Adhesive sheet

Abstract

An adhesive sheet (100) of the present invention has: a first resin layer (10) containing a 4-methyl-1-pentene polymer; and a design layer (30), wherein at least a portion of the first resin layer (10) is exposed on a surface (11) and a surface (12) of the adhesive sheet (100) to form an adhesive surface, and the following requirement (i) is satisfied. (i) There is at least one temperature in the range of 10°C to 100°C at which the loss tangent (tan δ), obtained by dynamic viscoelasticity measurement under conditions of a rate of temperature increase of 4 °C / min, a frequency of 1.59 Hz, and a strain amount of 0.1%, is a maximum value, and the maximum value of the loss tangent is 0.5-3.5.

Description

Technical Field

[0001] The present invention relates to an adhesive sheet. More specifically, it relates to an adhesive sheet, a piece cut from the adhesive sheet, and a piece set.

Background Art

[0002] Conventionally, an adhesive sheet in which the film itself has adhesiveness and the films can be freely attached and detached from each other is known. For example, Patent Document 1 discloses a self-adhesive sheet using a vinyl resin composition containing a vinyl chloride-based resin, a specific acrylic block copolymer, and a plasticizer.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the prior art focused on more firmly fixing the adhesive sheets to each other. Therefore, it was difficult for relatively weak elderly people, children, etc. to easily attach and detach the adhesive sheets.

Means for Solving the Problems

[0005] The present inventors focused on newly using an adhesive sheet containing a 4-methyl-1-pentene polymer as a toy, and considered imparting design properties while appropriately controlling the adhesiveness of the adhesive sheet. And, as a result of intensive studies, in an adhesive sheet provided with a resin layer containing a 4-methyl-1-pentene polymer as an adhesive surface, by controlling this using a predetermined loss tangent in the adhesive sheet as an index, stable adhesiveness can be obtained, and by devising the arrangement, ratio, composition, etc. of the design layer so that at least a part of the adhesive surface is exposed, it was found that the design properties can be enhanced while maintaining appropriate adhesiveness, and the present invention was completed.

[0006] That is, according to the present invention, there are provided an adhesive sheet shown below, a piece cut therefrom, and a toy piece set using these.

[0007] [1] An adhesive sheet having a resin layer containing a 4-methyl-1-pentene polymer and a design layer, wherein at least a part of the resin layer is exposed on at least one surface of the adhesive sheet to form an adhesive surface, and an adhesive sheet that satisfies the following requirement (i). (i) The temperature showing the maximum value of the loss tangent (tanδ) obtained by dynamic viscoelasticity measurement under the conditions of a heating rate of 4 ° C / min, a frequency of 1.59 Hz, and a strain of 0.1% is at least one in the range of 10 ° C or more and 100 ° C or less, and the maximum value of the loss tangent is 0.5 or more and 3.5 or less. [2] An adhesive sheet having a resin layer containing a 4-methyl-1-pentene polymer and a design layer, wherein at least a part of the resin layer is exposed on at least one surface of the adhesive sheet to form an adhesive surface, the design layer is a printed layer, and the area ratio of the printed layer in a plan view of the adhesive sheet is 25 to 95% with respect to the planar area of the adhesive sheet, and an adhesive sheet that satisfies the following requirement (i). (i) The temperature at which the maximum value of the loss tangent (tanδ) obtained by dynamic viscoelasticity measurement under the conditions of a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1% is at least one in the range of 10°C or higher and 100°C or lower, and the maximum value of the loss tangent is 0.5 or higher and 3.5 or lower. [3] An adhesive sheet having a resin layer containing a 4-methyl-1-pentene polymer, wherein at least a part of the resin layer is exposed on at least one surface of the adhesive sheet to form an adhesive surface, the resin layer contains one or more selected from pigments and colorants to form a colored design layer, and an adhesive sheet that satisfies the following requirement (i). (i) The temperature at which the maximum value of the loss tangent (tanδ) obtained by dynamic viscoelasticity measurement under the conditions of a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1% is at least one in the range of 10°C or higher and 100°C or lower, and the maximum value of the loss tangent is 0.5 or higher and 3.5 or lower. [4] An adhesive sheet according to any one of [1] to [3] that satisfies the following requirement (ii). (ii) When the adhesive surfaces of the adhesive sheet prepared at 23°C are pressure-bonded at 40°C and 0.026 MPa and a tensile test is performed at 23°C, the maximum shear stress is 1.0 MPa or higher and less than 5.0 MPa. [5] The adhesive sheet according to any one of [1] to [4], wherein the 4-methyl-1-pentene polymer contains a structural unit (c1) derived from 4-methyl-1-pentene and a structural unit (c2) derived from a linear α-olefin having 2 to 3 carbon atoms other than 4-methyl-1-pentene. [6] The adhesive sheet according to [5], wherein when the total of the structural unit (c1) and the structural unit (c2) is 100 mol%, the content of the structural unit (c1) is 10 mol% or higher and 90 mol% or lower. [7] The pressure-sensitive adhesive sheet according to any one of [1] to [6], having a plurality of the design layers, and comprising the design layer on each of both sides of at least one of the resin layers. [8] The pressure-sensitive adhesive sheet according to any one of [1] to [7], comprising the design layer inside the pressure-sensitive adhesive sheet. [9] The pressure-sensitive adhesive sheet according to any one of [1] to [8], wherein a plurality of the design layers are laminated in the thickness direction, and the plurality of the design layers have different designs from each other.

[10] The pressure-sensitive adhesive sheet according to [9], wherein at least one of the different designs is different in arrangement, shape, pattern, and color.

[11] The pressure-sensitive adhesive sheet according to any one of [1] to

[10] , having a plurality of the resin layers, and both outer surfaces of the pressure-sensitive adhesive sheet being respectively constituted by the resin layers.

[12] The pressure-sensitive adhesive sheet according to [2], wherein the area ratio of the printing layer in a plan view of the pressure-sensitive adhesive sheet is 30 to 70% with respect to the planar area of the pressure-sensitive adhesive sheet.

[13] The pressure-sensitive adhesive sheet according to

[12] , wherein the printing layer is formed by at least one printing method selected from inkjet printing, gravure printing, screen printing, offset printing, and transfer printing.

[14] The pressure-sensitive adhesive sheet according to any one of [1] to

[13] , wherein the resin layer is transparent.

[15] The pressure-sensitive adhesive sheet according to any one of [1] to

[14] , wherein the total light transmittance of the resin layer is 30 to 99.9%.

[16] The pressure-sensitive adhesive sheet according to any one of [1] to

[15] , having a plurality of the resin layers, and the interlayer adhesion strength between one of the resin layers and another adjacent resin layer being 0.5 N / 15 mm or more.

[17] The pressure-sensitive adhesive sheet according to any one of [1] to

[16] , having an average thickness of 0.01 mm or more and 30 mm or less.

[18] A piece obtained by cutting the pressure-sensitive adhesive sheet according to any one of [1] to

[17] into a predetermined size.

[19] The piece according to

[18] , wherein in a plan view, the design layer is not disposed on at least a part of the peripheral portion.

[20] A piece set in which a plurality of pieces of

[18] or

[19] are used as toys.

[21] The piece set according to

[20] , wherein the plurality of pieces include at least two pieces having the same shape as each other and / or the same design as each other.

[22] A method of using the piece set according to

[20] or

[21] , including a step of heating the piece, and a step of combining one or more selected from the steps of adhering the pieces to each other, peeling the adhered pieces from each other, and deforming the pieces. A method of using the piece set having the above steps.

[23] A method of using the piece set according to

[22] , further including a step of cooling the piece after the combining step. A method of using the piece set.

[24] A method of using the piece set according to

[22] or

[23] , wherein the step of heating the piece is performed by the body temperature of a human.

[25] A method for producing a pressure-sensitive adhesive sheet having a resin layer containing a 4-methyl-1-pentene-based polymer and a design layer, including a step of forming the design layer by printing on the resin layer, wherein an adhesive surface is formed by exposing at least a part of the resin layer on at least one surface of the pressure-sensitive adhesive sheet, the area ratio of the design layer in a plan view of the pressure-sensitive adhesive sheet is 25 to 95% with respect to the plan area of the pressure-sensitive adhesive sheet, and A method for manufacturing an adhesive sheet, wherein the adhesive sheet satisfies the following requirement (i). (i) The temperature at which the maximum value of the loss tangent (tanδ) obtained by dynamic viscoelasticity measurement under the conditions of a temperature increase rate of 4 °C / min, a frequency of 1.59 Hz, and a strain of 0.1% is at least one or more in the range of 10 °C or more and 100 °C or less, and the maximum value of the loss tangent is 0.5 or more and 3.5 or less.

[26] A step of obtaining an adhesive sheet by the method for manufacturing an adhesive sheet according to

[25] , A step of cutting the obtained adhesive sheet into a predetermined size, A method for manufacturing a piece, including the above steps.

Effect of the Invention

[0008] According to the present invention, it is possible to provide an adhesive sheet having good design properties and appropriate adhesiveness, a piece cut therefrom, and a toy piece set using these.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Modes for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In all the drawings, similar components are denoted by similar reference numerals, and the description thereof will be omitted as appropriate. To avoid complexity, (i) when there are a plurality of identical components in the same drawing, only one of them is labeled, and not all of them are labeled, or (ii) in the drawings after FIG. 2, the same components as those in FIG. 1 may not be labeled again. All the drawings are for illustrative purposes only. The shapes and dimensional ratios of the respective members in the drawings do not necessarily correspond to actual articles.

[0011] In this specification, the notation "a to b" in the description of a numerical range represents a to b, unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% or more and 5 mass% or less".

[0012] In this specification, the "sheet" is a concept that includes not only what is generally called a "sheet" but also what is generally called a "film". Note that what is generally called a "sheet" has a thickness of 250 μm or more, and what is generally called a "film" has a thickness of less than 250 μm.

