Stacked body

Abstract

A laminate including a laminated structure of a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend is provided, and the laminate can simultaneously exhibit high adhesive strength and high impact resistance. The laminate includes a laminated structure of a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend, wherein the outermost layer of the pressure-sensitive adhesive sheet on the side of the reinforcing layer is a pressure-sensitive adhesive layer. The adhesive strength when the pressure-sensitive adhesive sheet is peeled from the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the SUS plate, from the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the polycarbonate plate, and from the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the aluminum plate at a tensile speed of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH is 20 N / 20 mm or more, and the impact resistance of the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the SUS plate at 23°C and 50% RH is 0.35 J or more.

Description

Technical Field

[0001] The present invention relates to a laminate. Typically, the present invention relates to a laminate having a laminated structure including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend. Background Art

[0002] In recent years, with the trend of complication of various performances of mobile devices, complication of various performances of various constituent members used in mobile devices has been required. In mobile devices, a pressure-sensitive adhesive sheet is sometimes used for bonding a housing or the like. In recent years, complication of various performances of the pressure-sensitive adhesive sheet has also been required, and various studies have been conducted (for example, Japanese Patent Application Laid-Open No. 2019-147851).

[0003] When the pressure-sensitive adhesive sheet to be used in a mobile device does not have high adhesive strength, the sheet peels off during use, resulting in malfunctions or the like. In particular, in a case where the pressure-sensitive adhesive sheet is used for bonding a housing or the like, various adherends such as SUS, polycarbonate, and aluminum can be assumed as the adherend of the pressure-sensitive adhesive sheet. In view of the foregoing, a pressure-sensitive adhesive sheet that can be used in a mobile device and has strong adhesive strength for such various adherends has been required.

[0004] In addition, there is a risk that a mobile device may fall depending on its usage form. Therefore, a mobile device having high impact resistance has been required. In order to improve the impact resistance of a mobile device, an impact-absorbing member can be disposed outside its housing. However, in this form, the size of the mobile device increases, or its designability is impaired.

[0005] In view of the foregoing, it has been desired to impart excellent impact resistance to the pressure-sensitive adhesive sheet that can be disposed in a mobile device.

[0006] Recently, a double-sided pressure-sensitive adhesive sheet having impact resistance has been reported (Japanese Patent Application Laid-Open No. 2015-120876). As an essential configuration, the double-sided pressure-sensitive adhesive sheet includes a foamed base material to exhibit impact resistance. However, when the foamed body is stretched to a certain degree or more or a force is applied thereto, the foamed body is damaged, resulting in a smaller area or becoming thinner. As a result, the following problem occurs: the cell portion of the foamed body occupies most of the adhesive portion of the sheet, thereby reducing its adhesiveness.

[0007] Therefore, a pressure-sensitive adhesive sheet for a mobile device is required to have both high adhesive strength for various adherends that can be used in a mobile device and high impact resistance. However, the conventional pressure-sensitive adhesive sheets alone cannot achieve these performances simultaneously, and thus there is a need for a technique that can simultaneously exhibit high adhesive strength for various adherends that can be used in a mobile device and high impact resistance. Summary of the Invention

[0008] An object of the present invention is to provide a laminate including a laminated structure of a pressure-sensitive adhesive sheet, a reinforcing agent layer, and an adherend, which can simultaneously exhibit high adhesive strength and high impact resistance.

[0009] According to at least one embodiment of the present invention, there is provided a laminate including a laminated structure of a pressure-sensitive adhesive sheet, a reinforcing agent layer, and an adherend, wherein the outermost layer of the pressure-sensitive adhesive sheet on the reinforcing agent layer side is a pressure-sensitive adhesive layer, wherein the adhesive strength of the laminate when peeling the pressure-sensitive adhesive sheet from the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing agent layer, and a SUS plate at a tensile speed of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH is 20 N / 20 mm or more, wherein the adhesive strength of the laminate when peeling the pressure-sensitive adhesive sheet from the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing agent layer, and a polycarbonate plate at a tensile speed of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH is 20 N / 20 mm or more, wherein the adhesive strength of the laminate when peeling the pressure-sensitive adhesive sheet from the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing agent layer, and an aluminum plate at a tensile speed of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH is 20 N / 20 mm or more, and wherein the impact resistance of the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing agent layer, and the SUS plate at 23°C and 50% RH is 0.35 J or more.

[0010] In at least one embodiment of the present invention, the pressure-sensitive adhesive layer, which is the outermost layer of the pressure-sensitive adhesive sheet on the reinforcing agent layer side, is formed of a pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition contains at least one selected from the group consisting of a monomer composition (M) and a polymer component (P) obtained from the monomer composition (M), and the monomer composition (M) contains 50 wt% or more of a (meth)acrylate having an alkyl ester with 1 to 12 carbon atoms, and contains 1 wt% to 10 wt% of (meth)acrylic acid.

[0011] In at least one embodiment of the present invention, the monomer composition (M) contains 85 wt% or more of the (meth)acrylate having an alkyl ester with 1 to 12 carbon atoms.

[0012] In at least one embodiment of the present invention, the (meth)acrylate having an alkyl ester with 1 to 12 carbon atoms is n-butyl acrylate.

[0013] In at least one embodiment of the present invention, the thickness of the pressure-sensitive adhesive sheet is 100 μm to 400 μm.

[0014] In at least one embodiment of the present invention, the thickness of the reinforcing agent layer is 0.10 μm to 4.00 μm.

[0015] In at least one embodiment of the present invention, the reinforcing agent layer is formed of a reinforcing agent, and the reinforcing agent contains an aqueous polyurethane resin crosslinked by an isocyanate-based crosslinking agent, and the resin has at least one selected from the group consisting of an ester skeleton, an ether skeleton, and a carbonate skeleton.

[0016] In at least one embodiment of the present invention, the elongation at break of the aqueous polyurethane resin is 300% to 1,000%.

[0017] In at least one embodiment of the present invention, the aqueous polyurethane resin is a non-reactive aqueous polyurethane resin.

[0018] In at least one embodiment of the present invention, the non-reactive aqueous polyurethane resin is a self-emulsifying aqueous polyurethane resin.

[0019] In at least one embodiment of the present invention, the adherend is an electronic device component.

[0020] In at least one embodiment of the present invention, the material of the bonding portion of the adherend is at least one selected from the group consisting of SUS, polycarbonate, aluminum, polyolefin resin, styrene resin, polyester resin, acrylic resin, polyimide resin, and glass fiber.

[0021] In at least one embodiment of the present invention, the laminate according to at least one embodiment of the present invention is used for an electronic device.

[0022] According to at least one embodiment of the present invention, there is provided a mobile electronic device including a laminate according to at least one embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a schematic cross-sectional view of a laminate according to at least one embodiment of the present invention.

[0024] Figure 2 is a schematic cross-sectional view of a laminate according to at least one embodiment of the present invention. DETAILED DESCRIPTION

[0025] As used herein, the term "(meth)acryloyl" means at least one selected from the group consisting of acryloyl and methacryloyl, and the term "(meth)acrylate" means at least one selected from the group consisting of acrylate and methacrylate.

[0026] <<<<1. Laminate>>>>

[0027] The laminate according to at least one embodiment of the present invention is a laminate having a laminated structure including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend, and the outermost layer of the pressure-sensitive adhesive sheet on the side of the reinforcing layer is a pressure-sensitive adhesive layer.

[0028] To such an extent that the effects of the present invention are not impaired, the laminate according to at least one embodiment of the present invention may include any suitable other layers as long as the laminate has a laminated structure including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend.

[0029] Figure 1 is a schematic cross-sectional view of the laminate according to at least one embodiment of the present invention. In Figure 1 , the laminate 1000 is formed of a pressure-sensitive adhesive sheet 100, a reinforcing layer 200, and an adherend 300. The outermost layer of the pressure-sensitive adhesive sheet 100 on the side of the reinforcing layer 200 is a pressure-sensitive adhesive layer 10a. Figure 1 shows an embodiment in which the entire pressure-sensitive adhesive sheet 100 is a pressure-sensitive adhesive layer 10a.

[0030] Figure 2 is a schematic cross-sectional view of the laminate according to at least one embodiment of the present invention. In Figure 2 , the laminate 1000 is formed of a pressure-sensitive adhesive sheet 100, a reinforcing layer 200, and an adherend 300, and the pressure-sensitive adhesive sheet 100 is formed of three layers, namely, a pressure-sensitive adhesive layer 10b, a base material layer 15, and a pressure-sensitive adhesive layer 10a.

[0031] When the pressure-sensitive adhesive sheet and the reinforcing layer, which are constituent materials of the laminate according to at least one embodiment of the present invention, are laminated with an SUS plate to prepare a laminated structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the SUS plate, and the laminated structure is aged at 23°C and 50% RH for 30 minutes, and then the pressure-sensitive adhesive sheet is peeled at a peeling rate of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH, the adhesive strength of the laminate according to at least one embodiment of the present invention is 20 N / 20 mm or more, preferably 23 N / 20 mm or more, more preferably 25 N / 20 mm or more, still more preferably 28 N / 20 mm or more, and particularly preferably 34 N / 20 mm or more. In the case where the adhesive strength is so low as to deviate from this range, a laminate capable of exhibiting a high adhesive strength cannot be provided. The upper limit of the adhesive strength is preferably 60 N / 20 mm or less. In the case where the adhesive strength is so high as to deviate from this range, when disassembling components during the repair of a mobile device, the pressure-sensitive adhesive sheet cannot be peeled from the laminated structure while the components maintain their normal state, and thus the components may be damaged or the device may not be repairable.

[0032] When a pressure-sensitive adhesive sheet and a reinforcing layer, which are constituent materials of a laminate according to at least one embodiment of the present invention, are laminated with a polycarbonate sheet to prepare a laminated structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the polycarbonate sheet, and the laminated structure is aged at 23°C and 50% RH for 30 minutes, and then the pressure-sensitive adhesive sheet is peeled at a peeling rate of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH, the adhesive strength of the laminate according to at least one embodiment of the present invention is 20 N / 20 mm or more, preferably 23 N / 20 mm or more, more preferably 28 N / 20 mm or more, still more preferably 31 N / 20 mm or more, and particularly preferably 34 N / 20 mm or more. In a case where the adhesive strength is so low as to deviate from this range, a laminate capable of exhibiting a high adhesive strength cannot be provided. The upper limit of the adhesive strength is preferably 60 N / 20 mm or less. In a case where the adhesive strength is so high as to deviate from this range, when disassembling components during the repair of a mobile device, the pressure-sensitive adhesive sheet cannot be peeled from the laminated structure while the components maintain their normal state, and thus the components may be damaged or the device may not be repairable.

[0033] When a pressure-sensitive adhesive sheet and a reinforcing layer, which are constituent materials of a laminate according to at least one embodiment of the present invention, are laminated with an aluminum plate to prepare a laminated structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the aluminum plate, and the laminated structure is aged at 23°C and 50% RH for 30 minutes, and then the pressure-sensitive adhesive sheet is peeled at a peeling rate of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH, the adhesive strength of the laminate according to at least one embodiment of the present invention is 20 N / 20 mm or more, preferably 24 N / 20 mm or more, more preferably 28 N / 20 mm or more, still more preferably 31 N / 20 mm or more, and particularly preferably 34 N / 20 mm or more. In a case where the adhesive strength is so low as to deviate from this range, a laminate capable of exhibiting a high adhesive strength cannot be provided. The upper limit of the adhesive strength is preferably 60 N / 20 mm or less. In a case where the adhesive strength is so high as to deviate from this range, when disassembling components during the repair of a mobile device, the pressure-sensitive adhesive sheet cannot be peeled from the laminated structure while the components maintain their normal state, and thus the components may be damaged or the device may not be repairable.

