WO2020179465A1 - Lamination film, adhesive tape, and adhesion body - Google Patents

Lamination film, adhesive tape, and adhesion body Download PDF

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Publication number
WO2020179465A1
WO2020179465A1 PCT/JP2020/006759 JP2020006759W WO2020179465A1 WO 2020179465 A1 WO2020179465 A1 WO 2020179465A1 JP 2020006759 W JP2020006759 W JP 2020006759W WO 2020179465 A1 WO2020179465 A1 WO 2020179465A1
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WO
WIPO (PCT)
Prior art keywords
adhesive tape
adhesive
pressure
sensitive adhesive
styrene
Prior art date
Application number
PCT/JP2020/006759
Other languages
French (fr)
Japanese (ja)
Inventor
晃 山上
大亮 渡辺
Original Assignee
Dic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.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to CN202080016925.9A priority Critical patent/CN113490595A/en
Priority to JP2020537035A priority patent/JP6933305B2/en
Priority to KR1020217026979A priority patent/KR20210135230A/en
Publication of WO2020179465A1 publication Critical patent/WO2020179465A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to laminated films, adhesive tapes and adhesives.
  • the adhesive tape Since the adhesive tape has excellent workability and high adhesion reliability, it can be used as a joining means in various industrial fields such as OA equipment, IT/home appliances, automobiles, etc. for fixing parts, temporarily fixing parts, and products. It is widely used for labels that display information (for example, Patent Document 1).
  • the adhesive tape 22 is between the housing 21 and the component 20. Is provided. However, when disassembling the product for recycling or the like as described above, in order to remove the part 20, it is necessary to pull the handle portion of the adhesive tape 22 to peel off the adhesive tape, but conventionally, the adhesive tape is peeled off. There was something I could't do. More specifically, in a device for mounting components at high density, other members are also attached to the housing in close proximity to the components attached using, for example, an adhesive tape having a rubber base material. Then, in order to peel off the adhesive tape while avoiding the other members, the handle portion of the adhesive tape is pulled in a direction of a high angle (for example, 60 ° or more) with respect to the sticking surface to peel off, which is high. Pulling at an angle puts a load on the adhesive tape, which could tear it. In addition, since the adhesive tape cannot be easily removed in this manner, it has been a factor of increasing the work cost.
  • a high angle for example, 60 ° or more
  • the present invention has been made in view of the above problems, and even when the adhesive tape is peeled off at an angle with respect to the sticking surface as described above, the load on the adhesive tape is reduced to prevent tearing. It is an object of the present invention to provide a laminated film, an adhesive tape and an adhesive which can be prevented.
  • the present inventors have found that when the component 20 is fixed to the housing 21 or the like using the adhesive tape 22 as shown in FIG.
  • the adhesive tape 22 is pulled from the component 20 at an angle with respect to the attachment surface, when the adhesive tape 22 is pulled, a large force is applied to the portion of the adhesive tape 22 that is attached to the vicinity of the corner 23 of the component 20 at the beginning of its extension. It was found that the load on the adhesive tape 22 can be reduced if the portion of the outer surface of the adhesive tape 22 in contact with the corner 23 of the component 20 extends smoothly at the beginning of the extension of the adhesive tape.
  • the present invention has been achieved. That is, the invention of the present application is as follows.
  • a laminated film provided with a base material layer and adhesive layers on both sides of the base material layer. It has a glueless portion on at least one surface of the laminated film in which the pressure-sensitive adhesive layer does not exist.
  • An adhesive tape provided with a base material layer and adhesive layers on both sides of the base material layer. It has a glueless portion on the surface of at least one end side of the adhesive tape in which the adhesive layer is not present.
  • the adhesive tape wherein the base material layer has a breaking elongation of 200 to 3000% and a breaking strength of 1.5 to 80 MPa.
  • An adhesive body comprising a pasted second adherend, A portion of the adhesive tape on the end side of the adhesive-free portion is located outside the first attaching surface of the first adherend to which the adhesive tape is attached, An adhesive body, characterized in that an angle defining the first attachment surface is located on the glueless portion.
  • the present invention can provide a laminated film, an adhesive tape, and an adhesive that can reduce the load on the adhesive tape and prevent tearing even when the adhesive tape is peeled off at an angle to the sticking surface. it can.
  • FIG. 1 It is a top view which shows the laminated film which concerns on one Embodiment of this invention. It is a top view which shows the modification of the laminated film of FIG. It is a perspective view which shows the adhesive tape which concerns on one Embodiment of this invention. It is a perspective view which shows the modification of the adhesive tape shown in FIG. It is sectional drawing of the said adhesive tape which shows the state which adhered the adherend using the adhesive tape of FIG. It is a figure which shows the state which the component was attached to the housing using the conventional adhesive tape.
  • the laminated film 1 of the present embodiment includes a base material layer and pressure-sensitive adhesive layers 4 on both surfaces of the base material layer, and the pressure-sensitive adhesive layer 4 is provided on at least one surface of the laminated film 1.
  • the base material layer has a breaking elongation of 200 to 3000% and a breaking strength of 1.5 to 80 MPa.
  • the laminated film 1 of the present embodiment even when the adhesive tape obtained from the laminated film 1 is peeled off at an angle with respect to the sticking surface, the load on the adhesive tape can be reduced and tearing can be prevented.
  • the laminated film 1 is cut out so as to have the glueless portion 2 on the surface of one end side of the adhesive tape, and then the adherend such as a part is cut out using the obtained adhesive tape, for example.
  • the components are attached so that the corners (the corners that define the attachment surface to which the adhesive tape is attached) are located on the glueless portion 2.
  • the laminated film 1 is a film for producing an adhesive tape as shown in FIG. 1, and specifically, the laminated film 1 is shown by a broken line 3 in the drawing, for example.
  • a plurality of adhesive tapes can be manufactured by cutting out the adhesive tape so that the glueless portion 2 is present on the surface of one end side of the adhesive tape.
  • the shape and size of the adhesive-free portion 2 on the surface of the laminated film 1 in plan view of the laminated film 1 may vary depending on the shape, size, etc. of the adhesive tape produced by the laminated film 1, and is particularly limited. Instead, it can be arbitrary.
  • the glueless portion 2 can have any shape, but the length measured along one direction (TD direction in the example of FIG. 1) is at least 0.5 mm, and the one direction It is preferable that the length measured along the direction orthogonal to (in the example of FIG. 1, the MD direction) is at least 0.5 mm. Further, more preferably, the glueless portion 2 has a length measured along one direction of at least 3 mm, and a length measured along a direction orthogonal to the one direction is at least 3 mm.