[0013] 1. Adhesive sheet <First Embodiment> FIG. 1 is a schematic cross-sectional view of an adhesive sheet 100 according to the first embodiment. The adhesive sheet 100 includes a first resin layer 10 containing a 4-methyl-1-pentene-based polymer and a design layer 30. The first resin layer 10 constitutes an adhesive surface 11 and an adhesive surface 12, and the entire surface of the adhesive surface 11 and a part of the adhesive surface 12 are exposed, satisfying the following requirement (i).

[0014] [Requirement (i)] The pressure-sensitive adhesive sheet 100 according to the present embodiment has at least one temperature in the range of 10°C or higher and 100°C or lower at which the maximum value of the loss tangent (tanδ), obtained by dynamic viscoelasticity measurement under the conditions of a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1%, and the maximum value of the loss tangent is 0.5 or higher and 3.5 or lower.

[0015] For the dynamic viscoelasticity measurement, for example, the pressure-sensitive adhesive sheet 100 can be cut into test pieces with a length of 50 mm and a width of 5 mm, and measured using a rheometer under the conditions of a frequency of 1.59 Hz, a heating rate of 4°C / min, a measurement temperature range of 0°C to 110°C, a strain of 0.1%, a chuck distance of 20 mm, and a tensile mode.

[0016] By satisfying the requirement (i), the pressure-sensitive adhesive sheet 100 of the present embodiment can obtain flexibility and shape followability, and good adhesiveness. Although the details of such reasons are not clear, it is considered as follows. First, by increasing the loss tangent (tanδ) in a relatively low-frequency region of 1.59 Hz, it becomes easier to follow a force that takes time (also called a slow force) compared to a force such as an instantaneous impact. Therefore, it is presumed that when the pressure-sensitive adhesive sheets 100 are adhered to each other or when a force is applied during use after adhesion, the surface shapes of the pressure-sensitive adhesive sheets 100 follow each other, and the fixing force increases against the force to peel them off (especially the force in the plane direction). Furthermore, the pressure-sensitive adhesive sheet 100 having a maximum value of the loss tangent within the above range in the range of 10°C or higher and 100°C or lower can convert most of the mechanical energy applied during deformation into thermal energy and absorb a large amount of energy. Therefore, it is considered that the recovery speed after deformation becomes slow. As a result, while maintaining the flexibility of the pressure-sensitive adhesive sheet 100, it can follow deformation well, and as a result, appropriate adhesiveness can be obtained.

[0017] In the pressure-sensitive adhesive sheet 100 according to the present embodiment, it is preferable that there is one or more temperatures at which the maximum value of the loss tangent (tanδ) of the dynamic viscoelasticity is in the range of at least 10°C or more and 80°C or less, more preferably in the range of 10°C or more and 60°C or less, still more preferably in the range of 10°C or more and 50°C or less, and even more preferably there is one in the range of 10°C or more and 50°C or less. As a result, when the pressure-sensitive adhesive sheet 100 comes into contact with a person and reaches about 25°C to 40°C, better flexibility and adhesiveness can be obtained. Therefore, when the pressure-sensitive adhesive sheet 100 is applied to a toy, children or the like can pick up the pressure-sensitive adhesive sheet 100 by hand and warm the pressure-sensitive adhesive sheet 100 by hand to obtain appropriate adhesiveness, and the pressure-sensitive adhesive sheets 100 can be easily stuck together and peeled off, and due to good flexibility, it can be freely deformed.

[0018] Further, in the pressure-sensitive adhesive sheet 100 according to the present embodiment, the maximum value of the loss tangent is preferably 0.8 or more, more preferably 1.0 or more, and still more preferably 1.2 or more. And in the pressure-sensitive adhesive sheet 100 according to the present embodiment, the maximum value of the loss tangent is preferably 3.0 or less, and more preferably 2.8 or less. Thereby, while obtaining the adhesiveness of the pressure-sensitive adhesive sheet 100 according to the present embodiment, the performance balance of flexibility and shape followability can be made better. Here, the larger the maximum value of the loss tangent, the stronger the viscous property of the pressure-sensitive adhesive sheet 100. A pressure-sensitive adhesive sheet 100 with a strong viscous property can convert more of the mechanical energy applied during deformation into thermal energy and can absorb more energy, so it is considered that the recovery speed after deformation becomes even slower. As a result, it is considered that while maintaining the flexibility of the pressure-sensitive adhesive sheet 100, the shape after deformation can be better maintained or can follow the deformation better.

[0019] Also, from the viewpoint of improving adhesiveness, the pressure-sensitive adhesive sheet 100 according to the present embodiment is preferably uncrosslinked. That is, the pressure-sensitive adhesive sheet 100 is preferably an uncrosslinked sheet that has not been subjected to crosslinking treatment such as ionizing radiation crosslinking using electron beams or γ-rays. Thereby, the maximum value of the loss tangent in the range of 10°C or higher and 100°C or lower can be improved, and a pressure-sensitive adhesive sheet 100 having even better adhesiveness can be obtained.

[0020] [Requirement (ii)] The pressure-sensitive adhesive sheet 100 of the present embodiment preferably further satisfies the following requirement (ii). (ii) When the adhesive surfaces 11 of the pressure-sensitive adhesive sheet 100 prepared at 23°C are pressure-bonded to each other at 40°C and 0.026 MPa and a tensile test is performed at 23°C, the maximum shear stress is 1.0 MPa or more and less than 5.0 MPa. Thereby, more appropriate adhesiveness of the pressure-sensitive adhesive sheet 100 can be obtained. Specifically, by warming the pressure-sensitive adhesive sheet 100 with human skin so as to approach about 40°C, the adhesiveness of the pressure-sensitive adhesive sheet 100 increases, and the adhesive surfaces of the pressure-sensitive adhesive sheet 100 can be adhered to each other. Then, when cooled to about room temperature, the pressure-sensitive adhesive sheets 100 can be peeled off with a relatively weak force. As a result, when the pressure-sensitive adhesive sheet 100 of the present embodiment is applied to a toy, a child can pick up the pressure-sensitive adhesive sheet 100 and warm it to obtain appropriate adhesiveness and flexibility, and can freely stick, peel, and shape it. When the temperature drops to about room temperature, the adhesiveness decreases, and the pressure-sensitive adhesive sheet 100 that has been bonded or assembled can be easily removed. Note that the pressure-sensitive adhesive sheet 100 prepared at 23°C as described above is intended to place the pressure-sensitive adhesive sheet 100 in an environment of 23°C so that the temperature of the pressure-sensitive adhesive sheet 100 itself becomes equal to the environmental temperature.

[0021] The pressure-sensitive adhesive sheet 100 that satisfies the above requirements (i) and (ii) can be realized, for example, by appropriately adjusting (1) the type and blending ratio of the 4-methyl-1-pentene polymer (a1) described later, (2) the presence or absence of crosslinking of the pressure-sensitive adhesive sheet 100, (3) the molding method of the pressure-sensitive adhesive sheet 100, and the like. Specifically, for example, increasing the blending ratio of the 4-methyl-1-pentene polymer (a1) in the pressure-sensitive adhesive sheet 100, not performing a crosslinking treatment on the pressure-sensitive adhesive sheet 100, and the like can be mentioned.

[0022] [Thickness] The average thickness of the pressure-sensitive adhesive sheet 100 is not particularly limited, but is preferably in the range of 0.01 mm or more and 30 mm or less, more preferably in the range of 0.01 mm or more and 10 mm or less, still more preferably in the range of 0.1 mm or more and 5 mm or less, and even more preferably in the range of 0.5 mm or more and 2 mm or less. By setting the average thickness of the pressure-sensitive adhesive sheet 100 to be equal to or greater than the above lower limit value, while improving the adhesiveness, a good balance of shape followability, mechanical properties, moldability, and moisture resistance can be obtained. On the other hand, by setting the average thickness of the pressure-sensitive adhesive sheet 100 to be equal to or less than the above upper limit value, while maintaining good adhesiveness, light weight, appearance, and handleability can be improved.

[0023] [Density] The density of the pressure-sensitive adhesive sheet 100 measured according to ASTM D 1505 (water displacement method) is preferably 0.3 to 1.5 g / cm 3 , more preferably 0.5 to 1.2 g / cm 3 , still more preferably 0.8 to 0.9 g / cm 3 , and even more preferably 0.83 to 0.85 g / cm 3 .

[0024] [Transparency] In the pressure-sensitive adhesive sheet 100 of the present embodiment, the regions extending from the design layer 30 to both outer surfaces of the pressure-sensitive adhesive sheet 100 are transparent. Thereby, the design layer 30 can be visually recognized not only from the adhesive surface 12 side of the pressure-sensitive adhesive sheet 100 but also from the adhesive surface 11 side. Specifically, it is preferable that the total light transmittance in the region extending from the outermost surface of the design layer 30 to both outer surfaces of the adhesive sheet 100 is 30 to 99%, and the internal haze is 0.1 to 99.9%. The measurement of the total light transmittance can be performed by a Haze meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd. based on JIS K 7361 (TRANS). The internal haze is a value obtained by excluding the haze derived from the surface shape such as unevenness from the total haze. The measurement of the internal haze can be performed in accordance with JIS K 7136 (HAZE) using cyclohexanol and a Haze meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd.

[0025] Hereinafter, the details of each component of the adhesive sheet 100 will be described.

[0026] [First Resin Layer] The first resin layer 10 of the present embodiment constitutes one adhesive surface 11 and the adhesive surface 12 of the adhesive sheet 100. Thereby, adhesiveness is obtained on both surfaces of the adhesive sheet 100. The adhesiveness is intended to be such that the maximum shear stress (MPa) in a tensile test (chuck distance 50 mm, tensile speed 50 mm / min) after applying a pressure of 0.026 MPa for 1 second using a heat sealer (TP701B manufactured by Tester Sangyo Co., Ltd.) with the adhesive surfaces of the adhesive sheet 100 set at 40°C and leaving it for 24 hours in an environment of a temperature of 23°C and a relative humidity of 50% is 1.0 to 5.0 MPa.

