WO2022244286A1 - 粘着シート - Google Patents

粘着シート Download PDF

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Publication number
WO2022244286A1
WO2022244286A1 PCT/JP2021/045080 JP2021045080W WO2022244286A1 WO 2022244286 A1 WO2022244286 A1 WO 2022244286A1 JP 2021045080 W JP2021045080 W JP 2021045080W WO 2022244286 A1 WO2022244286 A1 WO 2022244286A1
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WO
WIPO (PCT)
Prior art keywords
adhesive sheet
pressure
sensitive adhesive
resin layer
layer
Prior art date
Application number
PCT/JP2021/045080
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English (en)
French (fr)
Japanese (ja)
Inventor
茂雄 西川
Original Assignee
三井化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 三井化学株式会社 filed Critical 三井化学株式会社
Priority to JP2023522198A priority Critical patent/JP7695349B2/ja
Publication of WO2022244286A1 publication Critical patent/WO2022244286A1/ja

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    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
    • A63H33/00—Other toys
    • A63H33/04—Building blocks, strips, or similar building parts
    • A63H33/14—Building blocks, strips, or similar building parts specially adapted to be assembled by adhesive or cement
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive sheet. More specifically, it relates to an adhesive sheet, a piece obtained by cutting the adhesive sheet, and a piece set.
  • Patent Document 1 discloses a self-adhesive sheet using a vinyl resin composition containing a vinyl chloride resin, a specific acrylic block copolymer, and a plasticizer.
  • the present inventors have focused on the use of a pressure-sensitive adhesive sheet containing a 4-methyl-1-pentene polymer as a new toy, and have sought to impart designability while appropriately controlling the adhesiveness of the pressure-sensitive adhesive sheet. investigated. Then, as a result of intensive studies, in a pressure-sensitive adhesive sheet having a resin layer containing a 4-methyl-1-pentene-based polymer as the pressure-sensitive adhesive surface, a predetermined loss tangent in the pressure-sensitive adhesive sheet is used as an index and controlled to achieve stable adhesion. In addition, by devising the arrangement, ratio, composition, etc. of the design layer so that at least a part of the adhesive surface is exposed, it is possible to improve the design while maintaining appropriate adhesiveness. , completed the present invention.
  • a pressure-sensitive adhesive sheet having a resin layer containing a 4-methyl-1-pentene polymer and a design layer A pressure-sensitive adhesive sheet that constitutes a pressure-sensitive adhesive surface by exposing at least part of the resin layer on at least one surface of the pressure-sensitive adhesive sheet, and that satisfies the following requirement (i).
  • the temperature at which the maximum value of the loss tangent (tan ⁇ ) is 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 10 ° C. or higher. There is one or more in the range of 100° C.
  • a pressure-sensitive adhesive sheet having a resin layer containing a 4-methyl-1-pentene polymer and a design layer, forming an adhesive surface by exposing at least part of the resin layer on at least one surface of the adhesive sheet;
  • the design layer is a printed layer, the area ratio of the printed layer in plan view of the pressure-sensitive adhesive sheet is 25 to 95% of the planar area of the pressure-sensitive adhesive sheet, and the following requirement (i) is satisfied: sheet.
  • the temperature at which the maximum value of the loss tangent (tan ⁇ ) is 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 10 ° C. or higher. There is one or more in the range of 100° C. or less, and the maximum value of the loss tangent is 0.5 or more and 3.5 or less.
  • a pressure-sensitive adhesive sheet having a resin layer containing a 4-methyl-1-pentene polymer, forming an adhesive surface by exposing at least part of the resin layer on at least one surface of the adhesive sheet;
  • a pressure-sensitive adhesive sheet wherein the resin layer contains one or more selected from pigments and colorants to form a colored design layer and satisfies the following requirement (i).
  • the temperature at which the maximum value of the loss tangent (tan ⁇ ) is 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 10 ° C. or higher. There is one or more in the range of 100° C.
  • the 4-methyl-1-pentene-based polymer is derived from a linear ⁇ -olefin having 2 to 3 carbon atoms other than the structural unit (c1) derived from 4-methyl-1-pentene and 4-methyl-1-pentene
  • the pressure-sensitive adhesive sheet according to any one of [1] to [4], comprising the structural unit (c2) of [6] [5], wherein the content of the structural unit (c1) is 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% adhesive sheet.
  • the pressure-sensitive adhesive sheet according to [9] wherein the mutually different designs differ in at least one or more of arrangement, shape, pattern, and color.
  • [15] The adhesive sheet according to any one of [1] to [14], wherein the resin layer has a total light transmittance of 30 to 99.9%.
  • [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.
  • a method for producing a pressure-sensitive adhesive sheet wherein the area ratio of the design layer of the pressure-sensitive adhesive sheet in plan view is 25 to 95% of the planar area of the pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive sheet satisfies the following requirement (i).
  • FIG. 1 is a schematic cross-sectional view of an adhesive sheet 100 of a first embodiment
  • FIG. FIG. 10 is a schematic cross-sectional view of an adhesive sheet 101 of a second embodiment
  • FIG. 10 is a schematic cross-sectional view of an adhesive sheet 102 of a third embodiment
  • FIG. 10 is a schematic cross-sectional view of an adhesive sheet 103 of a fourth embodiment
  • It is a top view which shows an example of the piece of this embodiment.
  • FIG. 4 is an exploded view showing the design layer of the piece of the present embodiment
  • It is a photograph figure which shows the usage example of the piece of this embodiment.
  • FIG. 11 is a schematic cross-sectional view of an adhesive sheet 104 of a fifth embodiment
  • sheet is a concept including not only what is generally called “sheet” but also what is generally called “film”.
  • sheet has a thickness of 250 ⁇ m or more
  • film has a thickness of less than 250 ⁇ m.
  • FIG. 1 is a schematic cross-sectional view of the pressure-sensitive adhesive sheet 100 of the first embodiment.
  • the adhesive sheet 100 includes a first resin layer 10 containing a 4-methyl-1-pentene polymer and a design layer 30, and the first resin layer 10 constitutes the adhesive surface 11 and the adhesive surface 12. , the entire surface of the adhesive surface 11 and a part of the adhesive surface 12 are exposed, and satisfy the following requirement (i).
  • the pressure-sensitive adhesive sheet 100 has a maximum value of loss tangent (tan ⁇ ) obtained by dynamic viscoelasticity measurement under 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. to 100° C., and the maximum value of the loss tangent is 0.5 to 3.5.
  • the pressure-sensitive adhesive sheet 100 is cut into a test piece of 50 mm long and 5 mm wide, and the frequency is 1.59 Hz, the temperature rise rate is 4° C./min, the measurement temperature range is 0° C. to 110° C., and the amount of strain is 0.5° C. It can be measured using a rheometer under the conditions of 1%, chuck-to-chuck distance of 20 mm, and tensile mode.