  • a desired adhesive tape can be produced by using the laminated film 1 of the present embodiment by making the glueless portion 2 have such a size.
  • the laminated film 1 has a length of 0.5 mm or more in one direction and a length of 0.5 mm or more in a direction orthogonal to the direction with respect to the glueless portion 2 in the one direction. Within the adjacent, at least 30 mm length range, it is preferred that the pressure-sensitive adhesive layer 4 is substantially present over the entire surface. Thereby, even if the adhesive-free portion 2 is provided on the adhesive tape obtained from the laminated film 1, the adhesive force of the adhesive tape can be easily secured.
  • substantially present on the entire surface here means that there is a slight portion other than the adhesive layer 4 within a length range of at least 30 mm, which is adjacent to the glueless portion 2 in one direction. Even if they are scattered, it is permissible if the adhesive strength is considered to be the same as a whole. Further, more preferably, the pressure-sensitive adhesive layer 4 is present on the entire surface within the range.
  • a plurality of glueless portions 2 may be provided on the surface of the laminated film 1.
  • each glueless portion 2 may be extended in the MD direction as shown in FIG. 1, or the illustration is omitted. However, it may extend in the TD direction, or may extend in a direction inclined with respect to the MD direction and the TD direction.
  • the glueless portion 2 is formed to extend on the surface of the laminated film 1, as shown in FIG.
  • the glueless portion 2 is not on the center side of the adhesive tape, A plurality of desired adhesive tapes can be manufactured by cutting out the laminated film 1 at the position shown by the broken line 3 in FIG. 1 so as to be located on the end side.
  • the adhesive layer 4 is present in a portion on the end side of the non-adhesive portion 2 in the range of one adhesive tape, and the adhesive tape obtained by cutting out this range is The pressure-sensitive adhesive layer 4 also exists on the end side portion.
  • the pressure-sensitive adhesive layer 4 does not exist in the portion on the end side of the pressure-sensitive adhesive tape obtained by cutting out the laminated film 1.
  • the non-adhesive portion 2 on the surface of the laminated film 1 has a sea-like shape and the adhesive layer 4 has an island-like shape.
  • the non-coated portion 2 and the pressure-sensitive adhesive layer 4 may be formed in a sea-island shape (conversely, the glue-less portion 2 may be formed in an island shape and the pressure-sensitive adhesive layer 4 may be formed in a sea shape).
  • the pressure-sensitive adhesive layer 4 of the laminated film 1 is formed into an island shape, for example, by cutting out the laminated film 1 at the position indicated by the broken line 3 in FIG. 2, the adhesive has a plurality of (three or more in the drawing) ends. You can get the tape.
  • a rectangular adhesive tape is manufactured from the laminated film 1
  • an adhesive tape having three or more ends is manufactured from the laminated film 1.
  • the shape and size of the adhesive tape manufactured from can be arbitrary.
  • the glueless portion 2 is formed on one surface of the laminated film 1 in the illustrated example, but is also preferably on the surface of the other side in a plan view of the laminated film 1.
  • the glueless portion 2 is a portion where the pressure-sensitive adhesive layer 4 forming the surface of the laminated film 1 is not formed.
  • the glueless portion 2 can be a portion where the base material layer of the laminated film 1 is exposed, but it is permissible that the adhesive is present at a thickness of 10% or less of the thickness of the adhesive layer. To do.
  • the laminated film 1 of the present embodiment has a base material layer 13 as a carrier of an adhesive layer 14, as shown in an adhesive tape 11 obtained from the laminated film of FIG.
  • the base material layer of the laminated film 1 in the present embodiment has a breaking elongation of 200 to 3000% and a breaking strength of 1.5 to 80 MPa.
  • the material of the base material layer in the present embodiment is not particularly limited as long as the base material layer 13 has the above-mentioned elongation at break and breaking strength, but for example, it contains a vinyl aromatic block copolymer (A).
  • a vinyl aromatic block copolymer (A) that can be used as the material of the base material layer, one or more copolymers selected from block copolymers of an aromatic vinyl compound and a conjugated diene compound are used.
  • a styrene copolymer in which the aromatic vinyl compound is styrene is preferable.
  • the conjugated diene compound isoprene, butadiene, ethylene butylene and ethylene propylene are preferable.
  • the block copolymer (A) is a diblock copolymer such as a styrene-isoprene copolymer, a styrene-butadiene copolymer, a styrene-ethylenebutylene copolymer, a styrene-ethylenepropylene copolymer.
  • One or more copolymers selected from triblock copolymers such as styrene-isoprene-styrene copolymers and styrene-butadiene-styrene copolymers are preferable.
  • Styrene-isoprene copolymers styrene- One or more copolymers selected from butadiene copolymer, styrene-ethylene butylene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-ethylene butylene copolymer Copolymers are more preferable, and styrene-isoprene copolymer and styrene-isoprene-styrene copolymer are particularly preferable.
  • the ratio of the vinyl aromatic block copolymer (A) contained in the material of the base material layer in the present embodiment is preferably 50 to 100% by mass, and 60 to 100% by mass when the material is 100% by mass. It is more preferably 100% by mass, further preferably 65 to 100% by mass, and even more preferably 70 to 100% by mass. Within such a range, the excellent breaking elongation and breaking stress of the styrene-based copolymer can be obtained.
  • various thermoplastic resins such as polyolefin and polycarbonate can be used as the material of the base material layer in the present embodiment, and one kind or plural kinds thereof are used at the same time. be able to.
  • styrene-based copolymer 13% by mass to 60% by mass of the structural unit represented by the following chemical formula (1) is based on the total mass of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer. It is preferable to use one having a range of 15 to 50% by mass, more preferably one having a range of 15 to 50% by mass, and further preferably to use one having a range of 16 to 45% by mass. It is even more preferable to use one having a mass in the range of%. This makes it easier to obtain the breaking elongation and breaking stress in a suitable range.
  • the styrene-based copolymer one containing two or more kinds of copolymers having different structures is used, and one containing a combination of a styrene-isoprene copolymer and a styrene-isoprene-styrene copolymer is used. be able to.
  • the styrene-based copolymer contains the styrene-isoprene copolymer in a range of 0% by mass to 80% by mass based on the total mass of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer.