[0027] Further, the first resin layer 10 of the present embodiment is preferably transparent. Thereby, the transparency of the adhesive sheet 100 is obtained, and the design layer 30 can be visually recognized not only from the adhesive surface 12 side but also from the adhesive surface 11 side of the adhesive sheet 100. Specifically, the first resin layer 10 preferably has a total light transmittance of 30 to 99.9% and an internal haze of 0.1 to 99.0%, more preferably a total light transmittance of 50 to 99.9% and an internal haze of 0.1 to 70.0%, and still more preferably a total light transmittance of 70 to 99.9% and an internal haze of 0.1 to 50.0%

[0028] The first resin layer 10 of the present embodiment contains a 4-methyl-1-pentene-based polymer. Hereinafter, each component contained in the first resin layer 10 will be described.

[0029] (4-methyl-1-pentene-based polymer) The pressure-sensitive adhesive sheet 100 according to the present embodiment contains a 4-methyl-1-pentene-based polymer (a1). Thereby, the maximum value of the loss tangent (tanδ) can be made larger. Examples of the 4-methyl-1-pentene-based polymer (a1) according to the present embodiment include a 4-methyl-1-pentene·α-olefin copolymer (c) containing a structural unit (c1) derived from 4-methyl-1-pentene and a structural unit (c2) derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene. Here, in the present embodiment, "α-olefin having 2 to 20 carbon atoms" means not containing 4-methyl-1-pentene unless otherwise specified.

[0030] From the viewpoint of further improving the flexibility and adhesiveness of the pressure-sensitive adhesive sheet 100, the 4-methyl-1-pentene·α-olefin copolymer (c) according to the present embodiment preferably has a content of the structural unit (c1) of 10 mol% or more and 90 mol% or less, and a content of the structural unit (c2) of 10 mol% or more and 90 mol% or less when the total of the structural unit (c1) and the structural unit (c2) is 100 mol%. Further, from the viewpoint of making the flexibility, mechanical properties, etc. of the pressure-sensitive adhesive sheet 100 better, when the total of the constitutional unit (c1) and the constitutional unit (c2) is 100 mol%, the content of the constitutional unit (c1) is more preferably 30 mol% or more and 90 mol% or less, and the content of the constitutional unit (c2) is more preferably 10 mol% or more and 70 mol% or less. Even more preferably, the content of the constitutional unit (c1) is 50 mol% or more and 90 mol% or less, and the content of the constitutional unit (c2) is 10 mol% or more and 50 mol% or less. Even more preferably, the content of the constitutional unit (c1) is 60 mol% or more and 90 mol% or less, and the content of the constitutional unit (c2) is 10 mol% or more and 40 mol% or less. Particularly preferably, the content of the constitutional unit (c1) is 65 mol% or more and 90 mol% or less, and the content of the constitutional unit (c2) is 10 mol% or more and 35 mol% or less.

[0031] In the present embodiment, examples of the α-olefin having 2 to 20 carbon atoms used in the 4-methyl-1-pentene·α-olefin copolymer (c) include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, functionalized vinyl compounds, etc., and linear α-olefins are preferred.

[0032] The number of carbon atoms of the linear α-olefin is preferably 2 to 10, more preferably 2 to 3. Examples of the linear α-olefin include ethylene, propylene, 1-butene, 1-pentene, etc. One or more selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene are preferred, and at least one selected from ethylene and propylene is more preferred. The number of carbon atoms of the branched α-olefin is preferably 5 to 20, more preferably 5 to 15. Examples of the branched α-olefin include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, etc. The number of carbon atoms of the cyclic olefin is preferably 5 to 15. Examples of the cyclic olefin include cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylcyclohexane, and the like.

[0033] Examples of the aromatic vinyl compound include mono- or polyalkylstyrenes such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and the like. The number of carbon atoms of the conjugated diene is preferably 4 to 20, more preferably 4 to 10. Examples of the conjugated diene include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, and the like.

[0034] Examples of the functionalized vinyl compound include hydroxyl group-containing olefins, halogenated olefins, unsaturated carboxylic acids such as (meth)acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, and their acid anhydrides and acid halides, unsaturated amines such as allylamine, 5-hexenamine, 6-heptenamine, (2,7-octadienyl)succinic anhydride, pentapropenyl succinic anhydride, unsaturated epoxy compounds, ethylenically unsaturated silane compounds, and the like. Examples of the hydroxyl group-containing olefin include linear or branched terminal hydroxyl group-containing α-olefins having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms. Examples of the halogenated olefin include linear or branched halogenated α-olefins having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms.

[0035] These α-olefins having 2 to 20 carbon atoms can be used alone or in combination of two or more. Among them, ethylene and propylene are preferred, and propylene is particularly preferred in that it can better improve flexibility and the like.

[0036] In addition, the 4-methyl-1-pentene / α-olefin copolymer (c) may contain constitutional units other than the constitutional unit (c1) and the constitutional unit (c2) as long as the object of the present invention is not impaired. Examples of other constitutions include constitutional units derived from non-conjugated polyenes. Examples of the non-conjugated polyene include linear, branched or cyclic dienes having preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, various norbornenes, norbornadienes and the like. Among them, 5-vinylidene-2-norbornene and 5-ethylidene-2-norbornene are preferred.

[0037] The intrinsic viscosity [η] of the 4-methyl-1-pentene-based polymer according to this embodiment in decalin at 135 °C is preferably 0.01 to 5.0 dL / g, more preferably 0.1 to 4.0 dL / g, still more preferably 0.5 to 3.0 dL / g, and particularly preferably 1.0 to 2.8 dL / g from the viewpoint of better flexibility and mechanical strength of the adhesive sheet 100.

[0038] The density of the 4-methyl-1-pentene-based polymer according to this embodiment measured according to ASTM D 1505 (water substitution method) is preferably 0.810 to 0.850 g / cm 3 , more preferably 0.820 to 0.850 g / cm 3 , still more preferably 0.830 to 0.850 g / cm 3 is.

[0039] The 4-methyl-1-pentene polymer according to this embodiment can be produced by various methods. For example, it can be produced using known catalysts such as magnesium-supported titanium catalysts; metallocene catalysts described in WO 01 / 53369, WO 01 / 027124, JP-A-3-193796, and JP-A-02-41303; and olefin polymerization catalysts containing metallocene compounds described in WO 2011 / 055803.

[0040] The content of the 4-methyl-1-pentene polymer (a1) in the pressure-sensitive adhesive sheet 100 according to this embodiment is not particularly limited, but when the whole pressure-sensitive adhesive sheet 100 is 100% by mass, it is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, even more preferably 70% by mass or more, and even more preferably 75% by mass or more. On the other hand, it is preferably 100% by mass or less, more preferably 99.5% by mass or less, still more preferably 99% by mass or less, even more preferably 98% by mass or less, and even more preferably 97% by mass or less. Thereby, a pressure-sensitive adhesive sheet 100 having an excellent balance in impact absorbency, flexibility, shape followability, light weight, mechanical properties, handleability, appearance, moldability, moisture resistance, etc. can be obtained.

[0041] The pressure-sensitive adhesive sheet 100 according to this embodiment may contain components other than the above 4-methyl-1-pentene polymer (a1).

[0042] (Modified resin (a2)) The pressure-sensitive adhesive sheet 100 according to this embodiment may contain a modified resin (a2) from the viewpoint of improving appearance, texture, and adhesiveness. Examples of the modified resin (a2) according to this embodiment include one or more selected from thermoplastic resins, thermoplastic elastomers, and rubbers. However, the modified resin (a2) excludes the 4-methyl-1-pentene polymer (a1).

[0043] Examples of the above thermoplastic resin (excluding the 4-methyl-1-pentene polymer (a1) according to the present embodiment) include thermoplastic polyolefin resins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, high-pressure low-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1-butene, ethylene·α-olefin copolymer, propylene·α-olefin copolymer, 1-butene·α-olefin copolymer, cyclic olefin copolymer, chlorinated polyolefin; thermoplastic polyamide resins such as aliphatic polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612), polyether block amide copolymer; thermoplastic polyester resins such as polyethylene terephthalate, polybutylene terephthalate; thermoplastic vinyl aromatic resins such as polystyrene, ABS resin, AS resin; vinyl chloride resin; vinylidene chloride resin; acrylic resin; ethylene·vinyl acetate copolymer; ethylene·methacrylic acid acrylate copolymer; ionomer; ethylene·vinyl alcohol copolymer; polyvinyl alcohol; fluorine-based resins such as polyvinyl fluoride resin, polytetrafluoroethylene, polyvinylidene fluoride, ETFE; polycarbonate; polyacetal; polyphenylene oxide; polyphenylene sulfide; polyimide; polyarylate; polysulfone; polyether sulfone; rosin-based resin; terpene-based resin; petroleum resin, etc. Examples of the rubber include ethylene·α-olefin·diene copolymer rubber, propylene·α-olefin·diene copolymer rubber, etc. Furthermore, examples of the thermoplastic elastomer include olefin-based elastomer, styrene-based elastomer, acid-modified styrene-based elastomer, vinyl chloride-based elastomer, urethane-based elastomer, ester-based elastomer, amide-based elastomer, etc. Also, these modified resins (a2) may be acid-modified with acrylic acid, methacrylic acid, maleic acid, etc. These modified resins (a2) may be used alone or in combination of two or more.

[0044] Among these modified resins (a2), one or more selected from low-density polyethylene, medium-density polyethylene, high-density polyethylene, low-density polyethylene by high-pressure method, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1-butene, ethylene·α-olefin copolymer, propylene·α-olefin copolymer, 1-butene·α-olefin copolymer are preferred. One or more selected from polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene·α-olefin copolymer, propylene·α-olefin copolymer, 1-butene·α-olefin copolymer, ethylene·vinyl acetate copolymer, polyether block amide, ionomer, fluororesin, acid-modified fluororesin, rosin resin, terpene resin, petroleum resin and styrene-based elastomer, which can improve the melt tension by addition, are more preferred. Moreover, those having appropriate compatibility with the 4-methyl-1-pentene-based polymer (a1) according to this embodiment are more preferred. Further, among styrene-based elastomers, vinyl SIS (product name: Hybrar, brand 5127), vinyl SEPS (product name: Hybrar, brand 7125) manufactured by Kuraray Co., Ltd., and SEBS (product name: S.O.E, brands: S1605, S1611, and L609) manufactured by Asahi Kasei Corporation can also be preferably used from the viewpoints of compatibility, the temperature range showing the maximum value of loss tangent, and the magnitude of the maximum value of loss tangent.