[0034] When, as described above, at 23°C and 50% RH, (1) the adhesive strength of the laminate according to at least one embodiment of the present invention when the pressure-sensitive adhesive sheet is peeled from the laminate structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the SUS plate at a peeling rate of 300 mm / min and a peeling angle of 180°, (2) its adhesive strength when the pressure-sensitive adhesive sheet is peeled from the laminate structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the polycarbonate plate at a peeling rate of 300 mm / min and a peeling angle of 180°, and (3) its adhesive strength when the pressure-sensitive adhesive sheet is peeled from the laminate structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the aluminum plate at a peeling rate of 300 mm / min and a peeling angle of 180° fall within the above ranges, a laminate including a laminate structure of a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can exhibit high adhesive strength.

[0035] The laminate according to at least one embodiment of the present invention is as follows: When the pressure-sensitive adhesive sheet and the reinforcing layer, which are constituent materials of the laminate according to at least one embodiment of the present invention, are laminated with the SUS plate to prepare a laminate structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the SUS plate, and its impact resistance is measured at 23°C and 50% RH, the impact resistance is 0.35 J or more, preferably 0.36 J or more, more preferably 0.41 J or more, still more preferably 0.47 J or more, and particularly preferably 0.52 J or more. When the impact resistance is so low as to deviate from this range, a laminate that can exhibit high impact resistance cannot be provided.

[0036] When the laminate according to at least one embodiment of the present invention is as follows: the impact resistance of the laminate structure of the pressure-sensitive adhesive sheet, the reinforcing layer, and the SUS plate at 23°C and 50% RH falls within the above range, a laminate including a laminate structure of a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can exhibit high impact resistance.

[0037] The laminate according to at least one embodiment of the present invention is typically used in electronic devices. In addition, a mobile electronic device including the laminate according to at least one embodiment of the present invention is a mobile electronic device according to at least one embodiment of the present invention.

[0038] <<1-1. Pressure-sensitive adhesive sheet>>

[0039] To such an extent that the effects of the present invention are not impaired, the pressure-sensitive adhesive sheet can have any suitable constitution as long as at least one outermost layer thereof is a pressure-sensitive adhesive layer.

[0040] The pressure-sensitive adhesive sheet can be, for example, Figure 1Such a substrate-free pressure-sensitive adhesive sheet formed only of the pressure-sensitive adhesive layer 10a as shown, or may be a substrate-containing pressure-sensitive adhesive sheet including a substrate layer. For example, the substrate-containing pressure-sensitive adhesive sheet may be such a double-sided pressure-sensitive adhesive sheet formed of three layers, namely, the pressure-sensitive adhesive layer 10b, the substrate layer 15, and the pressure-sensitive adhesive layer 10a as shown in Figure 2 or may be a single-sided pressure-sensitive adhesive sheet including a pressure-sensitive adhesive layer only on one side of the substrate layer.

[0041] The pressure-sensitive adhesive layers may be used alone or in combination. When the pressure-sensitive adhesive layer is a laminate of two or more layers, its interface can be observed by, for example, differential interference microscopy of the LEXT OLS 4000 manufactured by Olympus Corporation.

[0042] The thickness of the pressure-sensitive adhesive sheet is preferably 100 μm or more because the effects of the present invention can be further exhibited, and the thickness is more preferably 150 μm to 2,000 μm, still more preferably 150 μm to 1,000 μm, particularly preferably 150 μm to 550 μm, and particularly preferably 150 μm to 400 μm.

[0043] To such an extent that the effects of the present invention are not impaired, any suitable release liner can be disposed on the surface of the pressure-sensitive adhesive layer, for example, to protect the laminate until the laminate is used. Examples of the release liner include: a release liner obtained by subjecting the surface of a substrate (liner substrate) such as paper or a plastic film to silicone treatment; and a release liner obtained by laminating a polyolefin resin on the surface of a substrate (liner substrate) such as paper or a plastic film. Examples of the plastic film as the liner substrate include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film. The plastic film as the liner substrate is preferably a polyethylene film.

[0044] The thickness of the release liner is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, still more preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm.

[0045] <1-1-1. Pressure-Sensitive Adhesive Layer>

[0046] The pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition.

[0047] The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition by any suitable method. Examples of such methods include: a method (direct method) involving coating a pressure-sensitive adhesive composition, which is a forming material of the pressure-sensitive adhesive layer, onto any suitable substrate (e.g., a substrate film), and drying the composition as needed to form a pressure-sensitive adhesive layer on the substrate; and a method (transfer method) involving coating a pressure-sensitive adhesive composition onto a surface having releasability (release surface), drying the composition as needed to form a pressure-sensitive adhesive layer on the surface having releasability (release surface), and transferring the pressure-sensitive adhesive layer onto any suitable substrate (e.g., a substrate film). The surface having releasability (release surface) is, for example, the surface of the aforementioned release liner.

[0048] To such an extent that the effects of the present invention are not impaired, any suitable coating method can be used as the coating method for the pressure-sensitive adhesive composition. Examples of such coating methods include roll coating, gravure coating, reverse coating, roll brushing, spraying, air knife coating method, and extrusion coating using a die coater, etc. Actinic ray irradiation such as UV irradiation can be performed to cure the coating layer formed by coating.

[0049] From the viewpoint of, for example, accelerating the crosslinking reaction of the composition and improving the production efficiency of the laminate, the drying of the pressure-sensitive adhesive composition can be carried out under heating. The drying temperature can typically be set to, for example, 40°C to 150°C, and preferably 60°C to 130°C. After drying the pressure-sensitive adhesive composition, aging can be further carried out for the purpose of, for example, regulating the migration of components in the pressure-sensitive adhesive layer, promoting the crosslinking reaction, and reducing the strain that may exist in the pressure-sensitive adhesive layer.

[0050] The thickness of the pressure-sensitive adhesive layer can be appropriately set in accordance with the thickness of the finally formed pressure-sensitive adhesive layer laminate and the number of pressure-sensitive adhesive layers. The thickness of such a pressure-sensitive adhesive layer is preferably 50 μm or more, more preferably 50 μm to 2,000 μm, still more preferably 100 μm to 1,000 μm, particularly preferably 100 μm to 500 μm, and most preferably 150 μm to 300 μm.

[0051] The light transmittance in the XY direction and the Z direction of the pressure-sensitive adhesive layer is each preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, still more preferably 0.5% or less, particularly preferably 0.1% or less, and most preferably 0.04% or less. When the light transmittance in the XY direction and the Z direction of the pressure-sensitive adhesive layer each falls within this range, the pressure-sensitive adhesive layer can exhibit excellent light-shielding properties. The light transmittance in the XY direction of the pressure-sensitive adhesive layer is preferably 0.03% or less, more preferably 0.02% or less, still more preferably 0.01% or less. The light transmittance in the Z direction of the pressure-sensitive adhesive layer is preferably 0.03% or less, more preferably 0.02% or less, still more preferably 0.01% or less.

[0052] The pressure-sensitive adhesive composition preferably contains at least one selected from the group consisting of the monomer composition (M) and the polymer component (P) obtained by polymerizing the monomer composition (M). That is, typically, the pressure-sensitive adhesive composition can have any of the following forms: a form containing the polymer component (P) and substantially no monomer composition (M) (Form 1); a form containing the monomer composition (M) and substantially no polymer component (P) (Form 2); and a form containing both the monomer composition (M) and the polymer component (P) (Form 3).

[0053] The form containing the polymer component (P) and substantially no monomer composition (M) (Form 1) is as follows: at the stage of preparing the pressure-sensitive adhesive composition, the polymer component (P) is substantially formed by polymerizing the monomer composition (M).

[0054] The form containing the monomer composition (M) and substantially no polymer component (P) (Form 2) is as follows: at the stage of preparing the pressure-sensitive adhesive composition, substantially no polymerization of the monomer composition (M) occurs and thus the polymer component (P) has not been formed. In this form, the polymer component (P) can be formed by, for example, curing the coating layer formed from the pressure-sensitive adhesive composition prepared by coating by irradiating with active energy rays such as UV radiation.

[0055] The form containing both the monomer composition (M) and the polymer component (P) (Form 3) is as follows: at the stage of preparing the pressure-sensitive adhesive composition, a part of the monomers of the monomer composition (M) polymerize to form a part of the polymer, and the unreacted monomers of the monomer composition (M) remain. In this form, the polymer component (P) can be formed by, for example, curing the coating layer formed from the pressure-sensitive adhesive composition prepared by coating by irradiating with active energy rays such as UV radiation.

[0056] In the case of Form 1 (a form containing a polymer component (P) and substantially no monomer composition (M)), the content of the polymer component (P) in the pressure-sensitive adhesive composition is as follows: when the total amount of the pressure-sensitive adhesive composition is set to 100 parts by weight, the content of the polymer component (P) is preferably 50 wt% to 100 wt%, more preferably 60 wt% to 100 wt%, still more preferably 70 wt% to 100 wt%, and particularly preferably 80 wt% to 100 wt%.

[0057] In the case of Form 2 (a form containing a monomer composition (M) and substantially no polymer component (P)), the content of the monomer composition (M) in the pressure-sensitive adhesive composition is as follows: when the total amount of the pressure-sensitive adhesive composition is set to 100 parts by weight, the content of the monomer composition (M) is preferably 50 wt% to 100 wt%, more preferably 60 wt% to 100 wt%, still more preferably 70 wt% to 100 wt%, and particularly preferably 80 wt% to 100 wt%.

[0058] In the case of Form 3 (a form containing both a monomer composition (M) and a polymer component (P)), the total content of the polymer component (P) and the monomer composition (M) in the pressure-sensitive adhesive composition is as follows: when the total amount of the pressure-sensitive adhesive composition is set to 100 parts by weight, the total content of the polymer component (P) and the monomer composition (M) is preferably 50 wt% to 100 wt%, more preferably 60 wt% to 100 wt%, still more preferably 70 wt% to 100 wt%, and particularly preferably 80 wt% to 100 wt%.

[0059] Preferably, the monomer composition (M) contains more than 50 wt% of (meth)acrylate having an alkyl ester with 1 to 12 carbon atoms, and contains 1 wt% to 10 wt% of (meth)acrylic acid, because the effects of the present invention can be further exhibited. The term "(meth)acrylate having an alkyl ester with 1 to 12 carbon atoms" used herein does not include the acrylic monomers having an alicyclic structure described later.

[0060] The content of the (meth)acrylate ester having an alkyl ester with 1 to 12 carbon atoms in the monomer composition (M) is preferably 50 wt% to 100 wt%, more preferably 75 wt% to 99.5 wt%, still more preferably 85 wt% to 99 wt%, still more preferably 86 wt% to 98 wt%, still more preferably 87 wt% to 98 wt%, still more preferably 88 wt% to 97 wt%, still more preferably 89 wt% to 97 wt%, still more preferably 90 wt% to 97 wt%, still more preferably 91 wt% to 97 wt%, particularly preferably 92 wt% to 97 wt%, and most preferably 93 wt% to 97 wt%. When the content of the (meth)acrylate ester having an alkyl ester with 1 to 12 carbon atoms in the monomer composition (M) is adjusted within this range, a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0061] Examples of the (meth)acrylate ester having an alkyl ester with 1 to 12 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. Among them, n-butyl acrylate is preferred because the effects of the present invention can be further exhibited.

[0062] Therefore, when n-butyl acrylate is used as the (meth)acrylate ester having an alkyl ester with 1 to 12 carbon atoms, the content of n-butyl acrylate in the monomer composition (M) is preferably 50 wt% to 100 wt%, more preferably 75 wt% to 99.5 wt%, still more preferably 85 wt% to 99 wt%, still more preferably 86 wt% to 98 wt%, still more preferably 87 wt% to 98 wt%, still more preferably 88 wt% to 97 wt%, still more preferably 89 wt% to 97 wt%, still more preferably 90 wt% to 97 wt%, still more preferably 91 wt% to 97 wt%, particularly preferably 92 wt% to 97 wt%, and most preferably 93 wt% to 97 wt%. When the content of n-butyl acrylate in the monomer composition (M) is adjusted within this range, a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0063] The content of (meth)acrylic acid in the monomer composition (M) is preferably 1 wt% to 10 wt%, more preferably 1 wt% to 8 wt%, still more preferably 2 wt% to 7 wt%, still more preferably 2 wt% to 6 wt%, particularly preferably 2.5 wt% to 5.5 wt%, and most preferably 3 wt% to 5.5 wt%. When the content of (meth)acrylic acid in the monomer composition (M) is adjusted within this range, a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0064] The monomer composition (M) may contain any other monomers. Such other monomers can be used alone or in combination.