  • the weight average molecular weight (gel permeation chromatography, SC-8020 manufactured by Toso Co., Ltd., high molecular weight column TSKgelGMHR) measured in terms of standard polystyrene using a gel permeation chromatograph (GPC).
  • GPC gel permeation chromatograph
  • -H solvent: tetrahydrofuran
  • the heating fluidity and the compatibility at the time of solvent dilution can be ensured, so that the workability in the manufacturing process is good, and it is more preferable for obtaining an adhesive tape having heat durability.
  • the styrene-based copolymer may have a single structure such as a linear structure, a branched structure or a multi-branched structure, but may have a mixture of different structures. ..
  • the styrene-based copolymer rich in linear structure gives the laminated film 1 of the present embodiment an excellent breaking elongation.
  • those having a branched structure or a multi-branched structure with a styrene block arranged at the terminal of the molecule can have a pseudo cross-linked structure and can give excellent cohesive force. For this reason, it is preferable to mix and use it according to required mechanical characteristics.
  • the method for producing the styrene-isoprene-styrene copolymer is not particularly limited, and conventionally known production methods can be applied. For example, a method of sequentially polymerizing a styrene block and an isoprene block by an anionic living polymerization method, or a block copolymer having a living active terminal is produced and then reacted with a coupling agent to produce a coupled block copolymer. There is a way.
  • the method for producing the styrene-isoprene copolymer is not particularly limited, and conventionally known production methods can be applied. For example, there is a method of sequentially polymerizing a styrene block and an isoprene block by an anionic living polymerization method.
  • the method for producing the mixture of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer is not particularly limited, and conventionally known production methods can be applied. For example, there is a method in which the styrene-isoprene copolymer produced above and the styrene-isoprene-styrene copolymer are mixed and used. It is also possible to produce them as a mixture at the same time in one polymerization step.
  • a styrene monomer is polymerized using an anionic polymerization initiator to form a polystyrene block having a living active terminal.
  • anionic polymerization initiator to form a polystyrene block having a living active terminal.
  • isoprene is polymerized from the living active end of the polystyrene block to obtain a styrene-isoprene diene block copolymer having a living active end.
  • a part of the styrene-isoprene diene block copolymer having a living active terminal is reacted with a coupling agent to form a coupled styrene-isoprene-styrene block copolymer.
  • the rest of the styrene-isoprene diene block copolymer having a living active end is deactivated with a polymerization terminator to deactivate the living active end of the styrene-isoprene diene block copolymer.
  • a tackifying resin can be used in the base material layer for the purpose of enhancing the adhesiveness with the pressure-sensitive adhesive layer 4 and enhancing the heat resistance.
  • a tackifier resin having a softening point of 80 ° C. or higher can be preferably used, and the softening point is more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and even more preferably 110 ° C. or higher. preferable.
  • the softening point refers to a value measured by a method (dry-bulb type) specified in JIS K2207.
  • tackifier resin for example, a solid resin at room temperature (23 ° C.) is preferably used, and petroleum resins such as C5 petroleum resin, C5 / C9 petroleum resin, and alicyclic petroleum resin are used. can do.
  • the petroleum resin is easily compatible with the polyisoprene structure constituting the styrene-isoprene block copolymer or the styrene-isoprene block-styrene copolymer, and as a result, the initial adhesive strength and heat durability of the pressure-sensitive adhesive tape are improved. It can be further improved.
  • an aliphatic petroleum resin can be used, for example, Escolets 1202, 1304, 1401 (manufactured by Tonen Chemical Corporation), Wing Tuck 95 (manufactured by Goodyear Tire and Rubber Company). ), Quinton K100, R100, F100 (manufactured by Zeon Corporation), PicoTac 95, Picopel 100 (manufactured by Rika Hercules) and the like can be used.
  • the C5 / C9 petroleum resin a copolymer of the C5 petroleum resin and the C9 petroleum resin can be used.
  • Escolets 2101 manufactured by Tonex
  • Quinton G115 manufactured by Zeon Corporation
  • Harcotac 1149 manufactured by Rika Hercules
  • the alicyclic petroleum resin is obtained by hydrogenating the C9 petroleum resin described above.
  • Escolets 5300 manufactured by Tonex
  • Archon P-100 manufactured by Arakawa Chemical Industries
  • Rigalite R101 Rosika Fine). Tech
  • the tackifier resin examples include polymerized rosin-based resin, C9-based petroleum resin, terpene-based resin, and rosin-based resin, in addition to the C5-based petroleum resin, C5-based / C9-based petroleum resin, and alicyclic petroleum resin.
  • Terpene-phenol resin, styrene resin, coumarone-indene resin, xylene resin, phenol resin and the like can be used.
  • the tackifying resin is preferably used in the range of 0% by mass to 100% by mass, and 0% by mass to 70% by mass, based on the total amount of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer. Is more preferably used in the range of 0% by mass to 50% by mass, further preferably in the range of 0% by mass to 30% by mass. By using it in the above range, it becomes easy to achieve both excellent breaking elongation and thermal durability of the adhesive tape while enhancing the interfacial adhesion between the pressure-sensitive adhesive layer 4 and the base material layer.
  • the resin substrate if necessary, other polymer components, a cross-linking agent, an antioxidant, an ultraviolet absorber, a filler, a polymerization inhibitor, a surface adjustment, as long as the characteristics are not impaired.
  • Additives; those containing inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide and the like can be used.
  • the base material preferably has a thickness of 10 to 2490 ⁇ m, more preferably 30 to 300 ⁇ m, further preferably 60 to 200 ⁇ m, and further preferably 70 ⁇ m to 150 ⁇ m.
  • the adhesive tape can easily follow the strain of the adherend and obtain high adhesive strength, and the stress required for peeling while stretching the adhesive tape becomes large. It is preferable because it is not too much.
  • the breaking elongation of the base material layer is 200 to 3000%, preferably 650 to 2800%, more preferably 700 to 2700%, and further preferably 750 to 2600%.
  • the breaking elongation of the base material layer is at least the lower limit of the range, the stress for stretching the pressure-sensitive adhesive tape when peeling the pressure-sensitive adhesive tape even when the pressure-sensitive adhesive tape is firmly adhered to the adherend It does not become too large, and the adhesive tape can be easily peeled off without being excessively stretched even in the peeling step.
  • the breaking elongation of the base material layer is equal to or less than the upper limit of the above range because the stretching distance of the pressure-sensitive adhesive tape at the time of peeling the pressure-sensitive adhesive tape is not too long and the work can be performed in a small space.