[0045] The pressure-sensitive adhesive sheet 100 according to this embodiment can be used alone with one of these modified resins (a2), or can be used in combination of two or more.

[0046] The content of the modified resin (a2) in the pressure-sensitive adhesive sheet 100 according to the present embodiment is not particularly limited. However, when the total amount of the pressure-sensitive adhesive sheet 100 is 100% by mass, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 3% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less. When the content of the modified resin (a2) is equal to or higher than the above lower limit value, the appearance, feel, adhesiveness, etc. of the pressure-sensitive adhesive sheet 100 according to the present embodiment can be improved. When the content of the modified resin (a2) is equal to or lower than the above upper limit value, the performance balance such as adhesiveness and flexibility of the pressure-sensitive adhesive sheet 100 according to the present embodiment can be improved.

[0047] (Other components) The pressure-sensitive adhesive sheet 100 according to the present embodiment may be blended with additives such as a foaming agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a pigment, an antistatic agent, a copper corrosion inhibitor, a flame retardant, a neutralizing agent, a plasticizer, a nucleating agent, a weather stabilizer, a light stabilizer, an anti-aging agent, a fatty acid metal salt, a softening agent, a dispersant, a colorant, a lubricant, a natural oil, a synthetic oil, and a wax, if necessary. Among these, the plasticizer, the softening agent, the natural oil, and the synthetic oil may be used by controlling the type and the addition amount in order to adjust the temperature at which the maximum value of the loss tangent (tanδ) of the solid viscoelasticity of the pressure-sensitive adhesive sheet 100 according to the present embodiment is shown and the maximum value of the loss tangent.

[0048] Examples of the above foaming agent include a chemical foaming agent and a physical foaming agent. Examples of the chemical foaming agent include sodium bicarbonate, ammonium bicarbonate, various carboxylates, sodium borohydride, azodicarbonamide, N,N-dinitrosopentamethylenetetramine, P,P-oxybis(benzenesulfonylhydrazide), azobisisobutyronitrile, paratoluenesulfonylhydrazide, sodium bicarbonate citrate, etc. Examples of the physical foaming agent include carbon dioxide, nitrogen, or a mixture of carbon dioxide and nitrogen, etc., and any of them can be supplied in a gaseous, liquid, or supercritical state.

[0049] The resin composition containing the 4-methyl-1-pentene polymer (a1) can be prepared by mixing or melt-kneading each component by means of dry blending, a tumbler mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a high-speed twin-screw extruder, a hot roll, etc.

[0050] Also, the pressure-sensitive adhesive sheet 100 of the present embodiment may be in a foamed state. In this case, the density of the pressure-sensitive adhesive sheet 100 is preferably 3 0.10 to 1.0 g / cm 3 more preferably 0.5 to 0.9 g / cm 3 even more preferably 0.7 to 0.8 g / cm.

[0051] Also, when the pressure-sensitive adhesive sheet 100 of the present embodiment is in a foamed state, for example, it can be obtained by blending and uniformly mixing with the composition before charging the chemical foaming agent into the extrusion molding machine. Further, when using carbon dioxide as the physical foaming agent, it can be obtained by directly injecting carbon dioxide into the extrusion molding machine after the composition is kneaded and plasticized in the extrusion molding machine. The foaming ratio is not particularly limited and can be appropriately determined in consideration of applications, etc.

[0052] [Design layer] The design layer 30 is a layer having color development, gloss, pattern, etc., and may be colored or colorless, and may be transparent, translucent, or opaque, or a combination thereof.

[0053] In the present embodiment, the design layer 30 is formed on one adhesive surface 12 of the first resin layer 10, but at least a part of the adhesive surface 12 is exposed and the design layer 30 is not formed. Thereby, the pressure-sensitive adhesive sheet 100 can obtain good adhesiveness at the adhesive surface 12. The area ratio of the design layer 30 to the area of the adhesive sheet 100 in plan view is less than 100%, preferably 95% or less, more preferably 90% or less, and even more preferably 85% or less, 80% or less, and 70% or less in this order. This makes it easier to maintain the adhesiveness of the adhesive surface 12 well. On the other hand, the lower limit value of the area ratio occupied by the design layer 30 is not particularly limited, but from the viewpoint of enhancing the design property, it is preferably 5% or more, more preferably 10% or more, even more preferably 20% or more, and still more preferably 25% or more.

[0054] The design layer 30 of the present embodiment is a printing layer. The printing layer refers to a layer formed by using a known printing method. As the printing layer, it is preferably printed by at least one printing method selected from inkjet printing, gravure printing, screen printing, offset printing, and transfer printing. This makes it easier to obtain good color development, colors, patterns, etc., and can improve the design property of the adhesive sheet 100. Also, it becomes easier to apply to mass production of the adhesive sheet 100.

[0055] The printing layer is not limited to the case of printing on the entire surface of the adhesive sheet 100, and can have various patterns and designs such as dot-like, lattice-like, pattern-like, and linear. Also, the area ratio of the printing layer to the area of the adhesive sheet 100 in plan view is preferably 25 to 95%, and more preferably 30 to 70%. By setting the area ratio to be equal to or less than the above upper limit value, it becomes easier to exhibit the flexibility and adhesiveness of the adhesive sheet 100. On the other hand, by setting the area ratio to be equal to or more than the above lower limit value, the design property can be further improved. Note that the thickness of the printing layer is extremely small and does not affect the thickness of the entire adhesive sheet 100.

[0056] [Manufacturing method of adhesive sheet] An example of the manufacturing method of the adhesive sheet 100 according to the present embodiment will be described. First, the first resin layer 10 can be formed into a sheet shape by a known method using a resin composition containing a 4-methyl-1-pentene-based polymer (a1). The forming device and forming conditions are not particularly limited, and conventionally known forming devices and forming conditions can be adopted. For example, known methods such as extrusion molding, inflation molding, and calendar ring molding can be applied. Among them, it is preferable to perform molding by an extrusion molding device. Also, when the first resin layer 10 and the second resin layer 20 are each a multilayer structure, known methods such as coextrusion (extrusion using a multi-die) and various lamination methods can be appropriately applied. Next, when the design layer 30 is a printing layer, for example, printing may be performed on one surface of the first resin layer 10 using a method such as inkjet printing to form the design layer 30.

[0057] [Usage] The adhesive sheet 100 of the present embodiment can be widely applied to applications where repeated detachment is required, and can be used, for example, in various industrial fields such as clothing, medical and nursing care products, and housing equipment. More specifically, it can be used for daily necessities such as toys, stationery, binding bands, wraps, and seal materials, and as clothing and fashion accessories such as inners such as bras, sports and outdoor clothing, dresses, glasses, hats, helmets, wigs, headphones, earphones, watches, belts, sneakers, pumps, and sandals. Also, for medical use, it can be used, for example, for fixing tapes, bands, belts, and supporters, and as a material for wearable devices, it can be used, for example, for base materials and members of biosensing devices, e-sports devices, technosports devices, VR (virtual reality) and AR (augmented reality), smartwatches, smart glasses, and robot suits. Also, from the viewpoint that the above-mentioned adhesive sheet can be easily detached at a temperature close to body temperature, daily necessities such as containers such as bags, cups, and boxes can be easily manufactured. Taking advantage of this ease, it can be used, for example, for outdoor goods, sports-related goods, base materials and members in the event of disasters or emergencies. From the same viewpoint, it can be used as a new material for art, fine arts, handicrafts, etc. such as DIY materials, art work materials, and origami substitute materials. Among them, it can be preferably used in daily necessities such as toys and stationery that require design and are directly touched and handled by people. Note that the temperature close to body temperature refers to 30 to 39°C, and body temperature refers to 35 to 38°C.

[0058] In the first embodiment, the case where the design layer 30 is formed on one surface 12 side of the first resin layer 10 has been described. Further, a design layer may also be formed on the other surface 11 side of the first resin layer 10. Thereby, the design property can be further improved. The details of the aspects and effects in the case of having a plurality of design layers will be described in the fourth embodiment.

[0059] <Second Embodiment> In the first embodiment, the case where the design layer 30 is disposed on the first resin layer 10 has been described. In the second embodiment, the case where the first resin layer 10 and the second resin layer 20 constituting the adhesive surface have the design layer 30 laminated as an intermediate layer will be described. Hereinafter, in this embodiment, the description of the configurations, components, and effects common to the first embodiment will be omitted as appropriate.

[0060] FIG. 2 is a schematic cross-sectional view of the adhesive sheet 101 of the second embodiment. In FIG. 2, the adhesive sheet 101 has a first resin layer 10 containing a 4-methyl-1-pentene-based polymer and a second resin layer 20 containing a 4-methyl-1-pentene-based polymer. The first resin layer 10 constitutes the adhesive surface 11, and the second resin layer 20 constitutes the adhesive surface 21 on the side opposite to the first resin layer 10. The entire surface of both sides of the adhesive sheet 101 of this embodiment is the adhesive surface 11, 21. Further, the design layer 30 is interposed between the first resin layer 10 and the second resin layer 20 and is inside the adhesive sheet 101.

[0061] The adhesive sheet 101 of this embodiment satisfies the requirements (i) and (ii) in the same manner as the above-described adhesive sheet 100, and the thickness, density, etc. are also the same as those of the adhesive sheet 100.