  • the pressure-sensitive adhesive sheet 100 of the present embodiment can obtain flexibility and shape followability, and obtain good adhesiveness. Although the details of this reason are not clear, it is considered as follows. First, by increasing the loss tangent (tan ⁇ ) in the relatively low frequency region of 1.59 Hz, the force that takes time (also called slow force) compared to the force such as instantaneous impact easier to follow. Therefore, the surface shape of the adhesive sheet 100 follows each other due to the force applied when the adhesive sheets 100 are adhered to each other or when the adhesive sheet 100 is used after adhesion. It is speculated that the fixing force will increase. Furthermore, the pressure-sensitive adhesive sheet 100 having a maximum value of loss tangent within the range of 10° C. or higher and 100° C.
  • the pressure-sensitive adhesive sheet 100 can well follow deformation while maintaining the flexibility of the pressure-sensitive adhesive sheet 100, and as a result, appropriate adhesiveness can be obtained.
  • At least one temperature exhibiting the maximum value of the loss tangent (tan ⁇ ) of dynamic viscoelasticity is in the range of 10° C. or higher and 80° C. or lower, and 10° C. or higher and 60° C. It is more preferable to have one or more in the range below, more preferably one or more in the range of 10°C to 50°C, and even more preferably one in the range of 10°C to 50°C. As a result, when the pressure-sensitive adhesive sheet 100 touches a person and reaches a temperature of about 25° C. to 40° C., better flexibility and adhesiveness can be obtained.
  • the pressure-sensitive adhesive sheet 100 when the pressure-sensitive adhesive sheet 100 is applied to a toy, a child or the like picks up the pressure-sensitive adhesive sheet 100 and warms the pressure-sensitive adhesive sheet 100 with his or her hands to obtain an appropriate level of adhesiveness, and the pressure-sensitive adhesive sheets 100 can be easily attached to each other. It can be attached and peeled off, and can be freely deformed due to its good flexibility.
  • the maximum value of the loss tangent is preferably 0.8 or more, more preferably 1.0 or more, and even more preferably 1.2 or more. .
  • the maximum value of the loss tangent is preferably 3.0 or less, more preferably 2.8 or less.
  • the adhesive sheet 100 having strong viscous properties can convert more of the mechanical energy given during deformation into heat energy, and can absorb more energy, so it is thought that the recovery speed after deformation will be much slower. be done. As a result, it is considered that the shape after deformation can be more favorably maintained and that the shape can follow the deformation more favorably while maintaining the flexibility of the pressure-sensitive adhesive sheet 100 .
  • the adhesive sheet 100 according to the present embodiment is preferably uncrosslinked from the viewpoint of improving adhesiveness. That is, the adhesive sheet 100 is preferably an uncrosslinked sheet that has not undergone crosslinking treatment such as ionizing radiation crosslinking using electron beams or ⁇ rays. Thereby, the maximum value of the loss tangent in the range of 10° C. to 100° C. can be improved, and the adhesive sheet 100 having even better adhesiveness can be obtained.
  • crosslinking treatment such as ionizing radiation crosslinking using electron beams or ⁇ rays.
  • the pressure-sensitive adhesive sheet 100 of this embodiment preferably further satisfies the following requirement (ii).
  • the maximum shear stress is 1.0 MPa or more and less than 5.0 MPa. be.
  • more moderate adhesiveness of the adhesive sheet 100 is obtained.
  • the adhesiveness of the adhesive sheet 100 increases, and the adhesive surfaces of the adhesive sheet 100 can be bonded together.
  • the adhesive sheets 100 can be peeled off with a relatively weak force when cooled.
  • a child picks up the pressure-sensitive adhesive sheet 100 and warms it to obtain appropriate adhesiveness and flexibility, so that it can be freely attached, peeled off, and shaped.
  • the pressure-sensitive adhesive sheet 100 can be easily removed when the pressure-sensitive adhesive sheet 100 is adhered or assembled by lowering the temperature to about room temperature.
  • the pressure-sensitive adhesive sheet 100 prepared at 23° C. means that the pressure-sensitive adhesive sheet 100 is placed in an environment of 23° C. so that the temperature of the pressure-sensitive adhesive sheet 100 itself becomes equal to the environmental temperature.
  • the pressure-sensitive adhesive sheet 100 satisfying the above requirements (i) and (ii) includes, for example, (1) the type and blending ratio of the 4-methyl-1-pentene polymer (a1) described later, and (2) the pressure-sensitive adhesive sheet 100. This can be achieved by appropriately adjusting the presence or absence of cross-linking, (3) the method of forming the pressure-sensitive adhesive sheet 100, and the like. Specifically, for example, the proportion of the 4-methyl-1-pentene polymer (a1) in the adhesive sheet 100 is increased, and the adhesive sheet 100 is not crosslinked.
  • the average thickness of the 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 0.01 mm or more and 10 mm or less, and still more preferably 0.1 mm or more and 5 mm or less. and more preferably in the range of 0.5 mm or more and 2 mm or less.
  • the average thickness of the pressure-sensitive adhesive sheet 100 is set to the above lower limit or more, it is possible to obtain a good balance among shape followability, mechanical properties, moldability, moisture resistance, etc. while improving the adhesiveness.
  • the average thickness of the pressure-sensitive adhesive sheet 100 to be equal to or less than the above upper limit value, lightness, appearance, and handleability can be improved while maintaining good adhesiveness.
  • the density of the adhesive sheet 100 measured according to ASTM D 1505 is preferably 0.3 to 1.5 g/cm 3 , more preferably 0.5 to 1.2 g/cm 3 , still more preferably 0. 0.8 to 0.9 g/cm 3 , more preferably 0.83 to 0.85 g/cm 3 .
  • the pressure-sensitive adhesive sheet 100 of this embodiment has a transparent region extending from the design layer 30 to both outer surfaces of the pressure-sensitive adhesive sheet 100 .
  • the design layer 30 can be visually recognized not only from the adhesive surface 12 side of the adhesive sheet 100 but also from the adhesive surface 11 side.
  • the total light transmittance in the region from the outermost surface of the design layer 30 to both outer surfaces of the adhesive sheet 100 is preferably 30 to 99%, and the internal haze is preferably 0.1 to 99.9%.
  • the total light transmittance can be measured by Haze meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd. based on JIS K 7361 (TRANS).
  • the internal haze is the total haze excluding the haze derived from the surface shape such as unevenness.
  • the internal haze can be measured using cyclohexanol and a Haze meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd. in accordance with JIS K 7136 (HAZE).
  • the first resin layer 10 of this embodiment constitutes one adhesive surface 11 and one adhesive surface 12 of the adhesive sheet 100 .
  • both sides of the adhesive sheet 100 are tacky.
  • the adhesiveness is measured by 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 to 40 ° C., a temperature of 23 ° C., and a relative humidity of 50%. It is intended to have a maximum shear stress (MPa) of 1.0 to 5.0 MPa in a tensile test (distance between chucks: 50 mm, tensile speed: 50 mm/min) after being placed in an environment for 24 hours.
  • MPa maximum shear stress
  • the 1st resin layer 10 of this embodiment is 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 of the adhesive sheet 100 but also from the adhesive surface 11 side.
  • the first resin layer 10 preferably has a total light transmittance of 30 to 99.9%, an internal haze of 0.1 to 99.0%, and a total light transmittance of 50 to 99.9. % and an internal haze of 0.1 to 70.0%, more preferably a total light transmittance of 70 to 99.9% and an internal haze of 0.1 to 50.0%.