  • the breaking strength of the base material layer is 1.5 to 80 MPa, preferably 2.0 to 60 MPa, more preferably 2.5 to 50 MPa, and further preferably 3.0 to 40 MPa. More preferred.
  • the breaking strength of the base material layer is at least the lower limit of the above range, it is possible to prevent the adhesive tape from being torn even when the adhesive tape is stretched and peeled off, and the load for stretching the adhesive tape becomes excessive. Since it does not become too much, the peeling work by peeling becomes easy. Further, the force required for stretching and deforming the adhesive tape also depends on the thickness of the adhesive tape. For example, when an adhesive tape having a large thickness and a high breaking strength is stretched to be peeled, it cannot be sufficiently stretched and cannot be peeled.
  • the stress at 25% elongation of the base material layer is preferably 0.15 to 10.0 MPa, more preferably 0.25 to 7.0 MPa, and further preferably 0.35 to 5.0 MPa. It is more preferably 0.45 to 2.0 MPa.
  • the 25% elongation stress of the adhesive tape is within the above range, the adhesive strength suitable for the adhesive tape can be obtained, and the adhesive tape can be peeled off relatively easily even in the peeling step. If it is less than the above range, there is a concern that the adhesive tape may be peeled off when a load is applied to the adhesive tape in the shearing direction while fixing the hard adherends to each other. On the other hand, if it exceeds the above range, the force necessary for extending the adhesive tape in the peeling step of the adhesive tape becomes excessive.
  • the stress at 50% elongation of the base material layer is preferably 0.15 to 10.5 MPa, more preferably 0.25 to 7.5 MPa, and further preferably 0.35 to 5.0 MPa. It is preferably 0.5 to 2.5 MPa, and even more preferably 0.5 to 2.5 MPa.
  • the adhesive strength suitable for the pressure-sensitive adhesive tape can be obtained, and the adhesive tape can be relatively easily peeled even in the peeling step. If it is less than the above range, the adhesive tape may be peeled off when a load is applied in the shearing direction of the adhesive tape while fixing the hard adherends to each other. On the other hand, if it exceeds the above range, the force necessary for extending the adhesive tape in the peeling step of the adhesive tape becomes excessive.
  • the 50% elongation stress of the base material layer is preferably 100 to 160% of the 25% elongation stress, more preferably 103 to 150%, further preferably 105 to 140%, 110. It is even more preferable that it is ⁇ 130%.
  • the 50% elongation stress of the adhesive tape is within the above range with respect to the 25% elongation stress of the adhesive tape, it is possible to stabilize the stress required for peeling when the adhesive tape is peeled off.
  • the storage elastic modulus E'(23 ° C.) of the base material layer is preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 8 Pa, preferably 5.0 ⁇ 10 4 to 5.0 ⁇ 10 7 Pa. It is more preferably 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa, and even more preferably 3.0 ⁇ 10 5 to 7.0 ⁇ 10 6 Pa.
  • breaking point stress of the base material layer is within the above range, it is easy to follow the strain of the adherend and obtain excellent adhesive strength, and the dimensional stability of the adhesive tape can be ensured. Suitable sticking workability can be obtained.
  • a primer layer is provided for the purpose of further improving the adhesion with the pressure-sensitive adhesive layer 4, surface roughening treatment by a sand blast method or a solvent treatment method, corona discharge treatment , Chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, oxidation treatment and other surface treatments can be used.
  • the method for producing the base material layer there are a cast method by extrusion molding, a uniaxial stretching method, a sequential secondary stretching method, a simultaneous biaxial stretching method, an inflation method, a tube method, a calender method, a solution method and the like.
  • the cast method by extrusion molding, the uniaxial stretching method, the sequential secondary stretching method, the simultaneous biaxial stretching method, the inflation method, the tube method can be preferably used, and the mechanical strength required for the laminated film 1 of the present embodiment can be suitably used. It may be selected according to.
  • the base material layer may have a single-layer structure, a double-layer structure, a three-layer structure, or a multi-layer structure of two or more layers.
  • a multi-layer structure it is preferable that at least one layer is a layer having the above-mentioned resin composition because it is easy to exhibit necessary mechanical properties.
  • a base material layer having a three-layer structure can be obtained by a method of coextruding a thermoplastic resin such as polypropylene and the styrene-isoprene-styrene copolymer. This may be used as a suitable configuration for the laminated film 1 of the present embodiment, for example, when it is desired to have appropriate dimensional stability and elasticity.
  • the pressure-sensitive adhesive of the pressure-sensitive adhesive layer 4 is not particularly limited, but one having good adhesion to the base material layer can be used, for example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive. , Silicone-based adhesives and the like. Further, in the present embodiment, a water-dispersible emulsion type pressure-sensitive adhesive can also be used as the pressure-sensitive adhesive of the pressure-sensitive adhesive layer 4. In the present embodiment, an acrylic pressure-sensitive adhesive is preferable because a relatively strong adhesive force can be easily obtained.
  • the acrylic pressure-sensitive adhesive is not particularly limited, but includes, for example, at least one acrylic polymer containing a (meth)acrylic acid alkyl ester monomer as a monomer unit.
  • the (meth)acrylic acid alkyl ester monomer is, for example, a (meth)acrylic acid alkyl ester having an alkyl group with 2 to 14 carbon atoms, and examples thereof include, but are not limited to, ethyl acrylate and acryl.
  • the acrylic polymer may be copolymerized with an acrylic acid ester having a polar group such as a hydroxyl group, a carboxyl group, or an amino group in the side chain or another vinyl-based monomer in the range of 0.1 to 15% by mass. preferable. Further, it is preferable to copolymerize the acrylic acid unit in the range of 2 to 10% by mass because of its excellent adhesiveness. As a result, the structural units derived from these monomers serve as crosslinking points in the acrylic polymer, and the hardness of the pressure-sensitive adhesive component can be adjusted to develop the desired adhesive strength.
  • an acrylic acid ester having a polar group such as a hydroxyl group, a carboxyl group, or an amino group in the side chain or another vinyl-based monomer in the range of 0.1 to 15% by mass.
  • the structural units derived from these monomers serve as crosslinking points in the acrylic poly
  • the acrylic polymer can be obtained by copolymerization by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, an ultraviolet irradiation method, or an electron beam irradiation method.
  • the weight average molecular weight of the acrylic polymer is preferably 400,000 to 1,400,000, and more preferably 600,000 to 1,200,000 in order to achieve both coating properties and adhesive properties.