[0062] [Transparency] In the pressure-sensitive adhesive sheet 101 of this embodiment, the regions extending from the design layer 30 to both outer surfaces of the pressure-sensitive adhesive sheet 101 are transparent. That is, both the first resin layer 10 and the second resin layer 20 are transparent. Thereby, even if the design layer 30 is disposed inside the pressure-sensitive adhesive sheet 101, the design layer 30 can be observed from both outer surfaces of the pressure-sensitive adhesive sheet 101, and the design property of the pressure-sensitive adhesive sheet 101 can be effectively enhanced. Specifically, it is preferable that the total light transmittance in the regions extending from the outermost surface of the design layer 30 to both outer surfaces of the pressure-sensitive adhesive sheet 101 is 30 to 99.9%, and the internal haze is 0.1 to 99.9%.

[0063] [Second resin layer] The second resin layer 20 of this embodiment constitutes one adhesive surface 21 of the pressure-sensitive adhesive sheet 101. Also, the thicknesses of the first resin layer 10 and the second resin layer 20 of this embodiment may be the same or different from each other.

[0064] Both the first resin layer 10 and the second resin layer 20 of this embodiment contain a 4-methyl-1-pentene-based polymer. The first resin layer 10 and the second resin layer 20 only need to contain a 4-methyl-1-pentene-based polymer, and they may be formed using the same components as each other, or may be formed using different components according to the purpose and application. Regarding each component contained in the second resin layer 20, it is the same as that described in the first embodiment.

[0065] [Design layer] In this embodiment, the design layer 30 is disposed so as to be interposed between the first resin layer 10 and the second resin layer 20. In other words, the pressure-sensitive adhesive sheet 10 has the design layer 30 inside. Thereby, the decrease in the adhesiveness of the pressure-sensitive adhesive sheet 100 can be more effectively suppressed.

[0066] Also, the area ratio of the design layer 30 to the area of the adhesive sheet 101 in this embodiment is the same as that described in the first embodiment. However, in this embodiment, by setting the area ratio of the design layer 30 to be equal to or less than the above upper limit value, there is an advantage that the occurrence of delamination due to the interposition of the design layer 30 between the first resin layer 10 and the second resin layer 20 can be suppressed.

[0067] In this embodiment, the first resin layer 10 and the second resin layer 20 are adjacent to each other, and the interlayer adhesion strength between the two is preferably 0.5 to 20 N / 15 mm, more preferably 0.6 to 15 N / 15 mm or more. This suppresses the peeling of the first resin layer 10 and the second resin layer 20 due to the interposition of the design layer 30, suppresses the occurrence of delamination, and facilitates the exhibition of the flexibility and adhesiveness of the adhesive sheet 101. Furthermore, when the adhesive sheet 101 is applied to a toy, higher flexibility against stress is required. According to the adhesive sheet 101 of this embodiment, high flexibility can be obtained while maintaining appropriate adhesiveness.

[0068] The interlayer adhesion strength can be measured using a tensile tester in accordance with JIS Z 1707:1997. Details will be described in the examples.

[0069] When the design layer 30 is a printing layer, for example, after printing is performed on the surface opposite to the adhesive surface 11 of the first resin layer 10 to form the design layer 30, the second resin layer 20 is formed so as to cover the design layer 30. This makes it easier to suppress the peeling of the printing layer.

[0070] After forming the printing layer, a coating layer may be further formed thereon. In this case, the coating layer is preferably one that can be thermally bonded, and specifically, polyolefin-based resins and the like can be mentioned. As the polyolefin-based resin, one or more selected from ethylene-based polymers, polypropylene-based polymers, ethylene·α-olefin copolymers, propylene·α-olefin copolymers, 1-butene·α-olefin copolymers, cyclic olefin copolymers, chlorinated polyolefins, etc. are preferable. However, it is desirable that the coat layer does not reduce the adhesion between the first resin layer 10 and the second resin layer 20.

[0071] [Method for manufacturing an adhesive sheet] An example of a method for manufacturing the adhesive sheet 101 according to the present embodiment will be described. First, the first resin layer 10 and the second resin layer 20 may be formed into sheets by known methods using the resin compositions (resin materials) constituting the first resin layer 10 and the second resin layer 20 in the same manner as described in the first embodiment, and then laminated by a known method. Specifically, when the design layer 30 is a printed layer, for example, after forming the design layer 30 by performing printing on one surface of the first resin layer 10 using a method such as inkjet printing, the adhesive sheet 101 can be obtained by laminating the second resin layer 20 so as to cover the obtained design layer 30. Note that the lamination procedure of the first resin layer 10 and the second resin layer 20 is not limited to this, and the first resin layer 10 may be laminated so as to cover the design layer 30 after forming the design layer 30 on one surface of the second resin layer 20. The lamination method is not particularly limited, and known methods such as various lamination methods and thermocompression bonding can be used.

[0072] <Third Embodiment> In the first embodiment and the second embodiment, the case where the design layer 30 is a printed layer has been described. In the third embodiment, the case where the first resin layer 10 and the second resin layer 20 constituting the adhesive surface are provided and the design layer 30 is not a printed layer will be described. Hereinafter, descriptions of configurations, components, and effects common to the first embodiment and the second embodiment will be omitted as appropriate.

[0073] Figure 3 is a schematic cross-sectional view of the pressure-sensitive adhesive sheet 102 of the third embodiment. The pressure-sensitive adhesive sheet 102 has a first resin layer 10 containing a 4-methyl-1-pentene polymer and a second resin layer 20 containing a 4-methyl-1-pentene polymer. The first resin layer 10 constitutes the adhesive surface 11, and the second resin layer 20 constitutes the adhesive surface 21 on the side opposite to the first resin layer 10. The pressure-sensitive adhesive sheet 102 of this embodiment has adhesive surfaces 11 and 21 on both sides. Further, the design layer 32 is interposed between the first resin layer 10 and the second resin layer 20 and is inside the pressure-sensitive adhesive sheet 102.

[0074] The pressure-sensitive adhesive sheet 102 of this embodiment satisfies the requirements (i) and (ii) in the same manner as the above-described pressure-sensitive adhesive sheets 100 and 101, and the thickness, density, transparency, etc. are also the same as those of the pressure-sensitive adhesive sheets 100 and 101.

[0075] [Design layer] The design layer 32 of this embodiment is a dyeing layer containing a 4-methyl-1-pentene polymer and one or more selected from dyes and pigments. Thereby, while maintaining good adhesiveness, the design property can be enhanced. In addition, examples of the material used for the design layer 32 include the same materials as those of the first resin layer 10 described above.

[0076] The above dyes are not particularly limited, and known dyes can be used. For example, disperse dyes, reactive dyes, direct dyes, composite dyes, acid dyes, metal complex dyes, mordant dyes, sulfur dyes, azo dyes, fluorescent dyes, dyes for resin coloring, and other functional dyes can be mentioned. These may be used alone or in combination of two or more. The above pigments are not particularly limited, and known pigments can be used. For example, extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, purple pigments, metal powder pigments, luminescent pigments, pearl pigments, and other organic pigments and inorganic pigments, and further plastic pigments can be mentioned. These may be used alone or in combination of two or more.

[0077] The thickness of the design layer 32 is not particularly limited, but is preferably 0.05 to 2 mm, and more preferably 0.1 to 1.0 mm. By setting the thickness of the design layer 32 to be equal to or greater than the above lower limit value, the design property can be enhanced. On the other hand, by setting the thickness of the design layer 32 to be equal to or less than the above upper limit value, it is possible to suppress the overall thickness of the adhesive sheet 102 from becoming too high, and the handleability, flexibility, etc. can be maintained well. Also, the design layer 32 may be a single layer or a plurality of layers. Further, when there are a plurality of design layers 32, each layer may have a different design from each other.

[0078] The design layer 32 may be obtained, for example, by molding a resin composition containing a 4-methyl-1-pentene-based polymer (a1) and one or more selected from dyes and pigments into a sheet shape by a known method. Also, after obtaining a transparent resin sheet by the same method as the above-described first resin layer 10 and second resin layer 20, the transparent resin sheet may be immersed in a dyeing solution containing a dye or a pigment, etc. for dyeing.

[0079] An example of the manufacturing method of the adhesive sheet 102 of the present embodiment will be described. The adhesive sheet 102 of the present embodiment may be laminated after molding the design layer 32, the first resin layer 10, and the second resin layer 20 into a sheet shape by known methods respectively, or a coextrusion (extrusion using a multi-die) method may be used using the resin materials constituting the design layer 32, the first resin layer 10, and the second resin layer 20.

[0080] <Fourth Embodiment> In the second embodiment, the case where the first resin layer 10 and the second resin layer 20 constituting the adhesive surface are provided and the design layer 30 is laminated as an intermediate layer has been described. In the fourth embodiment, the case where the design layers of the intermediate layer are laminated in two layers in the thickness direction will be described. Hereinafter, in the present embodiment, the description of the configurations, components, and effects common to the first to third embodiments will be omitted as appropriate.

[0081] FIG. 4 is a schematic cross-sectional view of the pressure-sensitive adhesive sheet 103 of the fourth embodiment. The pressure-sensitive adhesive sheet 103 has a first resin layer 10 containing a 4-methyl-1-pentene polymer and a second resin layer 20 containing a 4-methyl-1-pentene polymer. The first resin layer 10 constitutes an adhesive surface 11, and the second resin layer 20 constitutes an adhesive surface 21 on the side opposite to the first resin layer 10. In the pressure-sensitive adhesive sheet 103 of this embodiment, the entire both sides are the adhesive surfaces 11 and 21. Furthermore, in this embodiment, the design layers 33 and 34 are laminated via a third resin layer 40. That is, the pressure-sensitive adhesive sheet 103 has a laminated structure in which the first resin layer 10, the design layer 33, the third resin layer 40, the design layer 34, and the second resin layer 20 are laminated in this order.