  • the first resin layer 10 of this embodiment contains a 4-methyl-1-pentene polymer. Each component contained in the first resin layer 10 will be described below.
  • the adhesive sheet 100 contains a 4-methyl-1-pentene polymer (a1). This makes it possible to further increase the maximum value of the loss tangent (tan ⁇ ).
  • the 4-methyl-1-pentene-based polymer (a1) according to the present embodiment includes, for example, a structural unit (c1) derived from 4-methyl-1-pentene and a carbon atom other than 4-methyl-1-pentene. and a 4-methyl-1-pentene/ ⁇ -olefin copolymer (c) containing a structural unit (c2) derived from an ⁇ -olefin of number 2 to 20.
  • ⁇ -olefin having 2 to 20 carbon atoms means not containing 4-methyl-1-pentene unless otherwise specified.
  • the 4-methyl-1-pentene/ ⁇ -olefin copolymer (c) according to the present embodiment includes 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, and the content of the structural unit (c2) is 10 mol% or more and 90 mol% or less.
  • the 4-methyl-1-pentene/ ⁇ -olefin copolymer (c) according to the present embodiment has the structural unit (c1) from the viewpoint of improving the flexibility and mechanical properties of the pressure-sensitive adhesive sheet 100.
  • the structural unit (c2) is 100 mol%, the content of the structural unit (c1) is 30 mol% or more and 90 mol% or less, and the content of the structural unit (c2) is 10 mol% or more. It is more preferably 70 mol% or less, the content of the structural unit (c1) is 50 mol% or more and 90 mol% or less, and the content of the structural unit (c2) is 10 mol% or more and 50 mol% or less.
  • the content of the structural unit (c1) is 60 mol% or more and 90 mol% or less, and the content of the structural unit (c2) is 10 mol% or more and 40 mol% or less, It is particularly preferable that the content of the structural unit (c1) is 65 mol% or more and 90 mol% or less, and the content of the structural unit (c2) is 10 mol% or more and 35 mol% or less.
  • the ⁇ -olefin having 2 to 20 carbon atoms used in the 4-methyl-1-pentene/ ⁇ -olefin copolymer (c) includes, for example, a linear or branched ⁇ -olefin , cyclic olefins, aromatic vinyl compounds, conjugated dienes, functionalized vinyl compounds, etc., and linear ⁇ -olefins are preferred.
  • the linear ⁇ -olefin preferably has 2 to 10 carbon atoms, more preferably 2 to 3 carbon atoms.
  • Linear ⁇ -olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, and ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene.
  • One or two or more selected from are preferable, and at least one selected from ethylene and propylene is more preferable.
  • the number of carbon atoms in the branched ⁇ -olefin is preferably 5-20, more preferably 5-15.
  • Examples of branched ⁇ -olefins include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene and the like.
  • the number of carbon atoms in the cyclic olefin is preferably 5-15.
  • Examples of cyclic olefins include cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylcyclohexane and the like.
  • aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p- Examples include mono- or polyalkylstyrenes such as ethylstyrene.
  • the number of carbon atoms in the conjugated diene is preferably 4-20, more preferably 4-10.
  • conjugated dienes examples 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.
  • Examples of functionalized vinyl compounds include hydroxyl group-containing olefins, halogenated olefins, (meth)acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, and 7-octene.
  • Acids unsaturated carboxylic acids such as 8-nonenoic acid, 9-decenoic acid and 10-undecenoic acid and their acid anhydrides and acid halides, unsaturated amines such as allylamine, 5-hexeneamine and 6-heptenamine, (2, 7-octadienyl)succinic anhydride, pentapropenyl succinic anhydride, unsaturated epoxy compounds, ethylenically unsaturated silane compounds, and the like.
  • unsaturated carboxylic acids such as 8-nonenoic acid, 9-decenoic acid and 10-undecenoic acid and their acid anhydrides and acid halides
  • unsaturated amines such as allylamine, 5-hexeneamine and 6-heptenamine, (2, 7-octadienyl)succinic anhydride, pentapropenyl succinic anhydride, unsaturated epoxy compounds, ethylenically unsatur
  • Examples of the hydroxyl group-containing olefins include linear or branched ⁇ -olefins having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, and hydroxyl-terminated ⁇ -olefins.
  • Examples of the halogenated olefins include linear or branched halogenated ⁇ -olefins having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms.
  • ⁇ -olefins having 2 to 20 carbon atoms can be used alone or in combination of two or more.
  • ethylene and propylene are preferable, and propylene is particularly preferable because it can improve flexibility and the like.
  • the 4-methyl-1-pentene/ ⁇ -olefin copolymer (c) contains structural units other than the structural unit (c1) and the structural unit (c2) within a range that does not impair the object of the present invention. good too.
  • Other configurations include structural units derived from non-conjugated polyenes.
  • Non-conjugated polyenes include linear, branched or cyclic dienes having preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, various norbornenes, norbornadiene, and the like. Among these, 5-vinylidene-2-norbornene and 5-ethylidene-2-norbornene are preferred.
  • the intrinsic viscosity [ ⁇ ] of the 4-methyl-1-pentene polymer according to the present embodiment in decalin at 135° C. is 0.00, from the viewpoint of improving the flexibility and mechanical strength of the pressure-sensitive adhesive sheet 100 .
  • the density of the 4-methyl-1-pentene-based polymer according to the present embodiment measured according to ASTM D 1505 (water substitution method) is preferably 0.810 to 0.850 g/cm 3 , more preferably 0.820. ⁇ 0.850 g/cm 3 , more preferably 0.830 to 0.850 g/cm 3 .
  • the 4-methyl-1-pentene polymer according to this embodiment can be produced by various methods. For example, magnesium-supported titanium catalysts; metallocene catalysts described in WO 01/53369, WO 01/027124, JP-A-3-193796, and JP-A-02-41303; It can be produced using a known catalyst such as an olefin polymerization catalyst containing a metallocene compound described in 2011/055803.
  • the content of the 4-methyl-1-pentene polymer (a1) in the pressure-sensitive adhesive sheet 100 according to the present embodiment is not particularly limited, but when the pressure-sensitive adhesive sheet 100 as a whole is 100% by weight, it is preferably 50% by weight. above, more preferably 60% by mass or more, still more preferably 65% by mass or more, even more preferably 70% by mass or more, even more preferably 75% by mass or more, while preferably 100% by mass or less, more preferably It is 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, and even more preferably 97% by mass or less.
  • the pressure-sensitive adhesive sheet 100 which is excellent in the balance of impact absorption, flexibility, conformability, light weight, mechanical properties, handleability, appearance, moldability, moisture resistance, and the like.
  • the adhesive sheet 100 according to this embodiment may contain components other than the 4-methyl-1-pentene polymer (a1).
  • the pressure-sensitive adhesive sheet 100 according to the present embodiment may contain a modified resin (a2) from the viewpoint of improving the appearance, feel, and adhesiveness.
