanol peeling force N1 GLA / adhesive force N0 GLA )) x 100 ; % or more (for example, approximately 50% or more). Adhesive sheets with a high adhesive strength reduction rate S GLA have sufficient adhesive strength when attached to an adherend (for example, an adherend whose surface is made of glass), but when peeled off and removed, adhesive sheets such as ethanol etc. By peeling using an alcohol solution, the load applied to the adherend during peeling can be significantly reduced. Utilizing this property, for example, it is possible to suppress the positional shift or lifting of an adhesive sheet attached to an adherend (for example, an adherend whose adherend surface is made of glass), and to have good peeling and removability. It is possible to achieve both. In some embodiments, the adhesive force reduction rate S GLA is suitably more than 70%, preferably 90% or more, for example, it may be 92% or more, it may be 95% or more, it may be 97% or more. But that's fine. The upper limit of the adhesive force reduction rate S GLA is 100% in principle, and is, for example, less than 100%.
　＜粘着シートの構成＞
　ここに開示される粘着シートの一構成例を図１に示す。この粘着シート１は、一方の表面１０Ａが被着体への貼付面となっている粘着剤層１０と、粘着剤層１０の他方の表面１０Ｂに積層された支持体２０と、を含む片面接着性の粘着シートとして構成されている。粘着剤層１０は支持体２０の一方の表面２０Ａに固定的に接合している。支持体２０としては、例えばポリエステルフィルム等のプラスチックフィルムが用いられ得る。図１に示す例では、粘着剤層１０は単層構造である。すなわち、粘着剤層１０の一方の表面（粘着面）１０Ａを構成するＡ層によって粘着剤層１０の全体が構成されている。使用前（被着体への貼付け前）の粘着シート１は、例えば図１に示すように、粘着面１０Ａが、少なくとも該粘着剤層側が剥離性表面（剥離面）となっている剥離ライナー３０で保護された、剥離ライナー付き粘着シート５０の形態であり得る。あるいは、支持体２０の第二面２０Ｂ（第一面２０Ａとは反対側の表面であり、背面ともいう。）が剥離面となっており、第二面１０Ｂに粘着面１０Ａが当接するように巻回または積層されることで粘着面１０Ａが保護された形態であってもよい。 <Configuration of adhesive sheet>
FIG. 1 shows an example of the configuration of the adhesive sheet disclosed herein. This adhesive sheet 1 is a one-sided adhesive including an adhesive layer 10 whose one surface 10A is a surface to be attached to an adherend, and a support 20 laminated on the other surface 10B of the adhesive layer 10. It is constructed as a sticky adhesive sheet. The adhesive layer 10 is fixedly bonded to one surface 20A of the support 20. As the support 20, for example, a plastic film such as a polyester film can be used. In the example shown in FIG. 1, the adhesive layer 10 has a single-layer structure. That is, the entire adhesive layer 10 is constituted by the A layer that constitutes one surface (adhesive surface) 10A of the adhesive layer 10. The adhesive sheet 1 before use (before being attached to an adherend) is, for example, as shown in FIG. It may be in the form of an adhesive sheet 50 with a release liner, which is protected by a release liner. Alternatively, the second surface 20B (the surface opposite to the first surface 20A, also referred to as the back surface) of the support 20 is a release surface, and the adhesive surface 10A is in contact with the second surface 10B. The adhesive surface 10A may be protected by being wound or laminated.
　剥離ライナーとしては、特に限定されず、例えば樹脂フィルムや紙等のライナー基材の表面が剥離処理された剥離ライナーや、フッ素系ポリマー（ポリテトラフルオロエチレン等）やポリオレフィン系樹脂（ポリエチレン、ポリプロピレン等）の低接着性材料からなる剥離ライナー等を用いることができる。上記剥離処理には、例えば、シリコーン系、長鎖アルキル系等の剥離処理剤が用いられ得る。いくつかの態様において、剥離処理された樹脂フィルムを剥離ライナーとして好ましく採用し得る。 The release liner is not particularly limited, and includes, for example, a release liner in which the surface of a liner base material such as a resin film or paper has been subjected to release treatment, a fluorine-based polymer (such as polytetrafluoroethylene), or a polyolefin-based resin (such as polyethylene, polypropylene, etc.). ) can be used, such as a release liner made of a low adhesive material. For example, a silicone-based, long-chain alkyl-based, or other release agent may be used for the above-mentioned peeling treatment. In some embodiments, a release-treated resin film may be preferably employed as the release liner.
　＜被着体＞
　ここに開示される技術における粘着シートは、アルコール液を用いて被着体から容易に剥離し得ることからリワーク性がよく、かつ接合時には被着体との接着信頼性に優れるという特長を活かして、例えば各種の携帯機器（ポータブル機器）、自動車、家電製品等を構成する部材を被着体とし、該被着体に貼り付けられる態様で、該部材の固定、接合、成形、装飾、保護、支持等の用途に用いられ得る。上記部材の少なくとも表面を構成する材質は、例えば、アルカリガラス板や無アルカリガラス等のガラス；樹脂フィルム、ステンレス鋼（ＳＵＳ）、アルミニウム等の金属材料；アクリル樹脂、ＡＢＳ樹脂、ポリカーボネート樹脂、ポリスチレン樹脂等の樹脂材料；等であり得る。ここに開示される粘着シートは、アクリル系、ポリエステル系、アルキド系、メラミン系、ウレタン系、酸エポキシ架橋系、あるいはこれらの複合系（例えばアクリルメラミン系、アルキドメラミン系）等の塗料による塗装面や、亜鉛メッキ鋼板等のメッキ面に貼り付けられてもよい。ここに開示される粘着シートは、例えば、このような部材（被着体）が該粘着シートに接合された粘着シート付き部材の構成要素であり得る。以下、粘着シート付き部材を「接合体」ともいう。ここに開示される粘着シートの剥離方法は、上記のような粘着シート付き部材（接合体）の分離方法としても把握され得る。 <Adherend>
The adhesive sheet in the technology disclosed herein has good reworkability because it can be easily peeled off from the adherend using an alcohol solution, and has excellent adhesion reliability with the adherend during bonding. For example, fixing, bonding, molding, decoration, protection, etc. of the members in the form of attaching them to the adherends, for example, members constituting various mobile devices, automobiles, home appliances, etc. It can be used for purposes such as support. The material constituting at least the surface of the above member includes, for example, glass such as an alkali glass plate or non-alkali glass; metal materials such as resin film, stainless steel (SUS), and aluminum; acrylic resin, ABS resin, polycarbonate resin, and polystyrene resin. resin materials such as; etc. The adhesive sheet disclosed herein has a surface coated with a paint such as acrylic, polyester, alkyd, melamine, urethane, acid-epoxy crosslinked, or a composite of these (e.g., acrylic-melamine, alkyd-melamine). Alternatively, it may be attached to a plated surface such as a galvanized steel plate. The adhesive sheet disclosed herein may be, for example, a component of a member with an adhesive sheet, in which such a member (adherent) is joined to the adhesive sheet. Hereinafter, the member with the adhesive sheet will also be referred to as a "joint body". The adhesive sheet peeling method disclosed herein can also be understood as a method for separating a member (joined body) with an adhesive sheet as described above.
　このような粘着シート付き部材（接合体）において、上記部材の上記粘着剤層と接する面（すなわち、上記被着体の上記粘着シートが貼り付けられる面、以下「接合面」ともいう。）は、エタノールに対する接触角が、例えば６０度以下、好ましくは５０度以下となる程度にエタノール親和性を示す表面であり得る。いくつかの態様において、上記接合面のエタノール接触角は、４０度以下であることが好ましく、より好ましくは３０度以下（例えば２５度以下）であり、さらに好ましくは２０度以下であり、１５度以下でもよい。上記接合面のエタノール接触角が小さくなると、該接合面に沿ってアルコール液が濡れ広がりやすくなり、粘着シートのアルコール剥離性が向上する傾向にある。このことは、上記接合面に上記粘着シートを貼り合わせて粘着シート付き部材を作製する際の再剥離性向上の観点から好ましい。なお、上記接合面の接触角は、少なくとも粘着シートを貼り合わせる時期（例えば、貼り合わせの３０分前）に上述したいずれかの角度以下であれば、該接触角が所定以下であることによる再剥離性向上効果が発揮され得る。エタノールに対する接触角の下限は、原理上０度である。いくつかの態様において、上記接合面のエタノール接触角は、０度超でもよく、１度以上でもよく、３度以上でもよく、５度以上でもよい。 In such a member with an adhesive sheet (joint body), the surface of the member that comes into contact with the adhesive layer (that is, the surface of the adherend to which the adhesive sheet is attached, hereinafter also referred to as the "joining surface") is The surface may have an affinity for ethanol such that the contact angle with respect to ethanol is, for example, 60 degrees or less, preferably 50 degrees or less. In some embodiments, the ethanol contact angle of the bonded surface is preferably 40 degrees or less, more preferably 30 degrees or less (for example, 25 degrees or less), still more preferably 20 degrees or less, and 15 degrees or less. The following may be used. When the ethanol contact angle of the bonding surface becomes smaller, the alcohol liquid tends to wet and spread along the bonding surface, and the alcohol removability of the pressure-sensitive adhesive sheet tends to improve. This is preferable from the viewpoint of improving re-peelability when producing a member with a pressure-sensitive adhesive sheet by bonding the pressure-sensitive adhesive sheet to the bonding surface. In addition, if the contact angle of the bonding surface is at least one of the angles mentioned above at the time when the adhesive sheets are bonded together (for example, 30 minutes before bonding), then the contact angle is less than the predetermined value. The effect of improving releasability can be exhibited. The lower limit of the contact angle with respect to ethanol is 0 degrees in principle. In some embodiments, the ethanol contact angle of the bonded surface may be greater than 0 degrees, greater than or equal to 1 degree, greater than or equal to 3 degrees, or greater than or equal to 5 degrees.
　上記部材の上記粘着剤層と接する面（接合面）は、蒸留水に対する接触角が、例えば３０度以上、好ましくは３５度以上となる程度に低い親水性を示す表面であってもよい。いくつかの態様において、上記接合面の蒸留水に対する接触角は４０度以上であってもよく、４５度以上でもよく、５０度以上でもよく、６０度以上（例えば６０度超）でもよい。ここに開示される技術は、親水性が比較的低い表面に対しても、被着体に対する接着力と再剥離性とが両立できる傾向にある。このことは、従来の水剥離の技術が適用されづらい被着体に対しても、好ましく適用可能であるという点で有意義である。 The surface (bonding surface) of the member that comes into contact with the adhesive layer may be a surface that exhibits such low hydrophilicity that the contact angle with respect to distilled water is, for example, 30 degrees or more, preferably 35 degrees or more. In some embodiments, the contact angle of the bonded surface with distilled water may be 40 degrees or more, 45 degrees or more, 50 degrees or more, or 60 degrees or more (for example, more than 60 degrees). The technology disclosed herein tends to be able to achieve both adhesion to adherends and removability even on surfaces with relatively low hydrophilicity. This is significant in that it can be preferably applied to adherends to which conventional water peeling techniques are difficult to apply.
　また、いくつかの態様において、上記接合面の蒸留水に対する接触角は例えば６０度以下、好ましくは５０度以下となる程度の親水性を示す表面であり得る。いくつかの態様において、上記接合面の蒸留水に対する接触角は、例えば４５度以下であってよく、４０度以下でもよく、３５度以下でもよく、３０度以下でもよい。上記接合面の接触角が小さくなると、該接合面に沿ってアルコール液が濡れ広がりやすくなり、粘着シートのアルコール剥離性が向上する傾向にある。このことは、上記接合面に上記粘着シートを貼り合わせて粘着シート付き部材を作製する際のリワーク性向上の観点から好ましい。なお、上記接合面の蒸留水に対する接触角は、少なくとも粘着シートを貼り合わせる時期（例えば、貼り合わせの３０分前）に上述したいずれかの角度の範囲であれば、該接触角が所定範囲であることによるリワーク性向上効果が発揮され得る。接触角の下限は、原理上０度である。いくつかの態様において、上記接合面の蒸留水に対する接触角は、０度超でもよく、１度以上でもよく、３度以上でもよく、５度以上でもよい。 In some embodiments, the bonded surface may have such hydrophilicity that the contact angle with respect to distilled water is, for example, 60 degrees or less, preferably 50 degrees or less. In some embodiments, the contact angle of the bonded surface to distilled water may be, for example, 45 degrees or less, 40 degrees or less, 35 degrees or less, or 30 degrees or less. When the contact angle of the bonding surface becomes smaller, the alcohol liquid tends to wet and spread along the bonding surface, and the alcohol removability of the pressure-sensitive adhesive sheet tends to improve. This is preferable from the viewpoint of improving reworkability when producing a member with a pressure-sensitive adhesive sheet by bonding the pressure-sensitive adhesive sheet to the bonding surface. In addition, if the contact angle of the bonded surface with distilled water is within any of the above-mentioned angle ranges at least at the time when the adhesive sheets are bonded together (for example, 30 minutes before bonding), then the contact angle is within the predetermined range. The effect of improving reworkability can be exhibited by this. The lower limit of the contact angle is 0 degrees in principle. In some embodiments, the contact angle of the bonded surface with distilled water may be greater than 0 degrees, may be greater than 1 degree, may be greater than 3 degrees, or may be greater than 5 degrees.
　なお、上記接合面のエタノールに対する接触角および蒸留水に対する接触角は、次のとおり測定する。すなわち、測定雰囲気２３℃、５０％ＲＨの環境下において、接触角計（協和界面科学株式会社製、商品名「ＤＭｏ－５０１型」、コントロールボックス「ＤＭＣ－２」、制御・解析ソフト「ＦＡＭＡＳ（バージョン５．０．３０）」）を用いて液滴法により測定を行う。エタノールに対する接触角を測定する場合のエタノールの滴下量および蒸留水に対する接触角を測定する場合の蒸留水の滴下量はそれぞれ２μＬとし、滴下５秒後の画像からΘ／２法により接触角を算出する（Ｎ５で実施）。 Note that the contact angle of the bonded surface with respect to ethanol and with respect to distilled water is measured as follows. That is, in a measurement atmosphere of 23°C and 50% RH, a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., trade name "DMo-501 type", a control box "DMC-2", and a control/analysis software "FAMAS") was used. Measurements are performed by the droplet method using version 5.0.30). The amount of ethanol dropped when measuring the contact angle for ethanol and the amount of distilled water dropped when measuring the contact angle for distilled water are each 2 μL, and the contact angle is calculated using the Θ/2 method from the image 5 seconds after dropping. (Implemented on N5).
　好ましい用途の一例として、光学用途が挙げられる。より具体的には、例えば、光学部材を貼り合わせる用途（光学部材貼り合わせ用）や上記光学部材が用いられた製品（光学製品）の製造用途等に用いられる光学用粘着シートの剥離方法として、ここに開示される剥離方法は好ましく実施することができる。 An example of a preferred use is optical use. More specifically, for example, as a method for peeling an optical pressure-sensitive adhesive sheet used for bonding optical members (for bonding optical members) or for manufacturing products (optical products) in which the above-mentioned optical members are used, The peeling method disclosed herein can be preferably implemented.
　上記光学部材とは、光学的特性（例えば、偏光性、光屈折性、光散乱性、光反射性、光透過性、光吸収性、光回折性、旋光性、視認性等）を有する部材をいう。上記光学部材としては、光学的特性を有する部材であれば特に限定されないが、例えば、表示装置（画像表示装置）、入力装置等の機器（光学機器）を構成する部材またはこれらの機器に用いられる部材が挙げられ、例えば、偏光板、波長板、位相差板、光学補償フィルム、輝度向上フィルム、導光板、反射フィルム、反射防止フィルム、ハードコート（ＨＣ）フィルム、衝撃吸収フィルム、防汚フィルム、フォトクロミックフィルム、調光フィルム、透明導電フィルム（ＩＴＯフィルム）、意匠フィルム、装飾フィルム、表面保護板、プリズム、レンズ、カラーフィルター、透明基板や、さらにはこれらが積層されている部材（これらを総称して「機能性フィルム」と称する場合がある。）等が挙げられる。なお、上記の「板」および「フィルム」は、それぞれ板状、フィルム状、シート状等の形態を含むものとし、例えば、「偏光フィルム」は、「偏光板」、「偏光シート」等を含むものとする。 The above-mentioned optical member refers to a member having optical properties (for example, polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, optical rotation, visibility, etc.). say. The above-mentioned optical member is not particularly limited as long as it has optical properties, but for example, it may be a member constituting a device (optical device) such as a display device (image display device) or an input device, or a member used in these devices. Members include, for example, polarizing plates, wavelength plates, retardation plates, optical compensation films, brightness enhancement films, light guide plates, reflective films, antireflection films, hard coat (HC) films, shock absorption films, antifouling films, Photochromic films, light control films, transparent conductive films (ITO films), design films, decorative films, surface protection plates, prisms, lenses, color filters, transparent substrates, and members on which these are laminated (collectively referred to as (sometimes referred to as "functional film"). Note that the above-mentioned "plate" and "film" each include forms such as plate, film, and sheet. For example, "polarizing film" includes "polarizing plate", "polarizing sheet", etc. .
　上記表示装置としては、例えば液晶表示装置、有機ＥＬ表示装置、ＰＤＰ、電子ペーパー等が挙げられ、特に、フォルダブル表示装置や車載用の表示装置のように高価な部材を含む場合に、ここに開示される技術は好ましく適用される。また上記表示装置は、タッチパネル等の入力可能な表示装置を包含する。上記表示装置は、リサイクル、リユース等の要請が強く、ここに開示される技術を適用することが特に有意義である。 Examples of the above-mentioned display devices include liquid crystal display devices, organic EL display devices, PDPs, electronic paper, etc. In particular, when expensive components are included, such as foldable display devices and vehicle-mounted display devices, The disclosed technology is preferably applied. Further, the display device includes a display device that allows input, such as a touch panel. There is a strong demand for recycling, reuse, etc. of the display device, and it is particularly meaningful to apply the technology disclosed herein.
　上記光学部材としては、特に限定されないが、例えば、ガラス、アクリル樹脂、ポリカーボネート、ポリエチレンテレフタレート、金属薄膜等からなる部材（例えば、シート状やフィルム状、板状の部材）等が挙げられる。なお、この明細書における「光学部材」には、表示装置や入力装置の視認性を保ちながら加飾や保護の役割を担う部材（意匠フィルム、装飾フィルムや表面保護フィルム等）も含むものとする。 The above-mentioned optical member is not particularly limited, but includes, for example, a member (for example, a sheet-like, film-like, or plate-like member) made of glass, acrylic resin, polycarbonate, polyethylene terephthalate, metal thin film, etc. Note that the term "optical member" in this specification also includes members (design films, decorative films, surface protection films, etc.) that serve to decorate and protect while maintaining the visibility of display devices and input devices.
　他の用途の一例として、ここに開示される接合体や、該接合体を含む製品や装置、構造体は、部材の接合時には粘着シートによる高い接着信頼性が求められる一方、構成部材の修理や交換、検査、リサイクル等の際にスムーズな除去が求められる電子機器（好適には携帯型電子機器）の構成要素であり得る。例えば、携帯電話、スマートフォン、タブレット型パソコン、ノート型パソコン、各種ウェアラブル機器（例えば、腕時計のように手首に装着するリストウェア型、クリップやストラップ等で体の一部に装着するモジュラー型、メガネ型（単眼型や両眼型。ヘッドマウント型も含む。）を包含するアイウェア型、シャツや靴下、帽子等に例えばアクセサリの形態で取り付ける衣服型、イヤホンのように耳に取り付けるイヤウェア型等）、デジタルカメラ、デジタルビデオカメラ、音響機器（携帯音楽プレーヤー、ＩＣレコーダー等）、計算機（電卓等）、携帯ゲーム機器、電子辞書、電子手帳、電子書籍、車載用情報機器、携帯ラジオ、携帯テレビ、携帯プリンター、携帯スキャナ、携帯モデム等の携帯型電子機器の構成要素であり得る。また、上記表示装置は、デスクトップ型パソコンやディスプレイ、テレビ（液晶、プラズマ、有機ＥＬ等）等の電子機器の構成要素であり得る。なお、この明細書において「携帯」とは、単に携帯することが可能であるだけでは十分ではなく、個人（標準的な成人）が相対的に容易に持ち運び可能なレベルの携帯性を有することを意味するものとする。 As an example of other uses, the bonded body disclosed herein and the products, devices, and structures that include the bonded body require high adhesion reliability using adhesive sheets when joining members, while repairing and repairing component parts. It can be a component of an electronic device (preferably a portable electronic device) that requires smooth removal during replacement, inspection, recycling, etc. For example, mobile phones, smartphones, tablet computers, notebook computers, various wearable devices (e.g., wristwear type that is worn on the wrist like a wristwatch, modular type that is worn on a part of the body with a clip or strap, etc.), and glasses type. (Eyewear types including monocular and binocular types, including head-mounted types, clothing types that are attached to shirts, socks, hats, etc. in the form of accessories, earwear types that are attached to the ears like earphones, etc.), Digital cameras, digital video cameras, audio equipment (portable music players, IC recorders, etc.), calculators (calculators, etc.), mobile game devices, electronic dictionaries, electronic notebooks, electronic books, in-vehicle information devices, mobile radios, mobile televisions, mobile phones It can be a component of a portable electronic device such as a printer, a portable scanner, a portable modem, etc. Further, the display device may be a component of an electronic device such as a desktop personal computer, a display, or a television (liquid crystal, plasma, organic EL, etc.). Note that in this specification, "portable" does not mean that it is simply portable; it also means that it has a level of portability that allows an individual (standard adult) to carry it relatively easily. shall mean.
　また、他の好ましい用途の一例として、ここに開示される剥離方法は、ガラスや金属・有機材料（例えばＰＥＴ、ＰＩ等）等の加工、運搬、保管等の際に、これらの表面を損傷や汚れから防止する目的で該表面に接着して用いられる表面保護シートの剥離方法に好ましく適用することができる。上記表面保護シートは、被着体の表面を保護するためにある程度の接着信頼性が必要となる一方、保護目的が達成された後には、適当なタイミングで除去される必要があるため、被着体から容易に剥離除去できることが望まれる。ここに開示される技術によると、従来の水剥離技術を適用しにくい親水性の低い被着体を含む、幅広い被着体に適用されて、優れた剥離力低減効果を示すため、表面保護シートの剥離方法として有用である。 In addition, as an example of another preferred application, the peeling method disclosed herein can damage or damage the surfaces of glass, metals, organic materials (e.g., PET, PI, etc.) during processing, transportation, storage, etc. It can be preferably applied to a method for peeling off a surface protection sheet that is used by adhering to the surface for the purpose of preventing staining. The above-mentioned surface protection sheet requires a certain degree of adhesion reliability in order to protect the surface of the adherend, but it also needs to be removed at an appropriate time after the protective purpose is achieved. It is desired that it can be easily peeled off and removed from the body. According to the technology disclosed herein, it can be applied to a wide range of adherends, including adherends with low hydrophilicity to which conventional water peeling techniques are difficult to apply, and exhibits an excellent peeling force reduction effect. It is useful as a peeling method.