[0082] [Design layer] In the pressure-sensitive adhesive sheet 103 of the fourth embodiment, two design layers 33 and the design layer 34 are laminated in the thickness direction, and the first resin layer 10 and the second resin layer 20 are provided on each of the outer surfaces of the pressure-sensitive adhesive sheet 103, respectively. Thereby, while maintaining the adhesiveness of the pressure-sensitive adhesive sheet 103, the designability can be enhanced. In this embodiment, the design layer 33 and the design layer 34 may have the same arrangement, shape, pattern, color, and thickness, or may be different. From the viewpoint of enhancing the designability of the pressure-sensitive adhesive sheet 103, it is preferable that at least one of the arrangement, shape, pattern, and color is different. Hereinafter, specific examples will be described with reference to FIG. 6, but it is merely an example and is not limited thereto.

[0083] FIG. 6 is a plan view showing each design layer constituting a piece (FIG. 5) described later obtained by cutting the pressure-sensitive adhesive sheet into a cross shape. For example, as shown in FIG. 6(a), both the design layer I and the design layer II have the same shape and the same stripe pattern, but different colors from each other. Also, as shown in FIG. 6(a), the repeating units of the stripe pattern may be arranged so as to be shifted between the design layer I and the design layer II. Thereby, when the design layer I and the design layer II are laminated, the respective designs can be combined to obtain one design (pattern, color) as a whole. Further, as shown in FIG. 6(b), the design layer I is a dot (polka dot) pattern, the design layer II is a pattern in which the dots (polka dots) are white-outlined, and their colors are different from each other. Also, as shown in FIG. 6(b), the dots (polka dots) of the design layer I may be arranged so as to match the white-outlined portions of the design layer II. Thereby, when the design layer I and the design layer II are laminated, the respective designs are combined to obtain a single design (pattern, color) as a whole. Similarly, as shown in FIG. 6(c), the design layer I is a check pattern in which vertical and horizontal lines intersect, the design layer II is a pattern in which the square shapes corresponding to the intersection portions of the check pattern are white-outlined, and their colors are different from each other. Also, as shown in FIG. 6(c), the design layer II may be arranged so as to fill the blank portions of the design layer I. Thereby, when the design layer I and the design layer II are laminated, the respective designs are combined to obtain a single design (pattern, color) as a whole.

[0084] Also, the area ratios occupied by the design layer 33 and the design layer 34 with respect to the area of the adhesive sheet 103 in plan view are less than 100%, preferably 95% or less, more preferably 90% or less, and even more preferably 85% or less, 80% or less, and 70% or less in that order. The area ratios of the design layer 33 and the design layer 34 may be the same as or different from each other. By controlling the area ratios of the design layer 33 and the design layer 34, it becomes easier to suppress peeling between the first resin layer 10 and the third resin layer 40 and between the second resin layer 20 and the third resin layer 40. On the other hand, the lower limit value of the area ratio occupied by the design layer 33 and the design layer 34 is not particularly limited, but from the viewpoint of enhancing the design property, it is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more, and even more preferably 25% or more. Also, in the present embodiment, the total value of the area ratio of the design layer 33 and the area ratio of the design layer 34 is not particularly limited and may be 100% or more. That is, in plan view of the laminated state of the design layer 33 and the design layer 34, there may be an overlapping portion.

[0085] [Third Resin Layer] The third resin layer 40 of the present embodiment is interposed between the design layer 33 and the design layer 34, and is used to suppress delamination between layers, realize multi-layerization of the design layer, and improve the design property.

[0086] The third resin layer 40 is not particularly limited as long as it can be formed in a film shape and can be used. For example, films such as polyolefin and polyethylene terephthalate can be mentioned. When used as a toy that can be picked up by hand, attached or peeled off by warming, the third resin layer 40 may be formed using the above resin raw materials used for the first resin layer 10 and the second resin layer 20. Thereby, flexibility can be obtained by picking up and warming by hand in the same manner as the first resin layer 10 and the second resin layer 20, and the feeling of becoming soft when touched by hand can be enjoyed more, which is preferable.

[0087] The thickness of the third resin layer 40 is not particularly limited, but from the viewpoint of enhancing the design property while maintaining the handleability and flexibility of the adhesive sheet 103, 30 μm to 5 mm is preferable, and 50 μm to 1 mm is more preferable.

[0088] The third resin layer 40 is preferably transparent. Thereby, good design property can be maintained. Specifically, the total light transmittance of the third resin layer 40 is preferably 30 to 99%, and the internal haze is preferably 0.1 to 99.9%.

[0089] An example of the manufacturing method of the adhesive sheet 103 of the present embodiment will be described. The adhesive sheet 103 can be obtained, for example, by printing one side of the first resin layer 10 and the second resin layer 20 by a known method to form the design layer 33 and the design layer 34 respectively, and then laminating them in the order of the first resin layer 10 / design layer 33 / third resin layer 40 / design layer 34 / second resin layer 20. In addition, the adhesive sheet 103 of the present embodiment can also be obtained by first printing both sides of the third resin layer 40 by a known method to form the design layer 33 and the design layer 34 respectively, and then laminating the first resin layer 10 on the design layer 33 and the second resin layer 20 on the design layer 34.

[0090] In the fourth embodiment, the case where both the design layer 33 and the design layer 34 are printing layers has been described, but either one or both of them may be a dyeing layer. Further, when there are a plurality of design layers, the number thereof is not particularly limited, and may be three or more. In this case, in order to suppress delamination, it is desirable that a third resin layer is interposed between the design layers.

[0091] <Fifth Embodiment> In the above embodiment, the case where the resin layer and the design layer are laminated as separate layers has been described, but in the fifth embodiment, the case where the resin layer has design properties and constitutes the design layer will be described. Hereinafter, in this embodiment, the description of the configurations, components, and effects common to the first to fourth embodiments will be appropriately omitted.

[0092] FIG. 9 is a schematic cross-sectional view of the pressure-sensitive adhesive sheet 104 of the fifth embodiment. The pressure-sensitive adhesive sheet 104 has a fourth resin layer 51 containing a 4-methyl-1-pentene polymer and a fifth resin layer 52 containing a 4-methyl-1-pentene polymer. The fourth resin layer 51 constitutes the adhesive surface 11, and the fifth resin layer 52 constitutes the adhesive surface 21 on the side opposite to the fourth resin layer 51. The entire both sides of the pressure-sensitive adhesive sheet 104 of this embodiment are the adhesive surfaces 11 and 21. Furthermore, in this embodiment, both the fourth resin layer 51 and the fifth resin layer 52 contain one or more selected from pigments and colorants to form a colored design layer. The pressure-sensitive adhesive sheet 104 of the fifth embodiment also has a third resin layer 40. As described above, the third resin layer 40 is an intermediate layer interposed between the fourth resin layer 51 and the fifth resin layer 52, and is used to suppress delamination between the fourth resin layer 51 and the fifth resin layer 52 and to realize multi-layerization of the colored design layer to improve design properties.

[0093] [Colored Design Layer] The colored design layer contains a 4-methyl-1-pentene polymer, at least partially constitutes the adhesive surface of the pressure-sensitive adhesive sheet 104, and has design properties by containing a dye or a colorant. Examples of colorants used in the colored design layer include known dyes and the like. Further, as the dyes and pigments used in the colored design layer, the same ones as those described for the above-described dyeing layer can be used.

[0094] The degree of coloring of the colored design layer is adjusted by adjusting the types and concentrations of dyes and pigments, immersion time, etc. Thereby, the adhesiveness of the adhesive sheet 104 can be controlled.

[0095] Also, the thickness of the colored design layer is not particularly limited, but is preferably 0.05 to 2 mm, and more preferably 0.1 to 1.0 mm. By setting the thickness of the colored design layer to be equal to or greater than the above lower limit value, the design property can be enhanced. On the other hand, by setting the thickness of the colored design layer to be equal to or less than the above upper limit value, it is possible to suppress the overall thickness of the adhesive sheet 104 from becoming too high, and the handleability, flexibility, etc. can be maintained well. Also, the colored design layer may be a single layer or a plurality of layers. Further, when there are a plurality of colored design layers, each layer may have a different design. In the present embodiment, the colored design layers obtained from the fourth resin layer 51 and the fifth resin layer 52 may have different designs from each other, for example, different colors and different patterns.

[0096] It is preferable that the total light transmittance of the colored design layer of the present embodiment is 30 to 99% and the internal haze is 0.1 to 99.9%. From the viewpoint of improving colorability and color development property, it is more preferable that the total light transmittance is 30 to 80% and the internal haze is 0.1 to 70.0%.

[0097] The method for forming the colored design layer is not particularly limited, and the same method as that described for the above-described design layer 32 can be used.

[0098] As the fourth resin layer 51 and the fifth resin layer 52, the same materials as those described for the above-described first resin layer 10 and second resin layer 20 can be used except that they contain pigments and colorants.

[0099] In the fifth embodiment, the case where the colored design layer has two layers has been described, but the present invention is not limited thereto, and three or more layers may be used. In this case, it is preferable that there is an intermediate layer between the layers to suppress delamination.

[0100] <Modification Example> The pressure-sensitive adhesive sheet in the first to fifth embodiments described above is an example, and the pressure-sensitive adhesive sheet according to the present embodiment is not limited thereto. For example, the design layer disposed inside the pressure-sensitive adhesive sheet may be embedded from one surface side of the pressure-sensitive adhesive sheet. Further, within a range where the effects of the present invention are not impaired, the first resin layer, the second resin layer, and the design layer may be single layers or multiple layers, and may include layers other than these.

[0101] 2. Piece and Piece Set The piece of the present embodiment is obtained by cutting each of the above-described various pressure-sensitive adhesive sheets into a predetermined size. The cutting method is not particularly limited, and a known method can be used. The size of the piece is not particularly limited, but from the viewpoint of being taken by a person's hand and exhibiting flexibility and adhesiveness when warmed by a person's body temperature, it is preferably about the same as the palm of the hand. Further, the shape of the piece is not particularly limited, and includes a wide range such as circular, elliptical, triangular, rectangular, polygonal, cross-shaped, animal or plant-shaped, and star-shaped. Further, from the viewpoints of making it easy to feel softness and gentleness when visually observing or picking up by hand, and making it easy to suppress delamination, it is preferable to have rounded corners. For example, as shown in FIG. 5, it can be a cross-shaped piece. In addition, although the piece of the present embodiment exhibits appropriate adhesiveness and design properties, it is preferable that the design layer is not disposed at least in part of the peripheral portion in a plan view. This makes it easier to suppress delamination due to the interposition of the design layer.