  • the weight average molecular weight is converted to standard polystyrene by gel permeation chromatography (GPC).
  • TSKgel GMHXL manufactured by Tosoh
  • the column temperature is 40 ° C.
  • the eluent is tetrahydrofuran
  • the flow rate is 1.0 mL / min
  • TSK standard polystyrene is used as the standard polystyrene.
  • cross-linking agent in order to further increase the cohesive force of the pressure-sensitive adhesive.
  • the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and chelate-based cross-linking agents.
  • the pressure-sensitive adhesive layer 4 it is preferable to use an isocyanate-based cross-linking agent or an epoxy-based cross-linking agent.
  • the amount of the cross-linking agent added is preferably adjusted so that the gel fraction of the pressure-sensitive adhesive layer 4 is 25 to 80%. A more preferred gel fraction is 30-70%. Among them, 35 to 60% is the most preferable.
  • the adhesive When the gel fraction is 25% or more, the adhesive has an appropriate cohesive force, so that deviation is unlikely to occur in the keystroke test. On the other hand, when the gel fraction is 80% or less, the adhesive does not become too hard and the adhesive force to the adherend such as a substrate is good.
  • the gel fraction is expressed as a percentage with respect to the original mass by measuring the mass of the insoluble matter remaining after immersing the composition of the adhesive layer 4 after curing in toluene and leaving it for 24 hours.
  • rubber-based pressure-sensitive adhesive one or more of natural rubber-based polymers such as natural rubber and its modified products, synthetic rubber-based polymers, and rubber-based polymers such as vinyl aromatic block copolymer (B) are used. Including. Further, as the rubber-based pressure-sensitive adhesive, those containing a vinyl aromatic block copolymer (B) are preferable. Among them, one or more copolymers selected from block copolymers of an aromatic vinyl compound and a conjugated diene compound can be used, and a styrene copolymer in which the aromatic vinyl compound is styrene is preferable. ..
  • the conjugated diene compound isoprene, butadiene, ethylene butylene and ethylene propylene are preferable.
  • the block copolymer (B) is a diblock copolymer such as a styrene-isoprene copolymer, a styrene-butadiene copolymer, a styrene-ethylenebutylene copolymer, and a styrene-ethylenepropylene copolymer.
  • One or more copolymers selected from triblock copolymers such as styrene-isoprene-styrene copolymer and styrene-butadiene-styrene copolymer are preferable, and styrene-isoprene copolymer and styrene-
  • One or more copolymers selected from a butadiene copolymer, a styrene-ethylenebutylene copolymer, a styrene-isoprene-styrene copolymer, and a styrene-butadiene-styrene copolymer are more preferable, and styrene-isoprene.
  • One or more copolymers selected from copolymers and styrene-isoprene-styrene copolymers are particularly preferable.
  • the vinyl aromatic block copolymer contains 10% by mass to 80% by mass of the structural unit represented by the following chemical formula (2) with respect to the total mass of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer. It is preferable to use one having a range of 12 to 60% by mass, more preferably 12 to 60% by mass, and still more preferably one having a range of 15 to 40% by mass. It is even more preferable to use one having a range of about 35% by mass. Thereby, excellent adhesiveness and heat resistance can be obtained.
  • the vinyl aromatic block copolymer one containing two or more kinds of copolymers having different structures can be used, and a styrene-isoprene copolymer and a styrene-isoprene-styrene copolymer are contained in combination. You can use what you do.
  • the styrene-based resin contains the styrene-isoprene copolymer in the range of 0% by mass to 80% by mass based on the total mass of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer.
  • the laminated film 1 of the present embodiment can have both excellent adhesive performance and thermal durability.
  • the weight average molecular weight (gel permeation chromatography, SC-8020 manufactured by Toso Co., Ltd., high molecular weight column TSKgelGMHR) measured in terms of standard polystyrene using a gel permeation chromatograph (GPC).
  • -H solvent: tetrahydrofuran
  • -H solvent: tetrahydrofuran
  • the styrene-based copolymer may have a single structure such as a linear structure, a branched structure or a multi-branched structure, but may have a mixture of different structures. ..
  • a styrene-based resin having abundant linear structures is used for the pressure-sensitive adhesive layer 4, the laminated film 1 of this embodiment has excellent adhesive performance.
  • a branched structure or a multi-branched structure having a styrene block at the terminal of the molecule can have a pseudo cross-linking structure and can give excellent cohesive force, and thus can give high holding power. .. These are preferably mixed and used according to the required characteristics.
  • the method for producing the styrene-isoprene-styrene copolymer is not particularly limited, and a conventionally known production method can be applied, and the production method can be the same as that described for the base material layer.
  • the tackifying resin added to the pressure-sensitive adhesive layer 4 of the laminated film 1 of the present embodiment is a rosin-based resin such as rosin or an esterification product of rosin; a terpene-based resin such as a diterpene polymer or an ⁇ -pinene-phenol copolymer; Examples include petroleum resins such as aliphatic (C5) and aromatic (C9) resins; styrene resins, phenol resins, xylene resins and the like. Further, an acrylic resin other than the acrylic copolymer may be added as a tackifier resin.
  • the pressure-sensitive adhesive resin is an acrylic polymer
  • the pressure-sensitive adhesive resin is a rubber-based resin
  • the pressure-sensitive adhesive resin is a silicone-based resin, the tackifying resin is not added.
  • the pressure-sensitive adhesive contains the vinyl aromatic block copolymer (B)
  • a tackifier resin having a softening point of 80° C. or higher can be used as the tackifier resin that can be contained in the pressure-sensitive adhesive.
  • the softening point refers to a value measured by a method (dry bulb method) specified in JIS K2207.
  • a solid resin at room temperature (23° C.) for example, a C5 petroleum resin, a C5/C9 petroleum resin, an alicyclic petroleum resin, or the like.
  • the petroleum resin is easily compatible with the polyisoprene structure constituting the styrene-based resin, and as a result, the initial adhesive strength and thermal durability of the pressure-sensitive adhesive and pressure-sensitive adhesive tape can be further improved.
  • the C5 petroleum resin an aliphatic petroleum resin can be used, for example, Escolets 1202, 1304, 1401 (manufactured by Tonen Chemical Corporation), Wing Tuck 95 (manufactured by Goodyear Tire and Rubber Company). ), Quinton K100, R100, F100 (manufactured by Zeon Corporation), PicoTac 95, Picopel 100 (manufactured by Rika Hercules) and the like can be used.