[0065] The content of other monomers in the total amount of the monomer composition (M) is preferably 0 wt% to 10 wt%, more preferably 0 wt% to 8 wt%, still more preferably 0 wt% to 6 wt%, particularly preferably 0 wt% to 4 wt%, and most preferably 0 wt% to 2 wt%. When the content of other monomers in the monomer composition (M) is adjusted within this range, a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0066] Examples of other monomers include acrylic monomers containing an alicyclic structure, monomers containing a hydroxyl group, carboxyl group-containing monomers other than (meth)acrylic acid, monomers containing a nitrogen-containing cyclic structure, monomers containing a cyclic ether group, diol-based acrylate monomers, styrene-based monomers, monomers containing an amide group, monomers containing an amino group, monomers containing an imide group, vinyl ether monomers, silane-based monomers, and polyfunctional monomers.

[0067] The acrylic monomer containing an alicyclic structure is preferably an acrylic monomer having a cyclic aliphatic hydrocarbon structure. The number of carbon atoms in the cyclic aliphatic hydrocarbon structure is preferably 3 or more, more preferably 6 to 24, still more preferably 6 to 18, and particularly preferably 6 to 12. Specific examples of such acrylic monomers containing an alicyclic structure include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentyl (meth)acrylate.

[0068] Specific examples of the hydroxyl group-containing monomers include: hydroxyalkyl (meth)acrylates, such as 2-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate; hydroxyalkyl cycloalkane (meth)acrylates, such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate; and other hydroxyl group-containing monomers, such as hydroxyethyl (meth)acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol mono vinyl ether. Among these hydroxyl group-containing monomers, hydroxyalkyl (meth)acrylates are preferred because they can exhibit more excellent impact resistance, and hydroxyalkyl (meth)acrylates having a hydroxyl alkyl group with 2 to 6 carbon atoms are more preferred, and 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate are even more preferred.

[0069] Specific examples of the carboxyl group-containing monomers other than (meth)acrylic acid include carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.

[0070] Specific examples of the monomers containing a nitrogen-containing cyclic structure include: lactam-based vinyl monomers, such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinyl-based monomers each having a nitrogen-containing heterocycle, such as vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, and vinylmorpholine; and (meth)acrylic acid-based monomers each containing a heterocycle such as a morpholine ring, a piperidine ring, a pyrrolidine ring, or a piperazine ring (for example, N-acrylylmorpholine, N-acrylpiperidine, N-methylacrylylpiperidine, and N-acrylylpyrrolidine).

[0071] Specific examples of the monomers containing a cyclic ether group include: epoxy group-containing monomers, such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl ether of 4-hydroxybutyl (meth)acrylate, methyl glycidyl (meth)acrylate, and allyl glycidyl ether; and oxetanyl-containing monomers, such as 3-oxetanylmethyl (meth)acrylate, 3-methyl-oxetanylmethyl (meth)acrylate, 3-ethyl-oxetanylmethyl (meth)acrylate, 3-butyl-oxetanylmethyl (meth)acrylate, and 3-hexyl-oxetanylmethyl (meth)acrylate.

[0072] Specific examples of the diol-based acrylate monomers include polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate.

[0073] Specific examples of the styrene-based monomers include styrene and α-methylstyrene.

[0074] Specific examples of the amide group-containing monomers include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N,N-(dimethyl)methacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebisacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, diacetoneacrylamide, and N,N-hydroxyethylacrylamide.

[0075] Specific examples of the amino group-containing monomers include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate.

[0076] Specific examples of the imide group-containing monomers include cyclohexyl maleimide, isopropyl maleimide, N-cyclohexyl maleimide, and itaconic imide.

[0077] Specific examples of the silane-based monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, and 10-acryloxydecyltriethoxysilane.

[0078] Specific examples of the polyfunctional monomer include: ester compounds of polyhydric alcohols and (meth)acrylic acid, such as (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tetramethylolmethane tri(meth)acrylate; allyl (meth)acrylate; vinyl (meth)acrylate; divinylbenzene; epoxy acrylate; polyester acrylate; polyurethane acrylate; butyl di(meth)acrylate; and hexyl di(meth)acrylate.

[0079] The polymer component (P) is obtained by polymerizing the monomer composition (M). The polymer component (P) is typically an acrylic polymer. The polymer component (P) can be used alone or in combination.

[0080] To such an extent that the effects of the present invention are not impaired, any suitable manufacturing method can be used as the manufacturing method of the polymer component (P). Examples of such manufacturing methods include various radical polymerizations, which include: solution polymerization; active energy ray polymerization, such as UV polymerization; bulk polymerization; and emulsion polymerization. To such an extent that the effects of the present invention are not impaired, any suitable polymerization conditions can be used as the polymerization conditions.

[0081] To such an extent that the effects of the present invention are not impaired, any suitable polymerization structure can be used as the polymerization structure of the obtained polymer component (P). Examples of such polymerization structures include random copolymers, block copolymers, and graft copolymers.

[0082] To such an extent that the effects of the present invention are not impaired, any suitable additives can be used as additives for radical polymerization, such as polymerization initiators, chain transfer agents, or emulsifiers.

[0083] Polymerization solvents that can be used in solution polymerization, etc. are, for example, ethyl acetate or toluene. The polymerization solvents can be used alone or in combination.

[0084] In a stream of an inert gas such as nitrogen, after adding a polymerization initiator, solution polymerization is typically carried out under reaction conditions of a temperature of about 50 °C to about 70 °C and a time of about 5 hours to about 30 hours.

[0085] To the extent that does not impair the effects of the present invention, any suitable thermal polymerization initiator can be used as a polymerization initiator that can be used in solution polymerization and the like. The polymerization initiator can be used alone or in combination thereof. Examples of such polymerization initiators include: azo initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), azoisopentanenitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropamidine) disulfate, 2,2'-azobis(N,N'-dimethylisobutylamidine), and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.); peroxide initiators including: persulfates such as potassium persulfate and ammonium persulfate, di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyneopentanoate, tert-butyl peroxyneopentanoate, dilauroyl peroxide, dioctanoyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, di(4-methylbenzoyl) peroxide, benzoyl peroxide, tert-butyl peroxyisobutyrate, 1,1-bis(tert-hexylperoxy) cyclohexane, tert-butyl hydroperoxide, and hydrogen peroxide; and redox initiators obtained by combining peroxides and reducing agents respectively, such as the combination of persulfate and sodium bisulfite, and the combination of peroxide and sodium ascorbate.

[0086] The amount of the polymerization initiator is preferably 1 part by weight or less, more preferably 0.005 part by weight to 1 part by weight, still more preferably 0.01 part by weight to 0.7 part by weight, and particularly preferably 0.02 part by weight to 0.5 part by weight, relative to the total amount of 100 parts by weight of the monomer composition (M), because for example, for the following reasons: the polymerization reaction can be effectively promoted.

[0087] To the extent that does not impair the effects of the present invention, any suitable chain transfer agent can be used as a chain transfer agent. The chain transfer agent can be used alone or in combination thereof. Examples of such chain transfer agents include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl mercaptoacetate, and 2,3-dimercapto-1-propanol.

[0088] The amount of the chain transfer agent is preferably 0.1 part by weight or less, relative to the total amount of 100 parts by weight of the monomer composition (M), because, for example, for the following reasons: the polymerization reaction can proceed effectively.

[0089] To such an extent that does not impair the effects of the present invention, any suitable emulsifier can be used as the emulsifier. The emulsifiers can be used alone or in combination thereof. Examples of such emulsifiers include: anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, and sodium polyoxyethylene alkyl phenyl ether sulfate; and nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer.

[0090] From the viewpoints of polymerization stability and mechanical stability, the amount of the emulsifier is preferably 5 parts by weight or less, more preferably 0.3 part by weight to 5 parts by weight, still more preferably 0.4 part by weight to 3 parts by weight, and particularly preferably 0.5 part by weight to 1 part by weight, relative to the total amount of 100 parts by weight of the monomer composition (M).

[0091] When performing UV polymerization, a photoinitiator is preferably used.

[0092] To such an extent that does not impair the effects of the present invention, any suitable photoinitiator can be used as the photoinitiator. The photoinitiators can be used alone or in combination thereof. Examples of such photoinitiators include benzoin ether-based photoinitiators, acetophenone-based photoinitiators, α-ketol-based photoinitiators, aromatic sulfonyl chloride-based photoinitiators, photoactive oxime-based photoinitiators, benzoin-based photoinitiators, benzil-based photoinitiators, benzophenone-based photoinitiators, ketal-based photoinitiators, thioxanthone-based photoinitiators, and acylphosphine oxide-based photoinitiators.

[0093] Specific examples of the benzoin ether-based photoinitiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one (e.g., a commercially available product available under the product name "Irgacure 651" from BASF), and anisole methyl ether.

[0094] Specific examples of acetophenone-based photoinitiators include 1-hydroxycyclohexyl phenyl ketone (e.g., commercially available under the product name "Irgacure 184" from BASF), 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (e.g., commercially available under the product name "Irgacure 2959" from BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., commercially available under the product name "DAROCUR 1173" from BASF), and methoxyacetophenone.

[0095] Specific examples of α-ketol-based photoinitiators include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one.

[0096] A specific example of an aromatic sulfonyl chloride-based photoinitiator is 2-naphthalenesulfonyl chloride.

[0097] A specific example of a photoactive oxime-based photoinitiator is 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.

[0098] A specific example of a benzoin-based photoinitiator is benzoin.

[0099] A specific example of a benzil-based photoinitiator is benzil.

[0100] Specific examples of benzophenone-based photoinitiators include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexyl phenyl ketone.

[0101] A specific example of a ketal-based photoinitiator is benzyl dimethyl ketal.

[0102] Specific examples of thioxanthone-based photoinitiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

[0103] Specific examples of acylphosphine-based photoinitiators include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-tert-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentyloxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-din-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, and tris(2-methylbenzoyl)phosphine oxide.

[0104] From the viewpoint of, for example, exhibiting satisfactory aggregability, the amount of the photoinitiator is preferably 5 parts by weight or less, more preferably 0.01 to 5 parts by weight, still more preferably 0.05 to 3 parts by weight, particularly preferably 0.05 to 1.5 parts by weight, and most preferably 0.1 to 1 part by weight, based on the total amount of 100 parts by weight of the monomer composition (M).

[0105] When performing UV polymerization, a polyfunctional (meth)acrylate is preferably used.

[0106] To such an extent that the effects of the present invention are not impaired, any suitable polyfunctional (meth)acrylate can be used as the polyfunctional (meth)acrylate. The polyfunctional (meth)acrylate can be used alone or in combination thereof. Specific examples of such polyfunctional (meth)acrylates include: ester compounds of polyhydric alcohols and (meth)acrylic acid, such as (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tetramethylolmethane tri(meth)acrylate; allyl (meth)acrylate; vinyl (meth)acrylate; divinylbenzene; epoxy acrylate; polyester acrylate; polyurethane acrylate; butyl di(meth)acrylate; and hexyl di(meth)acrylate.