  • the modified resin (a2) according to the present embodiment includes, for example, one or more selected from thermoplastic resins, thermoplastic elastomers and rubbers. However, the modified resin (a2) excludes the 4-methyl-1-pentene polymer (a1).
  • thermoplastic resins examples include, for example, 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/ ⁇ -olefin copolymer, propylene/ ⁇ -olefin copolymer, 1-butene/ ⁇ - thermoplastic polyolefin resins such as olefin copolymers, cyclic olefin copolymers, chlorinated polyolefins; aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612), polyether block amide co Thermoplastic polyamide resins such as polymers; Thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthal
  • thermoplastic elastomers include olefin elastomers, styrene elastomers, acid-modified styrene elastomers, vinyl chloride elastomers, urethane elastomers, ester elastomers, and amide elastomers.
  • these modified resins (a2) may be acid-modified with acrylic acid, methacrylic acid, maleic acid, or the like. These modified resins (a2) may be used singly or in combination of two or more.
  • low-density polyethylene 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- One or two or more selected from 1-butene, ethylene/ ⁇ -olefin copolymer, propylene/ ⁇ -olefin copolymer, and 1-butene/ ⁇ -olefin copolymer are preferred, and polyethylene, polypropylene, and poly(1) -butene, poly 4-methyl-1-pentene, ethylene/ ⁇ -olefin copolymer, propylene/ ⁇ -olefin copolymer, 1-butene/ ⁇ -olefin copolymer, ethylene/vinyl acetate copolymer, poly One or two or more selected from ether block amides, ionomers, fluorine resins, acid-modified fluorine resins,
  • styrene elastomers Kuraray Co., Ltd. vinyl SIS (product name: Hybler, brand 5127), vinyl SEPS (product name: Hybler, brand 7125), and Asahi Kasei Corporation SEBS (product name: S.O. E, brands: S1605, S1611, and L609) can also be preferably used from the viewpoint of compatibility, the temperature range showing the maximum value of loss tangent, and the magnitude of the maximum value of loss tangent.
  • the pressure-sensitive adhesive sheet 100 according to the present embodiment can use one of these modified resins (a2) alone, or can use two or more of them in combination.
  • the content of the modified resin (a2) in the adhesive sheet 100 according to the present embodiment is not particularly limited, but when the entire adhesive sheet 100 is taken as 100% by mass, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably is 30% by mass or less, more preferably 25% by mass or less.
  • the content of the modifying resin (a2) is at least the above lower limit, the appearance, feel, adhesiveness, etc. of the pressure-sensitive adhesive sheet 100 according to the present embodiment can be improved.
  • the adhesive sheet 100 according to the present embodiment can have better performance balance such as adhesiveness and flexibility.
  • the pressure-sensitive adhesive sheet 100 optionally contains a foaming agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a pigment, an antistatic agent, a copper damage inhibitor, a flame retardant, a neutralizer, and a plasticizer. , nucleating agents, weather stabilizers, light stabilizers, anti-aging agents, fatty acid metal salts, softeners, dispersants, coloring agents, lubricants, natural oils, synthetic oils, waxes, and other additives.
  • plasticizers, softeners, natural oils, and synthetic oils adjust the temperature at which the solid viscoelasticity loss tangent (tan ⁇ ) of the PSA sheet 100 according to the present embodiment reaches its maximum value and the loss tangent maximum value. Therefore, the type and amount added may be controlled.
  • foaming agent examples include chemical foaming agents and physical foaming agents.
  • Chemical foaming agents include sodium bicarbonate, ammonium bicarbonate, various carboxylates, sodium borohydride, azodicarbamide, N,N-dinitrosopentamethylenetetramine, P,P-oxybis(benzenesulfonylhydrazide). , azobisisobutyronitrile, p-toluenesulfonyl hydrazide, sodium bicarbonate sodium citrate, and the like.
  • Physical blowing agents include carbon dioxide, nitrogen, a mixture of carbon dioxide and nitrogen, and the like, all of which can be supplied in a gaseous, liquid, or supercritical state.
  • a resin composition containing a 4-methyl-1-pentene polymer (a1) is prepared by dry blending each component, a tumbler mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a high-speed twin-screw extruder, and a hot roll. It can be prepared by mixing or melting and kneading by, for example.
  • the adhesive sheet 100 of this embodiment may be in a foamed state.
  • the density of the adhesive sheet 100 is preferably 0.10-1.0 g/cm 3 , more preferably 0.5-0.9 g/cm 3 , and more preferably 0.7-0.8 g/cm 3 . cm 3 is more preferred.
  • a chemical foaming agent can be blended with the composition and uniformly mixed before being fed into an extruder.
  • carbon dioxide is used as a physical blowing agent, the composition is kneaded in an extruder, and after being plasticized, it can be obtained by injecting carbon dioxide directly into the extruder.
  • the expansion ratio is not particularly limited, and can be appropriately determined in consideration of the application and the like.
  • the design layer 30 is a layer having coloring, gloss, pattern, etc., and may be colored or colorless, transparent, translucent, or opaque, or a combination thereof. good.
  • the design layer 30 is formed on one adhesive surface 12 of the first resin layer 10, but at least part of the adhesive surface 12 is exposed and the design layer 30 is not formed.
  • the adhesive sheet 100 can obtain good adhesiveness on the adhesive surface 12 .
  • the ratio of the area occupied by 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, 85% or less, 80% or less, and 70% or less. is more preferable in that order. Thereby, it becomes easy to maintain the adhesiveness of the adhesive surface 12 favorably.
  • the lower limit of the area ratio occupied by the design layer 30 is not particularly limited, but from the viewpoint of enhancing the designability, it is preferably 5% or more, more preferably 10% or more, and still more preferably 20% or more. , and more preferably 25% or more.
  • the design layer 30 of this embodiment is a printed layer.
  • a printed layer refers to a layer formed using a known printing method.
  • the printed layer 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 coloring, colors, patterns, etc., and improves the design of the pressure-sensitive adhesive sheet 100 .
  • the adhesive sheet 100 can be easily applied to mass production.
  • the printed layer is not limited to printing on the entire surface of the adhesive sheet 100, and various patterns and designs such as dots, grids, patterns, and lines can be used.
  • the area ratio of the printed layer to the area of the pressure-sensitive adhesive sheet 100 in plan view is preferably 25 to 95%, more preferably 30 to 70%. By making the said area ratio below the said upper limit, it becomes easy to exhibit the softness
  • the thickness of the printed layer is extremely small and does not affect the thickness of the adhesive sheet 100 as a whole.
  • a resin composition containing the 4-methyl-1-pentene polymer (a1) can be formed into a sheet by a known method.
  • the molding apparatus and molding conditions are not particularly limited, and conventionally known molding apparatuses and molding conditions can be employed.
  • known methods such as extrusion molding, inflation molding, and calendering molding can be applied.
  • the design layer 30 is a printed layer, for example, one surface of the first resin layer 10 may be printed using a method such as inkjet printing to form the design layer 30 .