  • the C5 / C9 petroleum resin a copolymer of the C5 petroleum resin and the C9 petroleum resin can be used.
  • Escolets 2101 manufactured by Tonex
  • Quinton G115 manufactured by Zeon Corporation
  • Harcotac 1149 manufactured by Rika Hercules
  • the alicyclic petroleum resin is obtained by hydrogenating the C9 petroleum resin described above.
  • Escolets 5300 manufactured by Tonex
  • Archon P-100 manufactured by Arakawa Chemical Industries
  • Rigalite R101 Rosika Fine). Tech
  • Examples of the tackifier resin having a softening point of 80 ° C. or higher include polymerized rosin-based resin and C9-based petroleum resin, in addition to the C5-based petroleum resin, C5-based / C9-based petroleum resin, and alicyclic petroleum resin.
  • a terpene resin, a rosin resin, a terpene-phenol resin, a styrene resin, a coumarone-indene resin, a xylene resin, a phenol resin or the like can be used. Among them, as the tackifying resin having a softening point of 80° C.
  • the tackifier resin having a softening point of 80 ° C. or higher is preferably used in the range of 3% by mass to 100% by mass with respect to the total amount of the styrene-based resin, and is used in the range of 5% by mass to 80% by mass. It is more preferable, and it is more preferable to use it in the range of 5% by mass to 80% by mass in order to obtain an adhesive and an adhesive tape having both further excellent adhesiveness and excellent thermal durability.
  • a tackifying resin having a softening point of ⁇ 5° C. or lower can be used in combination with the tackifying resin having a softening point of 80° C. or higher.
  • the pour point refers to a value measured by a method according to the method defined in JIS K2269.
  • the tackifier resin having a softening point of ⁇ 5 ° C. or lower it is preferable to use a tackifier resin that is liquid at room temperature.
  • Such a tackifying resin which is liquid at room temperature is preferably selected from the above known tackifying resins.
  • the tackifying resin having a softening point of ⁇ 5° C. or lower for example, liquid oils such as process oil, polyester, polybutene and the like can be used, and among them, polybutene is more excellent in initial adhesion. It is preferable for expressing the sex.
  • the tackifying resin having a softening point of ⁇ 5° C. or lower is preferably used in the range of 0% by mass to 40% by mass, and is used in the range of 0% by mass to 30% by mass with respect to the total amount of the tackifying resin. It is more preferable to do so.
  • the tackifying resin having a softening point of -5°C or lower is preferably used in the range of 0% by mass to 40% by mass, and in the range of 0% by mass to 30% by mass, based on the total amount of the styrene resin. By using it, the initial adhesive strength can be improved, good adhesion can be obtained, and sufficient thermal durability can be obtained.
  • the mass ratio of the tackifier resin having a softening point of 80 ° C. or higher and the tackifier resin having a softening point of ⁇ 5 ° C. or lower is preferably in the range of 5 to 50, and preferably in the range of 10 to 30. It is more preferable for obtaining a pressure-sensitive adhesive and a pressure-sensitive adhesive tape that have both excellent initial adhesiveness and excellent holding power.
  • the styrene resin and the tackifier resin are preferably used in combination in a range where the mass ratio represented by [styrene resin / tackifier resin] is 0.5 to 10.0, and is 0.6 to 10.0. By using it in the range of 9.0, the initial adhesive strength can be improved and excellent thermal durability can be obtained.
  • the mass ratio [styrene-based resin/tackifying resin] is preferably larger than 1 to prevent peeling due to the repulsive force of the adhesive tape when attached to a curved surface of an adherend (repulsion resistance). It is preferable in terms of
  • the pressure-sensitive adhesive of the pressure-sensitive adhesive layer 4 preferably contains filler particles.
  • the filler particles are exposed from the pressure-sensitive adhesive layer 4 when the pressure-sensitive adhesive sheet is elongated, and the adhesive area between the pressure-sensitive adhesive layer 4 and the adherend becomes small, so that the pressure-sensitive adhesive sheet Almost extends even if the extension direction is a high angle such as a direction perpendicular to the attachment surface of the attachment target (hereinafter, also referred to as "adherent") (also sometimes referred to as "90° direction”) It can be peeled off.
  • filler particles is not particularly limited and may be appropriately selected within a range that does not impair the effects of the present invention, and may be inorganic filler particles or organic filler particles. These may be used alone or in combination of two or more.
  • the inorganic filler particles include aluminum hydroxide, magnesium hydroxide, aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, titanium oxide, zirconium oxide, iron oxide, silicon carbide, boron nitride, aluminum nitride, titanium nitride, and the like.
  • organic filler particles include polystyrene filler, benzoguanamine filler, polyethylene filler, polypropylene filler, silicone filler, urea-formalin filler, styrene/methacrylic acid copolymer, silicon filler, fluorine filler. , Acrylic filler, polystyrene filler, polyurethane filler, polyamide filler, epoxy resin filler, thermosetting resin hollow filler and the like.
  • the shape of the filler particles is not particularly limited and may be appropriately selected depending on the intended purpose, and may be a regular shape or an irregular shape. Specific examples of the shape of the filler particles include a polygonal shape, a cubic shape, an elliptical shape, a spherical shape, a needle shape, a flat plate shape, and a scale shape. The filler particles having these shapes may be used alone or in combination of two or more. Further, the filler particles having these shapes may be aggregated. Among these, the shape of the filler particles is preferably elliptical, spherical, or polygonal.
  • the adhesive layer 4 slides well to the adherend when the adhesive sheet is stretched, and the adhesive sheet is stretched in the direction of attachment of the adherend. It can be easily stretched and peeled even in the 90 ° direction with respect to the surface.
  • the particle size distribution (D 90 /D 10 ) of the filler particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2.5 to 20 and is 2.5 in terms of impact resistance. -15 are more preferable, and 2.5-5 are further preferable.
  • the particle size distribution (D 90 /D 10 ) of the filler particles is within the above-mentioned preferred range, the pressure-sensitive adhesive sheet can be easily stretched and peeled even if the stretching direction is 90° with respect to the sticking surface of the adherend, and the sticking Even when the base material of the sheet is thin, it is difficult to be torn and is excellent in impact resistance, shear adhesive strength, and split adhesive strength.
  • the particle size distribution (D 90 / D 10 ) of the filler particles is less than 2.5, the stretch peelability when the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the sticking surface of the adherend. If it exceeds 20, the adhesive properties such as impact resistance, shear adhesive strength and split adhesive strength may be impaired.