[0107] From the viewpoint of, for example, exhibiting satisfactory crosslinkability, the amount of the polyfunctional (meth)acrylate is preferably 5 parts by weight or less, more preferably 0.01 to 5 parts by weight, still more preferably 0.05 to 3 parts by weight, particularly preferably 0.05 to 1.5 parts by weight, and most preferably 0.1 to 1 part by weight, based on the total amount of 100 parts by weight of the monomer composition (M).

[0108] To such an extent that the effects of the present invention are not impaired, any suitable UV polymerization method can be used as the method for UV polymerization. Such a UV polymerization method is, for example, as follows: The monomer composition (M) is admixed with a photoinitiator and, if necessary, a polyfunctional (meth)acrylate, and the resulting mixture is irradiated with UV light.

[0109] The weight-average molecular weight of the polymer component (P) is preferably from 100,000 to 3,000,000, more preferably from 300,000 to 2,000,000, still more preferably from 500,000 to 1,500,000, and particularly preferably from 500,000 to 1,000,000, because the effects of the present invention can be further exhibited. The weight-average molecular weight is a value measured by gel permeation chromatography (GPC) and calculated as polystyrene. It may be difficult to measure the weight-average molecular weight of the polymer component (P) obtained by living energy ray polymerization.

[0110] The pressure-sensitive adhesive composition may contain a tackifying resin. The tackifying resin may be used alone or in combination.

[0111] To such an extent that the effects of the present invention are not impaired, any suitable tackifying resin can be used as the tackifying resin. Examples of such tackifying resins include phenolic tackifying resins, terpene tackifying resins, modified terpene tackifying resins, rosin tackifying resins, hydrocarbon tackifying resins, epoxy tackifying resins, polyamide tackifying resins, elastomeric tackifying resins, and ketone tackifying resins.

[0112] Examples of phenolic tackifying resins include terpene-phenol resins, hydrogenated terpene-phenol resins, alkylphenol resins, and rosin-phenol resins. A terpene-phenol resin refers to a polymer including terpene residues and phenol residues, and is a concept including both a copolymer of terpenes and phenol compounds (terpene-phenol copolymer resin) and a phenol-modified product of a homopolymer or copolymer of terpenes (phenol-modified terpene resin). Examples of terpenes forming such terpene-phenol resins include monoterpenes such as α-pinene, β-pinene, and limonene (including d-type, l-type, and d / l-type (dipentene)). A hydrogenated terpene-phenol resin refers to a hydrogenated terpene-phenol resin having a structure obtained by hydrogenating such a terpene-phenol resin, and is sometimes referred to as a hydrogenated terpene-phenol resin. An alkylphenol resin is a resin obtained from an alkylphenol and formaldehyde (oily phenolic resin). Examples of alkylphenol resins include novolak-type and resole-type resins. Examples of rosin-phenol resins include phenol-modified products of rosins or various rosin derivatives (including rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters). A rosin-phenol resin is, for example, a rosin-phenol resin obtained by a method involving adding phenols and an acid catalyst to rosins or various rosin derivatives and subjecting the resulting product to thermal polymerization.

[0113] Examples of terpene tackifying resins include polymers of terpenes such as α-pinene, β-pinene, d-limonene, l-limonene, and dipentene (typically, monoterpenes). A homopolymer of one terpene is, for example, an α-pinene polymer, a β-pinene polymer, or a dipentene polymer.

[0114] Examples of the modified terpene resin include styrene-modified terpene resin and hydrogenated terpene resin.

[0115] The concept of rosin-based tackifying resins includes both rosin and rosin derivative resins. Examples of rosin include unmodified rosin (raw rosin), such as gum rosin, wood rosin, and tall oil rosin; and modified rosin (e.g., hydrogenated rosin, disproportionated rosin, polymerized rosin, and any other chemically modified rosin) obtained by modifying these unmodified rosins by means of hydrogenation, disproportionation, polymerization, etc.

[0116] Examples of rosin derivative resins include: rosin esters, such as unmodified rosin esters which are esters of unmodified rosin and alcohols, and modified rosin esters which are esters of modified rosin and alcohols; unsaturated fatty acid-modified rosins obtained by modifying rosins with unsaturated fatty acids; unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; rosin alcohols obtained by subjecting the carboxyl groups of rosins or rosin derivative resins (e.g., rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters) to reduction treatment; and metal salts thereof. Examples of rosin esters include methyl esters, triethylene glycol esters, glycerol esters, and pentaerythritol esters of unmodified rosin or modified rosin (e.g., hydrogenated rosin, disproportionated rosin, and polymerized rosin).

[0117] Examples of hydrocarbon-based tackifying resins include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, aliphatic-aromatic petroleum resins (e.g., styrene-olefin copolymers), aliphatic-alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins, and coumarone-indene resins.

[0118] The content of the tackifying resin in the pressure-sensitive adhesive composition is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, still more preferably 10 to 30 parts by weight, and particularly preferably 15 to 25 parts by weight, relative to the total amount of 100 parts by weight of the monomer composition (M). When the content of the tackifying resin in the pressure-sensitive adhesive composition is adjusted within this range, a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0119] The pressure-sensitive adhesive composition may contain a crosslinking agent. The crosslinking agent can be used alone or in combination. When the pressure-sensitive adhesive composition contains a crosslinking agent, a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0120] To the extent that the effects of the present invention are not impaired, any suitable crosslinking agent can be used as the crosslinking agent. Examples of such crosslinking agents include isocyanate-based crosslinking agents and non-isocyanate-based crosslinking agents.

[0121] To the extent that the effects of the present invention are not impaired, any suitable isocyanate-based crosslinking agent can be used as the isocyanate-based crosslinking agent. Examples of such isocyanate-based crosslinking agents include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, and dimers and trimers of these diisocyanates. Specific examples thereof include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, and m-tetramethylxylylene diisocyanate, and their dimers and trimers, and polyphenylmethanepolyisocyanate. In addition, the trimer can be, for example, an isocyanurate type, a biuret type, or a urethane type.

[0122] Commercially available products can be used as the isocyanate-based crosslinking agent. Examples of commercially available products of polyisocyanates include products available under the product name "TAKENATE 600" from Mitsui Chemicals, Inc., products available under the product name "DURANATE TPA100" from Asahi Kasei Chemicals Corporation, and products available under the product names "CORONATE L", "CORONATE HL", "CORONATE HK", "CORONATE HX", and "CORONATE 2096" from Nippon Polyurethane Industry Co., Ltd.

[0123] Examples of non-isocyanate-based crosslinking agents include epoxy-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, melamine-based crosslinking agents, carbodiimide-based crosslinking agents, hydrazine-based crosslinking agents, amine-based crosslinking agents, peroxide-based crosslinking agents, metal chelate-based crosslinking agents, metal alkoxide-based crosslinking agents, metal salt-based crosslinking agents, and silane coupling agents.

[0124] In at least one exemplary embodiment of the present invention, an epoxy-based crosslinking agent can be used as a non-isocyanate-based crosslinking agent. The epoxy-based crosslinking agent is preferably, for example, a compound having two or more epoxy groups in its molecule, and more preferably, for example, an epoxy-based crosslinking agent having 3 to 5 epoxy groups in its molecule.

[0125] Specific examples of the epoxy-based crosslinking agent include N,N,N′,N′-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polyglycerol polyglycidyl ether. Examples of commercially available products of the epoxy-based crosslinking agent include products available under the product names "TETRAD-C" and "TETRAD-X" from Mitsubishi Gas Chemical Company, products available under the product name "EPICLON CR-5L" from DIC Corporation, products available under the product name "DENACOL EX-512" from Nagase ChemteX Corporation, and products available under the product name "TEPIC-G" from Nissan Chemical Industries, Ltd.

[0126] The content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.1 parts by weight to 8 parts by weight, still more preferably 0.5 parts by weight to 7 parts by weight, and particularly preferably 1.5 parts by weight to 5 parts by weight, relative to the total amount of 100 parts by weight of the monomer composition (M). When the content of the crosslinking agent in the pressure-sensitive adhesive composition is adjusted within this range, a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0127] In a pressure-sensitive adhesive composition, an isocyanate-based crosslinking agent and a non-isocyanate-based crosslinking agent (e.g., an epoxy-based crosslinking agent) can be used in combination. In this case, the ratio of the content of the non-isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition to the content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is preferably 1 / 50 or less, more preferably 1 / 75 or less, still more preferably 1 / 100 or less, and particularly preferably 1 / 150 or less, because a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance. In addition, the ratio of the content of the non-isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition to the content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is preferably 1 / 1,000 or more, more preferably 1 / 500 or more, because a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0128] To such an extent that the effects of the present invention are not impaired, the pressure-sensitive adhesive composition may contain any suitable other components. Examples of such other components include resin components other than the polymer component (P), inorganic fillers, organic fillers, metal powders, colorants, foil products, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, rust preventives, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

[0129] From the viewpoint of, for example, adjusting light transmittance (light-shielding property), to such an extent that the effects of the present invention are not impaired, the pressure-sensitive adhesive composition may contain any suitable colorant. Known pigments or dyes may be used as such colorants. Examples of pigments include: inorganic pigments such as carbon black, zinc carbonate, zinc oxide, zinc sulfide, talc, kaolin, calcium carbonate, titanium oxide, silicon dioxide, lithium fluoride, calcium fluoride, barium sulfate, aluminum oxide, zirconium oxide, iron oxide-based pigments, iron hydroxide-based pigments, chromium oxide-based pigments, spinel-type calcined pigments, chromic acid-based pigments, chrome vermilion-based pigments, iron blue-based pigments, aluminum powder-based pigments, bronze powder-based pigments, silver powder-based pigments, and calcium phosphate; and organic pigments such as phthalocyanine-based pigments, azo-based pigments, condensed azo-based pigments, azo lake-based pigments, anthraquinone-based pigments, perinone-based pigments, indigo-based pigments, thioindigo-based pigments, isoindolinone-based pigments, azomethine-based pigments, dioxazine-based pigments, quinacridone-based pigments, aniline black-based pigments, and triphenylmethane-based pigments. Examples of dyes include azo-based dyes, anthraquinone, quinophthalone, styryl-based dyes, diphenylmethane, triphenylmethane, oxazine, triazine, xanthane, azomethine, acridine, and diazine. The colorants may be used alone or in combination thereof.

[0130] Specific examples of the black colorant are, for example, carbon black, graphite, copper oxide, manganese dioxide, aniline black, perylene black, titanium black, cyanine black, activated carbon, ferrite (e.g., non-magnetic ferrite or magnetic ferrite), magnetite, chromium oxide, iron oxide, molybdenum disulfide, chromium complex, or anthraquinone-based colorant.

[0131] The content of the colorant in the pressure-sensitive adhesive composition is preferably less than 30 wt%, more preferably less than 20 wt%, still more preferably less than 13 wt%, particularly preferably less than 10 wt%, and most preferably less than 8 wt%.

[0132] <1-1-2. Substrate layer>

[0133] The pressure-sensitive adhesive sheet may include a substrate layer.

[0134] The thickness of the substrate layer is preferably 1 μm to 100 μm, as the effects of the present invention can be further exhibited, and the thickness is more preferably 1 μm to 70 μm, still more preferably 1 μm to 50 μm, particularly preferably 5 μm to 30 μm, and most preferably 10 μm to 25 μm.

[0135] The base material layer preferably contains at least one selected from the group consisting of polyolefins, thermoplastic polyurethanes, and styrene-based polymers as the resin component, so that the effects of the present invention can be fully exhibited. The number of types of resins in the base material layer can be only one type, or two or more types.

[0136] The content of the resin component in the base material layer is preferably 50 wt% to 100 wt%, because the effects of the present invention can be more fully exhibited, and this content is more preferably 70 wt% to 100 wt%, still more preferably 90 wt% to 100 wt%, still more preferably 95 wt% to 100 wt%, particularly preferably 98 wt% to 100 wt%, and most preferably substantially 100 wt%.

[0137] Herein, the case described as "substantially 100 wt%" means that to such an extent that the effects of the present invention are not impaired, trace amounts of impurities, etc. are introduced, and such a case can typically be referred to as "100 wt%".