  • the pressure-sensitive adhesive sheet 100 of the present embodiment can be widely applied to applications that are repeatedly attached and detached, and can be used in various industrial fields such as clothing, medical and nursing care products, and housing equipment. More specifically, daily necessities such as toys, stationery, binding bands, wraps, and seal materials, and clothing and accessories such as innerwear such as brassieres, sports and outdoor clothing, dresses, glasses, and hats. , helmets, wigs, headphones, earphones, watches, belts, sneakers, pumps, sandals, etc. In addition, for medical use, for example, it can be used for fixing tapes, bands, belts, and supporters.
  • Wearable materials include, for example, biosensing devices, e-sports devices, techno-sports devices, VR (virtual reality ), AR (augmented reality), smart watches, smart glasses, robot suits, and the like.
  • daily necessities such as containers such as bags, cups, and boxes can be easily produced. Taking advantage of this easiness, it can be used, for example, for outdoor goods, sports-related goods, base materials and members in the event of a disaster or emergency. From the same point of view, it can be used as a new material for arts such as DIY materials, art work materials, origami substitute materials, fine arts, handicrafts, and the like. In particular, it can be suitably used in daily necessities such as toys, stationery, etc., which are required to have good design and are handled by human hands.
  • the temperature close to body temperature means 30 to 39°C, and body temperature means 35 to 38°C.
  • the design layer 30 is formed on the one surface 12 of the first resin layer 10 has been described, but the design layer is also formed on the other surface 11 of the first resin layer 10. may be Thereby, designability can be further improved.
  • details of aspects and effects in the case of having a plurality of design layers will be described in the fourth embodiment.
  • FIG. 2 is a schematic cross-sectional view of the adhesive sheet 101 of the second embodiment.
  • the adhesive sheet 101 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
  • the second resin layer 20 constitutes the adhesive surface 21 opposite to the first resin layer 10 .
  • the adhesive sheet 101 of this embodiment has adhesive surfaces 11 and 21 on both sides.
  • the design layer 30 is interposed between the first resin layer 10 and the second resin layer 20 and inside the adhesive sheet 101 .
  • the adhesive sheet 101 of this embodiment satisfies the requirements (i) and (ii) like the adhesive sheet 100 described above, and has the same thickness and density as the adhesive sheet 100.
  • the pressure-sensitive adhesive sheet 101 of this embodiment has a transparent region extending from the design layer 30 to both outer surfaces of the pressure-sensitive adhesive sheet 101 . That is, both the first resin layer 10 and the second resin layer 20 are transparent. Thereby, even if the design layer 30 is arranged inside the adhesive sheet 101, the design layer 30 can be observed from both outer surfaces of the adhesive sheet 101, and the design property of the adhesive sheet 101 can be effectively enhanced.
  • the total light transmittance in the region from the outermost surface of the design layer 30 to both outer surfaces of the adhesive sheet 101 is preferably 30 to 99.9%, and the internal haze is preferably 0.1 to 99.9%. .
  • the second resin layer 20 of this embodiment constitutes one adhesive surface 21 of the adhesive sheet 101 .
  • the thicknesses of the first resin layer 10 and the second resin layer 20 of the present embodiment may be the same or may be different from each other.
  • Both the first resin layer 10 and the second resin layer 20 of this embodiment contain a 4-methyl-1-pentene polymer.
  • the first resin layer 10 and the second resin layer 20 may contain a 4-methyl-1-pentene polymer, and may be formed using the same components as each other, depending on the purpose and application. It may be formed using different components.
  • Each component contained in the second resin layer 20 is the same as explained in the first embodiment.
  • the design layer 30 is arranged so as to be interposed between the first resin layer 10 and the second resin layer 20 .
  • the adhesive sheet 10 has the design layer 30 inside. Thereby, the decrease in the adhesiveness of the adhesive sheet 100 can be suppressed more effectively.
  • the area of the design layer 30 with respect to the area of the pressure-sensitive adhesive sheet 101 in this embodiment is the same as described in the first embodiment.
  • the thickness is equal to or less than the upper limit, there is an advantage that delamination due to interposition of the design layer 30 between the first resin layer 10 and the second resin layer 20 can be suppressed.
  • 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 It is 0.6 to 15 N/15 mm or more. This prevents the first resin layer 10 and the second resin layer 20 from easily peeling off due to the interposition of the design layer 30, suppresses the occurrence of delamination, and improves the flexibility and adhesiveness of the adhesive sheet 101. It becomes easier to demonstrate sexuality. Furthermore, when the adhesive sheet 101 is applied to toys, higher flexibility against stress is required, but according to the adhesive sheet 101 of the present embodiment, moderate adhesiveness can be obtained while having high flexibility. .
  • the interlayer adhesive strength can be measured using a tensile tester in accordance with JIS Z 1707:1997. Details are described in the examples.
  • the design layer 30 is a printed layer, for example, after printing is applied to the surface of the first resin layer 10 opposite to the adhesive surface 11 to form the design layer 30, the design layer 30 is covered with a second layer. 2. A resin layer 20 is formed. This makes it easier to suppress peeling of the printed layer.
  • the coat layer is preferably one that can be thermally laminated, and specific examples thereof include polyolefin resins and the like.
  • Polyolefin resins include ethylene polymers, polypropylene polymers, ethylene/ ⁇ -olefin copolymers, propylene/ ⁇ -olefin copolymers, 1-butene/ ⁇ -olefin copolymers, and cyclic olefin copolymers. , chlorinated polyolefins and the like are preferable.
  • the coat layer does not reduce the adhesion between the first resin layer 10 and the second resin layer 20 .
  • FIG. 3 is a schematic cross-sectional view of the adhesive sheet 102 of the third embodiment.
  • the 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, and the first resin layer Reference numeral 10 constitutes an adhesive surface 11 , and the second resin layer 20 constitutes an adhesive surface 21 opposite to the first resin layer 10 .
  • the adhesive sheet 102 of this embodiment has an adhesive surface 11 and an adhesive surface 21 on both sides.
  • the design layer 32 is interposed between the first resin layer 10 and the second resin layer 20 and inside the adhesive sheet 102 .
  • the adhesive sheet 102 of the present embodiment satisfies the requirements (i) and (ii) similarly to the adhesive sheet 100 and the adhesive sheet 101 described above, and the thickness, density, transparency, etc. of the adhesive sheet 100 and the adhesive sheet 101 is similar to
  • the design layer 32 of this embodiment is a dyed layer containing a 4-methyl-1-pentene polymer and one or more selected from dyes and pigments. Thereby, designability can be improved, maintaining favorable adhesiveness.
  • the material used for the design layer 32 the same materials as those for the above-described first resin layer 10 can be cited.
  • the above-mentioned dyes are not particularly limited, and known ones can be used. Dyes, fluorescent dyes, resin-coloring dyes, and other functional dyes are included. These may be used singly or in combination of two or more.
  • the above pigments are not particularly limited, and known pigments can be used. Examples include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, and blue pigments. , purple pigments, metal powder pigments, luminescent pigments, pearlescent pigments, and other organic and inorganic pigments, as well as plastic pigments. These may be used singly or in combination of two or more.