  • the particle size distribution (D 90 /D 10 ) of the filler particles is converted into a particle size distribution by measuring the particle size of the filler particles by using a measuring machine (Microtrac) using a laser diffraction scattering method. It can be obtained by.
  • the volume average particle diameter of the filler particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 ⁇ m to 25 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m, still more preferably 5 ⁇ m to 14 ⁇ m.
  • the volume average particle diameter of the filler particles is within the preferable range, the pressure-sensitive adhesive sheet can be easily stretched and peeled even if the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the attachment surface of the adherend. Even when the base material is thin, it is not easily torn, and is excellent in impact resistance, shear adhesive strength, and split adhesive strength.
  • the volume average particle diameter of the filler particles is less than 3 ⁇ m, it may be difficult to stretch and peel the pressure-sensitive adhesive sheet when the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the attachment surface of the adherend. If it exceeds 25 ⁇ m, the adhesive performance such as impact resistance, shear adhesive strength, and split adhesive strength may be impaired.
  • the volume average particle diameter of the filler particles can be measured, for example, by using a measuring machine (Microtrac) using a laser diffraction scattering method.
  • the ratio between the volume average particle diameter of the filler particles and the average thickness of the pressure-sensitive adhesive layer 4 described below is not particularly limited and can be appropriately selected according to the purpose.
  • the average thickness of the pressure-sensitive adhesive layer] is preferably 5/100 or more, and the ratio of the volume average particle diameter of the filler particles to the average thickness of the pressure-sensitive adhesive layer 4 is preferably 5/100 to 95/100. More preferably, 10/100 to 75/100 is more preferable, and 20/100 to 60/100 is particularly preferable.
  • the ratio is within the preferred range, the pressure-sensitive adhesive sheet can be easily stretched and peeled even when the stretching direction is 90° with respect to the attaching surface of the adherend, and the thickness of the base material of the pressure-sensitive adhesive sheet is small.
  • the adhesive sheet can be easily stretched and peeled even when the stretched direction is 90° with respect to the attaching surface of the adherend, and the thickness of the base material of the adhesive sheet is Even if it is thin, it is not easily torn, and it is advantageous in that it has better adhesive performance such as impact resistance, shear adhesive force, and split adhesive force.
  • the ratio is less than 5/100, the stretch releasability may be impaired in the case where the stretching direction of the pressure-sensitive adhesive sheet is 90° with respect to the sticking surface of the adherend, and when it exceeds 95/100. , Impact resistance, shear adhesive strength, split adhesive strength, and other adhesive performance may be impaired.
  • the content of the filler particles in the pressure-sensitive adhesive layer 4 is preferably 9 to 50% by mass, more preferably 13 to 34% by mass, and 17 to 30% by mass with respect to 100% by mass of the pressure-sensitive adhesive. It is more preferable to have.
  • the content of the filler particles is less than 9% by mass relative to 100% by mass of the pressure-sensitive adhesive, the pressure-sensitive adhesive sheet cannot be stretch-peeled when the stretching direction is 90° to the sticking surface of the adherend, and the pressure-sensitive adhesive sheet The adhesive sheet does not stretch and cannot be peeled off.
  • the adhesive sheet does not elongate, the adhesive composition remains on the adherend, the impact resistance is deteriorated, and the shear resistance is reduced. Adhesive strength and split adhesive strength may be weakened.
  • the content of the filler particles with respect to 100% by mass of the pressure-sensitive adhesive is 9 to 50% by mass, the pressure-sensitive adhesive sheet can be easily stretched and peeled even if the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the sticking surface of the adherend.
  • the thickness of the base material of the pressure-sensitive adhesive sheet is small, it is hard to be torn and is excellent in impact resistance, shear adhesive strength, and split adhesive strength.
  • the content of the filler particles in the pressure-sensitive adhesive layer 4 can be appropriately adjusted when preparing the pressure-sensitive adhesive.
  • the volume ratio of the filler particles to the total volume of the pressure-sensitive adhesive layer 4 is 4% to 40%, preferably 5% to 30%, more preferably 5% to 20%, still more preferably 5% to 15%. Yes.
  • the volume ratio of the filler particles is less than 4%, the adhesive sheet cannot be stretch-peeled when the extending direction is 90° to the adherend surface of the adherend, and the adhesive sheet is torn. The adhesive sheet does not stretch and cannot be peeled off.
  • the volume ratio of the filler particles exceeds 40%, the pressure-sensitive adhesive sheet does not expand, the pressure-sensitive adhesive remains on the adherend, the impact resistance deteriorates, and the shear adhesive strength and split adhesive strength are weakened. May be.
  • the volume ratio of the filler particles is 4% to 40%, the pressure-sensitive adhesive sheet can be easily stretched and peeled even if the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the attachment surface of the adherend, and the base material of the pressure-sensitive adhesive sheet can be easily stretched and peeled off. Even if the thickness is small, it is not easily torn, and is excellent in impact resistance, shear adhesive strength, and split adhesive strength.
  • the volume ratio of the filler particles to the pressure-sensitive adhesive layer 4 can be calculated from the following formulas (1) to (3).
  • Adhesive resin * 1 mass A (g) / adhesive resin * 1 Density A (g / cm 3) adhesive resin * 1 volume A (cm 3) ⁇ ⁇ ⁇ Equation (1)
  • Mass B(g) of filler particles/density B(g/cm 3 ) of filler particles volume B(cm 3 ) of filler particles Equation (2)
  • x 100 Filler particle volume ratio (%) ... 3)
  • the pressure-sensitive adhesive resin represented by *1 may include other components as necessary.
  • the density is a value measured according to JIS Z 8804.
  • additives can be added, if necessary.
  • other known and commonly used additives can be added, if necessary.
  • other polymer components such as polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polysulfate, polymerization inhibitors, as necessary, as long as the properties are not impaired.
  • Antistatic agent defoaming agent, viscosity modifier, light resistance stabilizer, weather resistance stabilizer, heat resistance stabilizer, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, plasticizer, softener, flame retardant, Additives such as metal deactivators and organic beads; those containing inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be used.
  • the loss tangent of the dynamic viscoelastic spectrum of the adhesive at a frequency of 1 Hz is preferably 0.5 to 0.8 at 70°C. More preferably, it is 0.55 to 0.75. When it is 0.5 or more, the peeling resistance is excellent, and when it is 0.8 or less, the pressure-sensitive adhesive is less likely to seep to the printed portion at high temperature.