[0102] In addition, the piece set of this embodiment includes a plurality of such pieces and is used as a toy. When the pieces of this embodiment are touched by a person and warmed to about 25°C to 40°C, their flexibility and adhesiveness are enhanced. Therefore, when applied to a toy, children, the elderly, etc. can warm the pieces of this embodiment by hand, increasing the adhesiveness and flexibility, so that the pieces can be easily stuck together, assembled, or freely deformed. Also, the pieces of this embodiment can be easily separated even by the strength of children or the elderly even if they are stuck together. On the other hand, when the pieces are cooled, their flexibility decreases, their shape is retained, and their adhesiveness also decreases, so that the pieces naturally separate from each other. Moreover, since the pieces of this embodiment have good design properties, a more highly designed shape can be created. For example, four cross-shaped pieces can be combined to form a ring, or these can be stacked in three layers to form a tall cylinder as shown in FIG. 7. Also, as shown in FIG. 8, by arranging three cross-shaped pieces so that their ends are shifted while overlapping them in the thickness direction and further bending the ends of each piece upward, a flower-like shape can be formed.

[0103] The number of pieces is not particularly limited and may be from several tens to several hundreds. Also, the shapes, sizes, and designs of the pieces may be the same. Also, the plurality of pieces may be different from each other or partially different from each other. In other words, the plurality of pieces may include at least two or more pieces having the same shape as each other and / or the same design as each other.

[0104] [Usage method] In this embodiment, the usage method of the piece set includes the following steps. Step 1: The step of warming the pieces, Step 2: The step of combining one or more selected from among sticking the pieces together, peeling the stuck pieces apart, and deforming the pieces, Step 3: The step of cooling the pieces.

[0105] (Step 1) By warming the pieces, the flexibility and adhesiveness of the pieces are improved. The method of warming the pieces is not particularly limited, but from the viewpoint of simply and safely enhancing the flexibility and adhesiveness, it is preferable to warm the pieces by human body temperature, such as by picking up the pieces by hand.

[0106] (Step 2) Adhere or separate the pieces with improved adhesiveness obtained in Step 1, or deform and assemble the pieces with improved flexibility. As a result, the desired shape, color, etc. of the user can be obtained, and the function as a toy can be improved. Also, the feeling of touching can be enjoyed. For the adhesion of the pieces, a part of the pieces may be adhered to each other, the entire surfaces may be adhered to each other in a laminated manner, or a plurality of pieces may be freely combined and adhered. Examples of the deformation of the pieces include one or a combination of two or more selected from bending, twisting, folding, stretching, shrinking, molding, etc.

[0107] (Step 3) By cooling the warmed pieces, the pieces adhered in Step 2 can be fixed to each other, or the shape of the deformed pieces can be maintained. The cooling method is not particularly limited, and known simple methods such as releasing the pieces from the hand and allowing natural cooling, or blowing air, can be mentioned. After Step 3, the pieces may be warmed again to return each piece to its original shape and state.

[0108] Since Steps 1 to 3 can be repeated, the pieces of this embodiment can be used repeatedly.

[0109] As described above, the embodiments of the present invention have been described, but these are examples of the present invention, and various configurations other than the above can also be adopted. Also, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the range that can achieve the object of the present invention are included in the present invention.

Example

[0110] Hereinafter, this embodiment will be described in detail with reference to Examples and Comparative Examples. Note that this embodiment is not limited to the descriptions of these examples at all.

[0111] <Measurement Method> (1) Measurement of Dynamic Viscoelasticity of Adhesive Sheet The adhesive sheet was cut into strips with a length of 50 mm and a width of 5 mm to obtain test pieces. Then, for the obtained test pieces, using an RSAIII manufactured by TA Instruments, the temperature dependence of dynamic viscoelasticity in the temperature range of 0°C to 110°C was measured under the conditions of a chuck distance of 20 mm, a frequency of 1.59 Hz, a strain of 0.1%, a heating rate of 4°C / min, and a tensile mode. From the obtained graph, the temperature showing the maximum value of the loss tangent (tanδ) and the maximum value of tanδ were determined respectively.

[0112] (2) Tensile Test of Adhesive Sheet · Maximum Shearing Rate and Elongation (%) The adhesive sheet was cut into strips with a length of 85 mm and a width of 20 mm to obtain test pieces. Under the environment of a temperature of 23°C and a relative humidity of 50%, two test pieces were overlapped with the measurement surfaces shown in Table 1 facing each other at a pasting size of a width of 20 mm and a length of 25 mm, and a pressure of 0.026 MPa was applied for 1 second using a heat sealer (TP701B manufactured by Tester Sangyo) set at 40°C. Then, it was left for 24 hours under the environment of a temperature of 23°C and a relative humidity of 50%. Next, using a tensile testing machine (AG-X-5 manufactured by Shimadzu Corporation), a tensile test was performed at a chuck distance of 50 mm and a tensile speed of 50 mm / min, and the maximum shear stress (MPa) and elongation (%) at the time of peeling were measured. This measurement was performed 5 times, and the average values were taken as the maximum shear stress (MPa) and elongation (%).

[0113] (3) Interlayer Adhesion Strength A 15-mm-wide test piece was cut out from the adhesive sheet, and in accordance with JIS Z 1707:1997, the interlayer adhesion strength between the first resin layer and the second resin layer with the design layer interposed therebetween was measured using a tensile testing machine (for example, Autograph AG-X manufactured by Shimadzu Corporation). The interlayer adhesion strength was measured under the conditions of a chuck distance of 90 mm and a tensile speed of 500 mm / min.

[0114] (4) Total light transmittance of the first resin layer The total light transmittance of the 4-methyl-1-pentene-based polymer sheet (first resin layer) was measured using a Haze meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd. based on JIS K 7361 (TRANS).

[0115] (5) Haze (internal haze) of the first resin layer The 4-methyl-1-pentene-based polymer sheet (first resin layer) was immersed in cyclohexanol, and the measurement was carried out using a Haze meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd. based on JIS K 7136 (HAZE).

[0116] <Material> The raw materials used in the examples and comparative examples are shown below. (1) 4-methyl-1-pentene-based polymer · Copolymer of 4-methyl-1-pentene and propylene (content of structural units derived from 4-methyl-1-pentene: 72 mol%, content of structural units derived from propylene: 28 mol%) · Glass transition temperature: 30°C · Limiting viscosity [η] in decalin at 135°C: 1.5 dL / g · MFR: 28 g / 10 min

[0117] The limiting viscosity [η] and composition of the above 4-methyl-1-pentene-based polymer were measured as follows. · The limiting viscosity [η] was measured at 135°C using a decalin solvent. · The contents of 4-methyl-1-pentene and α-olefin in the 4-methyl-1-pentene-based polymer 13Quantification was performed by 13C-NMR.

[0118] (2) Colorant: · UV-curable inkjet ink (brand name; SQS ink, white) · Blue dye (brand name; resin dye SDN, manufactured by Osaka Chemical Products Co., Ltd.)

[0119] <Production of Adhesive Sheet> [Example 1] As the molding machine, a single-screw extrusion molding machine (cylinder inner diameter D: 65 mm, full-flight screw, T-die (die width: 750 mm), cooling roll, and take-up machine) was used. First, the 4-methyl-1-pentene-based polymer was charged into the extrusion molding machine, melted and kneaded under the conditions of the temperature of each part of the cylinder being 100 to 250 °C and the screw rotation speed being 23 rpm, and extruded from the T-die so that the extrusion amount was 15 kg / hour. The extruded sheet was cooled by a cooling roll (the temperature of the water flowing inside the roll was 20 °C), taken up using a take-up machine (take-up speed 1.3 m / min), and a 4-methyl-1-pentene-based polymer sheet (first resin layer) with a sheet thickness of 0.3 mm and a sheet width of about 700 mm was obtained. The obtained 4-methyl-1-pentene-based polymer sheet was set in an inkjet printer (manufactured by SwissQPrint), and printed on one surface of the sheet under the following conditions using a UV-curable inkjet ink (brand name; SQS ink) to form a design layer and obtain an adhesive sheet. Printing pattern; circular dots with a diameter of 0.5 mm Center-to-center distance of horizontally adjacent dots (horizontal pitch); 1.7 mm Center-to-center distance of vertically adjacent dots (vertical pitch); 0.85 mm Printed area; 30%

[0120] [Example 2] On one surface of the 4-methyl-1-pentene-based polymer sheet (first resin layer) obtained in Example 1, a design layer was formed under the same conditions except that the printing pattern described in Example 1 was changed to circular dots with a diameter of 0.85 mm and the printed area was changed to 50% to obtain an adhesive sheet.

[0121] [Example 3] On one surface of a 4-methyl-1-pentene-based polymer sheet (first resin layer) obtained in the same manner as in Example 1 except that the take-up speed was changed so that the thickness became 0.6 mm, a design layer was formed by the coating method described in Example 1. A 4-methyl-1-pentene-based polymer sheet (second resin layer) obtained in the same manner as in Example 1 except that the take-up speed was changed so that the thickness became 0.1 mm was separately prepared, and the first resin layer (thickness 0.6 mm), the design layer, and the second resin layer (thickness 0.1 mm) were stacked in this order, heated and pressed at 180 °C to weld each layer, and an adhesive sheet was obtained.

[0122] [Example 4] On one surface of a 4-methyl-1-pentene-based polymer sheet (first resin layer) obtained in the same manner as in Example 1 except that the take-up speed was changed so that the thickness became 0.6 mm, a design layer was formed by the coating method described in Example 2. A 4-methyl-1-pentene-based polymer sheet (second resin layer) obtained in the same manner as in Example 1 except that the take-up speed was changed and the thickness was adjusted to 0.1 mm was separately prepared, and the first resin layer (thickness 0.6 mm), the design layer, and the second resin layer (thickness 0.1 mm) were stacked in this order, heated and pressed at 180 °C to weld each layer, and an adhesive sheet was obtained.