[0138] To such an extent that the effects of the present invention are not impaired, any suitable polyolefin can be used as the polyolefin. Such a polyolefin is preferably at least one selected from the group consisting of polyethylene, polypropylene, and polybutene-1, because the effects of the present invention can be more fully exhibited, and the polyolefin is more preferably at least one selected from the group consisting of polyethylene and polypropylene.

[0139] Polyethylene is, for example, at least one selected from the group consisting of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene, medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and ultra-high-density polyethylene.

[0140] Polyethylene can be metallocene-catalyzed polyethylene obtained by using a metallocene catalyst. Commercially available products can be used as this polyethylene.

[0141] Polypropylene is, for example, at least one selected from the group consisting of atactic polypropylene, block polypropylene, and isotactic polypropylene.

[0142] Polypropylene can be metallocene-catalyzed polypropylene obtained by using a metallocene catalyst. Commercially available products can be used as this polypropylene.

[0143] Polybutene-1 can be metallocene-catalyzed polybutene-1 obtained by using a metallocene catalyst. Commercially available products can be used as this polybutene-1.

[0144] To the extent that the effects of the present invention are not impaired, any suitable thermoplastic polyurethane may be used as the thermoplastic polyurethane. Examples of such thermoplastic polyurethanes, commonly referred to as TPU, are block copolymers comprising hard segments and soft segments. Preferred examples of such thermoplastic polyurethanes are at least one selected from the group consisting of polyester-based TPU, polyether-based TPU, and polycarbonate-based TPU, because the effects of the present invention can be more fully exhibited.

[0145] Commercially available products may be used as the thermoplastic polyurethane.

[0146] To the extent that the effects of the present invention are not impaired, any suitable styrene-based polymer may be used as the styrene-based polymer. Such styrene-based polymers are preferably, for example, polymers including styrene-based thermoplastic elastomers, because the effects of the present invention can be more fully exhibited.

[0147] Examples of styrene-based thermoplastic elastomers include: AB-type block polymers such as hydrogenated styrene-butadiene rubber (HSBR), styrene-based block copolymers or their hydrogenated products, styrene-butadiene copolymer (SB), styrene-isoprene copolymer (SI), copolymers of styrene-ethylene-butene copolymer (SEB), and copolymers of styrene-ethylene-propylene copolymer (SEP); styrene-based random copolymers such as styrene-butadiene rubber (SBR); A-B-C-type styrene-olefin crystalline block polymers such as copolymers of styrene-ethylene-butene copolymer and olefin crystals (SEBC); and their hydrogenated products. Styrene-based thermoplastic elastomers are preferably, for example, at least one selected from the group consisting of hydrogenated styrene-butadiene rubber (HSBR) and styrene-based block copolymers or their hydrogenated products, because the effects of the present invention can be more fully exhibited.

[0148] Examples of hydrogenated styrene-butadiene rubber (HSBR) include DYNARON 1320P, 1321P, and 2324P manufactured by JSR Corporation.

[0149] Examples of the styrenic block copolymer include: styrenic ABA type block copolymers (triblock copolymers), such as styrene-butadiene-styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS); styrenic ABAB type block copolymers (tetrablock copolymers), such as styrene-butadiene-styrene-butadiene copolymer (SBSB) and styrene-isoprene-styrene-isoprene copolymer (SISI); styrenic ABABA type block copolymers (pentablock copolymers), such as styrene-butadiene-styrene-butadiene-styrene copolymer (SBSBS) and styrene-isoprene-styrene-isoprene-styrene copolymer (SISIS); and styrenic block copolymers each having a larger number of AB repeating units.

[0150] Examples of the hydrogenated product of the styrenic block copolymer include styrene-ethylene-butene copolymer-styrene copolymer (SEBS), styrene-ethylene-propylene copolymer-styrene copolymer (SEPS), and copolymer of styrene-ethylene-butene copolymer and styrene-ethylene-butene copolymer (SEBSEB).

[0151] Examples of styrene-ethylene-butene copolymer-styrene copolymer (SEBS) include DYNARON 8601P and 9901P manufactured by JSR Corporation.

[0152] The styrene content (styrene block content in the case of the styrenic block copolymer) in the styrenic thermoplastic elastomer is preferably 1 wt% to 40 wt%, because the effects of the present invention can be more fully exhibited, and this content is more preferably 5 wt% to 40 wt%, still more preferably 7 wt% to 30 wt%, still more preferably 9 wt% to 20 wt%, particularly preferably 9 wt% to 15 wt%, and most preferably 9 wt% to 13 wt%.

[0153] The hydrogenated product of the styrenic block copolymer having a repeating structure corresponding to a triblock copolymer or higher formed of styrene (A) and butadiene (B) (e.g., ABA type, ABAB type, or ABABA type) (e.g., SEBS, SEBSEB, or SEBSEBS) is suitable as the styrenic thermoplastic elastomer because the effects of the present invention can be more fully exhibited.

[0154] When the styrene-based thermoplastic elastomer is a hydrogenated product of a styrene-based block copolymer having a repeating structure corresponding to a triblock copolymer or higher formed from styrene (A) and butadiene (B) (e.g., ABA type, ABAB type, or ABABA type) (e.g., SEBS, SEBSEB, or SEBSEBS), the proportion of the butene structure in the ethylene-butene copolymer block is preferably 60 wt% or more because the effects of the present invention can be more fully exhibited, and this proportion is more preferably 70 wt% or more, and still more preferably 75 wt% or more. The proportion of the butene structure in the ethylene-butene copolymer block is preferably 90 wt% or less.

[0155] To such an extent that the effects of the present invention are not impaired, the styrene-based polymer may contain any suitable other polymer in addition to the styrene-based polymer. Examples of such other polymers include ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic ester copolymer, ethylene / methacrylic ester copolymer, ethylene / butene-1 copolymer, ethylene / propylene / butene-1 copolymer, copolymer of ethylene and an α-olefin having 5 to 12 carbon atoms, and ethylene / non-conjugated diene copolymer. Among them, ethylene / vinyl acetate copolymer is preferred.

[0156] A preferred embodiment of the styrene-based polymer is, for example, a blend product of a hydrogenated product of a styrene-based block copolymer (e.g., SEBS, SEBSEB, or SEBSEBS) and an ethylene / vinyl acetate copolymer because the effects of the present invention can be more fully exhibited, and this embodiment is preferably a blend product of SEBS and an ethylene / vinyl acetate copolymer.

[0157] The substrate layer may be formed of one layer (single layer) or two or more layers (multi-layer).

[0158] The substrate layer may contain any suitable additives as needed. Examples of additives that can be introduced into the substrate layer include release agents, UV absorbers, heat stabilizers, fillers, lubricants, colorants (e.g., dyes), antioxidants, anti-build up agents, anti-blocking agents, foaming agents, and polyethyleneimine. These additives may be used alone or in combination. The content of the additives in the substrate layer is preferably 10 wt% or less, more preferably 7 wt% or less, still more preferably 5 wt% or less, particularly preferably 2 wt% or less, and most preferably 1 wt% or less.

[0159] <1-1-3. Manufacture of Pressure-Sensitive Adhesive Sheet>

[0160] To the extent that does not impair the effects of the present invention, the pressure-sensitive adhesive sheet can be produced by any suitable method. Examples of such methods include: a method (direct method) involving coating a pressure-sensitive adhesive composition onto any suitable substrate (e.g., a substrate layer or a release liner), and drying the composition as needed to form a pressure-sensitive adhesive layer on the substrate (e.g., a substrate layer or a release liner); a method (transfer method) involving coating a pressure-sensitive adhesive composition onto a surface having releasability (the release surface of a release liner), and drying the composition as needed to form a pressure-sensitive adhesive layer on the release surface, and transferring the pressure-sensitive adhesive layer onto any suitable substrate (e.g., a substrate layer); and combinations of these methods. For example, a laminator can be used to laminate various layers. Additionally, after lamination, the resultant can be aged at any suitable temperature for any suitable time as needed.

[0161] <<1-2. Reinforcement layer>>

[0162] The reinforcement layer can be used alone or in combination.

[0163] The thickness of the reinforcement layer is preferably from 0.05 μm to 10.0 μm, because the effects of the present invention can be further exhibited, and the thickness is more preferably from 0.05 μm to 7.00 μm, still more preferably from 0.10 μm to 5.00 μm, particularly preferably from 0.19 μm to 4.00 μm, and most preferably from 0.19 μm to 1.00 μm.

[0164] The reinforcement layer is preferably formed of a reinforcing agent. To the extent that does not impair the effects of the present invention, any suitable method can be used as the method for forming the reinforcement layer. Such a method is, for example, a method involving coating a liquid reinforcing agent (the reinforcing agent itself when the reinforcing agent is liquid, or, in any other case, for example, a solution or a dispersion of the reinforcing agent) onto any suitable substrate (typically, an adherend), and drying the reinforcing agent as needed to form a reinforcement layer on the substrate (typically, an adherend). A solution or a dispersion of the reinforcing agent, etc. is preferably a solution in an aqueous medium (e.g., water or alcohol) or a dispersion in an aqueous medium (e.g., water or alcohol) in terms of the environment, and more preferably an aqueous solution or an aqueous dispersion.

[0165] The reinforcing agent preferably contains an aqueous polyurethane resin crosslinked by an isocyanate-based crosslinking agent, and the resin has at least one selected from the group consisting of an ester skeleton, an ether skeleton, and a carbonate skeleton. When the reinforcing agent contains such an aqueous polyurethane resin, a laminate including a pressure-sensitive adhesive sheet, a reinforcement layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0166] The content of the aqueous polyurethane resin in the reinforcing agent is preferably 50 wt% to 100 wt%, more preferably 70 wt% to 100 wt%, still more preferably 90 wt% to 100 wt%, still more preferably 95 wt% to 100 wt%, particularly preferably 98 wt% to 100 wt%, and most preferably substantially 100 wt% on a solid content basis.

[0167] The elongation at break of the aqueous polyurethane resin is preferably 300% to 1,500%, more preferably 300% to 1,200%, still more preferably 300% to 1,000%, particularly preferably 300% to 900%, and most preferably 300% to 800%. When the elongation at break of the aqueous polyurethane resin falls within this range, a laminate including a pressure-sensitive adhesive sheet, a reinforcing agent layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0168] The aqueous polyurethane resin is preferably a non-reactive aqueous polyurethane resin. When the aqueous polyurethane resin is a non-reactive aqueous polyurethane resin, a laminate including a pressure-sensitive adhesive sheet, a reinforcing agent layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0169] The non-reactive aqueous polyurethane resin is preferably a self-emulsifying aqueous polyurethane resin. When the non-reactive aqueous polyurethane resin is a self-emulsifying aqueous polyurethane resin, a laminate including a pressure-sensitive adhesive sheet, a reinforcing agent layer, and an adherend can be provided, and the laminate can simultaneously exhibit higher adhesive strength and higher impact resistance.

[0170] <<1-3. Adherend>>

[0171] To such an extent that the effects of the present invention are not impaired, any suitable adherend can be selected as the adherend. Such an adherend is preferably an electronic device member because the effects of the present invention can be further utilized. That is, when the laminate according to at least one embodiment of the present invention is a laminate having a laminated structure including a pressure-sensitive adhesive sheet, a reinforcing agent layer, and an electronic device member as the adherend, the laminate can simultaneously exhibit high adhesive strength and high impact resistance in a balanced manner, which is important for articles (typically, mobile devices) including electronic device members.

[0172] The material of the bonding portion of such an adherend is specifically, for example, at least one selected from the group consisting of SUS, polycarbonate, aluminum, polyolefin resin, styrene resin, polyester resin, acrylic resin, polyimide resin, and glass fiber.

[0173] <<<<2. Manufacturing method of the laminate>>>>

[0174] To the extent that does not impair the effects of the present invention, the laminate according to at least one embodiment of the present invention can be produced by any suitable method.