  • the thickness of the design layer 32 is not particularly limited, it is preferably 0.05 to 2 mm, more preferably 0.1 to 1.0 mm. Designability can be enhanced by setting the thickness of the design layer 32 to the lower limit value or more. On the other hand, by making the thickness of the design layer 32 equal to or less than the upper limit, it is possible to prevent the thickness of the adhesive sheet 102 as a whole from becoming too large, and to maintain good handleability, flexibility, and the like. Also, the design layer 32 may be a single layer or a plurality of layers. Moreover, when there are a plurality of design layers 32, each layer may have a different design.
  • a resin composition containing a 4-methyl-1-pentene polymer (a1) and one or more selected from dyes and pigments is formed into a sheet by a known method.
  • the transparent resin sheet is placed in a dyeing liquid containing dyes or pigments. It may be immersed and dyed.
  • the pressure-sensitive adhesive sheet 102 of the present embodiment may be formed by forming the design layer 32, the first resin layer 10, and the second resin layer 20 into sheets by a known method, and then laminating them.
  • a co-extrusion (extrusion using a multi-die) method may be used using the resin materials constituting the first resin layer 10 and the second resin layer 20 .
  • FIG. 4 is a schematic cross-sectional view of the adhesive sheet 103 of the fourth embodiment.
  • the 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, and the first resin layer Reference numeral 10 constitutes an adhesive surface 11 , and the second resin layer 20 constitutes an adhesive surface 21 opposite to the first resin layer 10 .
  • the adhesive sheet 103 of this embodiment has adhesive surfaces 11 and 21 on both sides.
  • the design layer 33 and the design layer 34 are laminated with the third resin layer 40 interposed therebetween. That is, the 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.
  • the pressure-sensitive adhesive sheet 103 of the fourth embodiment has two design layers 33 and 34 laminated in the thickness direction, and a first resin layer 10 and a second resin layer 20 are formed on both outer surfaces of the pressure-sensitive adhesive sheet 103, respectively. Prepare. As a result, the adhesiveness of the adhesive sheet 103 can be maintained, and the design can be improved.
  • the design layer 33 and the design layer 34 may have the same arrangement, shape, pattern, color, and thickness, or may have different thicknesses. From the viewpoint of enhancing the design of the adhesive sheet 103, it is preferable that at least one of arrangement, shape, pattern, and color be different. A specific example will be described below with reference to FIG. 6, but it is only an example and is not limited to this.
  • FIG. 6 is a plan view showing each design layer constituting a piece (FIG. 5) obtained by cutting the pressure-sensitive adhesive sheet in a cross shape, which will be described later.
  • the design layer I and the design layer II both have the same shape and stripe pattern, but different colors.
  • the design layer I and the design layer II may be arranged such that the repeating unit of the stripe pattern is shifted.
  • each design is combined to obtain one design (pattern, color) as a whole. Further, as shown in FIG.
  • the design layer I has a dot (polka dot) pattern
  • the design layer II has a dot (polka dot) pattern
  • the colors are different from each other.
  • the dots (polka dots) of the design layer I may be arranged so as to match the white portions of the design layer II.
  • each design is combined to obtain one design (pattern, color) as a whole.
  • design layer I has a checkered pattern in which vertical lines and horizontal lines intersect
  • design layer II has a pattern in which rectangular shapes corresponding to the intersections of the checkered patterns are outlined. Yes, they are different colors.
  • the blank portion of the design layer I may be filled with the design layer II.
  • each design is combined to obtain one design (pattern, color) as a whole.
  • the ratio of the area occupied by the design layer 33 and the design layer 34 to the area of the pressure-sensitive adhesive sheet 103 in plan view is less than 100%, preferably 95% or less, more preferably 90% or less, 85% or less, 80%, or less. % or less, and then 70% or less, in that order.
  • the area ratios of the design layer 33 and the design layer 34 may be the same or different.
  • the lower limit 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 designability, it is preferably 5% or more, more preferably 10% or more, and even more preferably. It is 20% or more, and more preferably 25% or more.
  • 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, the design layer 33 and the design layer 34 may have overlapping portions in a plan view of the laminated state.
  • 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 and realize a multi-layered design layer to improve designability. be done.
  • the third resin layer 40 is not particularly limited as long as it can be formed into a film, and can be used. Examples include films such as polyolefin and polyethylene terephthalate. When used as a toy to be picked up and attached to or peeled off by warming, the third resin layer 40 may be formed using the above-described resin material used for the first resin layer 10 and the second resin layer 20 . . As with the first resin layer 10 and the second resin layer 20, this is preferable because it is possible to obtain flexibility by holding it in the hand and warming it, and it is possible to further enjoy the feeling of being soft when touched with the hand.
  • the thickness of the third resin layer 40 is not particularly limited, it is preferably 30 ⁇ m to 5 mm, more preferably 50 ⁇ m to 1 mm, from the viewpoint of enhancing the designability while maintaining the handleability and flexibility of the adhesive sheet 103 .
  • the third resin layer 40 is preferably transparent. Thereby, good design property can be maintained. Specifically, the third resin layer 40 preferably has a total light transmittance of 30 to 99% and an internal haze of 0.1 to 99.9%.
  • the pressure-sensitive adhesive sheet 103 is formed, for example, by printing on one side of the first resin layer 10 and the second resin layer 20 by a known method to form a design layer 33 and a design layer 34, respectively, and then combining the first resin layer 10 and the design layer 33. /third resin layer 40/design layer 34/second resin layer 20 in this order.
  • first, both surfaces of the third resin layer 40 are printed by a known method to form the design layer 33 and the design layer 34, respectively. 10. It can also be obtained by laminating the second resin layer 20 on the design layer 34 .
  • the design layer 33 and the design layer 34 are both printed layers, but one or both of them may be dyed layers. Moreover, when there are a plurality of design layers, the number is not particularly limited, and may be three or more. In this case, it is desirable that a third resin layer be interposed between the design layers in order to suppress delamination.
  • FIG. 9 is a schematic cross-sectional view of the adhesive sheet 104 of the fifth embodiment.
  • the 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. constitutes the adhesive surface 11
  • the fifth resin layer 52 constitutes the adhesive surface 21 opposite to the fourth resin layer 51 .
  • the adhesive sheet 104 of this embodiment has adhesive surfaces 11 and 21 on both sides.
  • both the fourth resin layer 51 and the fifth resin layer 52 form colored design layers by containing one or more selected from pigments and colorants.
  • the adhesive sheet 104 of the fifth embodiment has the third resin layer 40 .
  • the third resin layer 40 is an intermediate layer interposed between the fourth resin layer 51 and the fifth resin layer 52. While suppressing delamination between the fourth resin layer 51 and the fifth resin layer 52, It is used to realize multi-layered colored design layers and improve designability.
  • the colored design layer contains a 4-methyl-1-pentene-based polymer, constitutes at least a part of the adhesive surface of the adhesive sheet 104, and contains a dye or a colorant to create a design. It is a layer having properties.
  • the coloring agent used in the colored design layer known dyes and the like can be used.
  • the dyes and pigments used in the colored design layer the same dyes and pigments as those used in the above dyed layer can be used.