　＜粘着剤＞
　ここに開示される粘着シートにおける粘着剤の形態は特に限定されず、例えば点状、ストライプ状等の規則的あるいはランダムなパターンであってもよいが、典型的には、連続的に形成された層状の粘着剤層の形態である。ここに開示される粘着シートは、例えば、粘着剤層からなる支持体レス両面粘着シートとして構成されているか、支持体（基材）の一方の面に粘着層が配置される片面接着性の粘着シート（片面粘着シート）として構成されていてもよく、基材層等の中間層を有する両面接着性の粘着シート（両面粘着シート）として構成されていてもよい。 <Adhesive>
The shape of the adhesive in the adhesive sheet disclosed herein is not particularly limited, and may be a regular or random pattern such as dots or stripes, but typically it is continuously formed. It is in the form of a layered adhesive layer. The adhesive sheet disclosed herein is, for example, configured as a support-less double-sided adhesive sheet consisting of an adhesive layer, or a single-sided adhesive in which an adhesive layer is arranged on one side of a support (substrate). It may be configured as a sheet (single-sided adhesive sheet), or it may be configured as a double-sided adhesive sheet (double-sided adhesive sheet) having an intermediate layer such as a base layer.
　上記粘着シートの粘着剤層は、単層構造に限定されず、同一または異なる組成の１または２以上の粘着剤層をさらに備えるものであってもよい。例えば、中間層を備える粘着シートにおいて、当該中間層は粘着剤層であってもよく、その場合、粘着シートは、当該粘着シートの表面を構成する第１、第２の粘着剤層と、中間層としての粘着剤層とを含む、少なくとも３層の粘着剤層を有するものであり得る。 The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is not limited to a single-layer structure, and may further include one or more pressure-sensitive adhesive layers having the same or different compositions. For example, in a pressure-sensitive adhesive sheet including an intermediate layer, the intermediate layer may be a pressure-sensitive adhesive layer, and in that case, the pressure-sensitive adhesive sheet includes first and second pressure-sensitive adhesive layers that constitute the surface of the pressure-sensitive adhesive sheet, and It may have at least three adhesive layers, including an adhesive layer as a layer.
　上記粘着層を構成する粘着剤は、例えば、アクリル系粘着剤、ゴム系粘着剤（天然ゴム系、合成ゴム系、これらの混合系等）、シリコーン系粘着剤、ポリエステル系粘着剤、ウレタン系粘着剤、ポリエーテル系粘着剤、ポリアミド系粘着剤、フッ素系粘着剤等の公知の各種粘着剤から選択される１種または２種以上の粘着剤を含んで構成された粘着剤であり得る。ここで、アクリル系粘着剤とは、アクリル系重合物を主成分（ベースポリマー）とする粘着剤をいう。ゴム系粘着剤その他の粘着剤についても同様の意味である。 Examples of the adhesive constituting the adhesive layer include acrylic adhesives, rubber adhesives (natural rubber, synthetic rubber, mixtures thereof, etc.), silicone adhesives, polyester adhesives, and urethane adhesives. The adhesive may include one or more types of adhesives selected from various known adhesives, such as adhesives, polyether adhesives, polyamide adhesives, and fluorine adhesives. Here, the acrylic adhesive refers to an adhesive whose main component (base polymer) is an acrylic polymer. The same meaning applies to rubber adhesives and other adhesives.
　なお、粘着剤の「ベースポリマー」とは、該粘着剤に含まれるゴム状ポリマーの主成分をいい、このこと以外、何ら限定的に解釈されるものではない。上記ゴム状ポリマーとは、室温付近の温度域においてゴム弾性を示すポリマーをいう。また、この明細書において「主成分」とは、重量基準で、含有成分のなかで最も多い割合で含まれる成分をいう。したがって、例えば粘着剤が３成分以上から構成されている場合、当該粘着剤中の主成分の含有量は３４重量％以上であり得る。 Note that the "base polymer" of the adhesive refers to the main component of the rubbery polymer contained in the adhesive, and is not interpreted in any limited manner other than this. The above-mentioned rubbery polymer refers to a polymer that exhibits rubber elasticity in a temperature range around room temperature. Furthermore, in this specification, the term "main component" refers to the component contained in the largest proportion among the contained components on a weight basis. Therefore, for example, when the adhesive is composed of three or more components, the content of the main components in the adhesive may be 34% by weight or more.
　また、この明細書において「アクリル系重合物」とは、アクリル系モノマーを５０重量％より多く含むモノマー成分に由来する重合物をいい、アクリル系ポリマーともいう。上記アクリル系モノマーとは、１分子中に少なくとも１つの（メタ）アクリロイル基を有するモノマーに由来するモノマーのことをいう。また、この明細書において「（メタ）アクリロイル」とは、アクリロイルおよびメタクリロイルを包括的に指す意味である。同様に、「（メタ）アクリレート」とはアクリレートおよびメタクリレートを、「（メタ）アクリル」とはアクリルおよびメタクリルを、それぞれ包括的に指す意味である。 Furthermore, in this specification, the term "acrylic polymer" refers to a polymer derived from a monomer component containing more than 50% by weight of an acrylic monomer, and is also referred to as an acrylic polymer. The above-mentioned acrylic monomer refers to a monomer derived from a monomer having at least one (meth)acryloyl group in one molecule. Furthermore, in this specification, "(meth)acryloyl" refers comprehensively to acryloyl and methacryloyl. Similarly, "(meth)acrylate" comprehensively refers to acrylate and methacrylate, and "(meth)acrylic" comprehensively refers to acrylic and methacrylic.
　（アクリル系粘着剤）
　いくつかの態様において、粘着剤の構成材料としてアクリル系粘着剤を好ましく採用し得る。具体的には、ここに開示される粘着剤は、アクリル系重合物を含むアクリル系粘着剤であり得る。アクリル系粘着剤は、透明性や耐候性、設計の自由度に優れる傾向がある。高い透明性を有するアクリル系粘着剤は、光学用途、ひいては表示装置用の接合用途に好ましく利用される。 (acrylic adhesive)
In some embodiments, an acrylic adhesive may be preferably employed as a constituent material of the adhesive. Specifically, the adhesive disclosed herein may be an acrylic adhesive containing an acrylic polymer. Acrylic adhesives tend to be superior in transparency, weather resistance, and design freedom. Acrylic pressure-sensitive adhesives with high transparency are preferably used for optical applications and, ultimately, for bonding applications for display devices.
　ここに開示される粘着剤としては、例えば、エステル末端に炭素原子数１以上２０以下の直鎖または分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステルを３３重量％以上の割合で含むモノマー成分から構成されたアクリル系重合物をベースポリマーとして含有するものが好ましい。以下、炭素原子数がＸ以上Ｙ以下のアルキル基をエステル末端に有する（メタ）アクリル酸アルキルエステルを「（メタ）アクリル酸ＣＸ－Ｙアルキルエステル」と表記することがある。特性のバランスをとりやすいことから、いくつかの態様に係るアクリル系重合物のモノマー成分全体のうち（メタ）アクリル酸Ｃ１－２０アルキルエステルの割合は、例えば３５重量％以上であり、５０重量％以上が適当であり、５５重量％以上であってよい。上記モノマー成分のうち（メタ）アクリル酸Ｃ１－２０アルキルエステルの割合は、例えば９９．９重量％以下であってよく、９９重量％以下でもよく、９５重量％以下でもよい。いくつかの態様に係るアクリル系重合物のモノマー成分全体に占める（メタ）アクリル酸Ｃ１－２０アルキルエステルの割合は、粘着剤の凝集性等の観点から、例えば８５重量％以下であってよく、７５重量％以下でもよく、６５重量％以下でもよい。（メタ）アクリル酸Ｃ１－２０アルキルエステルは、１種を単独でまたは２種以上を組み合わせて使用することができる。 The adhesive disclosed herein includes, for example, a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms at the ester end in a proportion of 33% by weight or more. Preferably, the base polymer contains an acrylic polymer composed of monomer components. Hereinafter, a (meth)acrylic acid alkyl ester having an alkyl group having at least X and Y or less carbon atoms at the ester end may be referred to as "(meth)acrylic acid C XY alkyl ester." Since it is easy to balance the properties, the proportion of (meth)acrylic acid C 1-20 alkyl ester in the total monomer components of the acrylic polymer according to some embodiments is, for example, 35% by weight or more, and 50% by weight. % or more is suitable, and may be 55% or more by weight. The proportion of (meth)acrylic acid C 1-20 alkyl ester among the monomer components may be, for example, 99.9% by weight or less, 99% by weight or less, or 95% by weight or less. The proportion of (meth)acrylic acid C 1-20 alkyl ester in the entire monomer component of the acrylic polymer according to some embodiments may be, for example, 85% by weight or less from the viewpoint of cohesive properties of the adhesive. , 75% by weight or less, or 65% by weight or less. The (meth)acrylic acid C 1-20 alkyl esters can be used alone or in combination of two or more.
　これらのうち、少なくとも（メタ）アクリル酸Ｃ４－２０アルキルエステルを用いることが好ましく、少なくとも（メタ）アクリル酸Ｃ４－１８アルキルエステルを用いることがより好ましい。例えば、上記モノマー成分としてアクリル酸ｎ－ブチル（ＢＡ）、アクリル酸２－エチルヘキシル（２ＥＨＡ）の少なくとも一種を含むことが好ましい。また、ＢＡおよび２ＥＨＡの少なくとも一種に加えて、（メタ）アクリル酸Ｃ１０－１４アルキルエステルをさらに用いることがより好ましい。上記（メタ）アクリル酸Ｃ１０－１４アルキルエステルとしては、例えばアクリル酸ラウリル（ＬＡ）が挙げられる。上記（メタ）アクリル酸Ｃ１０－１４アルキルエステルとしては、１種を単独でまたは２種以上を組み合わせて使用することができる。また、（メタ）アクリル酸Ｃ４－１８アルキルエステルは、１種を単独でまたは２種以上を組み合わせて使用することができる。 Among these, it is preferable to use at least C 4-20 alkyl (meth)acrylate, and more preferably to use at least C 4-18 alkyl (meth)acrylate. For example, it is preferable that the monomer component includes at least one of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA). Furthermore, it is more preferable to further use (meth)acrylic acid C 10-14 alkyl ester in addition to at least one of BA and 2EHA. Examples of the (meth)acrylic acid C 10-14 alkyl ester include lauryl acrylate (LA). As the (meth)acrylic acid C 10-14 alkyl ester, one type can be used alone or two or more types can be used in combination. Furthermore, (meth)acrylic acid C 4-18 alkyl esters can be used alone or in combination of two or more.
　アルコール剥離による粘着力低減の観点から、いくつかの態様において、アクリル系重合体のモノマー成分全体に占める（メタ）アクリル酸Ｃ１０－１４アルキルエステルの割合は、３重量％以上（例えば５重量％以上）であることが好ましく、より好ましくは１０重量％以上（例えば２０重量％以上）であり、さらに好ましくは２５重量％以上であり、３０重量％以上でもよく、４０重量％以上でもよく、４５重量％以上でもよく、５０重量％以上でもよい。粘着性能のバランスを取る観点から、アクリル系重合体のモノマー成分全体に占める（メタ）アクリル酸Ｃ１０－１４アルキルエステルの割合は、９５重量％以下であってもよく、９０重量％以下でもよく、８０重量％以下でもよく、７５重量％以下でもよく、７０重量％以下でもよく、６５重量％以下でもよい。 From the viewpoint of reducing adhesive strength by alcohol peeling, in some embodiments, the proportion of (meth)acrylic acid C 10-14 alkyl ester in the entire monomer component of the acrylic polymer is 3% by weight or more (for example, 5% by weight). or more), more preferably 10% by weight or more (for example, 20% by weight or more), still more preferably 25% by weight or more, 30% by weight or more, 40% by weight or more, 45% by weight or more. It may be at least 50% by weight, or at least 50% by weight. From the viewpoint of balancing adhesive performance, the proportion of (meth)acrylic acid C 10-14 alkyl ester in the entire monomer component of the acrylic polymer may be 95% by weight or less, or may be 90% by weight or less. , 80% by weight or less, 75% by weight or less, 70% by weight or less, or 65% by weight or less.
　いくつかの態様において、アクリル系重合物を構成するモノマー成分は、（メタ）アクリル酸Ｃ４－９アルキルエステルと、（メタ）アクリル酸Ｃ１０－１４アルキルエステルとを組み合わせて含み得る。アルコール剥離による粘着力低減の観点から、いくつかの態様において、アクリル系重合体のモノマー成分全体における、（メタ）アクリル酸Ｃ４－９アルキルエステルに対する（メタ）アクリル酸Ｃ１０－１４アルキルエステルの重量基準の含有量比は、０．１以上であることが好ましく、より好ましくは０．３以上である。いくつかの態様において、アクリル系重合体のモノマー成分全体における、（メタ）アクリル酸Ｃ４－９アルキルエステルに対する（メタ）アクリル酸Ｃ１０－１４アルキルエステルの重量基準の含有量比は、０．５以上でもよく、０．８以上でもよく、１．０以上でもよく、１．２以上でもよく、１．４以上でもよく、１．８以上でもよく、２．０以上でもよい。粘着性能のバランスを取る観点から、いくつかの態様において、アクリル系重合体のモノマー成分全体における、（メタ）アクリル酸Ｃ４－９アルキルエステルに対する（メタ）アクリル酸Ｃ１０－１４アルキルエステルの重量基準の含有量比は、１０以下であることが好ましく、より好ましくは５．０以下であり、４．０以下でもよく、３．０以下でもよい。 In some embodiments, the monomer components constituting the acrylic polymer may include a combination of (meth)acrylic acid C 4-9 alkyl ester and (meth)acrylic acid C 10-14 alkyl ester. From the viewpoint of reducing adhesive strength by alcohol peeling, in some embodiments, the ratio of (meth)acrylic acid C 10-14 alkyl ester to (meth)acrylic acid C 4-9 alkyl ester in the entire monomer component of the acrylic polymer is The weight-based content ratio is preferably 0.1 or more, more preferably 0.3 or more. In some embodiments, the weight-based content ratio of (meth)acrylic acid C 10-14 alkyl ester to (meth)acrylic acid C 4-9 alkyl ester in the entire monomer component of the acrylic polymer is 0. It may be 5 or more, 0.8 or more, 1.0 or more, 1.2 or more, 1.4 or more, 1.8 or more, or 2.0 or more. From the viewpoint of balancing adhesive performance, in some embodiments, the weight of (meth)acrylic acid C 10-14 alkyl ester relative to (meth)acrylic acid C 4-9 alkyl ester in the entire monomer component of the acrylic polymer The standard content ratio is preferably 10 or less, more preferably 5.0 or less, may be 4.0 or less, or may be 3.0 or less.
　上記アクリル系重合物を構成するモノマー成分は、（メタ）アクリル酸アルキルエステルとともに、必要に応じて、（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマー（共重合性モノマー）を含んでいてもよい。共重合性モノマーとしては、極性基（例えば、カルボキシ基、水酸基、窒素原子含有環等）を有するモノマーや、ホモポリマーのガラス転移温度が比較的高い（例えば１０℃以上の）モノマーを好適に使用することができる。極性基を有するモノマーは、アクリル系重合物に架橋点を導入したり、粘着剤の凝集力を高めたりするために役立ち得る。共重合性モノマーは、１種を単独でまたは２種以上を組み合わせて用いることができる。 The monomer components constituting the acrylic polymer include (meth)acrylic acid alkyl ester and, if necessary, other monomers (copolymerizable monomers) that can be copolymerized with (meth)acrylic acid alkyl ester. You can stay there. As the copolymerizable monomer, monomers having polar groups (e.g., carboxyl group, hydroxyl group, nitrogen atom-containing ring, etc.) and monomers with a relatively high homopolymer glass transition temperature (e.g., 10° C. or higher) are preferably used. can do. A monomer having a polar group can be useful for introducing crosslinking points into the acrylic polymer and increasing the cohesive force of the adhesive. The copolymerizable monomers can be used alone or in combination of two or more.
　共重合性モノマーの非限定的な例としては、カルボキシ基含有モノマー、酸無水物基含有モノマー、水酸基含有モノマー、スルホン酸基またはリン酸基を含有するモノマー、エポキシ基含有モノマー、シアノ基含有モノマー、イソシアネート基含有モノマー、アミド基含有モノマー、アミノ基含有モノマー、窒素原子含有環を有するモノマー、スクシンイミド骨格を有するモノマー、マレイミド類、（メタ）アクリル酸アミノアルキル類、アルコキシ基含有モノマー、アルコキシシリル基含有モノマー、ビニルエステル類、ビニルエーテル類、芳香族ビニル化合物、オレフィン類、脂環式炭化水素基を有する（メタ）アクリル酸エステル、芳香族炭化水素基を有する（メタ）アクリル酸エステル、その他、（メタ）アクリル酸テトラヒドロフルフリル等の複素環含有（メタ）アクリレート、塩化ビニルやフッ素原子含有（メタ）アクリレート等のハロゲン原子含有（メタ）アクリレート、シリコーン（メタ）アクリレート等のケイ素原子含有（メタ）アクリレート、テルペン化合物誘導体アルコールから得られる（メタ）アクリル酸エステル等が挙げられる。なかでも、カルボキシ基含有モノマー、水酸基含有モノマー、窒素原子含有環を有するモノマー、脂環式炭化水素基を有する（メタ）アクリル酸エステルが好ましい。 Non-limiting examples of copolymerizable monomers include carboxy group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, monomers containing sulfonic acid groups or phosphoric acid groups, epoxy group-containing monomers, and cyano group-containing monomers. , isocyanate group-containing monomer, amide group-containing monomer, amino group-containing monomer, monomer having a nitrogen atom-containing ring, monomer having a succinimide skeleton, maleimides, aminoalkyl (meth)acrylates, alkoxy group-containing monomer, alkoxysilyl group Containing monomers, vinyl esters, vinyl ethers, aromatic vinyl compounds, olefins, (meth)acrylic esters having an alicyclic hydrocarbon group, (meth)acrylic esters having an aromatic hydrocarbon group, others, ( Heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl meth)acrylate, halogen atom-containing (meth)acrylates such as vinyl chloride and fluorine atom-containing (meth)acrylates, and silicon-containing (meth)acrylates such as silicone (meth)acrylates. Examples include acrylates and (meth)acrylic acid esters obtained from terpene compound derivative alcohols. Among these, carboxy group-containing monomers, hydroxyl group-containing monomers, monomers having a nitrogen atom-containing ring, and (meth)acrylic acid esters having an alicyclic hydrocarbon group are preferred.
　共重合性モノマーの好適例であるカルボキシ基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等が挙げられる。
　水酸基含有モノマーとしては、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２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル、（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレート等の（メタ）アクリル酸ヒドロキシアルキル等が挙げられる。
　窒素原子含有環を有するモノマーとしては、例えば、Ｎ－ビニル－２－ピロリドン、Ｎ－メチルビニルピロリドン、Ｎ－ビニルピリジン、Ｎ－ビニルピペリドン、Ｎ－ビニルピリミジン、Ｎ－ビニルピペラジン、Ｎ－ビニルピラジン、Ｎ－ビニルピロール、Ｎ－ビニルイミダゾール、Ｎ－ビニルオキサゾール、Ｎ－（メタ）アクリロイル－２－ピロリドン、Ｎ－（メタ）アクリロイルピペリジン、Ｎ－（メタ）アクリロイルピロリジン、Ｎ－ビニルモルホリン、Ｎ－ビニル－３－モルホリノン、Ｎ－ビニル－２－カプロラクタム、Ｎ－ビニル－１，３－オキサジン－２－オン、Ｎ－ビニル－３，５－モルホリンジオン、Ｎ－ビニルピラゾール、Ｎ－ビニルイソオキサゾール、Ｎ－ビニルチアゾール、Ｎ－ビニルイソチアゾール、Ｎ－ビニルピリダジン等（例えば、Ｎ－ビニル－２－カプロラクタム等のラクタム類）が挙げられる。
　脂環式炭化水素基を有する（メタ）アクリル酸エステルとしては、例えば、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、アダマンチル（メタ）アクリレート等の脂環式炭化水素基含有（メタ）アクリレートが挙げられる。 Examples of carboxyl group-containing monomers that are suitable examples of copolymerizable monomers include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and the like. .
Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4) Examples include hydroxyalkyl (meth)acrylates such as -hydroxymethylcyclohexyl)methyl (meth)acrylate.
Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -vinylthiazole, N-vinylisothiazole, N-vinylpyridazine, etc. (eg, lactams such as N-vinyl-2-caprolactam).
Examples of (meth)acrylic esters having an alicyclic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate. Examples include alicyclic hydrocarbon group-containing (meth)acrylates such as acrylates.
　このような共重合性モノマーを使用する場合、その使用量は特に限定されず、例えばモノマー成分全体の０．０１重量％以上とすることが適当である。共重合性モノマーの使用効果をよりよく発揮する観点から、共重合性モノマーの使用量をモノマー成分全体の０．１重量％以上としてもよく、０．５重量％以上としてもよい。また、粘着特性のバランスをとりやすくする観点から、共重合性モノマーの使用量は、モノマー成分全体の６０重量％以下とすることが適当であり、５０重量％以下であってもよく、４０重量％以下でもよい。 When such a copolymerizable monomer is used, the amount used is not particularly limited, and is preferably 0.01% by weight or more based on the total monomer components. In order to better exhibit the effects of using the copolymerizable monomer, the amount of the copolymerizable monomer used may be 0.1% by weight or more, or 0.5% by weight or more based on the total monomer components. In addition, from the viewpoint of making it easier to balance the adhesive properties, it is appropriate that the amount of the copolymerizable monomer used is 60% by weight or less of the entire monomer component, and it may be 50% by weight or less, and 40% by weight or less. It may be less than %.