[0175] The method for manufacturing a laminate according to at least one embodiment of the present invention preferably includes: step (I) of applying an aqueous coating containing a reinforcing agent and an aqueous medium to the surface of an adherend to form a reinforcing agent layer; and step (II) of laminating a pressure-sensitive adhesive sheet onto the surface of the thus-formed reinforcing agent layer. To the extent that does not impair the effects of the present invention, the method for manufacturing a laminate according to at least one embodiment of the present invention can include any other suitable steps as long as the method includes step (I) and step (II).

[0176] <<2-1. Step (I)>>

[0177] In step (I), an aqueous coating containing a reinforcing agent and an aqueous medium is preferably applied to the surface of an adherend to form a reinforcing agent layer. To the extent that does not impair the effects of the present invention, any suitable coating method can be used as the coating method. Such coating methods are, for example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spraying, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, or extrusion coating using a die coater.

[0178] In step (I), heating or aging can be carried out as needed.

[0179] The aqueous coating preferably contains a reinforcing agent and an aqueous medium. To the extent that does not impair the effects of the present invention, the aqueous coating can contain any other suitable components.

[0180] The total content of the reinforcing agent and the aqueous medium in the aqueous coating is preferably 50 parts by weight to 100 parts by weight, more preferably 80 parts by weight to 100 parts by weight, still more preferably 90 parts by weight to 100 parts by weight, particularly preferably 95 parts by weight to 100 parts by weight, and most preferably substantially 100 parts by weight, relative to 100 parts by weight of the aqueous coating.

[0181] Examples of the aqueous medium include water and alcohols. Examples of the alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.

[0182] The content of the reinforcing agent in 100 parts by weight of the aqueous coating is preferably from 0.1 part by weight to 50 parts by weight, more preferably from 0.5 part by weight to 40 parts by weight, still more preferably from 1.0 part by weight to 30 parts by weight, particularly preferably from 1.5 parts by weight to 20 parts by weight, and most preferably from 1.5 parts by weight to 15 parts by weight. When the content of the reinforcing agent in 100 parts by weight of the aqueous coating is adjusted within this range, a laminate including a pressure-sensitive adhesive sheet, a reinforcing agent layer, and an adherend can be produced, and the laminate can exhibit higher impact resistance even when the thickness of the reinforcing agent layer is small, and can exhibit higher adhesive strength.

[0183] The method for forming the reinforcing agent layer preferably includes: coating the aqueous coating onto any suitable substrate (typically the adherend), and drying the coating as needed, thereby forming a reinforcing agent layer on the substrate (typically the adherend).

[0184] <<2-2. Step (II)>>

[0185] In step (II), the pressure-sensitive adhesive sheet is preferably adhered to the surface of the reinforcing agent layer.

[0186] To such an extent that the effects of the present invention are not impaired, any suitable adhesion method can be used as the method for adhering the pressure-sensitive adhesive sheet to the surface of the reinforcing agent layer. Examples of such adhesion methods include: a flat platen press configured to apply pressure horizontally, a hand roller, a room-temperature laminator, a heated laminator, a vacuum pressure laminator, and an autoclave.

[0187] Embodiment

[0188] Now, the present invention will be specifically described by way of examples. However, the present invention is in no way limited to the examples. The test and evaluation methods in the examples and the like are as described below. In the following description, the term "part" means "part by weight" unless otherwise specified, and the term "%" means "wt%" unless otherwise specified.

[0189] <Weight-average molecular weight>

[0190] The weight-average molecular weight is determined by the value based on standard polystyrene obtained by gel permeation chromatography (GPC). An apparatus available under the model name "HLC-8320GPC" (column: TSKgel GMH-H(S), manufactured by Tosoh Corporation) is used as the GPC apparatus.

[0191] <Measurement of the thickness of the reinforcing agent layer>

[0192] The thickness of the reinforcing agent layer is measured using a laser microscope (VK-X250, manufactured by Keyence Corporation).

[0193] <Adhesion strength measurement>

[0194] (1. Manufacture of a laminated structure of a reinforcing agent layer and a SUS plate for adhesion strength measurement)

[0195] The reinforcing agent solution for producing the laminate to be obtained in each example and comparative example was uniformly coated onto a stainless steel plate (SUS304BA plate) (manufactured by Nippon Kinzoku Co., Ltd.) that had been washed with toluene using a coater (manufactured by ASONE Corporation, 1-3777-01) so as to obtain the thickness of the reinforcing agent layer in the laminate to be obtained in each example and comparative example. Thereafter, the obtained product was dried in an oven at 70 °C for 5 minutes to produce a laminated structure (A) of a reinforcing agent layer and a SUS plate.

[0196] (2. Manufacture of a laminated structure of a reinforcing agent layer and a polycarbonate plate for adhesion strength measurement)

[0197] The reinforcing agent solution for producing the laminate to be obtained in each example and comparative example was uniformly coated onto a polycarbonate plate (manufactured by Mitsubishi Chemical Corporation) that had been washed with isopropyl alcohol using a coater (manufactured by ASONE Corporation, 1-3777-01) so as to obtain the thickness of the reinforcing agent layer in the laminate to be obtained in each example and comparative example. Thereafter, the obtained product was dried in an oven at 70 °C for 5 minutes to produce a laminated structure (B) of a reinforcing agent layer and a polycarbonate plate.

[0198] (3. Manufacture of a laminated structure of a reinforcing agent layer and an aluminum plate for adhesion strength measurement)

[0199] The reinforcing agent solution for producing the laminate to be obtained in each example and comparative example was uniformly coated onto an aluminum plate (Nippon Testpanel Co., Ltd.) using a coater (manufactured by ASONE Corporation, 1-3777-01) so as to obtain the thickness of the reinforcing agent layer in the laminate to be obtained in each example and comparative example. Thereafter, the obtained product was dried in an oven at 70 °C for 5 minutes to produce a laminated structure (C) of a reinforcing agent layer and an aluminum plate.

[0200] (Adhesion strength)

[0201] A PET film with a thickness of 50 μm (without release treatment) was adhered to the surface of one pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet for the laminate to be obtained in each example and comparative example so as to be behind the surface. The pressure-sensitive adhesive sheet with the backing was cut into a width of 20 mm to produce a test piece.

[0202] The surface of the pressure-sensitive adhesive layer of the obtained test piece was pressure-bonded to each of the above various laminated structures (A), (B), and (C) by passing it back and forth once with a 2 kg roller. The obtained product was placed in a measurement environment of 23°C and 50% RH for 30 minutes, and the adhesive strength (N / 20 mm) was measured using a tensile testing machine (manufactured by Shimadzu Corporation, "PRECISION UNIVERSAL TESTER AUTOGRAPH AG-IS 50N") in accordance with JIS Z 0237:2000 when peeling the pressure-sensitive adhesive sheet at a peeling speed of 300 mm / min and a peeling angle of 180°.

[0203] <Impact resistance measurement>

[0204] (Manufacture of laminated structure of reinforcing agent layer and SUS plate for impact resistance measurement)

[0205] A square stainless steel plate (SUS304BA) (X1) with a thickness of 2 mm, a length of 50 mm, and a width of 50 mm having a hole with a size of 20 mm in length × 20 mm in width in its central part and a square stainless steel plate (SUS304BA) (Y1) with a thickness of 3 mm, a length of 25 mm, and a width of 25 mm were prepared as adherends. First, each adherend was washed with toluene. After that, the reinforcing agent solution for producing the laminate to be obtained in each example and comparative example was uniformly coated onto each adherend using a coater (manufactured by AS ONE Corporation, 1-3777-01) so as to obtain the thickness of the reinforcing agent layer in the laminate to be obtained in each example and comparative example. After that, the obtained product was dried in an oven at 70°C for 5 minutes to provide a laminated structure (X) of a reinforcing agent layer and a SUS plate (X1) or a laminated structure (Y) of a reinforcing agent layer and a SUS plate (Y1).

[0206] (Impact resistance)

[0207] The pressure-sensitive adhesive sheet sandwiched between the release liners was punched into a square frame shape with a width of 2 mm, an outer longitudinal length of 24.5 mm, and an outer transverse length of 24.5 mm to provide an evaluation sample.

[0208] The evaluation sample was applied between the two laminated structures (X) and (Y) obtained above so that the shape was point-symmetrical about its center, and pressure bonding was performed therebetween (62 N × 10 seconds) in such a manner that a force was uniformly applied in the gravitational direction. Thereafter, the obtained product was left standing in an environment at 80°C for 30 minutes, removed from this environment, and then allowed to return to a temperature of 23°C overnight. Thus, a test piece was obtained. A columnar measuring table having a length of 50 mm, an outer diameter of 49 mm, and an inner diameter of 43 mm was placed on the base of a Dupont type impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.), and the test piece was mounted on the table with its square stainless steel plate (Y1) facing downward so that the shape was point-symmetrical about the center. A stainless steel impactor having a tip radius of 3.1 mm was mounted on the test piece, and the weight of the drop hammer and its dropping height were changed as follows so that the energy was increased until peeling between the laminated structures occurred: the weight was set to 100 g, and the height was changed from 50 mm to 500 mm in 50 mm increments; the weight was set to 150 g, and the height was changed from 350 mm to 500 mm in 50 mm increments; the weight was set to 200 g, and the height was changed from 400 mm to 500 mm in 50 mm increments; and the weight was set to 300 g, and the height was changed from 350 mm to 500 mm in 50 mm increments. At this time, the energy that had already been evaluated was not tested, and the load and height were set so that the amounts of energy did not overlap with each other. Thereafter, the energy before peeling was determined by the product of the load and the height.

[0209] [Production Example 1]: Production of Pressure-Sensitive Adhesive Sheet (1)

[0210] 95 parts of butyl acrylate (BA) and 5 parts of acrylic acid (AA) as monomer components and 233 parts of ethyl acetate as a polymerization solvent were put into a reaction vessel including a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel, and stirred for 2 hours while introducing nitrogen into the vessel. After the oxygen in the polymerization system had been removed as described above, 0.2 part of 2,2′-azobisisobutyronitrile was added to the mixture as a polymerization initiator, and the whole was subjected to solution polymerization at 60°C for 8 hours to provide a solution of an acrylic polymer. The weight-average molecular weight of the acrylic polymer was 700,000.

[0211] With respect to 100 parts of the acrylic polymer in the resulting acrylic polymer solution, 20 parts of a terpene-phenol resin (product name: "YS POLYSTER T-115", softening point: about 115°C, hydroxyl value: 30 mgKOH / g to 60 mgKOH / g, manufactured by Yasuhara Chemical Co., Ltd.) as a tackifying resin, 3 parts of an isocyanate-based crosslinking agent (product name: "CORONATE L", 75% ethyl acetate solution of a trimethylolpropane / toluene diisocyanate trimer adduct, manufactured by Tosoh Corporation) as a crosslinking agent, 0.02 parts of an epoxy-based crosslinking agent (product name: "TETRAD-C", 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical Company, Inc.), and 6 parts of a product obtainable under the product name "AT-DN101 BLACK" (manufactured by Dainichiseika Color&Chemicals Mfg. Co., Ltd.) as a black pigment were added to the solution, and the contents were stirred and mixed to prepare a pressure-sensitive adhesive composition (1).

[0212] The pressure-sensitive adhesive composition (1) was coated onto the release surface of a polyester release liner having a thickness of 38 μm (product name: "DIAFOIL MRF", manufactured by Mitsubishi Polyester Film, Inc.), and dried at 100°C for 2 minutes to form a pressure-sensitive adhesive layer (1) having a thickness of 100 μm.

[0213] The two pressure-sensitive adhesive layer surfaces of the resulting pressure-sensitive adhesive layer (1) on which the release liner was not disposed were adhered to each other. The resulting structure was passed through a laminator at room temperature (0.3 MPa, speed: 0.5 m / min) once, and then aged in an oven at 50°C for 1 day. Thereafter, the release liner was peeled off. Thus, a pressure-sensitive adhesive sheet (1) having a total thickness of 200 μm was obtained.