[0123] [Example 5] Resin dye SDN (manufactured by Osaka Chemical Products Co., Ltd.) and water were mixed at a ratio of 1:20 to prepare a 5% dyeing solution, and the dyeing solution was heated to 70 °C and kept warm. The entire 4-methyl-1-pentene-based polymer sheet obtained in the same manner as in Example 1 except that the take-up speed of 1.3 m / min in Example 1 was adjusted so that the thickness became 0.6 mm was immersed in the 70 °C dyeing solution for 10 minutes for dyeing. After dyeing, it was thoroughly washed with water and dried to obtain a dyed 4-methyl-1-pentene-based polymer sheet (dyeing layer). Two 4-methyl-1-pentene-based polymer sheets (thickness 0.1 mm) obtained in the same manner as in Example 1 except that the take-up speed was adjusted so that the thickness became 0.1 mm were prepared and used as the first resin layer and the second resin layer, respectively. The first resin layer, the dyeing layer, and the second resin layer were stacked in this order, heated and pressed at 180 °C to weld each layer, and an adhesive sheet was obtained.

[0124] [Example 6] A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, except that a design layer was formed by applying the printing conditions of the coating method described in Example 1 to the entire surface (printing area: 100%) of one surface of the 4-methyl-1-pentene polymer sheet (first resin layer) obtained in Example 1.

[0125] [Example 7] A design layer was formed and a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 2, except that a foamed 4-methyl-1-pentene polymer sheet (first resin layer) was obtained by the following procedure. As the molding machine, a single-screw extrusion molding machine (cylinder inner diameter D: 65 mm, full-flight screw, T-die (die width: 750 mm), cooling roll, and take-up machine) was used. First, a 4-methyl-1-pentene polymer and 3 parts by weight of a chemical foaming agent (polystyrene EE275F) were externally charged into the extrusion molding machine, and melted and kneaded under the conditions of a temperature of 120 to 220 °C for each part of the cylinder and a screw rotation speed of 19 rpm, and extruded from the T-die so that the extrusion amount was 15 kg / hour. The extruded sheet was cooled by a cooling roll (water temperature inside the roll: 20 °C), taken up using a take-up machine (take-up speed: 1.2 m / min), and a 4-methyl-1-pentene polymer sheet (first resin layer) with a sheet thickness of 0.5 mm and a sheet width of about 600 mm was obtained.

[0126] [Comparative Example 1] The 4-methyl-1-pentene polymer sheet (first resin layer) obtained in Example 1 was obtained as a pressure-sensitive adhesive sheet.

[0127] [Evaluation] Using each of the obtained sheets, the following evaluations were performed. The results are shown in Table 1. · Adhesiveness (detachability) Based on the following criteria, the adhesiveness was evaluated from the maximum shear stress obtained in the tensile test of the above pressure-sensitive adhesive sheet. (Criteria) ◎: Maximum shear stress 0.5 MPa or more and less than 1.50 MPa 〇: Maximum shear stress is 1.50 MPa or more and less than 1.90 MPa △: Maximum shear stress is 1.90 MPa or more and less than 5.0 MPa ×: Maximum shear stress is 5.0 MPa or more, or less than 0.5 MPa Note that the higher the maximum shear stress, the higher the adhesiveness, and it is intended that it becomes difficult to peel the adhesive sheets from each other. On the other hand, the lower the maximum shear stress, the lower the adhesiveness, and it is intended that it becomes difficult to stick the adhesive sheets to each other.

[0128] · Ease of color peeling (design property) Based on the following criteria, the ease of color peeling in the adhesive sheet was evaluated. (Criteria) ◎: No color peeling even when the adhesive sheet is pulled or stretched 〇: When the adhesive sheet is pulled or stretched, there are partially areas where the color peels off. △: The color does not peel off just by touching the adhesive sheet with hand, but peels off when pulled or stretched. ×: The color peels off just by slightly touching the adhesive sheet with hand.

[0129] · Transparency Each sheet was placed on a white paper with a grid pattern in which the grid line color is yellow and the line width is 1 mm, and it was evaluated based on the following criteria whether the grid pattern could be visually recognized under white light through the sheet. (Criteria) ○: The grid pattern could be clearly visually recognized. △: Part of the pattern such as the edge of the grid pattern was blurred. ×: The whole pattern was blurred, or the specific shape of the pattern could not be recognized.

[0130]

Table 1

[0131] This application claims the priority based on Japanese Application No. 2021-086438 filed on May 21, 2021, and incorporates all of its disclosure herein.

Explanation of Symbols

[0132] 10 First resin layer 11 Adhesive surface 12 Adhesive surface 20 Second resin layer 21 Adhesive surface 30 Design layer 32 Design layer 33 Design layer 34 Design layer 40 Third resin layer 51 Fourth resin layer 52 Fifth resin layer 100 Adhesive sheet 101 Adhesive sheet 102 Adhesive sheet 103 Adhesive sheet 104 Adhesive sheet

Claims

1. An adhesive sheet having a resin layer containing a 4-methyl-1-pentene-based polymer, wherein at least a part of the resin layer is exposed on both sides of the adhesive sheet to form an adhesive surface, the resin layer contains one or more selected from pigments and colorants to form a colored design layer, and an adhesive sheet that satisfies the following requirement (i). (i) The temperature showing the maximum value of the loss tangent (tan δ) obtained by dynamic viscoelasticity measurement under the conditions of a temperature increase rate of 4 ° C / min, a frequency of 1.59 Hz, and a strain of 0.1% is at least 10 ° C or more and 100 ° C or less There is one or more in the range, and the maximum value of the loss tangent is 0.5 or more and 3.5 or less.

2. The adhesive sheet according to claim 1, which satisfies the following requirement (ii). (ii) When the adhesive surfaces of the adhesive sheet prepared at 23 ° C are pressure-bonded at 40 ° C and 0.026 MPa and a tensile test is performed at 23 ° C, the maximum shear stress is 1.0 MPa or more and less than 5.0 MPa.

3. The adhesive sheet according to claim 1 or 2, wherein the 4-methyl-1-pentene-based polymer contains a structural unit (c1) derived from 4-methyl-1-pentene and a structural unit (c2) derived from a linear α-olefin having 2 to 3 carbon atoms other than 4-methyl-1-pentene.

4. The adhesive sheet according to claim 3, wherein when the total of the structural unit (c1) and the structural unit (c2) is 100 mol%, the content of the structural unit (c1) is 10 mol% or more and 90 mol% or less.

5. The adhesive sheet according to any one of claims 1 to 4, having a plurality of the design layers, and providing the design layer on both sides of at least one of the resin layers.

6. The adhesive sheet according to any one of claims 1 to 5, having the design layer inside the adhesive sheet.

7. The pressure-sensitive adhesive sheet according to any one of claims 1 to 6, wherein the plurality of the design layers are laminated in the thickness direction and the plurality of the design layers have different designs from each other.

8. The pressure-sensitive adhesive sheet according to claim 7, wherein at least one of the arrangement, shape, pattern, and color of the different designs is different.

9. The pressure-sensitive adhesive sheet according to any one of claims 1 to 8, having a plurality of the resin layers, wherein both outer surfaces of the pressure-sensitive adhesive sheet are each constituted by the resin layer.

10. The pressure-sensitive adhesive sheet according to any one of claims 1 to 9, wherein the resin layer is transparent.

11. The pressure-sensitive adhesive sheet according to any one of claims 1 to 10, wherein the total light transmittance of the resin layer is 30 to 99.9%.

12. The pressure-sensitive adhesive sheet according to any one of claims 1 to 11, having a plurality of the resin layers, wherein the interlayer adhesion strength between one of the resin layers and another adjacent resin layer is 0.5 N / 15 mm or more.

13. The pressure-sensitive adhesive sheet according to any one of claims 1 to 12, having an average thickness of 0.01 mm or more and 30 mm or less.

14. A piece obtained by cutting the pressure-sensitive adhesive sheet according to any one of claims 1 to 13 into a predetermined size.

15. The piece according to claim 14, wherein in a plan view, the design layer is not disposed at least in a part of a peripheral portion.

16. A method of using a piece set, wherein a plurality of pieces according to claim 14 or 15 are used as toys, a step of heating the pieces, a step of combining one or more selected from the steps of adhering the pieces to each other, peeling the adhered pieces from each other, and deforming the pieces, and having the method of using the piece set.

17. A method of using the piece set according to claim 16, comprising: further comprising a step of cooling the piece after the combining step; A method of using a piece set.

18. A method of using the piece set according to claim 16 or 17, comprising: the step of warming the piece is performed by the body temperature of a human; a method of using a piece set.

19. A method of using the piece set according to any one of claims 16 to 18, comprising: the plurality of pieces include at least two pieces having the same shape as each other and / or the same design as each other; a method of using a piece set.

20. A method for producing an adhesive sheet having a resin layer containing a 4-methyl-1-pentene-based polymer and a design layer, comprising: forming the design layer by performing printing on the resin layer; forming an adhesive surface by exposing at least a part of the resin layer on both sides of the adhesive sheet; the area ratio of the design layer in a plan view of the adhesive sheet is 25 to 95% with respect to the planar area of the adhesive sheet, and the adhesive sheet satisfies the following requirement (i); a method for producing an adhesive sheet. (i) The temperature showing the maximum value of the loss tangent (tan δ) obtained by dynamic viscoelasticity measurement under the conditions of a heating rate of 4 °C / min, a frequency of 1.59 Hz, and a strain amount of 0.1% is in the range of at least 10 °C or more and 100 °C or less, and the maximum value of the loss tangent is 0.5 or more and 3.5 or less.

21. A step of obtaining an adhesive sheet by the method for producing an adhesive sheet according to claim 20, and a step of cutting the obtained adhesive sheet into a predetermined size; A method for producing a piece, comprising.

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