　いくつかの態様において、アクリル系重合物を構成するモノマー成分は、水酸基含有モノマーを含み得る。水酸基含有モノマーの使用により、粘着剤の凝集力や架橋（例えば、イソシアネート架橋剤による架橋）の程度を好適に調節し得る。水酸基含有モノマーとしては上記で例示したもの等を用いることができ、例えばアクリル酸２－ヒドロキシエチル（ＨＥＡ）やアクリル酸４－ヒドロキシブチル（４ＨＢＡ）を好ましく採用し得る。水酸基含有モノマーは、１種を単独でまたは２種以上を組み合わせて使用することができる。水酸基含有モノマーを使用する場合における使用量は特に制限されず、いくつかの好ましい態様において、水酸基含有モノマーの使用量は、モノマー成分全体の１５重量％以上であり、２０重量％以上が適当であり、好ましくは２５重量％以上である。また、粘着剤の吸水性を抑制する観点から、いくつかの態様において、水酸基含有モノマーの使用量は、モノマー成分全体の例えば５０重量％以下（例えば４５重量％以下）とすることが適当であり、４０重量％以下としてもよく、３０重量％以下としてもよく、２０重量％以下としてもよい。 In some embodiments, the monomer component constituting the acrylic polymer may include a hydroxyl group-containing monomer. By using the hydroxyl group-containing monomer, the cohesive force and degree of crosslinking (for example, crosslinking using an isocyanate crosslinking agent) of the adhesive can be suitably adjusted. As the hydroxyl group-containing monomer, those exemplified above can be used, and for example, 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA) can be preferably employed. The hydroxyl group-containing monomers can be used alone or in combination of two or more. When using a hydroxyl group-containing monomer, the amount used is not particularly limited, and in some preferred embodiments, the amount of the hydroxyl group-containing monomer used is 15% by weight or more, preferably 20% by weight or more of the entire monomer component. , preferably 25% by weight or more. Further, from the viewpoint of suppressing water absorption of the adhesive, in some embodiments, it is appropriate that the amount of the hydroxyl group-containing monomer used is, for example, 50% by weight or less (for example, 45% by weight or less) of the entire monomer component. , 40% by weight or less, 30% by weight or less, or 20% by weight or less.
　いくつかの態様において、アクリル系重合物を構成するモノマー成分は、脂環式炭化水素基含有（メタ）アクリレートを含み得る。これにより、粘着剤の凝集力を高めることができる。脂環式炭化水素基含有（メタ）アクリレートとしては上記で例示したもの等を用いることができ、例えばシクロヘキシルアクリレート（ＣＨＡ）やイソボルニルアクリレートを好ましく採用し得る。脂環式炭化水素基含有（メタ）アクリレートは、１種を単独でまたは２種以上を組み合わせて使用することができる。脂環式炭化水素基含有（メタ）アクリレートを使用する場合における使用量は特に制限されず、例えばモノマー成分全体の１重量％以上、または５重量％以上とすることができ、１０重量％以上でもよい。脂環式炭化水素基含有（メタ）アクリレートの使用量の上限は、凡そ４０重量％以下とすることが適当であり、２５重量％以下（例えば１５重量％以下）であってもよい。 In some embodiments, the monomer component constituting the acrylic polymer may include an alicyclic hydrocarbon group-containing (meth)acrylate. Thereby, the cohesive force of the adhesive can be increased. As the alicyclic hydrocarbon group-containing (meth)acrylate, those exemplified above can be used, and for example, cyclohexyl acrylate (CHA) and isobornyl acrylate can be preferably employed. The alicyclic hydrocarbon group-containing (meth)acrylates can be used singly or in combination of two or more. When using the alicyclic hydrocarbon group-containing (meth)acrylate, the amount used is not particularly limited, and can be, for example, 1% by weight or more, or 5% by weight or more of the entire monomer component, and even 10% by weight or more. good. The upper limit of the amount of the alicyclic hydrocarbon group-containing (meth)acrylate used is suitably about 40% by weight or less, and may be 25% by weight or less (for example, 15% by weight or less).
　いくつかの態様において、アクリル系重合物を構成するモノマー成分は、窒素原子を有するモノマーを含み得る。これにより、粘着剤の凝集力を高めることができる。窒素原子を有するモノマーとしては上記で例示したもの等を用いることができる。窒素原子を有するモノマーの好適例としては、窒素原子含有環を有するモノマーが挙げられる。例えば、Ｎ－ビニル環状アミドが挙げられ、なかでも、Ｎ－ビニル－２－ピロリドンを好ましく採用し得る。窒素原子を有するモノマーは、１種を単独でまたは２種以上を組み合わせて使用することができる。窒素原子を有するモノマー（好ましくは窒素原子含有環を有するモノマー）の使用量は特に制限されず、例えばモノマー成分全体の１重量％以上であってもよく、５重量％以上であってもよく、さらには１０重量％以上とすることができる。また、窒素原子を有するモノマーの使用量は、モノマー成分全体の例えば４０重量％以下とすることが適当であり、３０重量％以下としてもよく、１５重量％以下としてもよい。 In some embodiments, the monomer component constituting the acrylic polymer may include a monomer having a nitrogen atom. Thereby, the cohesive force of the adhesive can be increased. As the monomer having a nitrogen atom, those exemplified above can be used. Preferred examples of the monomer having a nitrogen atom include monomers having a nitrogen atom-containing ring. For example, N-vinyl cyclic amides can be mentioned, and among them, N-vinyl-2-pyrrolidone can be preferably employed. Monomers having a nitrogen atom can be used alone or in combination of two or more. The amount of the monomer having a nitrogen atom (preferably a monomer having a nitrogen atom-containing ring) is not particularly limited, and may be, for example, 1% by weight or more, or 5% by weight or more of the entire monomer component, Furthermore, it can be 10% by weight or more. Further, the amount of the monomer having a nitrogen atom to be used is preferably, for example, 40% by weight or less of the entire monomer component, may be 30% by weight or less, or may be 15% by weight or less.
　いくつかの好ましい態様において、アクリル系重合物を構成するモノマー成分は、（メタ）アクリル酸Ｃ１０－１４アルキルエステルと窒素原子を有するモノマー（好ましくは窒素原子含有環を有するモノマー）を組み合わせて含み得る。このような態様において、アクリル系重合体のモノマー成分全体における、窒素原子を有するモノマー（好ましくは窒素原子含有環を有するモノマー）に対する（メタ）アクリル酸Ｃ１０－１４アルキルエステルの重量基準の含有量比は、１以上（例えば３以上）であることが好ましく、５以上でもよく、１０以上でもよい。また、いくつかの態様において、アクリル系重合体のモノマー成分全体における、窒素原子を有するモノマー（好ましくは窒素原子含有環を有するモノマー）に対する（メタ）アクリル酸Ｃ１０－１４アルキルエステルの重量基準の含有量比は、１００００以下であることが好ましく、５０００以下でもよく、３０００以下でもよく、２０００以下でもよい。いくつかの態様において、アクリル系重合体のモノマー成分全体における、窒素原子を有するモノマー（好ましくは窒素原子含有環を有するモノマー）に対する（メタ）アクリル酸Ｃ１０－１４アルキルエステルの重量基準の含有量比は、１０００以下でもよく、５００以下でもよく、２００以下でもよく、８０以下でもよく、４０以下でもよく、２０以下でもよい。 In some preferred embodiments, the monomer components constituting the acrylic polymer include a combination of a (meth)acrylic acid C 10-14 alkyl ester and a monomer having a nitrogen atom (preferably a monomer having a nitrogen atom-containing ring). obtain. In such an embodiment, the content of (meth)acrylic acid C 10-14 alkyl ester based on the weight of the monomer having a nitrogen atom (preferably the monomer having a nitrogen atom-containing ring) in the entire monomer component of the acrylic polymer. The ratio is preferably 1 or more (for example, 3 or more), may be 5 or more, or may be 10 or more. Further, in some embodiments, the weight-based ratio of (meth)acrylic acid C 10-14 alkyl ester to the monomer having a nitrogen atom (preferably the monomer having a nitrogen atom-containing ring) in the entire monomer component of the acrylic polymer is The content ratio is preferably 10,000 or less, may be 5,000 or less, may be 3,000 or less, or may be 2,000 or less. In some embodiments, the content of (meth)acrylic acid C 10-14 alkyl ester based on the weight of the monomer having a nitrogen atom (preferably the monomer having a nitrogen atom-containing ring) in the entire monomer component of the acrylic polymer. The ratio may be 1000 or less, 500 or less, 200 or less, 80 or less, 40 or less, or 20 or less.
　（メタ）アクリル酸Ｃ１０－１４アルキルエステルと窒素原子を有するモノマー（好ましくは窒素原子含有環を有するモノマー）を組み合わせて使用するいくつかの態様において、アクリル系重合物を構成するモノマー成分全体に占める（メタ）アクリル酸Ｃ１０－１４アルキルエステルと窒素原子を有するモノマー（好ましくは窒素原子含有環を有するモノマー）の合計含有量は、８重量％以上（例えば１０重量％以上）であることが好ましく、より好ましくは１５重量％以上（例えば２０重量％以上）であり、さらに好ましくは２５重量％以上であり、３０重量％以上でもよく、３５重量％以上でもよい。また、いくつかの態様において、アクリル系重合物を構成するモノマー成分全体に占める（メタ）アクリル酸Ｃ１０－１４アルキルエステルと窒素原子を有するモノマー（好ましくは窒素原子含有環を有するモノマー）の合計含有量は、９５重量％以下であってもよく、９０重量％以下でもよく、８０重量％以下でもよく、７０重量％以下でもよく、６０重量％以下でもよく、５０重量％以下でもよい。 In some embodiments in which (meth)acrylic acid C 10-14 alkyl ester and a monomer having a nitrogen atom (preferably a monomer having a nitrogen atom-containing ring) are used in combination, the entire monomer component constituting the acrylic polymer is The total content of (meth)acrylic acid C 10-14 alkyl ester and a monomer having a nitrogen atom (preferably a monomer having a nitrogen atom-containing ring) may be 8% by weight or more (for example, 10% by weight or more). It is preferably 15% by weight or more (for example, 20% by weight or more), still more preferably 25% by weight or more, may be 30% by weight or more, or may be 35% by weight or more. Further, in some embodiments, the total of (meth)acrylic acid C 10-14 alkyl ester and a monomer having a nitrogen atom (preferably a monomer having a nitrogen atom-containing ring) in the entire monomer components constituting the acrylic polymer The content may be 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less.
　いくつかの態様において、アクリル系重合物のモノマー成分に占めるカルボキシ基含有モノマーの割合は、例えば１０重量％未満であってよく、３重量％未満でもよく、１重量％未満（例えば０．１重量％未満）でもよい。アクリル系重合物のモノマー成分としてカルボキシ基含有モノマーを実質的に使用しなくてもよい。ここで、カルボキシ基含有モノマーを実質的に使用しないとは、少なくとも意図的にはカルボキシ基含有モノマーを使用しないことをいう。このような組成のアクリル系重合物は、金属を含む被着体に対しては金属腐食防止性を有するものとなり得る。 In some embodiments, the proportion of the carboxy group-containing monomer in the monomer components of the acrylic polymer may be, for example, less than 10% by weight, may be less than 3% by weight, and may be less than 1% by weight (for example, 0.1% by weight). (less than %). It is not necessary to substantially use a carboxy group-containing monomer as a monomer component of the acrylic polymer. Here, "substantially not using a carboxy group-containing monomer" means not using a carboxy group-containing monomer at least intentionally. An acrylic polymer having such a composition can have metal corrosion inhibiting properties for adherends containing metal.
　上記アクリル系重合物を構成するモノマー成分の組成は、該モノマー成分の組成に基づいてＦｏｘの式により求められるガラス転移温度Ｔｇが－７５℃以上１０℃以下となるように設定され得る。いくつかの態様において、上記Ｔｇは、接着力等の観点から、０℃以下であることが適当であり、－１０℃以下であることが好ましく、－２０℃以下または－３０℃以下であってもよい。また上記Ｔｇは、凝集性等の観点から、例えば－６０℃以上であってよく、－５０℃以上でもよく、－４５℃以上または－４０℃以上でもよい。 The composition of the monomer components constituting the acrylic polymer can be set so that the glass transition temperature Tg determined by the Fox equation is -75°C or more and 10°C or less based on the composition of the monomer components. In some embodiments, the above Tg is suitably 0°C or lower, preferably -10°C or lower, and -20°C or lower or -30°C or lower, from the viewpoint of adhesive strength or the like. Good too. Further, from the viewpoint of cohesiveness and the like, the Tg may be, for example, -60°C or higher, -50°C or higher, -45°C or higher, or -40°C or higher.
　ここで、上記Ｆｏｘの式とは、以下に示すように、共重合体のＴｇと、該共重合体を構成するモノマーのそれぞれを単独重合したホモポリマーのガラス転移温度Ｔｇｉとの関係式である。
　　　１／Ｔｇ＝Σ（Ｗｉ／Ｔｇｉ）
　なお、上記Ｆｏｘの式において、Ｔｇは共重合体のガラス転移温度（単位：Ｋ）、Ｗｉは該共重合体におけるモノマーｉの重量分率（重量基準の共重合割合）、Ｔｇｉはモノマーｉのホモポリマーのガラス転移温度（単位：Ｋ）を表す。Ｔｇの算出に使用するホモポリマーのガラス転移温度としては、公知資料、具体的には「Polymer Handbook」（第３版、John Wiley & Sons, Inc., 1989）に記載の数値を用いるものとする。本文献に複数種類の値が記載されている場合は、最も高い値を採用する。 Here, the above Fox equation is a relational equation between the Tg of a copolymer and the glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below. .
1/Tg=Σ(Wi/Tgi)
In the above Fox equation, Tg is the glass transition temperature of the copolymer (unit: K), Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio on a weight basis), and Tgi is the weight fraction of monomer i in the copolymer. Represents the glass transition temperature (unit: K) of a homopolymer. As the glass transition temperature of the homopolymer used to calculate Tg, the numerical value described in publicly known materials, specifically "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) shall be used. . If multiple types of values are listed in this document, the highest value is adopted.
　重合にあたっては、重合方法や重合態様等に応じて、公知または慣用の熱重合開始剤や光重合開始剤を使用し得る。熱重合開始剤としては、特に限定されるものではないが、例えばアゾ系重合開始剤、過酸化物系開始剤、過酸化物と還元剤との組合せによるレドックス系開始剤、置換エタン系開始剤等を使用することができる。光重合開始剤としては、特に限定されるものではないが、例えばケタール系光重合開始剤、アセトフェノン系光重合開始剤、ベンゾインエーテル系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤、α－ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、チオキサントン系光重合開始剤等を用いることができる。重合開始剤は、１種を単独でまたは２種以上を適宜組み合わせて用いることができる。このような熱重合開始剤または光重合開始剤の使用量は、重合方法や重合態様等に応じた通常の使用量とすることができ、特に限定されない。例えば、重合対象のモノマー１００重量部に対して重合開始剤凡そ０．００１～５重量部（典型的には凡そ０．０１～２重量部、例えば凡そ０．０１～１重量部）を用いることができる。 In the polymerization, a known or commonly used thermal polymerization initiator or photopolymerization initiator may be used depending on the polymerization method, polymerization mode, etc. The thermal polymerization initiator is not particularly limited, but includes, for example, an azo polymerization initiator, a peroxide initiator, a redox initiator based on a combination of a peroxide and a reducing agent, and a substituted ethane initiator. etc. can be used. The photopolymerization initiator is not particularly limited, but includes, for example, a ketal photopolymerization initiator, an acetophenone photopolymerization initiator, a benzoin ether photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and an α- Ketol photoinitiator, aromatic sulfonyl chloride photoinitiator, photoactive oxime photoinitiator, benzoin photoinitiator, benzyl photoinitiator, benzophenone photoinitiator, thioxanthone photoinitiator A polymerization initiator or the like can be used. The polymerization initiators can be used alone or in an appropriate combination of two or more. The amount of such a thermal polymerization initiator or photopolymerization initiator to be used can be a normal amount depending on the polymerization method, polymerization mode, etc., and is not particularly limited. For example, approximately 0.001 to 5 parts by weight (typically approximately 0.01 to 2 parts by weight, for example approximately 0.01 to 1 part by weight) of a polymerization initiator may be used for 100 parts by weight of the monomer to be polymerized. Can be done.
　上記重合には、必要に応じて、従来公知の各種の連鎖移動剤（分子量調節剤あるいは重合度調節剤としても把握され得る。）を使用することができる。連鎖移動剤としては、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、チオグリコール酸、α－チオグリセロール等のメルカプタン類を用いることができる。あるいは、硫黄原子を含まない連鎖移動剤（非硫黄系連鎖移動剤）を用いてもよい。連鎖移動剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。連鎖移動剤を使用する場合、その使用量は、モノマー成分１００重量部に対して、例えば凡そ０．０１～１重量部程度とすることができる。ここに開示される技術は、連鎖移動剤を使用しない態様でも好ましく実施され得る。 In the above polymerization, various conventionally known chain transfer agents (which can also be understood as molecular weight regulators or polymerization degree regulators) can be used as necessary. As the chain transfer agent, mercaptans such as n-dodecylmercaptan, t-dodecylmercaptan, thioglycolic acid, and α-thioglycerol can be used. Alternatively, a chain transfer agent that does not contain sulfur atoms (non-sulfur chain transfer agent) may be used. One type of chain transfer agent can be used alone or two or more types can be used in combination. When a chain transfer agent is used, the amount used can be, for example, approximately 0.01 to 1 part by weight per 100 parts by weight of the monomer component. The technology disclosed herein can also be preferably practiced in an embodiment that does not use a chain transfer agent.
　上記の各種重合法を適宜採用して得られるアクリル系重合物の分子量は特に制限されず、要求性能に合わせて適当な範囲に設定され得る。アクリル系重合物の重量平均分子量（Ｍｗ）は、例えば凡そ１０×１０４以上であり、凝集力と接着力とをバランスよく両立する観点から、３０×１０４超とすることが適当である。いくつかの態様に係るアクリル系重合物は、好ましくは凡そ５０×１０４以上のＭｗを有する。アクリル系重合物のＭｗの上限は、凡そ５００×１０４以下（例えば凡そ１５０×１０４以下）であり得る。上記Ｍｗは凡そ７５×１０４以下であってもよい。ここでＭｗとは、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により得られた標準ポリスチレン換算の値をいう。ＧＰＣ装置としては、例えば機種名「ＨＬＣ－８３２０ＧＰＣ」（カラム：ＴＳＫｇｅｌＧＭＨ－Ｈ（Ｓ）、東ソー社製）を使用すればよい。 The molecular weight of the acrylic polymer obtained by appropriately employing the various polymerization methods described above is not particularly limited, and can be set within an appropriate range depending on the required performance. The weight average molecular weight (Mw) of the acrylic polymer is, for example, approximately 10×10 4 or more, and from the viewpoint of achieving both cohesive force and adhesive force in a well-balanced manner, it is appropriate to set it to more than 30×10 4 . The acrylic polymer according to some embodiments preferably has a Mw of about 50×10 4 or more. The upper limit of Mw of the acrylic polymer may be approximately 500×10 4 or less (for example, approximately 150×10 4 or less). The Mw may be approximately 75×10 4 or less. Here, Mw refers to a standard polystyrene equivalent value obtained by gel permeation chromatography (GPC). As the GPC device, for example, a model name "HLC-8320GPC" (column: TSKgelGMH-H(S), manufactured by Tosoh Corporation) may be used.
　ここに開示される粘着剤は、上述のような組成のモノマー成分を、重合物、未重合物（すなわち、重合性官能基が未反応である形態）、あるいはこれらの混合物の形態で含む粘着剤組成物を用いて形成され得る。上記粘着剤組成物は、粘着剤（粘着成分）が水に分散した形態の水分散型粘着剤組成物、有機溶媒中に粘着剤を含む形態の溶剤型粘着剤組成物、紫外線や放射線等の活性エネルギー線により硬化して粘着剤を形成するように調製された活性エネルギー線硬化型粘着剤組成物、加熱溶融状態で塗工され、室温付近まで冷えると粘着剤を形成するホットメルト型粘着剤組成物等の種々の形態であり得る。いくつかの態様に係る粘着剤組成物は、溶剤型粘着剤組成物または無溶剤型粘着剤組成物である。無溶剤型粘着剤組成物には、活性エネルギー線硬化型粘着剤組成物およびホットメルト型粘着剤組成物が包含される。ここに開示されるアルコール剥離は、溶剤型粘着剤組成物から形成された溶剤型粘着剤、活性エネルギー線（典型的には紫外線硬）硬化型粘着剤組成物から形成された活性エネルギー線硬化型粘着剤（典型的には紫外線硬化型粘着剤）に対して効果的である。 The adhesive disclosed herein includes a monomer component having the composition described above in the form of a polymerized product, an unpolymerized product (that is, a form in which the polymerizable functional group is unreacted), or a mixture thereof. composition. The above adhesive compositions include water-dispersed adhesive compositions in which the adhesive (adhesive component) is dispersed in water, solvent-based adhesive compositions in which the adhesive is contained in an organic solvent, and UV and radiation resistant adhesive compositions. An active energy ray-curable adhesive composition prepared to be cured by active energy rays to form an adhesive, and a hot melt adhesive composition that is applied in a heated molten state and forms an adhesive when cooled to around room temperature. It can be in various forms such as a composition. The adhesive composition according to some embodiments is a solvent-based adhesive composition or a solvent-free adhesive composition. Solvent-free adhesive compositions include active energy ray-curable adhesive compositions and hot-melt adhesive compositions. The alcohol peeling disclosed herein is a solvent-based adhesive formed from a solvent-based adhesive composition, and an active energy ray-curable adhesive composition formed from an active energy ray (typically ultraviolet curing) curable adhesive composition. Effective against adhesives (typically UV-curable adhesives).
　いくつかの態様に係る粘着剤組成物は、活性エネルギー線硬化型粘着剤組成物であり得る。本明細書において「活性エネルギー線」とは、重合反応、架橋反応、開始剤の分解等の化学反応を引き起こし得るエネルギーをもったエネルギー線を指す。ここでいう活性エネルギー線の例には、紫外線、可視光線、赤外線のような光や、α線、β線、γ線、電子線、中性子線、Ｘ線のような放射線等が含まれる。活性エネルギー線硬化型粘着剤組成物の一好適例として、光硬化型粘着剤組成物が挙げられる。光硬化型の粘着剤組成物は、厚手の粘着剤層であっても容易に形成し得るという利点を有する。なかでも紫外線硬化型粘着剤組成物が好ましい。 The adhesive composition according to some embodiments may be an active energy ray-curable adhesive composition. As used herein, "active energy rays" refer to energy rays with energy capable of causing chemical reactions such as polymerization reactions, crosslinking reactions, and decomposition of initiators. Examples of active energy rays herein include light such as ultraviolet rays, visible rays, and infrared rays, and radiation such as α rays, β rays, γ rays, electron rays, neutron rays, and X rays. A preferred example of the active energy ray-curable adhesive composition is a photocurable adhesive composition. A photocurable pressure-sensitive adhesive composition has the advantage that even a thick pressure-sensitive adhesive layer can be easily formed. Among these, UV-curable pressure-sensitive adhesive compositions are preferred.