[0214] [Production Example 2]: Production of Pressure-Sensitive Adhesive Sheet (2)

[0215] The pressure-sensitive adhesive composition (1) obtained in Production Example 1 was coated onto the release surface of a polyester release liner having a thickness of 38 μm (product name: "DIAFOIL MRF", manufactured by Mitsubishi Polyester Film, Inc.), and dried at 100°C for 2 minutes to form a pressure-sensitive adhesive layer (2) having a thickness of 95 μm.

[0216] Next, the surface of the pressure-sensitive adhesive layer (2) where the release liner is not disposed is adhered to each of the two surfaces of a polyurethane substrate (SILKLON NES85, manufactured by Okura Industrial Co., Ltd.) having a thickness of 10 μm. The resulting structure is passed through a laminator (0.3 MPa, speed: 0.5 m / min) once at room temperature and then aged in an oven at 50°C for 1 day. Thereafter, the release liner is peeled off. Thus, a pressure-sensitive adhesive sheet (2) having a total thickness of 200 μm is obtained.

[0217] [Production Example 3]: Production of Pressure-Sensitive Adhesive Sheet (3)

[0218] The pressure-sensitive adhesive composition (1) obtained in Production Example 1 was coated on the release surface of a polyester release liner having a thickness of 38 μm (product name: "DIAFOIL MRF", manufactured by Mitsubishi Polyester Film, Inc.) and dried at 100°C for 2 minutes to form a pressure-sensitive adhesive layer (3) having a thickness of 87.5 μm.

[0219] Next, the surface of the pressure-sensitive adhesive layer (3) where the release liner is not disposed is adhered to each of the two surfaces of a polyurethane substrate (SILKLON NES85, manufactured by Okura Industrial Co., Ltd.) having a thickness of 25 μm. The resulting structure is passed through a laminator (0.3 MPa, speed: 0.5 m / min) once at room temperature and then aged in an oven at 50°C for 1 day. Thereafter, the release liner is peeled off. Thus, a pressure-sensitive adhesive sheet (3) having a total thickness of 200 μm is obtained.

[0220] [Production Example 4]: Production of Pressure-Sensitive Adhesive Sheet (4)

[0221] 90 parts of 2-ethylhexyl acrylate (2EHA) and 10 parts of acrylic acid as monomer components and 200 parts of ethyl acetate as a polymerization solvent were put into a reaction vessel including a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel, and stirred for 2 hours while introducing nitrogen into the vessel. After removing oxygen in the polymerization system as described above, 0.2 part of benzoyl peroxide was added to the mixture as a polymerization initiator, and the whole was subjected to solution polymerization at 60°C for 6 hours to provide a solution of the acrylic polymer according to this example. The weight-average molecular weight of the acrylic polymer was 1,200,000.

[0222] To 100 parts of the acrylic polymer in the resulting acrylic polymer solution, 20 parts of a terpene-phenol resin (product name: "YS POLYSTER T-115", softening point: about 115°C, hydroxyl value: 30 mgKOH / g to 60 mgKOH / g, manufactured by Yasuhara Chemical Co., Ltd.) as a tackifying resin, 3 parts of an isocyanate-based crosslinking agent (product name: "CORONATE L", 75% ethyl acetate solution of trimethylolpropane / toluene diisocyanate trimer adduct, manufactured by Tosoh Corporation) as a crosslinking agent, 0.02 parts of an epoxy-based crosslinking agent (product name: "TETRAD-C", 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical Company, Inc.), and 6 parts of a product available under the product name "AT-DN101 BLACK" (manufactured by Dainichiseika Color&Chemicals Mfg. Co., Ltd.) as a black pigment were added to the solution, and the contents were stirred and mixed to prepare a pressure-sensitive adhesive composition (4).

[0223] The pressure-sensitive adhesive composition (4) was coated on the release surface of a polyester release liner (product name: "DIAFOIL MRF", manufactured by Mitsubishi Polyester Film, Inc.) having a thickness of 38 μm and dried at 100°C for 2 minutes to form a pressure-sensitive adhesive layer (4) having a thickness of 100 μm.

[0224] The two pressure-sensitive adhesive layer surfaces of the resulting pressure-sensitive adhesive layer (4) on which the release liner was not disposed were brought into contact with each other. The resulting structure was passed through a laminator at room temperature (0.3 MPa, speed: 0.5 m / min) once, and then aged in an oven at 50°C for 1 day. Thereafter, the release liner was peeled off. Thus, a pressure-sensitive adhesive sheet (4) having a total thickness of 200 μm was obtained.

[0225] [Production Example 5]: Production of Pressure-Sensitive Adhesive Sheet (5)

[0226] 85 parts of butyl acrylate and 15 parts of acrylic acid as monomer components, and 250 parts of ethyl acetate as a polymerization solvent were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel, and stirred for 2 hours while introducing nitrogen into the vessel. After removing oxygen in the polymerization system as described above, 0.2 part of 2,2′-azobisisobutyronitrile was added as a polymerization initiator to the mixture, and the whole was subjected to solution polymerization at 60 °C for 8 hours to provide a solution of an acrylic polymer. The weight-average molecular weight of the acrylic polymer was 600,000.

[0227] With respect to 100 parts of the acrylic polymer in the obtained acrylic polymer solution, 20 parts of a terpene-phenol resin (product name: "YS POLYSTER T-115", softening point: about 115 °C, hydroxyl value: 30 mgKOH / g to 60 mgKOH / g, manufactured by Yasuhara Chemical Co., Ltd.) as a tackifying resin, 3 parts of an isocyanate-based crosslinking agent (product name: "CORONATE L", 75% ethyl acetate solution of trimethylolpropane / toluene diisocyanate trimer adduct, manufactured by Tosoh Corporation) as a crosslinking agent, and 0.02 part of an epoxy-based crosslinking agent (product name: "TETRAD-C", 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical Company, Inc.), and 6 parts of a product available under the product name "AT-DN101 BLACK" (manufactured by Dainichiseika Color&Chemicals Mfg. Co., Ltd.) as a black pigment were added to the solution, and the contents were stirred and mixed to prepare a pressure-sensitive adhesive composition (5).

[0228] The pressure-sensitive adhesive composition (5) was coated on the release surface of a polyester release liner having a thickness of 38 μm (product name: "DIAFOIL MRF", manufactured by Mitsubishi Polyester Film, Inc.) and dried at 100 °C for 2 minutes to form a pressure-sensitive adhesive layer (5) having a thickness of 100 μm.

[0229] The two pressure-sensitive adhesive layer surfaces of the obtained pressure-sensitive adhesive layer (5) on which the release liner was not disposed were brought into contact with each other. The obtained structure was passed through a laminator at room temperature (0.3 MPa, speed: 0.5 m / min) once, and then aged in an oven at 50 °C for 1 day. Thereafter, the release liner was peeled off. Thus, a pressure-sensitive adhesive sheet (5) having a total thickness of 200 μm was obtained.

[0230] [Example 1]: Manufacturing of the laminate (1)

[0231] A stainless steel plate (SUS304BA plate) washed with toluene (manufactured by Nippon Kinzoku Co., Ltd.), a polycarbonate plate washed with isopropyl alcohol (manufactured by Mitsubishi Chemical Corporation), and an aluminum plate (manufactured by Nippon Testpanel Co., Ltd.) were used as adherends (a), (b), and (c), respectively. And an aqueous dispersion of a self-emulsifying aqueous polyurethane resin with an elongation at break of 330% ("SUPERFLEX 150", non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was uniformly coated onto the surface of each of these adherends to have a thickness of 3.00 μm using a coater (manufactured by AS ONE Corporation, 1-3777-01). Thereafter, the obtained product was dried in an oven at 70°C for 5 minutes to produce a reinforcing agent layer (1) and a laminated structure of each of the three adherends (a), (b), and (c).

[0232] By passing a 2 kg roller back and forth once, one pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet (1) obtained in Production Example 1 was pressure-bonded to each laminated structure, thereby producing laminates (1a), (1b), or (1c) of the pressure-sensitive adhesive sheet (1), the reinforcing agent layer (1), and the adherend (a), (b), or (c).

[0233] The results are shown in Table 1.

[0234] [Example 2]: Manufacturing of the laminate (2)

[0235] Except that an aqueous dispersion of a self-emulsifying aqueous polyurethane resin with an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was uniformly coated onto the surface of each adherend to have a thickness of 1.50 μm, laminates (2a), (2b), or (2c) of the pressure-sensitive adhesive sheet (1), the reinforcing agent layer (2), and the adherend (a), (b), or (c) were obtained in the same manner as in Example 1.

[0236] The results are shown in Table 1.

[0237] [Example 3]: Manufacturing of the laminate (3)

[0238] Except that an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was uniformly coated on the surface of each adherend to have a thickness of 0.75 μm, a laminate (3a), (3b) or (3c) of the pressure-sensitive adhesive sheet (1), the reinforcing layer (3) and the adherends (a), (b) or (c) was obtained in the same manner as in Example 1.

[0239] The results are shown in Table 1.

[0240] [Example 4]: Manufacture of laminate (4)

[0241] Except that an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was uniformly coated on the surface of each adherend to have a thickness of 0.38 μm, a laminate (4a), (4b) or (4c) of the pressure-sensitive adhesive sheet (1), the reinforcing layer (4) and the adherends (a), (b) or (c) was obtained in the same manner as in Example 1.

[0242] The results are shown in Table 1.

[0243] [Example 5]: Manufacture of laminate (5)

[0244] Except that an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was uniformly coated on the surface of each adherend to have a thickness of 0.19 μm, a laminate (5a), (5b) or (5c) of the pressure-sensitive adhesive sheet (1), the reinforcing layer (5) and the adherends (a), (b) or (c) was obtained in the same manner as in Example 1.

[0245] The results are shown in Table 1.

[0246] [Example 6]: Manufacture of laminate (6)

[0247] Except that the pressure-sensitive adhesive sheet (1) was changed to the pressure-sensitive adhesive sheet (2) obtained in Production Example 2, a laminate (6a), (6b) or (6c) of the pressure-sensitive adhesive sheet (2), the reinforcing layer (1) and the adherends (a), (b) or (c) was obtained in the same manner as in Example 1.

[0248] The results are shown in Table 1.

[0249] [Example 7]: Manufacture of laminate (7)

[0250] A laminate (7a), (7b), or (7c) of the pressure-sensitive adhesive sheet (2), the reinforcing layer (2), and the adherend (a), (b), or (c) is obtained in the same manner as in Example 2, except that the pressure-sensitive adhesive sheet (1) is changed to the pressure-sensitive adhesive sheet (2) obtained in Production Example 2.

[0251] The results are shown in Table 1.

[0252] [Example 8]: Production of laminate (8)

[0253] A laminate (8a), (8b), or (8c) of the pressure-sensitive adhesive sheet (2), the reinforcing layer (3), and the adherend (a), (b), or (c) is obtained in the same manner as in Example 3, except that the pressure-sensitive adhesive sheet (1) is changed to the pressure-sensitive adhesive sheet (2) obtained in Production Example 2.

[0254] The results are shown in Table 1.

[0255] [Example 9]: Production of laminate (9)

[0256] A laminate (9a), (9b), or (9c) of the pressure-sensitive adhesive sheet (2), the reinforcing layer (4), and the adherend (a), (b), or (c) is obtained in the same manner as in Example 4, except that the pressure-sensitive adhesive sheet (1) is changed to the pressure-sensitive adhesive sheet (2) obtained in Production Example 2.

[0257] The results are shown in Table 1.