  • the degree of coloring of the colored design layer is achieved by adjusting the types and concentrations of dyes and pigments, the immersion time, etc. Thereby, the adhesiveness of the adhesive sheet 104 can be controlled.
  • the thickness of the colored design layer is not particularly limited, but is preferably 0.05 to 2 mm, more preferably 0.1 to 1.0 mm. Designability can be improved by setting the thickness of the colored design layer to the above lower limit or more. On the other hand, by setting the thickness of the colored design layer to the above upper limit value or less, it is possible to prevent the thickness of the adhesive sheet 104 as a whole from becoming too large, and to maintain good handleability, flexibility, and the like.
  • the colored design layer may be a single layer or a plurality of layers. Moreover, when there are a plurality of colored design layers, each layer may have a different design from each other. In this embodiment, the colored design layers respectively obtained from the fourth resin layer 51 and the fifth resin layer 52 may have different designs, for example, different colors or different patterns.
  • the colored design layer of the present embodiment preferably has a total light transmittance of 30 to 99% and an internal haze of 0.1 to 99.9%. More preferably, the haze is 30 to 80% and the internal haze is 0.1 to 70.0%.
  • the method for forming the colored design layer is not particularly limited, and the same method as described for the design layer 32 can be used.
  • the fourth resin layer 51 and the fifth resin layer 52 materials similar to those described for the first resin layer 10 and the second resin layer 20 can be used, except that they contain pigments and colorants.
  • the present invention is not limited to this, and the number of layers may be three or more.
  • an intermediate layer is preferably provided between each layer to suppress delamination.
  • the pressure-sensitive adhesive sheets in the first to fifth embodiments are examples, and the pressure-sensitive adhesive sheet according to this embodiment is not limited thereto.
  • the design layer placed inside the pressure-sensitive adhesive sheet may be embedded from one side of the pressure-sensitive adhesive sheet.
  • the first resin layer, the second resin layer, and the design layer may be a single layer or a plurality of layers as long as the effects of the present invention are not impaired, and layers other than these may be used. may contain.
  • the piece of the present embodiment is obtained by cutting the various adhesive sheets described above into a predetermined size.
  • a cutting method is not particularly limited, and a known method can be used.
  • the size of the piece is not particularly limited, but it is preferably about the same size as the palm of the hand from the viewpoint of being warmed by human body heat and exhibiting flexibility and adhesiveness.
  • the shape of the pieces is not particularly limited, and includes a wide range of shapes such as circles, ovals, triangles, rectangles, polygons, crosses, animal and plant shapes, and star shapes. In addition, it is preferable to have rounded corners from the viewpoint of making it easier to feel softness and gentleness when visually observed or picked up, and from the viewpoint of making it easier to suppress delamination. For example, as shown in FIG.
  • the piece of the present embodiment exhibits appropriate adhesiveness and designability, it is preferable that the design layer is not arranged on at least a part of the peripheral portion in a plan view. This makes it easier to suppress delamination due to interposition of the design layer.
  • the piece set of this embodiment has a plurality of such pieces and is used as a toy.
  • the piece of this embodiment is touched by a person and heated to about 25° C. to 40° C., its flexibility and adhesiveness increase. Therefore, when applied to a toy, the pieces of this embodiment can be easily attached to each other, assembled, and deformed freely because the adhesion and flexibility increase by warming the pieces of this embodiment by children and the elderly. can be done. Moreover, even if the pieces of this embodiment are stuck together, they can be easily peeled off by the strength of a child or an elderly person. On the other hand, when the pieces are cooled, the pieces become less flexible and retain their shape, and the tackiness is also reduced, allowing the pieces to come off naturally.
  • the piece of the present embodiment has a good design property, it is possible to perform modeling with a higher design property.
  • four cross-shaped pieces can be combined to form a ring, or three pieces can be stacked to form a tall cylinder as shown in FIG.
  • three cross-shaped pieces are superimposed in the thickness direction and arranged so that the ends are staggered. can be formed.
  • the number of pieces is not particularly limited, and may be from tens to hundreds. Moreover, the shape, size, and design 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 pieces having the same shape and/or the same design.
  • the method of using the piece set includes the following steps. Step 1: warming the piece; Step 2: A step of combining one or more selected from bonding the pieces together, peeling the bonded pieces together, and deforming the pieces; Step 3: Cooling the piece.
  • Step 1 By heating the pieces, the flexibility and stickiness of the pieces are improved.
  • the method of warming the piece is not particularly limited, but from the viewpoint of easily and safely increasing the flexibility and adhesiveness, it is preferable to warm the piece by human body temperature, for example, by picking it up.
  • Step 2 The pieces whose adhesiveness has been improved by the step 1 are adhered and peeled off, and the pieces whose flexibility has been improved are deformed and assembled. As a result, the shape and color desired by the user can be obtained, and the function as a toy can be improved. You can also enjoy the feeling of touching it with your hand.
  • the pieces may be bonded together by partially bonding the pieces, by bonding the entire surfaces of the pieces so as to be laminated, or by freely combining and bonding a plurality of pieces.
  • the deformation of the piece includes one or a combination of two or more selected from bending, twisting, folding, stretching, shrinking, embossing, and the like.
  • Step 3 By cooling the warmed pieces, the pieces adhered in step 2 can be fixed to each other or the deformed pieces can be kept in shape.
  • the cooling method is not particularly limited, and known simple methods such as releasing the piece from the hand and allowing it to cool naturally, blowing air, etc., can be used.
  • the pieces may be warmed again to restore each piece to its original shape and condition.
  • steps 1 to 3 can be repeated, the piece of this embodiment can be used repeatedly.
  • ⁇ Measurement method> Measurement of Dynamic Viscoelasticity of Adhesive Sheet
  • the adhesive sheet was cut into strips of 50 mm long and 5 mm wide to obtain test pieces.
  • the obtained test piece was treated with RSA III manufactured by TA Instruments Co., Ltd., with a chuck distance of 20 mm, a frequency of 1.59 Hz, a strain amount of 0.1%, a heating rate of 4 ° C./min, and a tensile mode.
  • the temperature dependence of dynamic viscoelasticity was measured in the temperature range from 0°C to 110°C under the conditions of . From the obtained graph, the temperature at which the loss tangent (tan ⁇ ) exhibits a maximum value and the maximum value of tan ⁇ were obtained.
  • Interlaminar adhesive strength A test piece with a width of 15 mm is cut out from the adhesive sheet, and a tensile tester (for example, Autograph AG-X manufactured by Shimadzu Corporation) is used in accordance with JIS Z 1707: 1997 to measure the design layer. The interlayer adhesive strength between the first resin layer and the second resin layer when interposed was measured. The interlayer adhesive strength was measured under the conditions of a distance between chucks of 90 mm and a tensile speed of 500 mm/min.
  • a tensile tester for example, Autograph AG-X manufactured by Shimadzu Corporation
  • the total light transmittance of the 4-methyl-1-pentene polymer sheet (first resin layer) was measured by Murakami Color Co., Ltd. based on JIS K 7361 (TRANS). It was measured with a Haze meter HM-150 manufactured by Technical Research Institute.