　光硬化型粘着剤組成物は、典型的には、該組成物のモノマー成分のうち少なくとも一部（モノマーの種類の一部であってもよく、分量の一部であってもよい。）を重合物の形態で含む。上記重合物を形成する際の重合方法は特に限定されず、従来公知の各種重合方法を適宜採用することができる。例えば、溶液重合、エマルション重合、塊状重合等の熱重合（典型的には、熱重合開始剤の存在下で行われる。）；紫外線等の光を照射して行う光重合（典型的には、光重合開始剤の存在下で行われる。）；β線、γ線等の放射線を照射して行う放射線重合；等を適宜採用することができる。なかでも光重合が好ましい。 A photocurable pressure-sensitive adhesive composition typically contains at least a portion of the monomer components of the composition (which may be a portion of the type of monomer or a portion of the amount). Contains in the form of polymers. The polymerization method used to form the above-mentioned polymer is not particularly limited, and various conventionally known polymerization methods can be employed as appropriate. For example, thermal polymerization such as solution polymerization, emulsion polymerization, and bulk polymerization (typically carried out in the presence of a thermal polymerization initiator); photopolymerization carried out by irradiating light such as ultraviolet rays (typically carried out in the presence of a thermal polymerization initiator); (Carried out in the presence of a photopolymerization initiator); Radiation polymerization carried out by irradiation with radiation such as β rays and γ rays; etc. can be employed as appropriate. Among these, photopolymerization is preferred.
　いくつかの好ましい態様に係る光硬化型粘着剤組成物は、モノマー成分の部分重合物（例えばアクリル系部分重合物）を含む。このような部分重合物は、典型的にはモノマー成分に由来する重合物と未反応のモノマーとの混合物であって、好ましくはシロップ状（粘性のある液状）を呈する。以下、かかる性状の部分重合物を「モノマーシロップ」または単に「シロップ」ということがある。モノマー成分を部分重合させる際の重合方法は特に制限されず、上述のような各種重合方法を適宜選択して用いることができる。効率や簡便性の観点から、光重合法を好ましく採用し得る。光重合によると、光の照射量（光量）等の重合条件によって、モノマー成分の重合転化率（モノマーコンバーション）を容易に制御することができる。 Photocurable pressure-sensitive adhesive compositions according to some preferred embodiments include a partial polymer of monomer components (for example, an acrylic partial polymer). Such a partially polymerized product is typically a mixture of a polymer derived from a monomer component and an unreacted monomer, and preferably takes the form of a syrup (viscous liquid). Hereinafter, a partially polymerized product having such properties may be referred to as "monomer syrup" or simply "syrup." The polymerization method for partially polymerizing the monomer components is not particularly limited, and various polymerization methods such as those described above can be appropriately selected and used. From the viewpoint of efficiency and convenience, a photopolymerization method can be preferably employed. According to photopolymerization, the polymerization conversion rate (monomer conversion) of monomer components can be easily controlled by controlling the polymerization conditions such as the amount of light irradiation (light amount).
　上記部分重合物におけるモノマー混合物の重合転化率は、特に限定されない。上記重合転化率は、例えば凡そ７０重量％以下とすることができ、上記部分重合物を含む粘着剤組成物の調製容易性や塗工性等の観点から、凡そ５０重量％以下が適当であり、凡そ４０重量％以下が好ましい。重合転化率の下限は特に制限されないが、典型的には凡そ１重量％以上であり、凡そ５重量％以上とすることが適当である。 The polymerization conversion rate of the monomer mixture in the above partially polymerized product is not particularly limited. The above polymerization conversion rate can be, for example, about 70% by weight or less, and from the viewpoint of ease of preparation and coatability of the adhesive composition containing the above partially polymerized product, it is suitably about 50% by weight or less. , preferably about 40% by weight or less. Although the lower limit of the polymerization conversion rate is not particularly limited, it is typically about 1% by weight or more, and suitably about 5% by weight or more.
　上記部分重合物を含む粘着剤組成物には、必要に応じて用いられる他の成分（例えば、光重合開始剤や、後述のような界面活性剤、架橋剤、多官能性モノマー、アクリル系オリゴマー、粘着付与樹脂、シランカップリング剤等）が配合され得る。そのような他の成分を配合する方法は特に限定されず、例えば上記モノマー混合物にあらかじめ含有させてもよく、上記部分重合物に添加してもよい。 The adhesive composition containing the above partially polymerized product may contain other components used as necessary (for example, a photopolymerization initiator, a surfactant as described below, a crosslinking agent, a polyfunctional monomer, an acrylic oligomer, etc.). , tackifier resin, silane coupling agent, etc.) may be blended. The method of blending such other components is not particularly limited, and for example, they may be included in the monomer mixture in advance, or may be added to the partially polymerized product.
　いくつかの態様に係る粘着剤は、水分散型粘着剤組成物から形成された粘着剤である。水分散型粘着剤組成物の代表例として、エマルション型粘着剤組成物が挙げられる。エマルション型粘着剤組成物は、典型的には、モノマー成分の重合物と、必要に応じて用いられる添加剤とを含有する。モノマー成分のエマルション重合は、通常、乳化剤の存在下で行われる。エマルション重合によると、モノマー成分の重合物が水に分散したエマルション形態の重合反応液が得られる。粘着剤の形成に用いる水分散型粘着剤組成物は、上記重合反応液を用いて好ましく製造され得る。 The adhesive according to some embodiments is an adhesive formed from a water-dispersed adhesive composition. A typical example of a water-dispersed adhesive composition is an emulsion-type adhesive composition. An emulsion type adhesive composition typically contains a polymer of monomer components and additives used as necessary. Emulsion polymerization of monomer components is usually carried out in the presence of an emulsifier. According to emulsion polymerization, a polymerization reaction solution in the form of an emulsion in which a polymer of monomer components is dispersed in water is obtained. A water-dispersed adhesive composition used for forming an adhesive can be preferably manufactured using the above polymerization reaction liquid.
　エマルション重合用の乳化剤としては、特に制限されず、公知のアニオン性乳化剤、ノニオン性乳化剤等を用いることができる。乳化剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。アニオン性乳化剤の非限定的な例としては、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンラウリル硫酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸アンモニウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルスルホコハク酸ナトリウム等が挙げられる。ノニオン性乳化剤の非限定的な例としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンブロックポリマー等が挙げられる。反応性官能基を有する乳化剤（反応性乳化剤）を用いてもよい。反応性乳化剤の例としては、上述したアニオン性乳化剤またはノニオン性乳化剤に、プロペニル基やアリルエーテル基等のラジカル重合性官能基が導入された構造のラジカル重合性乳化剤が挙げられる。 The emulsifier for emulsion polymerization is not particularly limited, and known anionic emulsifiers, nonionic emulsifiers, etc. can be used. The emulsifiers can be used alone or in combination of two or more. Non-limiting examples of anionic emulsifiers include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkylphenyl ether sulfate, Examples include sodium ethylene alkyl phenyl ether sulfate and sodium polyoxyethylene alkyl sulfosuccinate. Non-limiting examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyoxypropylene block polymers, and the like. An emulsifier having a reactive functional group (reactive emulsifier) may also be used. Examples of the reactive emulsifier include radically polymerizable emulsifiers having a structure in which a radically polymerizable functional group such as a propenyl group or an allyl ether group is introduced into the above-mentioned anionic emulsifier or nonionic emulsifier.
　エマルション重合における乳化剤の使用量は、モノマー成分１００重量部に対して、例えば０．２重量部以上であってよく、０．５重量部以上でもよく、１．０重量部以上でもよく、１．５重量部以上でもよい。また、耐水粘着力向上や、あるいは粘着剤の透明性向上の観点から、いくつかの態様において、乳化剤の使用量は、モノマー成分１００重量部に対して１０重量部以下とすることが適当であり、５重量部以下とすることが好ましく、３重量部以下としてもよい。なお、ここでエマルション重合に使用する乳化剤は、後述する界面活性剤としても機能し得る。 The amount of emulsifier used in emulsion polymerization may be, for example, 0.2 parts by weight or more, 0.5 parts by weight or more, 1.0 parts by weight or more, based on 100 parts by weight of the monomer components. The amount may be 5 parts by weight or more. Further, from the viewpoint of improving water-resistant adhesive strength or transparency of the adhesive, in some embodiments, it is appropriate that the amount of emulsifier used is 10 parts by weight or less per 100 parts by weight of the monomer component. , is preferably 5 parts by weight or less, and may be 3 parts by weight or less. Note that the emulsifier used in the emulsion polymerization here can also function as a surfactant, which will be described later.
　いくつかの態様に係る粘着剤組成物は、溶剤型粘着剤組成物であり得る。溶剤型粘着剤組成物は、典型的には、モノマー成分の溶液重合物と、必要に応じて用いられる添加剤とを含有する。溶液重合に用いる溶媒（重合溶媒）は、従来公知の有機溶媒（例えばトルエン、酢酸エチル等）から適宜選択することができる。溶液重合によると、モノマー成分の重合物が重合溶媒に溶解した形態の重合反応液が得られる。ここに開示される溶剤型粘着剤組成物は、上記重合反応液を用いて好ましく製造され得る。 The adhesive composition according to some embodiments may be a solvent-based adhesive composition. A solvent-based adhesive composition typically contains a solution polymer of monomer components and additives used as necessary. The solvent (polymerization solvent) used in solution polymerization can be appropriately selected from conventionally known organic solvents (for example, toluene, ethyl acetate, etc.). According to solution polymerization, a polymerization reaction solution is obtained in which a polymer of monomer components is dissolved in a polymerization solvent. The solvent-based adhesive composition disclosed herein can be preferably manufactured using the above polymerization reaction solution.
　（界面活性剤）
　いくつかの態様において、上記粘着剤は界面活性剤を含む。粘着剤に界面活性剤を含有させることにより、通常、アルコール液を利用して剥離力を効果的に低下させることができ、アルコール剥離性が向上する。その理由は、特に限定解釈されるものではないが、一般に界面活性剤は親水性領域を有することにより粘着剤の表面に偏在しやすく、それによって該粘着剤表面の水親和性を効率よく高める作用が発揮され、該粘着剤がアルコール液と接触したときに剥離力を効果的に低下させ、アルコール剥離性が向上するものと考えられる。上記界面活性剤は、典型的には、遊離の形態で粘着剤組成物（ひいては粘着剤）に含まれている。界面活性剤としては、粘着剤組成物の調製容易性等の点から、常温（約２５℃）において液状であるものが好ましく用いられ得る。界面活性剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。 (surfactant)
In some embodiments, the adhesive includes a surfactant. By incorporating a surfactant into the adhesive, it is possible to effectively reduce the peeling force using an alcohol solution, thereby improving the alcohol peelability. The reason for this is not particularly limited, but in general, surfactants tend to be unevenly distributed on the surface of the adhesive because they have a hydrophilic region, thereby effectively increasing the water affinity of the surface of the adhesive. It is considered that this effect effectively reduces the peeling force when the adhesive comes into contact with an alcohol solution, and improves the alcohol peelability. The above-mentioned surfactant is typically contained in the adhesive composition (and thus the adhesive) in a free form. As the surfactant, one that is liquid at room temperature (about 25° C.) can be preferably used from the viewpoint of ease of preparing the adhesive composition. One kind of surfactant can be used alone or two or more kinds can be used in combination.
　界面活性剤としては、公知の非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤等を用いることができる。なかでも、非イオン性界面活性剤が好ましい。界面活性剤は１種を単独でまたは２種以上を組み合わせて用いることができる。 As the surfactant, known nonionic surfactants, anionic surfactants, cationic surfactants, etc. can be used. Among these, nonionic surfactants are preferred. One kind of surfactant can be used alone or two or more kinds can be used in combination.
　非イオン性界面活性剤の例としては、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル；ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル；ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート等のソルビタン脂肪酸エステル；ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリステアレート、ポリオキシエチレンソルビタントリイソステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタントリオレエート等のポリオキシエチレンソルビタン脂肪酸エステル；ポリオキシエチレングリセリルエーテル脂肪酸エステル；ポリオキシエレン－ポリオキシプロピレンブロックコポリマー；等が挙げられる。これらの非イオン性界面活性剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。 Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, and polyoxyethylene alkyl ether; Polyoxyethylene alkylphenyl ethers such as oxyethylene nonylphenyl ether; Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monooleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene Polyoxyethylene sorbitans such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, etc. Fatty acid ester; polyoxyethylene glyceryl ether fatty acid ester; polyoxyethylene-polyoxypropylene block copolymer; and the like. These nonionic surfactants can be used alone or in combination of two or more.
　アニオン性界面活性剤の例としては、ラウリル硫酸塩、オクタデシル硫酸塩等のアルキル硫酸塩；脂肪酸塩；ノニルベンゼンスルホン酸塩、ドデシルベンゼンスルホン酸塩等のアルキルベンゼンスルホン酸塩；ドデシルナフタレンスルホン酸塩等のナフタレンスルホン酸塩；ドデシルジフェニルエーテルジスルホン酸塩等のアルキルジフェニルエーテルジスルホン酸塩；ポリオキシエチレンオクタデシルエーテル硫酸塩、ポリオキシエチレンラウリルエーテル硫酸塩等のポリオキシエチレンアルキルエーテル硫酸塩；ポリオキシエチレンラウリルフェニルエーテル硫酸塩等のポリオキシエチレンアルキルフェニルエーテル硫酸塩；ポリオキシエチレンスチレン化フェニルエーテル硫酸塩；ラウリルスルホコハク酸塩、ポリオキシエチレンラウリルスルホコハク酸塩等のスルホコハク酸塩；ポリオキシエチレンアルキルエーテルリン酸塩；ポリオキシエチレンアルキルエーテル酢酸塩；等が挙げられる。アニオン性界面活性剤が塩を形成している場合、該塩は、例えばナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩等の金属塩（好ましくは一価金属の塩）、アンモニウム塩、アミン塩等であり得る。これらのアニオン性界面活性剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。 Examples of anionic surfactants include alkyl sulfates such as lauryl sulfate and octadecyl sulfate; fatty acid salts; alkylbenzenesulfonates such as nonylbenzenesulfonate and dodecylbenzenesulfonate; dodecylnaphthalenesulfonate, etc. naphthalene sulfonate; alkyl diphenyl ether disulfonate such as dodecyl diphenyl ether disulfonate; polyoxyethylene alkyl ether sulfate such as polyoxyethylene octadecyl ether sulfate, polyoxyethylene lauryl ether sulfate; polyoxyethylene lauryl phenyl ether Polyoxyethylene alkyl phenyl ether sulfates such as sulfates; polyoxyethylene styrenated phenyl ether sulfates; sulfosuccinates such as lauryl sulfosuccinate and polyoxyethylene lauryl sulfosuccinate; polyoxyethylene alkyl ether phosphates; Examples include polyoxyethylene alkyl ether acetate; and the like. When the anionic surfactant forms a salt, the salt may be, for example, a metal salt (preferably a monovalent metal salt) such as a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an ammonium salt, an amine salt, etc. It can be. These anionic surfactants can be used alone or in combination of two or more.
　粘着剤における界面活性剤の含有量は特に限定されず、該界面活性剤の使用効果が適切に発揮されるように設定することができる。いくつかの態様において、界面活性剤の含有量は、粘着剤に含まれる重合物（例えばアクリル系重合物）１００重量部あたり、例えば０．００１重量部以上とすることができ、０．０１重量部以上とすることが適当であり、好ましくは０．０５重量部以上であり、より好ましくは０．１重量部以上である。他のいくつかの態様において、界面活性剤の含有量は、粘着剤に含まれる重合物１００重量部に対して、例えば１．０重量部以上でもよく、１．５重量部以上でもよい。また、いくつかの態様において、界面活性剤の使用量は、上記重合物１００重量部に対して、凡そ３重量部以下とすることができ、凡そ２重量部以下とすることが適当であり、好ましくは１重量部未満、より好ましくは０．５重量部未満である。界面活性剤の使用量を制限することにより、接着力を維持しやすい傾向がある。 The content of the surfactant in the adhesive is not particularly limited, and can be set so that the effect of using the surfactant is appropriately exhibited. In some embodiments, the content of the surfactant can be, for example, 0.001 parts by weight or more per 100 parts by weight of the polymer (for example, acrylic polymer) contained in the adhesive, and 0.01 parts by weight. The amount is suitably at least 0.05 parts by weight, preferably at least 0.05 parts by weight, and more preferably at least 0.1 parts by weight. In some other embodiments, the content of the surfactant may be, for example, 1.0 parts by weight or more, or 1.5 parts by weight or more, based on 100 parts by weight of the polymer contained in the adhesive. In some embodiments, the amount of the surfactant used can be about 3 parts by weight or less, preferably about 2 parts by weight or less, based on 100 parts by weight of the polymer, Preferably it is less than 1 part by weight, more preferably less than 0.5 part by weight. By limiting the amount of surfactant used, it tends to be easier to maintain adhesive strength.
　（多官能性モノマー）
　粘着剤組成物（ひいては粘着剤）には、必要に応じて多官能性モノマーが用いられ得る。多官能性モノマーは、凝集力の調整等の目的のために役立ち得る。多官能性モノマーは、粘着剤層形成時や、被着体への貼付け後に光（例えば紫外線）照射等により上記エチレン性不飽和基を反応させることで、適度な柔軟性を有する架橋構造を形成し得る。したがって、本明細書において「多官能性モノマー」は、架橋剤と言い換えることができるものとする。例えば、光硬化型の粘着剤組成物から形成される粘着剤において、多官能性モノマーが好ましく用いられ得る。多官能性モノマーとしては、２個以上のエチレン性不飽和基を有する化合物が用いられ得る。多官能性モノマーは、１種を単独でまたは２種以上を組み合わせて用いることができる。 (polyfunctional monomer)
A polyfunctional monomer may be used in the adhesive composition (and thus the adhesive) as necessary. Multifunctional monomers can serve for purposes such as adjusting cohesion. The polyfunctional monomer forms a crosslinked structure with appropriate flexibility by reacting the above ethylenically unsaturated groups with light (e.g. ultraviolet light) irradiation when forming the adhesive layer or after pasting it on the adherend. It is possible. Therefore, in this specification, the term "polyfunctional monomer" can be interpreted as a crosslinking agent. For example, polyfunctional monomers can be preferably used in adhesives formed from photocurable adhesive compositions. As the polyfunctional monomer, a compound having two or more ethylenically unsaturated groups can be used. One type of polyfunctional monomer can be used alone or two or more types can be used in combination.
　多官能性モノマーが有するエチレン性不飽和基の例には、アクリロイル基、メタクリロイル基、ビニル基およびアリル基が含まれるが、これらに限定されない。光反応性の観点から好ましいエチレン性不飽和基として、アクリロイル基およびメタクリロイル基が挙げられる。なかでもアクリロイル基が好ましい。 Examples of ethylenically unsaturated groups possessed by the polyfunctional monomer include, but are not limited to, acryloyl groups, methacryloyl groups, vinyl groups, and allyl groups. Preferred ethylenically unsaturated groups from the viewpoint of photoreactivity include acryloyl and methacryloyl groups. Among them, an acryloyl group is preferred.
　多官能性モノマーの例としては、例えば、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、アリル（メタ）アクリレート、ビニル（メタ）アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、ブチルジオール（メタ）アクリレート、ヘキシルジオールジ（メタ）アクリレート等が挙げられる。なかでも、トリメチロールプロパントリ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートが好適である。 Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12 - Dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate , butyldiol (meth)acrylate, hexyldiol di(meth)acrylate, and the like. Among these, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are preferred.
　多官能性モノマーの使用量は、その分子量や官能基数等により異なるが、例えば、粘着剤に含まれる重合物を形成するモノマー成分（典型的には、アクリル系重合物または当該重合物のモノマー成分）１００重量部に対して０．０１重量部～３．０重量部程度の範囲とすることが適当である。 The amount of the polyfunctional monomer used varies depending on its molecular weight, number of functional groups, etc.; ) Appropriately, the amount is in the range of about 0.01 parts by weight to 3.0 parts by weight per 100 parts by weight.
　（架橋剤）
　ここに開示される粘着剤組成物は、主に粘着剤（層）内での架橋または粘着剤とその隣接面との架橋を目的として、必要に応じて架橋剤を含有させることができる。架橋剤の種類は特に制限されず、従来公知の架橋剤のなかから、例えば粘着剤組成物の組成に応じて、該架橋剤が粘着剤内で適切な架橋機能を発揮するように選択することができる。用いられ得る架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、カルボジイミド系架橋剤、メラミン系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、ヒドラジン系架橋剤、アミン系架橋剤等を例示することができる。これらは１種を単独でまたは２種以上を組み合わせて用いることができる。 (Crosslinking agent)
The adhesive composition disclosed herein may contain a crosslinking agent as necessary, mainly for the purpose of crosslinking within the adhesive (layer) or between the adhesive and its adjacent surface. The type of crosslinking agent is not particularly limited, and may be selected from among conventionally known crosslinking agents so that the crosslinking agent exhibits an appropriate crosslinking function within the adhesive, depending on the composition of the adhesive composition, for example. Can be done. Examples of crosslinking agents that can be used include isocyanate crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, carbodiimide crosslinking agents, melamine crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, and metals. Examples include chelate crosslinking agents, metal salt crosslinking agents, hydrazine crosslinking agents, and amine crosslinking agents. These can be used alone or in combination of two or more.
　架橋剤の含有量（２種以上の架橋剤を含む場合にはそれらの合計量）は特に限定されない。接着力や凝集力等の粘着特性をバランスよく発揮する粘着剤を実現する観点から、架橋剤の含有量は、粘着剤に含まれる重合物を形成するモノマー成分（例えば、アクリル系重合物または当該重合物のモノマー成分）１００重量部に対して、凡そ５重量部以下とすることが適当であり、凡そ０．００１～５重量部とすることが好ましく、凡そ０．００１～４重量部とすることがより好ましく、凡そ０．００１～３重量部とすることがさらに好ましい。あるいは、上述のような架橋剤を含まない粘着剤組成物であってもよい。ここに開示される粘着剤組成物として光硬化型粘着剤組成物を用いる場合には、当該粘着剤組成物は、イソシアネート系架橋剤等の架橋剤を実質的に含まないものであり得る。ここで粘着剤組成物が架橋剤（典型的にはイソシアネート系架橋剤）を実質的に含まないとは、上記モノマー成分１００重量部に対する架橋剤の量が０．０５重量部未満（例えば０．０１重量部未満）であることをいう。 The content of the crosslinking agent (if two or more types of crosslinking agents are included, the total amount thereof) is not particularly limited. From the perspective of realizing a pressure-sensitive adhesive that exhibits adhesive properties such as adhesive strength and cohesive force in a well-balanced manner, the content of the crosslinking agent is determined by the amount of crosslinking agent contained in the pressure-sensitive adhesive. It is appropriate that the amount is approximately 5 parts by weight or less, preferably approximately 0.001 to 5 parts by weight, and approximately 0.001 to 4 parts by weight per 100 parts by weight of the monomer component of the polymer. More preferably, the amount is about 0.001 to 3 parts by weight. Alternatively, the pressure-sensitive adhesive composition may not contain a crosslinking agent as described above. When a photocurable adhesive composition is used as the adhesive composition disclosed herein, the adhesive composition may be substantially free of crosslinking agents such as isocyanate crosslinking agents. Here, when the pressure-sensitive adhesive composition is substantially free of a crosslinking agent (typically an isocyanate-based crosslinking agent), it means that the amount of the crosslinking agent is less than 0.05 parts by weight (for example, 0.05 parts by weight) based on 100 parts by weight of the monomer components. 01 parts by weight).