[0258] [Example 10]: Production of laminate (10)

[0259] A laminate (10a), (10b), or (10c) of the pressure-sensitive adhesive sheet (2), the reinforcing layer (5), and the adherend (a), (b), or (c) is obtained in the same manner as in Example 5, except that the pressure-sensitive adhesive sheet (1) is changed to the pressure-sensitive adhesive sheet (2) obtained in Production Example 2.

[0260] The results are shown in Table 1.

[0261] [Example 11]: Production of laminate (11)

[0262] A laminate (11a), (11b), or (11c) of the pressure-sensitive adhesive sheet (3), the reinforcing layer (1), and the adherend (a), (b), or (c) is obtained in the same manner as in Example 1, except that the pressure-sensitive adhesive sheet (1) is changed to the pressure-sensitive adhesive sheet (3) obtained in Production Example 3.

[0263] The results are shown in Table 1.

[0264] [Example 12]: Production of laminate (12)

[0265] The laminate (12a), (12b), or (12c) of the pressure-sensitive adhesive sheet (3), the reinforcing layer (2), and the adherend (a), (b), or (c) was obtained in the same manner as in Example 2, except that the pressure-sensitive adhesive sheet (1) was changed to the pressure-sensitive adhesive sheet (3) obtained in Production Example 3.

[0266] The results are shown in Table 1.

[0267] [Example 13]: Production of laminate (13)

[0268] The laminate (13a), (13b), or (13c) of the pressure-sensitive adhesive sheet (3), the reinforcing layer (3), and the adherend (a), (b), or (c) was obtained in the same manner as in Example 3, except that the pressure-sensitive adhesive sheet (1) was changed to the pressure-sensitive adhesive sheet (3) obtained in Production Example 3.

[0269] The results are shown in Table 1.

[0270] [Example 14]: Production of laminate (14)

[0271] The laminate (14a), (14b), or (14c) of the pressure-sensitive adhesive sheet (3), the reinforcing layer (4), and the adherend (a), (b), or (c) was obtained in the same manner as in Example 4, except that the pressure-sensitive adhesive sheet (1) was changed to the pressure-sensitive adhesive sheet (3) obtained in Production Example 3.

[0272] The results are shown in Table 1.

[0273] [Example 15]: Production of laminate (15)

[0274] The laminate (15a), (15b), or (15c) of the pressure-sensitive adhesive sheet (3), the reinforcing layer (5), and the adherend (a), (b), or (c) was obtained in the same manner as in Example 5, except that the pressure-sensitive adhesive sheet (1) was changed to the pressure-sensitive adhesive sheet (3) obtained in Production Example 3.

[0275] The results are shown in Table 1.

[0276] [Example 16]: Production of laminate (16)

[0277] Except that the aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 750% (“SUPERFLEX 460”, non-volatile content = 38 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (1), a reinforcing layer (16), and a laminate (16a), (16b), or (16c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 1.

[0278] The results are shown in Table 2.

[0279] [Example 17]: Production of laminate (17)

[0280] Except that the aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 750% (“SUPERFLEX 460”, non-volatile content = 38 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (1), a reinforcing layer (17), and a laminate (17a), (17b), or (17c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 2.

[0281] The results are shown in Table 2.

[0282] [Example 18]: Production of laminate (18)

[0283] Except that the aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 750% (“SUPERFLEX 460”, non-volatile content = 38 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (2), a reinforcing layer (18), and a laminate (18a), (18b), or (18c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 6.

[0284] The results are shown in Table 2.

[0285] [Example 19]: Production of laminate (19)

[0286] Except that the aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% ("SUPERFLEX 150", non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 750% ("SUPERFLEX 460", non-volatile content = 38 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (2), a reinforcing layer (19), and a laminate (19a), (19b), or (19c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 7.

[0287] The results are shown in Table 2.

[0288] [Example 20]: Manufacture of laminate (20)

[0289] Except that the aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% ("SUPERFLEX 150", non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 750% ("SUPERFLEX 460", non-volatile content = 38 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (3), a reinforcing layer (20), and a laminate (20a), (20b), or (20c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 11.

[0290] The results are shown in Table 2.

[0291] [Example 21]: Manufacture of laminate (21)

[0292] Except that the aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% ("SUPERFLEX 150", non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 750% ("SUPERFLEX 460", non-volatile content = 38 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (3), a reinforcing layer (21), and a laminate (21a), (21b), or (21c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 12.

[0293] The results are shown in Table 2.

[0294] [Example 22]: Manufacture of laminate (22)

[0295] Except that the aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% ("SUPERFLEX 150", non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 340% ("SUPERFLEX 650", non-volatile content = 26 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (1), a reinforcing layer (22), and a laminate (22a), (22b), or (22c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 1.

[0296] The results are shown in Table 2.

[0297] [Example 23]: Manufacture of laminate (23)

[0298] Except that the aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% ("SUPERFLEX 150", non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 340% ("SUPERFLEX 650", non-volatile content = 26 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (2), a reinforcing layer (23), and a laminate (23a), (23b), or (23c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 6.

[0299] The results are shown in Table 2.

[0300] [Example 24]: Manufacture of laminate (24)

[0301] Except that the aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% ("SUPERFLEX 150", non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 340% ("SUPERFLEX 650", non-volatile content = 26 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (3), a reinforcing layer (24), and a laminate (24a), (24b), or (24c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 11.

[0302] The results are shown in Table 2.

[0303] [Comparative Example 1]: Manufacture of laminate (C1)

[0304] A laminate (C1a), (C1b), or (C1c) of the pressure-sensitive adhesive sheet (1) and the adherends (a), (b), or (c) was obtained in the same manner as in Example 1, except that the reinforcing agent layer (1) was not provided.

[0305] The results are shown in Table 3.

[0306] [Comparative Example 2]: Manufacture of laminate (C2)

[0307] A laminate (C2a), (C2b), or (C2c) of the pressure-sensitive adhesive sheet (1), the reinforcing agent layer (C2), and the adherends (a), (b), or (c) was obtained in the same manner as in Example 1, except that the aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 4% (“SUPERFLEX 870”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.).

[0308] The results are shown in Table 3.

[0309] [Comparative Example 3]: Manufacture of laminate (C3)

[0310] A laminate (C3a), (C3b), or (C3c) of the pressure-sensitive adhesive sheet (2), the reinforcing agent layer (C3), and the adherends (a), (b), or (c) was obtained in the same manner as in Example 6, except that the aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifying aqueous polyurethane resin having an elongation at break of 4% (“SUPERFLEX 870”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.).

[0311] The results are shown in Table 3.

[0312] [Comparative Example 4]: Manufacture of laminate (C4)

[0313] Except that the aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 5% (“SUPERFLEX 830HS”, non-volatile content = 27 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (1), a reinforcing layer (C4), and a laminate (C4a), (C4b), or (C4c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 1.

[0314] The results are shown in Table 3.

[0315] [Comparative Example 5]: Manufacture of laminate (C5)

[0316] Except that the aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 5% ("SUPERFLEX 210", non-volatile content = 35 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (2), a reinforcing layer (C5), and a laminate (C5a), (C5b), or (C5c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 6.

[0317] The results are shown in Table 3.

[0318] [Comparative Example 6]: Manufacture of laminate (C6)

[0319] Except that the aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 330% (“SUPERFLEX 150”, non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.) was changed to an aqueous dispersion of a self-emulsifiable aqueous polyurethane resin having an elongation at break of 1,500% ("SUPERFLEX 300", non-volatile content = 30 ± 1 wt%, manufactured by DKS Co., Ltd.), a pressure-sensitive adhesive sheet (1), a reinforcing layer (C6), and a laminate (C6a), (C6b), or (C6c) of an adherend (a), (b), or (c) were obtained in the same manner as in Example 1.

[0320] The results are shown in Table 3.

[0321] [Comparative Example 7]: Manufacture of laminate (C7)

[0322] A laminate (C7a), (C7b), or (C7c) of a pressure-sensitive adhesive sheet (4), a reinforcing layer (1), and an adherend (a), (b), or (c) was obtained in the same manner as in Example 1, except that the pressure-sensitive adhesive sheet (1) was changed to the pressure-sensitive adhesive sheet (4) obtained in Production Example 4.

[0323] The results are shown in Table 3.

[0324] [Comparative Example 8]: Production of laminate (C8)

[0325] A laminate (C8a), (C8b), or (C8c) of a pressure-sensitive adhesive sheet (5), a reinforcing layer (17), and an adherend (a), (b), or (c) was obtained in the same manner as in Example 17, except that the pressure-sensitive adhesive sheet (1) was changed to the pressure-sensitive adhesive sheet (5) obtained in Production Example 5.

[0326] The results are shown in Table 3.

[0327]

[0328]

[0329]

[0330] The laminate according to at least one embodiment of the present invention is typically used in electronic devices and can be used, for example, in articles (typically, mobile devices) including components of electronic devices.

[0331] According to at least one embodiment of the present invention, a laminate including a pressure-sensitive adhesive sheet, a reinforcing layer, and an adherend can be provided, and the laminate can simultaneously exhibit high adhesive strength and high impact resistance.

Claims

1. A laminate comprising a pressure-sensitive adhesive sheet, a reinforcing agent layer, and a laminated structure of an adherend, wherein the outermost layer of the pressure-sensitive adhesive sheet on the side of the reinforcing agent layer is a pressure-sensitive adhesive layer, wherein the adhesive strength of the laminate when the pressure-sensitive adhesive sheet is peeled from the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing agent layer, and a SUS plate at a peeling speed of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH is 20 N / 20 mm or more, wherein the adhesive strength of the laminate when the pressure-sensitive adhesive sheet is peeled from the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing agent layer, and a polycarbonate plate at a peeling speed of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH is 20 N / 20 mm or more, wherein the adhesive strength of the laminate when the pressure-sensitive adhesive sheet is peeled from the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing agent layer, and an aluminum plate at a peeling speed of 300 mm / min and a peeling angle of 180° at 23°C and 50% RH is 20 N / 20 mm or more, and wherein the impact resistance of the laminated structure of the pressure-sensitive adhesive sheet, the reinforcing agent layer, and the SUS plate at 23°C and 50% RH is 0.35 J or more, wherein the reinforcing agent layer is formed of a reinforcing agent, and the reinforcing agent contains an aqueous polyurethane resin crosslinked by an isocyanate-based crosslinking agent, and the aqueous polyurethane resin has at least one selected from the group consisting of an ester skeleton, an ether skeleton, and a carbonate skeleton, wherein the elongation at break of the aqueous polyurethane resin is 300% to 1,000%, wherein the aqueous polyurethane resin is a self-emulsifying aqueous polyurethane resin, wherein the pressure-sensitive adhesive layer, which is the outermost layer of the pressure-sensitive adhesive sheet on the side of the reinforcing agent layer, is formed of a pressure-sensitive adhesive composition, wherein the pressure-sensitive adhesive composition contains at least one selected from the group consisting of a monomer composition (M) and a polymer component (P) obtained from the monomer composition (M), and wherein the monomer composition (M) contains 93 wt% or more of (meth)acrylate having an alkyl ester with 1 to 12 carbon atoms, and contains 1 wt% to 7 wt% of (meth)acrylic acid, wherein the (meth)acrylate having an alkyl ester with 1 to 12 carbon atoms is n-butyl acrylate.

2. The laminate according to claim 1, wherein the thickness of the pressure-sensitive adhesive sheet is 100 μm to 400 μm.

3. The laminate according to claim 1, wherein the thickness of the reinforcing agent layer is 0.10 μm to 4.00 μm.

4. The laminate according to claim 1, wherein the adherend is an electronic device member.

5. The laminate according to claim 1, wherein the material of the bonding portion of the adherend is at least one selected from the group consisting of SUS, polycarbonate, aluminum, polyolefin-based resin, styrene-based resin, polyester-based resin, acrylic-based resin, polyimide-based resin, and glass fiber.

6. The laminate according to claim 1, wherein the laminate is used for an electronic device.

7. A mobile electronic device, which includes the laminate according to claim 1.

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