  • the intrinsic viscosity [ ⁇ ] and composition of the above 4-methyl-1-pentene polymer were measured as follows. - The intrinsic viscosity [ ⁇ ] was measured at 135°C using decalin solvent. ⁇ The contents of 4-methyl-1-pentene and ⁇ -olefin in the 4-methyl-1-pentene polymer were determined by 13 C-NMR.
  • Example 1 As a molding machine, a single-screw extruder (cylinder inner diameter D: 65 mm, full-flight screw, T-die (die width: 750 mm), cooling rolls, and a take-up machine was used. First, a 4-methyl-1-pentene polymer is put into an extruder and melted and kneaded under the conditions of a cylinder temperature of 100 to 250° C. and a screw rotation speed of 23 rpm so that the extrusion rate is 15 kg/hour. was extruded from a T-die.
  • the extruded sheet is cooled with a cooling roll (water flow temperature inside the roll: 20°C), taken up using a take-up machine (take-up speed: 1.3 m/min), and separated into 4 sheets with a sheet thickness of 0.3 mm and a sheet width of about 700 mm.
  • a -methyl-1-pentene polymer sheet (first resin layer) was obtained.
  • the resulting 4-methyl-1-pentene polymer sheet was set in an inkjet printer (manufactured by SwissQPrint), and UV curable inkjet ink (brand name: SQS ink) was used to print one side of the sheet under the following conditions.
  • a design layer was formed by printing on the surface of the adhesive sheet to obtain a pressure-sensitive adhesive sheet.
  • Print pattern 0.5 mm diameter circular dots Distance between centers of horizontally adjacent dots (horizontal pitch): 1.7 mm Distance between centers of vertically adjacent dots (vertical pitch): 0.85 mm Print area; 30%
  • Example 2 On one surface of the 4-methyl-1-pentene polymer sheet (first resin layer) obtained in Example 1, the printed pattern described in Example 1 was made into circular dots with a diameter of 0.85 mm, and the printed area was A design layer was formed under the same conditions except that the ratio was changed to 50% to obtain a pressure-sensitive adhesive sheet.
  • Example 3 On one side of a 4-methyl-1-pentene 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 was 0.6 mm, A design layer was formed by the coating method described in Example 1. A 4-methyl-1-pentene polymer sheet (second resin layer) obtained in the same manner as in Example 1 was prepared separately, except that the take-up speed was changed so that the thickness was 0.1 mm. A resin layer (thickness: 0.6 mm), a design layer, and a second resin layer (thickness: 0.1 mm) were laminated in this order, and heated and pressurized to 180°C to weld the layers to obtain an adhesive sheet.
  • Example 4 On one side of a 4-methyl-1-pentene 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 was 0.6 mm, A design layer was formed by the coating method described in Example 2.
  • a 4-methyl-1-pentene polymer sheet (second resin layer) obtained in the same manner as in Example 1 was prepared separately, except that the take-up speed was changed and the thickness was adjusted to 0.1 mm.
  • a first resin layer (thickness: 0.6 mm), a design layer, and a second resin layer (thickness: 0.1 mm) were laminated in this order, and heated and pressurized to 180° C. to weld the respective layers to obtain an adhesive sheet.
  • Example 5 A resin dye SDN (manufactured by Osaka Kaseihin 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 polymer sheet obtained in the same manner as in Example 1 was heated to 70° C., except that the take-up speed of Example 1 was adjusted to 1.3 m/min so that the thickness would be 0.6 mm. was immersed in a staining solution for 10 minutes for staining. After dyeing, the sheet was thoroughly washed with water and dried to obtain a dyed 4-methyl-1-pentene polymer sheet (dyed layer).
  • Two 4-methyl-1-pentene 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 was 0.1 mm were prepared.
  • a first resin layer and a second resin layer were used.
  • a first resin layer, a dyed layer, and a second resin layer were laminated in this order, and the layers were welded by heating and pressing at 180° C. to obtain an adhesive sheet.
  • Example 6 On one surface of the 4-methyl-1-pentene polymer sheet (first resin layer) obtained in Example 1, the entire surface is coated under the printing conditions of the coating method described in Example 1 (printing area 100%). A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, except that a design layer was formed.
  • Example 7 A design layer was formed 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 to obtain an adhesive sheet.
  • a molding machine a single-screw extruder (cylinder inner diameter D: 65 mm, full-flight screw, T-die (die width: 750 mm), cooling rolls, and a take-up machine was used.
  • a 4-methyl-1-pentene-based polymer and 3 parts by weight of a chemical foaming agent (polystyrene EE275F) are put into an extruder, and the temperature of each part of the cylinder is 120 to 220° C., and the screw rotation speed is 19 rpm.
  • the mixture was melted and kneaded under the conditions of , and extruded through a T-die at an extrusion rate of 15 kg/hour.
  • the extruded sheet is cooled with a cooling roll (water flow temperature inside the roll: 20°C), taken up using a take-up machine (take-up speed: 1.2 m/min), and separated into 4 sheets with a sheet thickness of 0.5 mm and a sheet width of about 600 mm.
  • a -methyl-1-pentene polymer sheet (first resin layer) was obtained.
  • Example 1 The 4-methyl-1-pentene polymer sheet (first resin layer) obtained in Example 1 was obtained as an adhesive sheet.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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DE19703038A1 (de) * 1997-01-29 1998-07-30 Reichenecker Hans Storopack Spielzeug
JP2003144774A (ja) * 2001-11-13 2003-05-20 Alpha Kagaku Kk 積木様若しくは学習用玩具
JP2013194132A (ja) * 2012-03-19 2013-09-30 Mitsui Chemicals Inc 粘着剤、積層体および表面保護フィルム
JP2015025884A (ja) * 2013-07-25 2015-02-05 株式会社ギケン 両面印刷ラベル及び両面印刷ラベルの作製方法
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JPS4915156U (enrdf_load_stackoverflow) * 1972-05-15 1974-02-08
JPS5118698U (enrdf_load_stackoverflow) * 1974-07-27 1976-02-10
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JP7275763B2 (ja) 2019-03-29 2023-05-18 住友ベークライト株式会社 粘着層付き化粧シート
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JPH0440699U (enrdf_load_stackoverflow) * 1990-08-01 1992-04-07
DE19703038A1 (de) * 1997-01-29 1998-07-30 Reichenecker Hans Storopack Spielzeug
JP2003144774A (ja) * 2001-11-13 2003-05-20 Alpha Kagaku Kk 積木様若しくは学習用玩具
JP2013194132A (ja) * 2012-03-19 2013-09-30 Mitsui Chemicals Inc 粘着剤、積層体および表面保護フィルム
JP2015025884A (ja) * 2013-07-25 2015-02-05 株式会社ギケン 両面印刷ラベル及び両面印刷ラベルの作製方法
WO2019131496A1 (ja) * 2017-12-27 2019-07-04 紀和化学工業株式会社 グラフィックシート、その製造方法及びその使用方法
JP2019172938A (ja) * 2018-03-29 2019-10-10 リンテック株式会社 粘着シートの製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7731187B1 (ja) 2024-09-12 2025-08-29 株式会社バンダイ 玩具の製造方法

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