　架橋反応をより効果的に進行させるために、架橋触媒を用いてもよい。また、粘着剤の形成に用いられる粘着剤組成物には、所望により、架橋遅延剤（例えばケト－エノール互変異性を生じる化合物）を含有させてもよい。架橋触媒、架橋遅延剤の使用量は、特定の範囲に限定されず、目的等に応じて適当量用いられる。 A crosslinking catalyst may be used to advance the crosslinking reaction more effectively. Further, the adhesive composition used to form the adhesive may contain a crosslinking retarder (for example, a compound that causes keto-enol tautomerism), if desired. The amounts of the crosslinking catalyst and crosslinking retarder to be used are not limited to a specific range, and are used in appropriate amounts depending on the purpose and the like.
　（粘着付与樹脂）
　粘着剤には粘着付与樹脂を含有させてもよい。粘着付与樹脂としては、例えば、ロジン系粘着付与樹脂、ロジン誘導体粘着付与樹脂、石油系粘着付与樹脂、テルペン系粘着付与樹脂、フェノール系粘着付与樹脂、ケトン系粘着付与樹脂等が挙げられる。これらは、１種を単独でまたは２種以上を組み合わせて使用することができる。なかでも、ロジン系粘着付与樹脂、ロジン誘導体粘着付与樹脂およびテルペンフェノール樹脂から選択される１種または２種以上を好ましく使用し得る。例えば、軟化点が８０℃以上（例えば１２０℃以上１８０℃以下）の粘着付与樹脂（好適にはロジン誘導体粘着付与樹脂）を好ましく使用し得る。 (tackifying resin)
The adhesive may contain a tackifying resin. Examples of the tackifier resin include rosin-based tackifier resin, rosin derivative tackifier resin, petroleum-based tackifier resin, terpene-based tackifier resin, phenol-based tackifier resin, ketone-based tackifier resin, and the like. These can be used alone or in combination of two or more. Among these, one or more selected from rosin-based tackifier resins, rosin derivative tackifier resins, and terpene phenol resins can be preferably used. For example, a tackifying resin (preferably a rosin derivative tackifying resin) having a softening point of 80° C. or higher (for example, 120° C. or higher and 180° C. or lower) can be preferably used.
　粘着付与樹脂の使用量は、その使用効果を好適に発揮させる観点から、粘着剤に含まれる重合物を構成するモノマー成分１００重量部に対して１重量部以上とすることが適当であり、５重量部以上でもよく、１０重量部以上でもよく、１５重量部以上でもよく、２０重量部以上でもよく、２５重量部以上でもよい。また、被着体に対する密着性と凝集性とをバランスよく両立する観点から、モノマー成分１００重量部に対する粘着付与樹脂の使用量は、例えば５０重量部以下でもよく、３０重量部以下でもよい。あるいは、粘着剤における上記粘着付与樹脂の含有量は、上記モノマー成分１００重量部に対して例えば１重量部未満であってもよく、上記粘着剤は粘着付与樹脂を実質的に含まないものであってもよい。 The amount of the tackifying resin to be used is preferably 1 part by weight or more per 100 parts by weight of the monomer component constituting the polymer contained in the adhesive, from the viewpoint of suitably exhibiting the effect of its use. It may be at least 10 parts by weight, at least 15 parts by weight, at least 20 parts by weight, or at least 25 parts by weight. Further, from the viewpoint of achieving both adhesion to the adherend and cohesiveness in a well-balanced manner, the amount of the tackifying resin used per 100 parts by weight of the monomer component may be, for example, 50 parts by weight or less, or 30 parts by weight or less. Alternatively, the content of the tackifying resin in the adhesive may be, for example, less than 1 part by weight per 100 parts by weight of the monomer component, and the adhesive may be substantially free of tackifying resin. It's okay.
　（アクリル系オリゴマー）
　ここに開示される粘着剤には、凝集力の向上や接着性向上等の観点から、アクリル系オリゴマーを含有させることができる。アクリル系オリゴマーとしては、上記アクリル系重合物のＴｇよりもＴｇが高い重合体を用いることが好ましい。例えば、粘着剤の作製の際に紫外線照射を利用する態様では、アクリル系オリゴマーは重合阻害を起こしにくい点で好適である。 (acrylic oligomer)
The adhesive disclosed herein can contain an acrylic oligomer from the viewpoint of improving cohesive force and adhesion. As the acrylic oligomer, it is preferable to use a polymer whose Tg is higher than that of the acrylic polymer. For example, in an embodiment in which ultraviolet irradiation is used in the production of an adhesive, acrylic oligomers are suitable because they are less likely to inhibit polymerization.
　アクリル系オリゴマーの好適例としては、例えば、ジシクロペンタニルメタクリレート（ＤＣＰＭＡ）、シクロヘキシルメタクリレート（ＣＨＭＡ）、イソボルニルメタクリレート（ＩＢＸＭＡ）、イソボルニルアクリレート（ＩＢＸＡ）、ジシクロペンタニルアクリレート（ＤＣＰＡ）、１－アダマンチルメタクリレート（ＡＤＭＡ）、１－アダマンチルアクリレート（ＡＤＡ）の各単独重合体のほか、ＤＣＰＭＡとメチルメタクリレート（ＭＭＡ）の共重合体、ＤＣＰＭＡとＩＢＸＭＡとの共重合体、ＡＤＡとＭＭＡの共重合体、ＣＨＭＡとイソブチルメタクリレート（ＩＢＭＡ）との共重合体、ＣＨＭＡとＩＢＸＭＡとの共重合体、ＣＨＭＡとアクリロイルモルホリン（ＡＣＭＯ）との共重合体、ＣＨＭＡとジエチルアクリルアミド（ＤＥＡＡ）との共重合体、ＣＨＭＡとＡＡとの共重合体等を挙げることができる。アクリル系オリゴマーは、１種を単独でまたは２種以上を組み合わせて使用することができる。 Suitable examples of acrylic oligomers include dicyclopentanyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), and dicyclopentanyl acrylate (DCPA). , 1-adamantyl methacrylate (ADMA), and 1-adamantyl acrylate (ADA), as well as copolymers of DCPMA and methyl methacrylate (MMA), copolymers of DCPMA and IBXMA, and copolymers of ADA and MMA. Polymers, copolymers of CHMA and isobutyl methacrylate (IBMA), copolymers of CHMA and IBXMA, copolymers of CHMA and acryloylmorpholine (ACMO), copolymers of CHMA and diethylacrylamide (DEAA) , a copolymer of CHMA and AA, and the like. Acrylic oligomers can be used alone or in combination of two or more.
　アクリル系オリゴマーのＭｗは、典型的には約１０００以上約３００００未満、好ましくは約１５００以上約１００００未満、さらに好ましくは約２０００以上約５０００未満であり得る。Ｍｗが上記範囲内にあると、凝集性や隣接する面との接着性を向上させる効果が好適に発揮されやすい。アクリル系オリゴマーのＭｗは、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定し、標準ポリスチレン換算の値として求めることができる。具体的には、東ソー社製のＨＰＬＣ８０２０に、カラムとしてＴＳＫｇｅｌＧＭＨ－Ｈ（２０）×２本を用いて、テトラヒドロフラン溶媒で流速約０．５ｍＬ／分の条件にて測定される。 The Mw of the acrylic oligomer is typically about 1,000 or more and less than about 30,000, preferably about 1,500 or more and less than about 10,000, and more preferably about 2,000 or more and less than about 5,000. When Mw is within the above range, the effect of improving cohesion and adhesion to adjacent surfaces is likely to be suitably exhibited. The Mw of the acrylic oligomer can be measured by gel permeation chromatography (GPC) and determined as a value in terms of standard polystyrene. Specifically, the measurement is performed using HPLC8020 manufactured by Tosoh Corporation with two columns of TSKgelGMH-H (20) at a flow rate of about 0.5 mL/min using tetrahydrofuran solvent.
　粘着剤にアクリル系オリゴマーを含有させる場合、その含有量は、上記ベースポリマー（典型的にはアクリル系重合物）１００重量部に対して、例えば０．０１重量部以上とすることができ、より高い効果を得る観点から０．０５重量部以上としてもよく、０．１重量部以上としてもよい。また、ベースポリマーとの相溶性等の観点から、上記アクリル系オリゴマーの含有量は、好ましくは３０重量部未満であり、例えば１０重量部以下であってもよく、１重量部以下としてもよい。 When the adhesive contains an acrylic oligomer, the content can be, for example, 0.01 part by weight or more based on 100 parts by weight of the base polymer (typically an acrylic polymer), and more From the viewpoint of obtaining high effects, the amount may be 0.05 part by weight or more, or may be 0.1 part by weight or more. Further, from the viewpoint of compatibility with the base polymer, the content of the acrylic oligomer is preferably less than 30 parts by weight, and may be, for example, 10 parts by weight or less, or 1 part by weight or less.
　（シランカップリング剤）
　ここに開示される粘着剤は、シランカップリング剤を含んでもよい。シランカップリング剤を含む態様において、シランカップリング剤は遊離の形態で粘着剤組成物（ひいては粘着剤）に含まれていることが好ましい。シランカップリング剤を含ませることにより、被着体（例えばガラス部材）に対する粘着剤の接着力は上昇する傾向がある。 (Silane coupling agent)
The adhesive disclosed herein may also include a silane coupling agent. In embodiments containing a silane coupling agent, the silane coupling agent is preferably contained in the adhesive composition (and thus the adhesive) in a free form. By including a silane coupling agent, the adhesive strength of the adhesive to an adherend (for example, a glass member) tends to increase.
　シランカップリング剤としては、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メチルジメトキシシラン、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構造を有するケイ素化合物；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等のアミノ基含有ケイ素化合物；３－クロロプロピルトリメトキシシラン；アセトアセチル基含有トリメトキシシラン；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。なかでも好ましい例として、３－グリシドキシプロピルトリメトキシシランおよびアセトアセチル基含有トリメトキシシランが挙げられる。シランカップリング剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。 As a silane coupling agent, a silicon compound having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane; 3-chloro Propyltrimethoxysilane; acetoacetyl group-containing trimethoxysilane; (meth)acrylic group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; 3-isocyanatepropyltriethoxysilane Examples include isocyanate group-containing silane coupling agents such as. Among these, preferred examples include 3-glycidoxypropyltrimethoxysilane and acetoacetyl group-containing trimethoxysilane. The silane coupling agents can be used alone or in combination of two or more.
　シランカップリング剤の使用量は、所望の使用効果が得られるように設定することができ、特に限定されない。いくつかの態様において、シランカップリング剤の使用量は、粘着剤に含まれる重合物を構成するモノマー成分１００重量部に対して、例えば０．００１重量部以上であってよく、より高い効果を得る観点から０．００５重量部以上でもよく、０．０１重量部以上でもよく、０．０１５重量部以上でもよい。また、いくつかの態様において、シランカップリング剤の使用量は、粘着剤を構成するモノマー成分１００重量部に対して、例えば３重量部以下であってよく、１重量部以下でもよく、０．５重量部以下でもよい。また、ここに開示される技術は、シランカップリング剤を実質的に含まない粘着剤を用いる態様で実施することができる。シランカップリング剤の使用量を制限したり、シランカップリング剤を使用しないことにより、被着体からの剥離性は向上する傾向がある。 The amount of the silane coupling agent used can be set so as to obtain the desired effect of use, and is not particularly limited. In some embodiments, the amount of the silane coupling agent used may be, for example, 0.001 parts by weight or more based on 100 parts by weight of the monomer components constituting the polymer contained in the adhesive, to achieve a higher effect. From the viewpoint of obtaining, the amount may be 0.005 part by weight or more, 0.01 part by weight or more, or 0.015 part by weight or more. Further, in some embodiments, the amount of the silane coupling agent used may be, for example, 3 parts by weight or less, 1 part by weight or less, and 0.5 parts by weight or less, based on 100 parts by weight of the monomer components constituting the adhesive. It may be 5 parts by weight or less. Moreover, the technology disclosed herein can be implemented in an embodiment using an adhesive that does not substantially contain a silane coupling agent. By limiting the amount of the silane coupling agent used or not using the silane coupling agent, the releasability from the adherend tends to improve.
　（その他の成分）
　ここに開示される粘着剤は、必要に応じて、粘度調整剤（例えば増粘剤）、ｐＨ調整剤、レベリング剤、可塑剤、充填剤、顔料や染料等の着色剤、安定剤、防腐剤、老化防止剤等の粘着剤の分野において一般的な各種の添加剤をその他の任意成分として含み得る。このような各種添加剤については、従来公知のものを常法により使用することができ、特に本発明を特徴づけるものではないので、詳細な説明は省略する。 (Other ingredients)
The adhesive disclosed herein may optionally contain a viscosity modifier (e.g., thickener), a pH adjuster, a leveling agent, a plasticizer, a filler, a coloring agent such as a pigment or dye, a stabilizer, and a preservative. , various additives common in the field of adhesives such as anti-aging agents may be included as other optional ingredients. Regarding such various additives, conventionally known ones can be used in a conventional manner, and since they do not particularly characterize the present invention, detailed explanations will be omitted.
　ここに開示される技術では、粘着剤に占めるベースポリマー（好適にはアクリル系重合物）以外の成分の量が制限されたものであり得る。ここに開示される技術において、粘着剤におけるベースポリマー以外の成分の量は、例えば凡そ３０重量％以下であり、凡そ１５重量％以下であることが適当であり、好ましくは凡そ１２重量％以下（例えば凡そ１０重量％以下）である。このような組成の粘着剤は、所定の光学特性（例えば透明性）を満足しやすく、光学用途に好ましく用いられ得る。いくつかの態様において、粘着剤におけるベースポリマー以外の成分の量は、凡そ５重量％以下であってもよく、凡そ３重量％以下であってもよく、凡そ１．５重量％以下（例えば凡そ１重量％以下）であってもよい。このようにベースポリマー（例えばアクリル系重合物）以外の成分量が制限された組成は、光硬化型粘着剤組成物に対して好ましく採用され得る。 In the technology disclosed herein, the amount of components other than the base polymer (preferably acrylic polymer) in the adhesive may be limited. In the technology disclosed herein, the amount of components other than the base polymer in the adhesive is, for example, about 30% by weight or less, suitably about 15% by weight or less, preferably about 12% by weight or less ( For example, about 10% by weight or less). A pressure-sensitive adhesive having such a composition easily satisfies predetermined optical properties (eg, transparency) and can be preferably used for optical applications. In some embodiments, the amount of components other than the base polymer in the adhesive may be about 5% by weight or less, about 3% by weight or less, about 1.5% by weight or less (e.g., about 1% by weight or less). A composition in which the amount of components other than the base polymer (eg, acrylic polymer) is limited in this way can be preferably employed in a photocurable pressure-sensitive adhesive composition.
　（粘着剤層の形成）
　粘着剤が粘着剤層の形態を有する場合、粘着剤層は、粘着剤組成物の硬化層であり得る。すなわち、該粘着剤層は、粘着剤組成物を適当な表面に付与（例えば塗布）した後、硬化処理を適宜施すことにより形成され得る。２種以上の硬化処理（乾燥、架橋、重合等）を行う場合、これらは、同時に、または多段階にわたって行うことができる。モノマー成分の部分重合物（アクリル系ポリマーシロップ）を用いた粘着剤組成物では、典型的には、上記硬化処理として、最終的な共重合反応が行われる。すなわち、部分重合物をさらなる共重合反応に供して完全重合物を形成する。例えば、光硬化性の粘着剤組成物であれば、光照射が実施される。必要に応じて、架橋、乾燥等の硬化処理が実施されてもよい。例えば、光硬化性粘着剤組成物で乾燥させる必要がある場合（例えば、モノマー成分の部分重合物が有機溶剤に溶解した形態の光硬化性粘着剤組成物の場合）は、該組成物を乾燥させた後に光硬化を行うとよい。完全重合物を用いた粘着剤組成物では、典型的には、上記硬化処理として、必要に応じて乾燥（加熱乾燥）、架橋等の処理が実施される。二層以上の多層構造の粘着剤層は、あらかじめ形成した粘着剤層を貼り合わせることによって作製することができる。あるいは、あらかじめ形成した第一の粘着剤層の上に粘着剤組成物を塗布し、該粘着剤組成物を硬化させて第二の粘着剤層を形成してもよい。 (Formation of adhesive layer)
When the adhesive has the form of an adhesive layer, the adhesive layer may be a cured layer of the adhesive composition. That is, the adhesive layer can be formed by applying (for example, coating) an adhesive composition to a suitable surface and then appropriately performing a curing treatment. When performing two or more types of curing treatments (drying, crosslinking, polymerization, etc.), these can be performed simultaneously or in multiple stages. In pressure-sensitive adhesive compositions using partial polymers of monomer components (acrylic polymer syrup), a final copolymerization reaction is typically performed as the curing treatment. That is, the partially polymerized product is further subjected to a copolymerization reaction to form a complete polymerized product. For example, in the case of a photocurable adhesive composition, light irradiation is performed. Curing treatments such as crosslinking and drying may be performed as necessary. For example, if it is necessary to dry the photocurable adhesive composition (for example, in the case of a photocurable adhesive composition in which a partial polymer of a monomer component is dissolved in an organic solvent), dry the composition. It is preferable to perform photocuring after this. In an adhesive composition using a complete polymer, typically, as the curing treatment, treatments such as drying (heat drying) and crosslinking are performed as necessary. An adhesive layer having a multilayer structure of two or more layers can be produced by bonding together adhesive layers formed in advance. Alternatively, a second adhesive layer may be formed by applying a pressure-sensitive adhesive composition onto a first pressure-sensitive adhesive layer formed in advance and curing the pressure-sensitive adhesive composition.
　粘着剤組成物の塗布は、例えば、グラビアロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター等の慣用のコーターを用いて実施することができる。 The adhesive composition can be applied using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, and a spray coater.
　（粘着剤層の厚さ）
　粘着剤層の厚さは特に限定されず、例えば３μｍ～２０００μｍ程度であり得る。段差追従性など被着体との密着性の観点から、いくつかの態様において、粘着剤層の厚さは、例えば３μｍ以上が適当であり、好ましくは１０μｍ以上であり、より好ましくは１５μｍ以上であり、さらに好ましくは２０μｍ以上である。また、粘着剤層の凝集破壊による糊残りの発生を防止する観点から、いくつかの態様において、粘着剤層の厚さは、通常５００μｍ以下であり、好ましくは２００μｍ以下、さらに好ましくは１００μｍ以下であり、５０μｍ以下でもよく、さらには３０μｍ以下でもよい。 (thickness of adhesive layer)
The thickness of the adhesive layer is not particularly limited, and may be, for example, about 3 μm to 2000 μm. In some embodiments, the thickness of the adhesive layer is suitably 3 μm or more, preferably 10 μm or more, and more preferably 15 μm or more, from the viewpoint of adhesion to the adherend such as step followability. The thickness is more preferably 20 μm or more. Further, from the viewpoint of preventing adhesive residue from occurring due to cohesive failure of the adhesive layer, in some embodiments, the thickness of the adhesive layer is usually 500 μm or less, preferably 200 μm or less, and more preferably 100 μm or less. The thickness may be 50 μm or less, or even 30 μm or less.
　（ヘイズ値）
　粘着剤は、好ましくは光学用粘着剤である。光学用粘着剤は、光学特性を損なわないものであり得る。粘着剤（層）、ひいては粘着シートのヘイズ値は特に限定されないが、いくつかの態様において、ヘイズ値は凡そ１０％以下であることが適当であり、凡そ５％以下（例えば凡そ３％以下）であり得る。上記ヘイズ値は１．０％以下であることが好ましい。このように透明性の高い粘着剤は、高い光透過性が求められる光学用途に好適である。上記ヘイズ値は、１．０％未満であってよく、０．７％未満であってもよく、０．５％以下（例えば０～０．５％）であってもよい。ヘイズ値は、例えば、粘着剤の組成や厚さ等の選択によって調節することができる。 (Haze value)
The adhesive is preferably an optical adhesive. The optical adhesive may be one that does not impair optical properties. The haze value of the adhesive (layer) and ultimately the adhesive sheet is not particularly limited, but in some embodiments, it is appropriate that the haze value is approximately 10% or less, and approximately 5% or less (for example, approximately 3% or less). It can be. The haze value is preferably 1.0% or less. Adhesives with such high transparency are suitable for optical applications that require high light transmittance. The haze value may be less than 1.0%, may be less than 0.7%, and may be 0.5% or less (for example, 0 to 0.5%). The haze value can be adjusted, for example, by selecting the composition and thickness of the adhesive.
　ここで「ヘイズ値」とは、測定対象に可視光を照射したときの全透過光に対する拡散透過光の割合をいう。くもり価ともいう。ヘイズ値は、以下の式で表すことができる。
　　　Ｔｈ［％］＝Ｔｄ／Ｔｔ×１００
　上記式において、Ｔｈはヘイズ値［％］であり、Ｔｄは散乱光透過率、Ｔｔは全光透過率である。ヘイズ値は、粘着剤層または粘着シートの粘着面をヘイズ値０．１％のアルカリガラスの片面に貼り付け、粘着剤層または粘着シートとアルカリガラスの積層体とした後、ヘイズメーター（例えば村上色彩技術研究所製の製品名「ＭＲ－１００」）を用いて測定することができる。測定にあたっては、粘着剤層または粘着シートの貼り付けられたアルカリガラスを、該粘着剤層または粘着シートが光源側になるように配置する。アルカリガラスのヘイズ値が０．１％であるため、測定値から０．１％を引いた値を粘着剤層または粘着シートのヘイズ値［％］とする。 Here, the "haze value" refers to the ratio of diffusely transmitted light to the total transmitted light when visible light is irradiated onto the measurement target. Also called cloudiness value. The haze value can be expressed by the following formula.
Th[%]=Td/Tt×100
In the above formula, Th is the haze value [%], Td is the scattered light transmittance, and Tt is the total light transmittance. The haze value is determined by pasting the adhesive side of the adhesive layer or adhesive sheet on one side of alkali glass with a haze value of 0.1% to form a laminate of the adhesive layer or adhesive sheet and alkali glass, and then using a haze meter (for example, Murakami). It can be measured using the product name "MR-100" manufactured by Color Technology Research Institute. In the measurement, the alkali glass to which the adhesive layer or adhesive sheet is attached is placed so that the adhesive layer or adhesive sheet faces the light source side. Since the haze value of alkali glass is 0.1%, the value obtained by subtracting 0.1% from the measured value is defined as the haze value [%] of the adhesive layer or adhesive sheet.
　（基材層）
　いくつかの態様において、粘着シートは基材層を備える。基材層は、粘着剤層を支持する支持体（支持層）である。基材層は、粘着シートの表面を構成する第１および第２の粘着剤層の間に配置された中間層であり得る。 (Base material layer)
In some embodiments, the adhesive sheet includes a base layer. The base layer is a support (support layer) that supports the adhesive layer. The base layer may be an intermediate layer disposed between the first and second adhesive layers that constitute the surface of the adhesive sheet.
　ここに開示される基材層としては、例えば、ポリオレフィンフィルム、ポリエステルフィルム、ポリ塩化ビニルフィルム等の各種樹脂フィルム；ポリウレタンフォーム、ポリエチレンフォーム、ポリクロロプレンフォーム等の発泡体からなる発泡体シート；各種の繊維状物質（麻、綿等の天然繊維、ポリエステル、ビニロン等の合成繊維、アセテート等の半合成繊維、等であり得る。）の単独または混紡等による織布および不織布；和紙、上質紙、クラフト紙、クレープ紙等の紙類；アルミニウム箔、銅箔、ステンレス鋼（ＳＵＳ）等の金属箔；等が挙げられる。これらを複合した構成の層状体であってもよい。このような複合構造の基材層の例として、例えば、金属箔と上記樹脂フィルムとが積層した構造の積層基材（多層構造基材）、ガラスクロス等の無機繊維で強化された樹脂シート等が挙げられる。 Examples of the base layer disclosed herein include various resin films such as polyolefin film, polyester film, and polyvinyl chloride film; foam sheets made of foams such as polyurethane foam, polyethylene foam, and polychloroprene foam; Woven fabrics and non-woven fabrics made of fibrous materials (natural fibers such as hemp and cotton, synthetic fibers such as polyester and vinylon, semi-synthetic fibers such as acetate, etc.) alone or in combination; Japanese paper, high-quality paper, and crafts. Examples include papers such as paper and crepe paper; metal foils such as aluminum foil, copper foil, and stainless steel (SUS); and the like. A layered body having a composite structure of these may also be used. Examples of base material layers with such composite structures include, for example, laminated base materials with a structure in which metal foil and the above-mentioned resin film are laminated (multilayer base materials), resin sheets reinforced with inorganic fibers such as glass cloth, etc. can be mentioned.
　基材層の材料としては、独立して形状維持可能な（自立型の、あるいは非依存性の）樹脂フィルムをベースフィルムとして含むものを好ましく用いることができる。ここで「樹脂フィルム」とは、非多孔質の構造であって、典型的には実質的に気泡を含まない（ボイドレスの）樹脂フィルムを意味する。したがって、上記樹脂フィルムは、発泡体フィルムや不織布とは区別される概念である。上記樹脂フィルムは、単層構造であってもよく、二層以上の多層構造（例えば三層構造）であってもよい。上記樹脂フィルムは透明なフィルムであり得る。透明樹脂フィルムは、光学用途に好適である。 As the material for the base layer, a material containing a base film that can independently maintain its shape (self-supporting or independent) can be preferably used. Here, the term "resin film" refers to a resin film that has a non-porous structure and typically is substantially void-free. Therefore, the resin film is a concept that is distinguished from foam films and nonwoven fabrics. The resin film may have a single-layer structure or a multi-layer structure of two or more layers (for example, a three-layer structure). The resin film may be a transparent film. Transparent resin films are suitable for optical applications.
　樹脂フィルムを構成する樹脂材料の好適例として、ポリエステル系樹脂、ポリフェニレンサルファイド（ＰＰＳ）樹脂、ポリオレフィン系樹脂、ポリイミド樹脂が挙げられる。基材層として好ましく利用し得る樹脂フィルムの具体例として、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリエチレンナフタレート（ＰＥＮ）フィルム、ＰＰＳフィルム、ポリエーテルエーテルケトン（ＰＥＥＫ）フィルム、透明ポリイミド（ＣＰＩ）フィルム、ポリプロピレン（ＰＰ）フィルム、トリアセチルセルロース（ＴＡＣ）フィルムが挙げられる。強度の点から好ましい例として、ＰＥＴフィルム、ＰＥＮフィルム、ＰＰＳフィルム、ＰＥＥＫフィルム、ＣＰＩフィルムが挙げられる。入手容易性、寸法安定性、光学特性等の観点から好ましい例としてＰＥＴフィルム、ＣＰＩフィルム、ＴＡＣフィルムが挙げられる。 Suitable examples of the resin material constituting the resin film include polyester resin, polyphenylene sulfide (PPS) resin, polyolefin resin, and polyimide resin. Specific examples of resin films that can be preferably used as the base layer include polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, PPS film, polyetheretherketone (PEEK) film, transparent polyimide (CPI) film, and polypropylene. (PP) film and triacetyl cellulose (TAC) film. Preferred examples from the viewpoint of strength include PET film, PEN film, PPS film, PEEK film, and CPI film. Preferred examples from the viewpoint of availability, dimensional stability, optical properties, etc. include PET film, CPI film, and TAC film.
　樹脂フィルムには、光安定剤、酸化防止剤、帯電防止剤、着色剤（染料、顔料等）、充填材、スリップ剤、アンチブロッキング剤等の公知の添加剤を、必要に応じて配合することができる。添加剤の配合量は特に限定されず、用途等に応じて適宜設定することができる。 Known additives such as light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, slip agents, anti-blocking agents, etc. may be added to the resin film as necessary. Can be done. The amount of additives to be blended is not particularly limited, and can be appropriately set depending on the application and the like.
　樹脂フィルムの製造方法は特に限定されない。例えば、押出成形、インフレーション成形、Ｔダイキャスト成形、カレンダーロール成形等の、従来公知の一般的な樹脂フィルム成形方法を適宜採用することができる。 The method for producing the resin film is not particularly limited. For example, conventionally known general resin film forming methods such as extrusion molding, inflation molding, T-die casting molding, and calender roll molding can be appropriately employed.
　上記基材層は、このような樹脂フィルムから実質的に構成されたものであり得る。あるいは、上記基材層は、上記樹脂フィルムの他に、補助的な層を含むものであってもよい。上記補助的な層の例としては、下塗り層、剥離層等の表面処理層が挙げられる。また、基材層の粘着剤層側表面には、必要に応じて、例えば、コロナ処理やプラズマ処理、紫外線照射処理、酸処理、アルカリ処理、下塗り剤（プライマー）の塗布、帯電防止処理、剥離処理等の、従来公知の表面処理が施されていてもよい。 The base material layer may be substantially composed of such a resin film. Alternatively, the base layer may include an auxiliary layer in addition to the resin film. Examples of the above-mentioned auxiliary layers include surface treatment layers such as undercoat layers and release layers. In addition, the surface of the base material layer on the adhesive layer side may be treated with corona treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of an undercoat (primer), antistatic treatment, peeling, etc., as necessary. A conventionally known surface treatment such as a treatment may be applied.
　基材層の厚さは、特に限定されず、例えば凡そ１０００μｍ以下であってよく、凡そ５００μｍ以下でもよく、軽量化や薄厚化の観点から、凡そ１００μｍ以下が適当であり、７０μｍ以下でもよい。また、取扱い性や加工性等の観点から、基材層の厚さは、例えば１μｍ以上であってよく、凡そ２０μｍ以上が適当であり、好ましくは凡そ３０μｍ以上である。 The thickness of the base material layer is not particularly limited, and may be, for example, approximately 1000 μm or less, approximately 500 μm or less, and from the viewpoint of weight reduction and thinning, approximately 100 μm or less is appropriate, and may be 70 μm or less. Further, from the viewpoint of handleability, processability, etc., the thickness of the base material layer may be, for example, 1 μm or more, suitably about 20 μm or more, and preferably about 30 μm or more.
　なお、この明細書により開示される事項には、以下のものが含まれる。
　（１）　被着体に貼り付けられた粘着シートの剥離方法であって、
　前記粘着シートに粘着力低減手段を適用することを含み、
　前記粘着力低減手段は、
　　前記粘着シートの前記被着体からの剥離前線における前記被着体と前記粘着シートとの界面にアルコール液を供給すること、および
　　前記界面に前記アルコール液が存在する状態で、前記粘着シートの前記剥離前線を剥離進行方向に移動させ、該剥離前線の移動に追随して前記アルコール液の前記界面への進入を進行させることを含む、剥離方法。
　（２）　前記粘着シートは、被着体としてのステンレス鋼板に前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、エタノール剥離力Ｎ１ＳＵＳが、０．５Ｎ／２０ｍｍ以下である、上記（１）に記載の剥離方法。
　（３）　前記粘着シートは、被着体としてのステンレス鋼板に、幅２０ｍｍの長方形状にカットされた前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＳＵＳが３０ｍｍ以上である、上記（１）または（２）に記載の剥離方法。
　（４）　前記粘着シートは、被着体としてのステンレス鋼板に前記粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＳＵＳが３．０Ｎ／２０ｍｍ以上である、上記（１）～（３）のいずれかに記載の剥離方法。
　（５）　前記粘着シートは、
　被着体としてのステンレス鋼板に前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、エタノール剥離力Ｎ１ＳＵＳ、および、被着体としてのステンレス鋼板に前記粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＳＵＳと、から下記式：粘着力低減率ＳＳＵＳ［％］＝（１－（Ｎ１ＳＵＳ／Ｎ０ＳＵＳ））×１００；で求められる粘着力低減率ＳＳＵＳが５０％以上であり、
　かつ、被着体としてのステンレス鋼板に、幅２０ｍｍの長方形状にカットされた前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＳＵＳが３０ｍｍ以上である、上記（１）～（４）のいずれかに記載の剥離方法。
　（６）　前記粘着シートは、被着体としてのフロート法で作製されたアルカリガラス板に前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、エタノール剥離力Ｎ１ＧＬＡが、０．５Ｎ／２０ｍｍ以下である、上記（１）～（５）のいずれかに記載の剥離方法。
　（７）　前記粘着シートは、被着体としてのフロート法で作製されたアルカリガラス板に、幅２０ｍｍの長方形状にカットされた前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＧＬＡが３０ｍｍ以上である、上記（１）～（６）のいずれかに記載の剥離方法。
　（８）　前記粘着シートは、被着体としてのフロート法で作製されたアルカリガラス板に前記粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＧＬＡが３．０Ｎ／２０ｍｍ以上である、上記（１）～（７）のいずれかに記載の剥離方法。
　（９）　前記粘着シートは、
　被着体としてのフロート法で作製されたアルカリガラス板に前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、エタノール剥離力Ｎ１ＧＬＡ、および、被着体としてのフロート法で作製されたアルカリガラス板に前記粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＧＬＡ、から下記式：粘着力低減率ＳＧＬＡ［％］＝（１－（Ｎ１ＧＬＡ／Ｎ０ＧＬＡ））×１００；で求められる粘着力低減率ＳＧＬＡが５０％以上であり、
　かつ、被着体としてのフロート法で作製されたアルカリガラス板に、幅２０ｍｍの長方形状にカットされた前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＧＬＡが３０ｍｍ以上である、上記（１）～（８）のいずれかに記載の剥離方法。
　（１０）　前記粘着シートは、基材層と、該基材層の少なくとも一方の面に配置された粘着剤層とを含み、
　前記粘着剤層は、ベースポリマーとしてアクリル系ポリマーを含むアクリル系粘着剤層である、上記（１）～（９）のいずれかに記載の剥離方法。
　（１１）　前記粘着剤層は、水分散型粘着剤組成物、溶剤型粘着剤組成物、活性エネルギー線硬化型粘着剤組成物またはホットメルト型粘着剤組成物から形成されたものである、上記（１０）に記載の剥離方法。
　（１２）　前記基材層は、樹脂フィルムから構成される、上記（１０）または（１１）に記載の剥離方法。
　（１３）　前記被着体は、該被着体の前記粘着シートが貼り付けられる面のエタノールに対する接触角が５０度以下、３０度以下、２０度以下または１５度以下である、上記（１）～（１２）のいずれかに記載の剥離方法。
　（１４）　前記被着体は、該被着体の前記粘着シートが貼り付けられる面の蒸留水に対する接触角が３０度以上、３５度以上、４０度以上、４５度以上、５０度以上、６０度以上または６０度超である、上記（１）～（１３）のいずれかに記載の剥離方法。 Note that the matters disclosed in this specification include the following.
(1) A method for peeling an adhesive sheet pasted on an adherend, the method comprising:
comprising applying an adhesive force reducing means to the adhesive sheet,
The adhesive force reducing means is
supplying an alcohol solution to an interface between the adherend and the adhesive sheet at a peeling front of the adhesive sheet from the adherend; A peeling method comprising moving a peeling front in a peeling advancing direction and allowing the alcohol solution to enter the interface following the movement of the peeling front.
(2) The adhesive sheet is prepared by attaching the adhesive sheet to a stainless steel plate as an adherend, and after one day at room temperature, dropping 2 μL of ethanol onto the adherend, and applying the ethanol to the adhesive sheet and the adherend. After entering one end of the interface with The peeling method according to (1) above, wherein the ethanol peeling force N1 SUS measured under the conditions of a tensile speed of 300 mm/min and a peeling angle of 180 degrees is 0.5 N/20 mm or less.
(3) The adhesive sheet was prepared by pasting the adhesive sheet cut into a rectangular shape with a width of 20 mm on a stainless steel plate as an adherend, and after one day at room temperature, dropping 2 μL of ethanol onto the adherend. After entering ethanol into one end of the interface between the adhesive sheet and the adherend, follow JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, In (1) or (2) above, the adhesive strength reduction distance R SUS is 30 mm or more, measured at a test temperature of 23 ° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. Peeling method described.
(4) The adhesive sheet described in (1) to (3) above has an adhesive force N0 SUS of 3.0 N/20 mm or more after one day at room temperature after pasting the adhesive sheet on a stainless steel plate as an adherend. The peeling method described in any of the above.
(5) The adhesive sheet includes:
After one day at room temperature after pasting the adhesive sheet on a stainless steel plate as an adherend, 2 μL of ethanol is dropped onto the adherend, and the ethanol is allowed to enter one end of the interface between the adhesive sheet and the adherend. After that, according to JIS Z0237:2009 10.4.1 Method 1: 180° peel adhesion force to the test plate, specifically, using a tensile tester at a test temperature of 23 ° C., the tensile speed was 300 mm/min, From the ethanol peeling force N1 SUS measured at a peeling angle of 180 degrees, and the adhesive force N0 SUS after one day at room temperature after pasting the adhesive sheet on a stainless steel plate as an adherend, the following formula: Adhesive force The adhesive strength reduction rate S SUS determined by the following equation is 50 % or more ,
Then, the adhesive sheet cut into a rectangular shape with a width of 20 mm is attached to a stainless steel plate as an adherend, and after one day at room temperature, 2 μL of ethanol is dropped onto the adherend, and the ethanol is mixed with the adhesive sheet. After entering one end of the interface with the adherend, according to JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, at a test temperature of 23 ° C. Peeling according to any one of (1) to (4) above, wherein the adhesive force reduction distance R SUS is 30 mm or more, measured using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. Method.
(6) The adhesive sheet is prepared by attaching the adhesive sheet to an alkali glass plate prepared by the float method as an adherend, and after one day at room temperature, dropping 2 μL of ethanol onto the adherend, and adding the ethanol to the adherend. After entering one end of the interface between the adhesive sheet and the adherend, follow JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, test temperature 23 (1) to (5) above, where the ethanol peel force N1 GLA is 0.5 N/20 mm or less, measured using a tensile tester at ℃ at a tensile speed of 300 mm/min and a peel angle of 180 degrees. The peeling method described in any of the above.
(7) The adhesive sheet was cut into a rectangular shape with a width of 20 mm and was pasted on an alkali glass plate made by the float method as an adherend, and after one day at room temperature, 2 μL was applied to the adherend. 10.4.1 method 1 of JIS Z0237:2009: 180° peeling adhesive force to the test plate Accordingly, specifically, the above (( The peeling method according to any one of 1) to (6).
(8) The adhesive sheet has an adhesive force N0 GLA of 3.0 N/20 mm or more after one day at room temperature after attaching the adhesive sheet to an alkali glass plate prepared by a float method as an adherend. The peeling method according to any one of 1) to (7).
(9) The adhesive sheet includes:
The adhesive sheet was attached to an alkali glass plate prepared by the float method as an adherend, and after one day at room temperature, 2 μL of ethanol was dropped onto the adherend, and the ethanol was applied to the adhesive sheet and the adherend. After entering one end of the interface of The ethanol peeling force N1 GLA was measured at a tensile speed of 300 mm/min and a peeling angle of 180 degrees. Adhesive force reduction rate S GLA is 50% or more , calculated from the following formula: Adhesive force reduction rate S GLA [%] = (1-(N1 GLA /N0 GLA )) x 100; ,
Then, the adhesive sheet cut into a rectangular shape with a width of 20 mm was attached to an alkali glass plate prepared by the float method as an adherend, and after one day at room temperature, 2 μL of ethanol was dropped onto the adherend, After the ethanol enters one end of the interface between the adhesive sheet and the adherend, according to JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, , the adhesion reduction distance R GLA is 30 mm or more, measured using a tensile tester at a test temperature of 23 ° C. at a tensile speed of 300 mm/min and a peel angle of 180 degrees, (1) to (8) above. The peeling method described in any of the above.
(10) The adhesive sheet includes a base layer and an adhesive layer disposed on at least one surface of the base layer,
The peeling method according to any one of (1) to (9) above, wherein the adhesive layer is an acrylic adhesive layer containing an acrylic polymer as a base polymer.
(11) The adhesive layer is formed from a water-dispersed adhesive composition, a solvent-based adhesive composition, an active energy ray-curable adhesive composition, or a hot-melt adhesive composition. The peeling method described in (10).
(12) The peeling method according to (10) or (11) above, wherein the base layer is composed of a resin film.
(13) The adherend has a contact angle with ethanol of 50 degrees or less, 30 degrees or less, 20 degrees or less, or 15 degrees or less on the surface of the adherend to which the pressure-sensitive adhesive sheet is attached, according to (1) above. The peeling method according to any one of (12) to (12).
(14) The adherend has a contact angle with respect to distilled water on the surface to which the adhesive sheet is attached, of 30 degrees or more, 35 degrees or more, 40 degrees or more, 45 degrees or more, 50 degrees or more, or 60 degrees or more. The peeling method according to any one of (1) to (13) above, wherein the peeling method is at least 60 degrees or more than 60 degrees.
　以下、本発明に関するいくつかの実施例を説明するが、本発明をかかる実施例に示すものに限定することを意図したものではない。なお、以下の説明において「部」および「％」は、特に断りがない限り重量基準である。 Hereinafter, some examples relating to the present invention will be described, but the present invention is not intended to be limited to what is shown in these examples. In the following description, "parts" and "%" are based on weight unless otherwise specified.
　＜粘着剤組成物の調製＞
　（粘着剤組成物Ｓ－１）
　冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器に、２－エチルヘキシルアクリレート（２ＥＨＡ）３８．５部、ラウリルアクリレート（ＬＡ）６０部、ｎ－ブチルアクリレート（ＢＡ）２．５部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）８部、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）０．０５部を、熱重合開始剤としての２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２部および重合溶媒としての酢酸エチルとともに投入し、窒素ガス気流下において６０℃で４時間反応させることにより、Ｍｗが６０万～１００万のアクリル系ポリマーＡを含有する溶液（固形分濃度３０％）を得た。このアクリル系ポリマーＡを含有する溶液の固形分１００部に対して、イソシアネート系架橋剤Ｃ１（商品名「タケネートＤ１０１Ｅ」、三井化学社製）０．０５部と、アクリル系オリゴマーＡを１．５部とを配合し、均一に攪拌混合して、溶剤型粘着剤組成物Ｓ－１を調製した。 <Preparation of adhesive composition>
(Adhesive composition S-1)
Into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 38.5 parts of 2-ethylhexyl acrylate (2EHA), 60 parts of lauryl acrylate (LA), and 2.5 parts of n-butyl acrylate (BA) were added. , 8 parts of 4-hydroxybutyl acrylate (4HBA), 0.05 parts of N-vinyl-2-pyrrolidone (NVP), and 0.0 parts of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator. A solution containing acrylic polymer A with an Mw of 600,000 to 1,000,000 (solid content concentration 30%) was prepared by adding 2 parts of acrylic polymer A and ethyl acetate as a polymerization solvent and reacting at 60°C for 4 hours under a nitrogen gas stream. ) was obtained. To 100 parts of the solid content of the solution containing acrylic polymer A, 0.05 part of isocyanate crosslinking agent C1 (trade name "Takenate D101E", manufactured by Mitsui Chemicals) and 1.5 parts of acrylic oligomer A were added. A solvent-based adhesive composition S-1 was prepared by uniformly stirring and mixing the following components.
　（粘着剤組成物Ｓ－２）
　粘着剤組成物Ｓ－１の調製において得られたアクリル系ポリマーＡを含有する溶液の固形分１００部に対して、イソシアネート系架橋剤（商品名「タケネートＤ１０１Ｅ」、三井化学社製）０．０５部と、アクリル系オリゴマーＡを１．５部と、ノニオン性界面活性剤Ａ１（ポリオキシエチレンラウリルエーテル、商品名「エマルゲン１０４Ｐ」、花王社製）０．５部とを配合し、均一に攪拌混合して、溶剤型粘着剤組成物Ｓ－２を調製した。 (Adhesive composition S-2)
0.05 isocyanate crosslinking agent (trade name "Takenate D101E", manufactured by Mitsui Chemicals, Inc.) per 100 parts solid content of the solution containing acrylic polymer A obtained in the preparation of adhesive composition S-1. 1 part, 1.5 parts of acrylic oligomer A, and 0.5 part of nonionic surfactant A1 (polyoxyethylene lauryl ether, trade name "Emulgen 104P", manufactured by Kao Corporation) and stirred uniformly. By mixing, a solvent-based adhesive composition S-2 was prepared.
　（粘着剤組成物Ｓ－３）
　粘着剤組成物Ｓ－１の調製において得られたアクリル系ポリマーＡを含有する溶液の固形分１００部に対して、イソシアネート系架橋剤（商品名「タケネートＤ１０１Ｅ」、三井化学社製）０．１部と、アクリル系オリゴマーＡを１．５部と、ノニオン性界面活性剤Ａ２（グリセロールモノオレエート、商品名「レオドールＭＯ－６０」、花王社製）０．５部とを配合し、均一に攪拌混合して、溶剤型粘着剤組成物Ｓ－３を調製した。 (Adhesive composition S-3)
0.1 isocyanate-based crosslinking agent (trade name "Takenate D101E", manufactured by Mitsui Chemicals, Inc.) per 100 parts of solid content of the solution containing acrylic polymer A obtained in the preparation of adhesive composition S-1. 1.5 parts of acrylic oligomer A, and 0.5 part of nonionic surfactant A2 (glycerol monooleate, trade name "Rheodol MO-60", manufactured by Kao Corporation) were mixed uniformly. By stirring and mixing, a solvent-based adhesive composition S-3 was prepared.
　（粘着剤組成物Ｓ－４）
　粘着剤組成物Ｓ－１の調製において得られたアクリル系ポリマーＡを含有する溶液の固形分１００部に対して、イソシアネート系架橋剤（商品名「タケネートＤ１０１Ｅ」、三井化学社製）０．１部と、アクリル系オリゴマーＡを１．５部と、ノニオン性界面活性剤Ａ４（ポリオキシエチレンアルキルエーテル、商品名「ナロアクティーＩＤ－６０」、三洋化成社製）０．３部とを配合し、均一に攪拌混合して、溶剤型粘着剤組成物Ｓ－４を調製した。 (Adhesive composition S-4)
0.1 isocyanate-based crosslinking agent (trade name "Takenate D101E", manufactured by Mitsui Chemicals, Inc.) per 100 parts of solid content of the solution containing acrylic polymer A obtained in the preparation of adhesive composition S-1. part, 1.5 parts of acrylic oligomer A, and 0.3 part of nonionic surfactant A4 (polyoxyethylene alkyl ether, trade name "NAROACTY ID-60", manufactured by Sanyo Chemical Co., Ltd.). , and were uniformly stirred and mixed to prepare a solvent-type adhesive composition S-4.
　（粘着剤組成物Ｓ－５）
　粘着剤組成物Ｓ－１の調製において得られたアクリル系ポリマーＡを含有する溶液の固形分１００部に対して、イソシアネート系架橋剤（商品名「タケネートＤ１０１Ｅ」、三井化学社製）０．５部と、アクリル系オリゴマーＡを１．５部と、ノニオン性界面活性剤Ａ３（ポリオキシエチレンポリオキシプロピレンアルキルエーテル、商品名「エマルゲンＭＳ－１１０」、花王社製）０．５部とを配合し、均一に攪拌混合して、溶剤型粘着剤組成物Ｓ－５を調製した。 (Adhesive composition S-5)
0.5 parts of an isocyanate-based crosslinking agent (trade name "Takenate D101E", manufactured by Mitsui Chemicals, Inc.) per 100 parts of solid content of the solution containing acrylic polymer A obtained in the preparation of adhesive composition S-1. 1.5 parts of acrylic oligomer A, and 0.5 part of nonionic surfactant A3 (polyoxyethylene polyoxypropylene alkyl ether, trade name "Emulgen MS-110", manufactured by Kao Corporation). The mixture was stirred and mixed uniformly to prepare a solvent-based adhesive composition S-5.
　（粘着剤組成物Ｕ－１）
　ラウリルアクリレート（ＬＡ）、２－エチルヘキシルアクリレート（２ＥＨＡ）、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）、４－ヒドロキシブチルアクリレート（４ＨＢＡ）、光重合開始剤Ａ１（商品名「イルガキュア１８４」、チバスペシャルティケミカルズ社製）および光重合開始剤Ａ２（商品名「イルガキュア６５１」、チバスペシャルティケミカルズ社製）を６０／２２／１０／８／０．１／０．１の重量比で混合したものを４つ口フラスコに投入し、窒素雰囲気下で粘度（ＢＨ粘度計、Ｎｏ．５ローター、１０ｒｐｍ、測定温度３０℃）が約１５Ｐａ・ｓになるまで紫外線を照射して光重合させることにより、上記モノマー混合物の部分重合物を含むモノマーシロップを調製した。
　このモノマーシロップ１００部に、架橋剤Ｃ２として１，６－ヘキサンジオールジアクリレート（ＨＤＤＡ）０．０８部、アクリル系オリゴマーＢを２部、２ＥＨＡ３７部およびノニオン性界面活性剤Ａ５（ポリエチレングリコールモノラウレート、花王社製のポリオキシエチレン脂肪酸エステル、商品名「エマノーン１１１２」、エチレンオキサイド付加モル数１２）０．３部を添加し、均一に混合して、紫外線硬化型粘着剤組成物Ｕ－１を調製した。 (Adhesive composition U-1)
Lauryl acrylate (LA), 2-ethylhexyl acrylate (2EHA), N-vinyl-2-pyrrolidone (NVP), 4-hydroxybutyl acrylate (4HBA), photoinitiator A1 (trade name "Irgacure 184", Ciba Specialty Chemicals) (manufactured by Ciba Specialty Chemicals) and photopolymerization initiator A2 (trade name "Irgacure 651", manufactured by Ciba Specialty Chemicals) in a weight ratio of 60/22/10/8/0.1/0.1. The monomer mixture was placed in a flask and photopolymerized by irradiating it with ultraviolet rays under a nitrogen atmosphere until the viscosity (BH viscometer, No. 5 rotor, 10 rpm, measurement temperature 30°C) reached approximately 15 Pa·s. A monomer syrup containing a partially polymerized product was prepared.
To 100 parts of this monomer syrup, 0.08 part of 1,6-hexanediol diacrylate (HDDA) as crosslinking agent C2, 2 parts of acrylic oligomer B, 37 parts of 2EHA, and nonionic surfactant A5 (polyethylene glycol monolaurate , polyoxyethylene fatty acid ester manufactured by Kao Corporation, trade name "Emanone 1112", ethylene oxide addition mole number 12) 0.3 parts were added and mixed uniformly to form UV curable adhesive composition U-1. Prepared.
　（粘着剤組成物Ｕ－２）
　ラウリルアクリレート（ＬＡ）、２－エチルヘキシルアクリレート（２ＥＨＡ）、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）、４－ヒドロキシブチルアクリレート（４ＨＢＡ）、光重合開始剤Ａ１（商品名「イルガキュア１８４」、チバスペシャルティケミカルズ社製）および光重合開始剤Ａ２（商品名「イルガキュア６５１」、チバスペシャルティケミカルズ社製）を３６．４／６０／２．５／１／０．０５／０．０５の重量比で混合したものを４つ口フラスコに投入し、窒素雰囲気下で粘度（ＢＨ粘度計、Ｎｏ．５ローター、１０ｒｐｍ、測定温度３０℃）が約１５Ｐａ・ｓになるまで紫外線を照射して光重合させることにより、上記モノマー混合物の部分重合物を含むモノマーシロップを調製した。
　このモノマーシロップ１００部に、架橋剤Ｃ２として１，６－ヘキサンジオールジアクリレート（ＨＤＤＡ）０．０８部、光重合開始剤Ａ２（商品名「イルガキュア６５１」、チバスペシャルティケミカルズ社製）０．１部、アクリル系オリゴマーＢを２部およびノニオン性界面活性剤Ａ６（ポリオキシエチレンソルビタンモノラウレート、商品名：レオドールＴＷ－Ｌ１０６、花王社製）０．３部を添加し、均一に混合して、紫外線硬化型粘着剤組成物Ｕ－２を調製した。 (Adhesive composition U-2)
Lauryl acrylate (LA), 2-ethylhexyl acrylate (2EHA), N-vinyl-2-pyrrolidone (NVP), 4-hydroxybutyl acrylate (4HBA), photoinitiator A1 (trade name "Irgacure 184", Ciba Specialty Chemicals) (manufactured by Ciba Specialty Chemicals) and photopolymerization initiator A2 (trade name "Irgacure 651", manufactured by Ciba Specialty Chemicals) in a weight ratio of 36.4/60/2.5/1/0.05/0.05. was placed in a four-necked flask and photopolymerized by irradiating it with ultraviolet rays under a nitrogen atmosphere until the viscosity (BH viscometer, No. 5 rotor, 10 rpm, measurement temperature 30°C) reached approximately 15 Pa·s. A monomer syrup containing a partial polymer of the above monomer mixture was prepared.
To 100 parts of this monomer syrup, 0.08 part of 1,6-hexanediol diacrylate (HDDA) as crosslinking agent C2 and 0.1 part of photopolymerization initiator A2 (trade name "Irgacure 651", manufactured by Ciba Specialty Chemicals) , 2 parts of acrylic oligomer B and 0.3 part of nonionic surfactant A6 (polyoxyethylene sorbitan monolaurate, trade name: Rheodol TW-L106, manufactured by Kao Corporation) were added and mixed uniformly. An ultraviolet curable adhesive composition U-2 was prepared.
　（粘着剤組成物Ｕ－３）
　ラウリルアクリレート（ＬＡ）、２－エチルヘキシルアクリレート（２ＥＨＡ）、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）、４－ヒドロキシブチルアクリレート（４ＨＢＡ）、光重合開始剤Ａ１（商品名「イルガキュア１８４」、チバスペシャルティケミカルズ社製）および光重合開始剤Ａ２（商品名「イルガキュア６５１」、チバスペシャルティケミカルズ社製）を３８．５／６０／２．５／８／０．０５／０．０５の重量比で混合したものを４つ口フラスコに投入し、窒素雰囲気下で粘度（ＢＨ粘度計、Ｎｏ．５ローター、１０ｒｐｍ、測定温度３０℃）が約１５Ｐａ・ｓになるまで紫外線を照射して光重合させることにより、上記モノマー混合物の部分重合物を含むモノマーシロップを調製した。
　このモノマーシロップ１００部に、ＨＤＤＡ０．０８部、光重合開始剤Ａ２（商品名：イルガキュア６５１、チバスペシャルティケミカルズ社製）０．１部、アクリル系オリゴマーＢを２部およびノニオン性界面活性剤Ａ６（ポリオキシエチレンソルビタンモノラウレート、商品名：レオドールＴＷ－Ｌ１０６、花王社製）０．３部を添加し、均一に混合して、紫外線硬化型粘着剤組成物Ｕ－３を調製した。 (Adhesive composition U-3)
Lauryl acrylate (LA), 2-ethylhexyl acrylate (2EHA), N-vinyl-2-pyrrolidone (NVP), 4-hydroxybutyl acrylate (4HBA), photoinitiator A1 (trade name "Irgacure 184", Ciba Specialty Chemicals) (manufactured by Ciba Specialty Chemicals) and photopolymerization initiator A2 (trade name "Irgacure 651", manufactured by Ciba Specialty Chemicals) in a weight ratio of 38.5/60/2.5/8/0.05/0.05. was placed in a four-necked flask and photopolymerized by irradiating it with ultraviolet rays under a nitrogen atmosphere until the viscosity (BH viscometer, No. 5 rotor, 10 rpm, measurement temperature 30°C) reached approximately 15 Pa·s. A monomer syrup containing a partial polymer of the above monomer mixture was prepared.
To 100 parts of this monomer syrup, 0.08 part of HDDA, 0.1 part of photoinitiator A2 (trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals), 2 parts of acrylic oligomer B, and nonionic surfactant A6 ( 0.3 part of polyoxyethylene sorbitan monolaurate (trade name: Rheodol TW-L106, manufactured by Kao Corporation) was added and mixed uniformly to prepare an ultraviolet curable adhesive composition U-3.
　（粘着剤組成物Ｓ－６）
　冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器に、２－エチルヘキシルアクリレート（２ＥＨＡ）６３部、メチルメタクリレート（ＭＭＡ）９部、２－ヒドロキシエチルアクリレート（ＨＥＡ）１３部、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）１５部を、熱重合開始剤としての２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２部および重合溶媒としての酢酸エチルとともに投入し、窒素ガス気流下において６０℃で４時間反応させることにより、Ｍｗが６０万～１００万のアクリル系ポリマーＥを含有する溶液（固形分濃度３０％）を得た。このアクリル系ポリマーＥを含有する溶液の固形分１００部に対して、イソシアネート系架橋剤（商品名「タケネートＤ１０１Ｅ」、三井化学社製）０．３部と、アクリル系オリゴマーＡを１．５部と、ノニオン性界面活性剤Ａ２（グリセロールモノオレエート、商品名「レオドールＭＯ－６０」、花王社製）０．３部とを配合し、均一に攪拌混合して、溶剤型粘着剤組成物Ｓ－６を調製した。 (Adhesive composition S-6)
In a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirring device, 63 parts of 2-ethylhexyl acrylate (2EHA), 9 parts of methyl methacrylate (MMA), 13 parts of 2-hydroxyethyl acrylate (HEA), and N- 15 parts of vinyl-2-pyrrolidone (NVP) was added together with 0.2 parts of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator and ethyl acetate as a polymerization solvent, and a nitrogen gas stream was added. By reacting at 60° C. for 4 hours under the conditions below, a solution (solid content concentration 30%) containing acrylic polymer E having an Mw of 600,000 to 1,000,000 was obtained. For 100 parts of the solid content of the solution containing this acrylic polymer E, 0.3 parts of an isocyanate crosslinking agent (trade name "Takenate D101E", manufactured by Mitsui Chemicals) and 1.5 parts of acrylic oligomer A. and 0.3 part of nonionic surfactant A2 (glycerol monooleate, trade name "Rheodol MO-60", manufactured by Kao Corporation) and were uniformly stirred and mixed to form a solvent-based adhesive composition S. -6 was prepared.
　（粘着剤組成物Ｓ－７）
　冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器に、２－エチルヘキシルアクリレート（２ＥＨＡ）７２部、メチルメタクリレート（ＭＭＡ）１部、２－ヒドロキシエチルアクリレート（ＨＥＡ）１３部、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）１４部を、熱重合開始剤としての２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２部、連鎖移動剤としてα－チオグリセロール（ＴＧＲ）０．１２部および重合溶媒としての酢酸エチルとともに投入し、窒素ガス気流下において６０℃で４時間反応させることにより、Ｍｗが６０万～１００万のアクリル系ポリマーＦを含有する溶液（固形分濃度３０％）を得た。このアクリル系ポリマーＦを含有する溶液の固形分１００部に対して、イソシアネート系架橋剤（商品名「タケネートＤ１０１Ｅ」、三井化学社製）０．３部と、ノニオン性界面活性剤Ａ７（ポリオキシエチレンソルビタンモノラウレート、商品名「レオドールＴＷ－Ｌ１２０」、花王社製）０．１部とを配合し、均一に攪拌混合して、溶剤型粘着剤組成物Ｓ－７を調製した。 (Adhesive composition S-7)
In a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirring device, 72 parts of 2-ethylhexyl acrylate (2EHA), 1 part of methyl methacrylate (MMA), 13 parts of 2-hydroxyethyl acrylate (HEA), and N- 14 parts of vinyl-2-pyrrolidone (NVP), 0.2 parts of 2,2'-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator, and 0.2 parts of α-thioglycerol (TGR) as a chain transfer agent. A solution containing acrylic polymer F with an Mw of 600,000 to 1,000,000 (solid content concentration 30%) was prepared by adding 12 parts of acrylic polymer F and ethyl acetate as a polymerization solvent and reacting at 60°C for 4 hours under a nitrogen gas stream. ) was obtained. To 100 parts of the solid content of the solution containing this acrylic polymer F, 0.3 parts of an isocyanate crosslinking agent (trade name "Takenate D101E", manufactured by Mitsui Chemicals) and a nonionic surfactant A7 (polyoxy 0.1 part of ethylene sorbitan monolaurate (trade name "Rheodol TW-L120", manufactured by Kao Corporation) was blended and uniformly stirred and mixed to prepare a solvent-based adhesive composition S-7.
　（粘着剤組成物Ｅ－１）
　２－エチルヘキシルアクリレート（２ＥＨＡ）４９部、ｎ－ブチルメタクリレート（ＢＭＡ）４９部、アクリル酸（ＡＡ）２部および乳化剤としてアニオン系乳化剤（第一工業製薬社製、アクアロンＢＣ２０２０）２部を、イオン交換水１００部中で混合して乳化することにより、モノマー混合物の水性エマルション（モノマーエマルション）を調製した。
　冷却管、窒素導入管、温度計および攪拌装置を備えた反応容器に上記モノマーエマルションを入れ、窒素ガスを導入しながら室温にて１時間以上攪拌した。次いで、系を６０℃に昇温し、重合開始剤として２，２’－アゾビス［Ｎ－（２－カルボキシエチル）－２－メチルプロピオンアミジン］ハイドレート（和光純薬工業社製、ＶＡ－０５７）０．１部を投入し、６０℃で６時間反応させて、アクリル系ポリマーＧの水分散液を得た。
　得られたアクリル系ポリマーＧの水分散液の固形分１００部に対して、オキサゾリン系架橋剤Ｃ４（日本触媒社製、エポクロスＷＳ－５００）を２部添加した。さらに、ｐＨ調整剤としての１０％アンモニア水および増粘剤としてのポリアクリル酸（不揮発分３６％の水溶液）を使用してｐＨ約７．５、粘度約９Ｐａ・ｓに調整することにより、エマルション型粘着剤組成物Ｅ－１を調製した。 (Adhesive composition E-1)
49 parts of 2-ethylhexyl acrylate (2EHA), 49 parts of n-butyl methacrylate (BMA), 2 parts of acrylic acid (AA), and 2 parts of an anionic emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Aqualon BC2020) as an emulsifier were subjected to ion exchange. An aqueous emulsion (monomer emulsion) of the monomer mixture was prepared by mixing and emulsifying in 100 parts of water.
The above monomer emulsion was placed in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, and stirred at room temperature for over 1 hour while introducing nitrogen gas. Next, the temperature of the system was raised to 60°C, and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057) was added as a polymerization initiator. ) and reacted at 60° C. for 6 hours to obtain an aqueous dispersion of acrylic polymer G.
To 100 parts of the solid content of the obtained aqueous dispersion of acrylic polymer G, 2 parts of oxazoline crosslinking agent C4 (manufactured by Nippon Shokubai Co., Ltd., Epocross WS-500) was added. Furthermore, by adjusting the pH to approximately 7.5 and the viscosity to approximately 9 Pa·s using 10% ammonia water as a pH adjuster and polyacrylic acid (an aqueous solution with a nonvolatile content of 36%) as a thickener, the emulsion was A type adhesive composition E-1 was prepared.
　（粘着剤組成物Ｕ－４）
　ｎ－ブチルメタクリレート（ＢＡ）、シクロヘキシルアクリレート（ＣＨＡ）、４－ヒドロキシブチルアクリレート（４ＨＢＡ）、光重合開始剤Ａ１（商品名「イルガキュア１８４」、チバスペシャルティケミカルズ社製）および光重合開始剤Ａ２（商品名「イルガキュア６５１」、チバスペシャルティケミカルズ社製）を６７／１４／１９／０．０９／０．０９の重量比で混合したものを４つ口フラスコに投入し、窒素雰囲気下で粘度（ＢＨ粘度計、Ｎｏ．５ローター、１０ｒｐｍ、測定温度３０℃）が約１５Ｐａ・ｓになるまで紫外線を照射して光重合させることにより、上記モノマー混合物の部分重合物を含むモノマーシロップを調製した。
　このモノマーシロップ１００部に、架橋剤Ｃ３（多官能モノマー）としてジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）０．１２部、２－ヒドロキシエチルアクリレート（ＨＥＡ）９部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）８部を添加し、均一に混合して、紫外線硬化型粘着剤組成物Ｕ－４を調製した。 (Adhesive composition U-4)
n-butyl methacrylate (BA), cyclohexyl acrylate (CHA), 4-hydroxybutyl acrylate (4HBA), photoinitiator A1 (product name "Irgacure 184", manufactured by Ciba Specialty Chemicals), and photoinitiator A2 (product name A mixture of Irgacure 651 (manufactured by Ciba Specialty Chemicals) in a weight ratio of 67/14/19/0.09/0.09 was put into a four-necked flask, and the viscosity (BH viscosity A monomer syrup containing a partial polymer of the monomer mixture was prepared by photopolymerizing the mixture by irradiating it with ultraviolet rays until the temperature reached approximately 15 Pa·s.
To 100 parts of this monomer syrup, 0.12 parts of dipentaerythritol hexaacrylate (DPHA), 9 parts of 2-hydroxyethyl acrylate (HEA), and 8 parts of 4-hydroxybutyl acrylate (4HBA) are added as crosslinking agent C3 (polyfunctional monomer). were added and mixed uniformly to prepare ultraviolet curable adhesive composition U-4.
　なお、上記の粘着剤組成物の調製において用いられたアクリル系オリゴマーＡおよびアクリル系オリゴマーＢとしては、以下の方法で合成されたものを用いた。 Note that acrylic oligomer A and acrylic oligomer B used in the preparation of the above adhesive composition were synthesized by the following method.
　［アクリル系オリゴマーＡの合成］
　トルエン１００部、シクロヘキシルメタクリレート（ＣＨＭＡ）（三菱ケミカル社製）９５部、アクリル酸（ＡＡ）５部、および連鎖移動剤としてα－チオグリセロール３．５部を４つ口フラスコに投入した。そして、７０℃にて窒素雰囲気下で１時間攪拌した後、熱重合開始剤としてＡＩＢＮ０．２部を投入し、７０℃で２時間反応させ、続いて８０℃で２時間反応させた。その後、反応液を１３０℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去することにより、固形状のアクリル系オリゴマーＡを得た。このアクリル系オリゴマーＡのＴｇは６７℃であり、Ｍｗは３５００であった。 [Synthesis of acrylic oligomer A]
100 parts of toluene, 95 parts of cyclohexyl methacrylate (CHMA) (manufactured by Mitsubishi Chemical Corporation), 5 parts of acrylic acid (AA), and 3.5 parts of α-thioglycerol as a chain transfer agent were charged into a four-necked flask. After stirring at 70°C for 1 hour under a nitrogen atmosphere, 0.2 parts of AIBN was added as a thermal polymerization initiator, and the mixture was reacted at 70°C for 2 hours, and then at 80°C for 2 hours. Thereafter, the reaction solution was placed in an atmosphere at a temperature of 130° C., and toluene, a chain transfer agent, and unreacted monomers were removed by drying to obtain a solid acrylic oligomer A. This acrylic oligomer A had a Tg of 67° C. and a Mw of 3,500.
　［アクリル系オリゴマーＢの合成］
　トルエン１００部、ジシクロペンタニルメタクリレート（ＤＣＰＭＡ）（商品名：ＦＡ－５１３Ｍ、日立化成工業株式会社製）６０部、メチルメタクリレート（ＭＭＡ）４０部、および連鎖移動剤としてα－チオグリセロール３．５部を４つ口フラスコに投入した。そして、７０℃にて窒素雰囲気下で１時間攪拌した後、熱重合開始剤としてＡＩＢＮ０．２部を投入し、７０℃で２時間反応させ、続いて８０℃で２時間反応させた。その後、反応液を１３０℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去することにより、固形状のアクリル系オリゴマーＢを得た。このアクリル系オリゴマーＢのＴｇは１４４℃であり、Ｍｗは４３００であった。 [Synthesis of acrylic oligomer B]
100 parts of toluene, 60 parts of dicyclopentanyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 40 parts of methyl methacrylate (MMA), and 3.5 parts of α-thioglycerol as a chain transfer agent. of the mixture was placed in a four-necked flask. After stirring at 70°C for 1 hour under a nitrogen atmosphere, 0.2 parts of AIBN was added as a thermal polymerization initiator, and the mixture was reacted at 70°C for 2 hours, and then at 80°C for 2 hours. Thereafter, the reaction solution was placed in an atmosphere at a temperature of 130° C., and toluene, a chain transfer agent, and unreacted monomers were removed by drying to obtain a solid acrylic oligomer B. This acrylic oligomer B had a Tg of 144° C. and a Mw of 4,300.
＜粘着シートの作製＞
　（例１）
　ポリエステルフィルムの片面が剥離面となっている厚さ３８μｍの剥離フィルムＲ１（三菱樹脂株式会社、ＭＲＦ＃３８）に粘着剤組成物Ｓ－１を塗布し、１３０℃で５分間乾燥させて、厚さ２５μｍの粘着剤層を形成した。剥離フィルムＲ１上の粘着剤層に、コロナ処理された厚さ５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムを貼り合わせることにより、本例に係る粘着シートを得た。 <Preparation of adhesive sheet>
(Example 1)
Adhesive composition S-1 was applied to a 38 μm thick release film R1 (Mitsubishi Plastics Co., Ltd., MRF#38) with one side of the polyester film serving as a release surface, and dried at 130°C for 5 minutes to reduce the thickness. An adhesive layer having a thickness of 25 μm was formed. A pressure-sensitive adhesive sheet according to this example was obtained by laminating a corona-treated polyethylene terephthalate (PET) film with a thickness of 50 μm to the pressure-sensitive adhesive layer on the release film R1.
　（例２）
　粘着剤組成物Ｓ－１に代えて粘着剤組成物Ｓ－２を用いた他は例１と同様にして、本例に係る粘着シートを得た。 (Example 2)
A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-2 was used instead of pressure-sensitive adhesive composition S-1.
　（例３）
　粘着剤組成物Ｓ－１に代えて粘着剤組成物Ｓ－３を用いた他は例１と同様にして、本例に係る粘着シートを得た。 (Example 3)
A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-3 was used instead of pressure-sensitive adhesive composition S-1.
　（例４）
　粘着剤組成物Ｓ－１に代えて粘着剤組成物Ｓ－４を用いた他は例１と同様にして、本例に係る粘着シートを得た。 (Example 4)
A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-4 was used instead of pressure-sensitive adhesive composition S-1.
　（例５）
　粘着剤組成物Ｓ－１に代えて粘着剤組成物Ｓ－５を用いた他は例１と同様にして、本例に係る粘着シートを得た。 (Example 5)
A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-5 was used instead of pressure-sensitive adhesive composition S-1.
　（例６）
　ポリエステルフィルムの片面が剥離面となっている厚さ３８μｍの剥離フィルムＲ１（三菱樹脂社製、製品名「ＭＲＦ＃３８」）に粘着剤組成物Ｕ－１を塗布し、ポリエステルフィルムの片面が剥離面となっている厚さ３８μｍの剥離フィルムＲ２（三菱樹脂社製、製品名「ＭＲＥ＃３８」）を被せて空気を遮断し、紫外線を照射して硬化させることにより、厚さ２５μｍの粘着剤層を形成した。紫外線の照射は、ブラックライトランプを用いて、照度４ｍＷ／ｃｍ２（ピーク感度波長約３５０ｎｍの工業用ＵＶチェッカー（トプコン社製、商品名「ＵＶＲ－Ｔ１」）により測定）で１８０秒照射する条件で行った。次いで、粘着剤層を覆う剥離フィルムＲ２を剥がし、コロナ処理された厚さ５０μｍのＰＥＴフィルムを貼り合わせることにより、本例に係る粘着シートを得た。 (Example 6)
Adhesive composition U-1 was applied to a 38 μm thick release film R1 (manufactured by Mitsubishi Plastics Co., Ltd., product name "MRF#38"), with one side of the polyester film being the release surface, and one side of the polyester film was released. By covering the surface with a 38 μm thick release film R2 (manufactured by Mitsubishi Plastics Co., Ltd., product name “MRE #38”) to block air, and curing it by irradiating it with ultraviolet rays, the 25 μm thick adhesive is released. formed a layer. The ultraviolet rays were irradiated using a black light lamp at an illuminance of 4 mW/cm 2 (measured with an industrial UV checker (manufactured by Topcon, trade name "UVR-T1") with a peak sensitivity wavelength of approximately 350 nm) for 180 seconds. I went there. Next, the release film R2 covering the adhesive layer was peeled off, and a corona-treated PET film having a thickness of 50 μm was bonded to the adhesive sheet, thereby obtaining an adhesive sheet according to this example.
　（例７）
　粘着剤組成物Ｕ－１に代えて粘着剤組成物Ｕ－２を用いた他は例６と同様にして、本例に係る粘着シートを得た。 (Example 7)
A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 6, except that pressure-sensitive adhesive composition U-2 was used instead of pressure-sensitive adhesive composition U-1.
　（例８）
　粘着剤組成物Ｕ－１に代えて粘着剤組成物Ｕ－３を用いた他は例６と同様にして、本例に係る粘着シートを得た。 (Example 8)
A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 6, except that pressure-sensitive adhesive composition U-3 was used instead of pressure-sensitive adhesive composition U-1.
　（例９）
　粘着剤組成物Ｓ－１に代えて粘着剤組成物Ｓ－６を用いた他は例１と同様にして、本例に係る粘着シートを得た。 (Example 9)
A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-6 was used instead of pressure-sensitive adhesive composition S-1.
　（例１０）
　粘着剤組成物Ｓ－１に代えて粘着剤組成物Ｓ－７を用いた他は例１と同様にして、本例に係る粘着シートを得た。 (Example 10)
A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that pressure-sensitive adhesive composition S-7 was used instead of pressure-sensitive adhesive composition S-1.
　（例１１）
　剥離フィルムＲ１（三菱樹脂株式会社、ＭＲＦ＃３８）に粘着剤組成物Ｅ－１を塗布し、１２０℃で３分間乾燥させて、厚さ２５μｍの粘着剤層を形成した。剥離フィルムＲ１上の粘着剤層に、コロナ処理された厚さ５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムを貼り合わせることにより、本例に係る粘着シートを得た。 (Example 11)
Adhesive composition E-1 was applied to release film R1 (Mitsubishi Plastics Co., Ltd., MRF #38) and dried at 120° C. for 3 minutes to form an adhesive layer with a thickness of 25 μm. A pressure-sensitive adhesive sheet according to this example was obtained by laminating a corona-treated polyethylene terephthalate (PET) film with a thickness of 50 μm to the pressure-sensitive adhesive layer on the release film R1.
　（例１２）
　粘着剤組成物Ｕ－１に代えて粘着剤組成物Ｕ－４を用いた他は例６と同様にして、本例に係る粘着シートを得た。 (Example 12)
A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 6, except that pressure-sensitive adhesive composition U-4 was used instead of pressure-sensitive adhesive composition U-1.
　各例の粘着シートについて、上述する測定方法に基づいて、ステンレス鋼板に対する粘着力Ｎ０ＳＵＳ、エタノール剥離力Ｎ１ＳＵＳ、粘着力低減距離ＲＳＵＳを測定した。また、各例の粘着シートについて、上述する測定方法に基づいて、ガラス板に対する粘着力Ｎ０ＧＬＡ、エタノール剥離力Ｎ１ＧＬＡ、粘着力低減距離ＲＧＬＡを測定した。
　得られた粘着力低減距離ＲＳＵＳが３０ｍｍ以上であった場合は、粘着力低減持続性（対ＳＵＳ）：Ｇ（良好）とし、粘着力低減距離ＲＳＵＳが３０ｍｍ未満であった場合は、粘着力低減持続性（対ＳＵＳ）：Ｐ（不良）と評価した。また、得られた粘着力低減距離ＲＧＬＡが３０ｍｍ以上であった場合は、粘着力低減持続性（対ガラス）：Ｇ（良好）とし、粘着力低減距離ＲＧＬＡが３０ｍｍ未満であった場合は、粘着力低減持続性（対ガラス）：Ｐ（不良）と評価した。得られた結果を表１の該当欄に示す。 For each example of the adhesive sheet, the adhesive force N0 SUS to the stainless steel plate, the ethanol peeling force N1 SUS , and the adhesive force reduction distance R SUS were measured based on the measurement method described above. Further, for each example of the adhesive sheet, the adhesive force N0 GLA to the glass plate, the ethanol peeling force N1 GLA , and the adhesive force reduction distance R GLA were measured based on the measurement method described above.
If the obtained adhesive strength reduction distance R SUS is 30 mm or more, the persistence of adhesive strength reduction (vs. SUS): G (good), and if the adhesive strength reduction distance R SUS is less than 30 mm, the adhesive strength is Force reduction durability (vs. SUS): Rated P (poor). In addition, if the obtained adhesive force reduction distance R GLA is 30 mm or more, the persistence of adhesive force reduction (on glass) is considered as G (good), and if the obtained adhesive force reduction distance R GLA is less than 30 mm, , Adhesive force reduction persistence (to glass): Rated P (poor). The obtained results are shown in the relevant column of Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示される結果から明らかなように、被着体としてステンレス鋼板を用いた場合と、ガラス板を用いた場合のいずれにおいても、粘着シートと被着体との界面にエタノールを供給し、上記界面にエタノールが存在する状態で、上記粘着シートの剥離前線を剥離進行方向に移動させてエタノールの上記界面への進入を進行させたことにより、例１～１２の粘着シートの粘着力（剥離力）はいずれも好適に低減した。特に、例１～例８の粘着シートは、エタノール剥離力Ｎ１ＳＵＳが０．５Ｎ／２０ｍｍ以下であり、粘着力Ｎ０ＳＵＳが３．０Ｎ／２０ｍｍ以上であり、かつ、粘着力低減持続性（対ＳＵＳ）が良好であった。また、例１～８の粘着シートは、エタノール剥離力Ｎ１ＧＬＡが０．５Ｎ／２０ｍｍ以下であり、粘着力Ｎ０ＧＬＡが３．０Ｎ／２０ｍｍ以上であり、かつ、粘着力低減持続性（対ガラス）が良好であった。ここに開示される剥離方法を、例１～８の粘着シートに用いると、被着体に対する接着力と再剥離性とを特に好適に両立させることができることが確かめられた。 As is clear from the results shown in Table 1, in both cases where a stainless steel plate is used as the adherend and a glass plate is used as the adherend, ethanol is supplied to the interface between the adhesive sheet and the adherend, In the presence of ethanol at the interface, the peeling front of the adhesive sheet was moved in the peeling direction to allow ethanol to enter the interface. force) were all suitably reduced. In particular, the adhesive sheets of Examples 1 to 8 have an ethanol peel force N1 SUS of 0.5 N/20 mm or less, an adhesive force N0 SUS of 3.0 N/20 mm or more, and a long-lasting adhesive force reduction ( SUS) was good. In addition, the adhesive sheets of Examples 1 to 8 have an ethanol peeling force N1 GLA of 0.5 N/20 mm or less, an adhesive force N0 GLA of 3.0 N/20 mm or more, and a long-lasting adhesive force reduction (toward glass). ) were good. It has been confirmed that when the peeling method disclosed herein is applied to the pressure-sensitive adhesive sheets of Examples 1 to 8, it is possible to particularly suitably achieve both adhesion to the adherend and removability.
　以上、本発明の具体例を詳細に説明したが、これらは例示にすぎず、請求の範囲を限定するものではない。請求の範囲に記載の技術には、以上に例示した具体例を様々に変形、変更したものが含まれる。 Although specific examples of the present invention have been described above in detail, these are merely illustrative and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes to the specific examples illustrated above.
　　１　　粘着剤（粘着シート）
　　２０　支持体
　　３０　剥離ライナー
　　５０　剥離ライナー付き粘着シート

  1 Adhesive (adhesive sheet)
20 Support 30 Release liner 50 Adhesive sheet with release liner

Claims (9)

  1. 　被着体に貼り付けられた粘着シートの剥離方法であって、
    　前記粘着シートに粘着力低減手段を適用することを含み、
    　前記粘着力低減手段は、
    　　前記粘着シートの前記被着体からの剥離前線における前記被着体と前記粘着シートとの界面にアルコール液を供給すること、および
    　　前記界面に前記アルコール液が存在する状態で、前記粘着シートの前記剥離前線を剥離進行方向に移動させ、該剥離前線の移動に追随して前記アルコール液の前記界面への進入を進行させること、を含む剥離方法。     A method for peeling an adhesive sheet stuck to an adherend, the method comprising:
    applying an adhesive force reducing means to the adhesive sheet,
    The adhesive force reducing means is
    supplying an alcohol solution to an interface between the adherend and the adhesive sheet at a peeling front of the adhesive sheet from the adherend; A peeling method comprising moving a peeling front in a peeling advancing direction and allowing the alcohol solution to enter the interface following the movement of the peeling front.
  2. 　前記粘着シートは、被着体としてのステンレス鋼板に前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、エタノール剥離力Ｎ１ＳＵＳが、０．５Ｎ／２０ｍｍ以下である、請求項１に記載の剥離方法。 The adhesive sheet is prepared by attaching the adhesive sheet to a stainless steel plate as an adherend, and after one day at room temperature, dropping 2 μL of ethanol onto the adherend, and applying the ethanol to the interface between the adhesive sheet and the adherend. After entering one end, tensile test was performed using a tensile tester at a test temperature of 23°C according to 10.4.1 Method 1 of JIS Z0237:2009: 180° peel adhesion to the test plate. The peeling method according to claim 1, wherein the ethanol peeling force N1 SUS measured at a speed of 300 mm/min and a peeling angle of 180 degrees is 0.5 N/20 mm or less.
  3. 　前記粘着シートは、被着体としてのステンレス鋼板に、幅２０ｍｍの長方形状にカットされた前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＳＵＳが３０ｍｍ以上である、請求項１または２に記載の剥離方法。 The adhesive sheet is prepared by pasting the adhesive sheet cut into a rectangular shape with a width of 20 mm on a stainless steel plate as an adherend, and after one day at room temperature, dropping 2 μL of ethanol onto the adherend. After entering one end of the interface between the adhesive sheet and the adherend, follow JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, at a test temperature of 23 The peeling method according to claim 1 or 2, wherein the adhesive force reduction distance R SUS is 30 mm or more, measured using a tensile tester at 300 mm/min at a tensile speed of 180 degrees at a peeling angle of 180 degrees.
  4. 　前記粘着シートは、被着体としてのステンレス鋼板に前記粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＳＵＳが３．０Ｎ／２０ｍｍ以上である、請求項１または２に記載の剥離方法。 The peeling method according to claim 1 or 2, wherein the adhesive sheet has an adhesive force N0 SUS of 3.0 N/20 mm or more after one day at room temperature after attaching the adhesive sheet to a stainless steel plate as an adherend.
  5. 　前記粘着シートは、
    　被着体としてのステンレス鋼板に前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定されるエタノール剥離力Ｎ１ＳＵＳ、および、被着体としてのステンレス鋼板に前記粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＳＵＳと、から下記式：粘着力低減率ＳＳＵＳ［％］＝（１－（エタノール剥離力Ｎ１ＳＵＳ／粘着力Ｎ０ＳＵＳ））×１００；で求められる粘着力低減率ＳＳＵＳが５０％以上であり、
    　かつ、被着体としてのステンレス鋼板に、幅２０ｍｍの長方形状にカットされた前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＳＵＳが３０ｍｍ以上である、請求項１または２に記載の剥離方法。     The adhesive sheet is
    After one day at room temperature after pasting the adhesive sheet on a stainless steel plate as an adherend, 2 μL of ethanol is dropped onto the adherend, and the ethanol is allowed to enter one end of the interface between the adhesive sheet and the adherend. After that, according to JIS Z0237:2009 10.4.1 Method 1: 180° peel adhesion force to the test plate, specifically, using a tensile tester at a test temperature of 23 ° C., the tensile speed was 300 mm/min, From the ethanol peeling force N1 SUS measured at a peeling angle of 180 degrees, and the adhesive force N0 SUS after one day at room temperature after pasting the adhesive sheet on a stainless steel plate as an adherend, the following formula: Adhesive force reduction The adhesive force reduction rate S SUS determined by the formula S SUS [%] = (1 - (ethanol peeling force N1 SUS / adhesive force N0 SUS )) x 100; is 50% or more,
    Then, the adhesive sheet cut into a rectangular shape with a width of 20 mm is attached to a stainless steel plate as an adherend, and after one day at room temperature, 2 μL of ethanol is dropped onto the adherend, and the ethanol is mixed with the adhesive sheet. After entering one end of the interface with the adherend, according to JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, at a test temperature of 23 ° C. The peeling method according to claim 1 or 2, wherein the adhesive force reduction distance R SUS is 30 mm or more, measured using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees.
  6. 　前記粘着シートは、被着体としてのフロート法で作製されたアルカリガラス板に前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、エタノール剥離力Ｎ１ＧＬＡが、０．５Ｎ／２０ｍｍ以下である、請求項１に記載の剥離方法。 The adhesive sheet is made by pasting the adhesive sheet on an alkali glass plate prepared by a float method as an adherend, and after one day at room temperature, 2 μL of ethanol is dropped onto the adherend, and the ethanol is mixed with the adhesive sheet. After entering one end of the interface with the adherend, according to JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, at a test temperature of 23 ° C. The peeling method according to claim 1, wherein the ethanol peeling force N1 GLA is 0.5 N/20 mm or less, measured using a tensile tester at a tensile speed of 300 mm/min and a peeling angle of 180 degrees.
  7. 　前記粘着シートは、被着体としてのフロート法で作製されたアルカリガラス板に、幅２０ｍｍの長方形状にカットされた前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＧＬＡが３０ｍｍ以上である、請求項１または６に記載の剥離方法。 The adhesive sheet was prepared by pasting the adhesive sheet cut into a rectangular shape with a width of 20 mm on an alkali glass plate prepared by the float method as an adherend, and after one day at room temperature, 2 μL of ethanol was added to the adherend. After dropping the ethanol into one end of the interface between the pressure-sensitive adhesive sheet and the adherend, the ethanol was peeled off according to JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force against the test plate. Specifically, the adhesion reduction distance R GLA is 30 mm or more, measured using a tensile tester at a test temperature of 23° C. at a tensile speed of 300 mm/min and a peel angle of 180 degrees. Peeling method described in.
  8. 　前記粘着シートは、被着体としてのフロート法で作製されたアルカリガラス板に前記粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＧＬＡが３．０Ｎ／２０ｍｍ以上である、請求項１または６に記載の剥離方法。 Claim 1 or 6, wherein the adhesive sheet has an adhesive force N0 GLA of 3.0 N/20 mm or more after one day at room temperature after pasting the adhesive sheet on an alkali glass plate prepared by a float method as an adherend. Peeling method described in.
  9. 　前記粘着シートは、
    　被着体としてのフロート法で作製されたアルカリガラス板に前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定されるエタノール剥離力Ｎ１ＧＬＡ、および、被着体としてのフロート法で作製されたアルカリガラス板に前記粘着シートを貼り付けて室温１日後の粘着力Ｎ０ＧＬＡ、から下記式：粘着力低減率ＳＧＬＡ［％］＝（１－（エタノール剥離力Ｎ１ＧＬＡ／粘着力Ｎ０ＧＬＡ））×１００；で求められる粘着力低減率ＳＧＬＡが５０％以上であり、
    　かつ、被着体としてのフロート法で作製されたアルカリガラス板に、幅２０ｍｍの長方形状にカットされた前記粘着シートを貼り付けて室温１日後、前記被着体に２μＬのエタノールを滴下し、該エタノールを前記粘着シートと前記被着体との界面の一端に進入させた後、ＪＩＳ　Ｚ０２３７：２００９の１０．４．１　方法１：試験板に対する１８０°引きはがし粘着力に従い、具体的には、試験温度２３℃にて引張試験機を用いて引張速度３００ｍｍ／分、剥離角度１８０度の条件で測定される、粘着力低減距離ＲＧＬＡが３０ｍｍ以上である、請求項１または６に記載の剥離方法。

          The adhesive sheet is
    The adhesive sheet was attached to an alkali glass plate prepared by the float method as an adherend, and after one day at room temperature, 2 μL of ethanol was dropped onto the adherend, and the ethanol was applied to the adhesive sheet and the adherend. After entering one end of the interface of Ethanol peeling force N1 GLA measured at a tensile speed of 300 mm/min and a peeling angle of 180 degrees, and one day after the adhesive sheet was attached to an alkali glass plate prepared by the float method as an adherend at room temperature. The adhesive force reduction rate S GLA is 50, which is calculated from the following formula: Adhesive force reduction rate S GLA [%] = (1 - (ethanol peeling force N1 GLA / adhesive force N0 GLA )) x 100 ; % or more,
    Then, the adhesive sheet cut into a rectangular shape with a width of 20 mm was attached to an alkali glass plate prepared by the float method as an adherend, and after one day at room temperature, 2 μL of ethanol was dropped onto the adherend, After the ethanol enters one end of the interface between the adhesive sheet and the adherend, according to JIS Z0237:2009 10.4.1 Method 1: 180° peeling adhesive force to the test plate, specifically, According to claim 1 or 6, the adhesive force reduction distance R GLA is 30 mm or more, measured at a test temperature of 23° C. using a tensile tester at a tensile speed of 300 mm/min and a peel angle of 180 degrees. Peeling method.
PCT/JP2023/027352 2022-07-29 2023-07-26 Method for peeling adhesive sheet WO2024024829A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004149559A (en) * 2002-10-28 2004-05-27 Nakagawa Chem:Kk Method for peeling pressure-sensitive adhesive sheet, sheet impregnated with liquid for peeling pressure-sensitive adhesive sheet, and device for applying the liquid for peeling pressure-sensitive adhesive sheet to be used therefor
JP2005089640A (en) * 2003-09-18 2005-04-07 Unon Giken:Kk Re-releasable pressure-sensitive adhesive sheet and method for releasing pressure-sensitive adhesive sheet
WO2020116497A1 (en) * 2018-12-04 2020-06-11 積水化学工業株式会社 Method for removing pressure-sensitive adhesive tape, pressure-sensitive adhesive tape, and electronic component
JP2021095449A (en) * 2019-12-13 2021-06-24 日東電工株式会社 Adhesive sheet peeling method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004149559A (en) * 2002-10-28 2004-05-27 Nakagawa Chem:Kk Method for peeling pressure-sensitive adhesive sheet, sheet impregnated with liquid for peeling pressure-sensitive adhesive sheet, and device for applying the liquid for peeling pressure-sensitive adhesive sheet to be used therefor
JP2005089640A (en) * 2003-09-18 2005-04-07 Unon Giken:Kk Re-releasable pressure-sensitive adhesive sheet and method for releasing pressure-sensitive adhesive sheet
WO2020116497A1 (en) * 2018-12-04 2020-06-11 積水化学工業株式会社 Method for removing pressure-sensitive adhesive tape, pressure-sensitive adhesive tape, and electronic component
JP2021095449A (en) * 2019-12-13 2021-06-24 日東電工株式会社 Adhesive sheet peeling method

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