  • the thickness of the pressure-sensitive adhesive layer 4 is not particularly limited, but is preferably 5 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, and further preferably 10 to 60 ⁇ m. Within this range, it is easy to achieve both adhesiveness and thin tape.
  • the pressure-sensitive adhesive layer 4 of the laminated film of the present embodiment has a stress at 50% elongation of 0.05 to 10.5 MPa, more preferably 0.07 to 7.5 MPa, and 0.1 to 5. It is more preferably 5 MPa, and even more preferably 0.15 to 3.5 MPa.
  • the 50% elongation stress of the pressure-sensitive adhesive layer 4 is within the above range, excellent adhesiveness and peelability of the pressure-sensitive adhesive tape can be obtained. That is, it is possible to easily follow the strain of the adherend and to obtain excellent adhesive strength, and it is possible to prevent the pressure-sensitive adhesive layer 4 from remaining on the adherend in the peeling step of the pressure-sensitive adhesive tape.
  • the adhesive layer 4 of the laminated film 1 of the present embodiment has a storage elastic modulus G′ (23° C.) of 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa, but 1.0 ⁇ 10 5 to 8 .0 ⁇ 10 6 Pa is preferable, 1.0 ⁇ 10 5 to 5.0 ⁇ 10 6 Pa is more preferable, 1.0 ⁇ 10 5 to 4.0 ⁇ 10 6 Pa is more preferable, and 1.0 ⁇ 10 Most preferably, it is 5 to 3.0 ⁇ 10 6 Pa.
  • the storage elastic modulus G′ (23° C.) of the pressure-sensitive adhesive layer 4 is in the above range, excellent adhesiveness and releasability of the pressure-sensitive adhesive tape can be obtained, and the adhesive tape was used particularly in a high temperature and high humidity environment. It is possible to prevent the adhesive layer 4 from remaining on the adherend in the process of peeling the adhesive tape later.
  • the thickness of the pressure-sensitive adhesive layer 4 is preferably 1/2 to 1/500, more preferably 1/3 to 1/300, and 1/5 to 1/300 with respect to the thickness of the base material layer. It is more preferably 200, and even more preferably 1/10 to 1/50.
  • the thickness ratio of the pressure-sensitive adhesive layer 4 and the base material layer of the pressure-sensitive adhesive tape is within the above range, excellent adhesiveness and peelability of the pressure-sensitive adhesive tape can be obtained.
  • the cohesive force of the pressure-sensitive adhesive layer 4 becomes lower than the cohesive force of the base material layer. Therefore, when the pressure-sensitive adhesive layer 4 is thicker than the above range, the pressure-sensitive adhesive tape is adhered in the peeling step. Only the agent layer 4 may remain on the adherend.
  • the pressure-sensitive adhesive layer 4 is thinner than the above range, there is a concern that the pressure-sensitive adhesive layer 4 cannot follow when the surface of the adherend is uneven and the adhesive strength is significantly reduced.
  • the stress at break of the pressure-sensitive adhesive layer 4 used in the laminated film 1 of the present embodiment is preferably 0.5 to 25.0 MPa, more preferably 0.8 to 20.0 MPa, and 1.0 It is more preferably ⁇ 17.0 MPa, even more preferably 1.2 to 15.0 MPa.
  • the stress at break of the pressure-sensitive adhesive layer 4 is in the above range, excellent adhesiveness can be exhibited, and the pressure-sensitive adhesive component remains on the adherend when the laminated film 1 of the present embodiment is stretched and peeled off. It is difficult and preferable.
  • the laminated film 1 of the present embodiment is not particularly limited and can be produced, for example, by a known method. Specifically, in the laminated film 1, a pressure-sensitive adhesive layer is applied to the surface of a release film (release liner) and dried to form a pressure-sensitive adhesive layer on both sides of the release film (that is, the pressure-sensitive adhesive is formed). Two release films are prepared). At this time, when forming the pressure-sensitive adhesive layer on the surface of at least one of the release films, for example, by a gravure printing method, a die coating method or a comma coating method, a portion not coated with the pressure-sensitive adhesive is formed on the release film. Then, the glueless portion 2 is formed in the adhesive layer. Next, the laminated film 1 can be obtained by laminating the pressure-sensitive adhesive layer having the above-mentioned release film on both surfaces of the prepared base material layer and applying pressure or the like as necessary.
  • a release film may be laminated for protecting the pressure-sensitive adhesive layer 4, as described in the above manufacturing method.
  • the release film is not particularly limited, but for example, at least one side of a synthetic resin film such as polyethylene, polypropylene, polyester film, paper, non-woven fabric, cloth, foam sheet or metal foil, and a base material layer such as a laminate thereof or It is possible to use those whose both surfaces have been subjected to a release treatment such as a silicone-based treatment, a long-chain alkyl-based treatment, or a fluorine-based treatment for enhancing the releasability from the adhesive.
  • a release treatment such as a silicone-based treatment, a long-chain alkyl-based treatment, or a fluorine-based treatment for enhancing the releasability from the adhesive.
  • the laminated film 1 of the present embodiment preferably has a total thickness of 50 to 3000 ⁇ m, more preferably 70 to 500 ⁇ m, and even more preferably 100 to 300 ⁇ m.
  • the laminated film 1 of the present embodiment preferably has an adhesive strength of 1 to 50 N / 20 mm, more preferably 10 to 30 N / 20 mm, still more preferably 15 to 20 mm, as measured by the method described in Examples described later. It is 25N / 20mm. When the content is in the above range, it is easy to achieve both good tear resistance and adhesiveness at the time of disassembling.
  • the pressure-sensitive adhesive tape 11 of the present embodiment includes a base material layer 13 and pressure-sensitive adhesive layers 14 on both surfaces of the base material layer 13. Further, the adhesive tape 11 has a glueless portion 12 on which the adhesive layer 14 does not exist on at least one surface of the adhesive tape 11 on one end side, and the base material layer 13 has a breaking elongation of 200 to It is 3000% and the breaking strength is 1.5 to 80 MPa. By having such a configuration, the adhesive tape 11 of the present embodiment reduces the load on the adhesive tape 11 and prevents tearing even when the adhesive tape 11 is peeled off at an angle with respect to the sticking surface. You can
  • the pressure-sensitive adhesive tape 11 of the present embodiment its shape can be arbitrary depending on the object to which the pressure-sensitive adhesive tape 11 is attached, but for example, as shown in FIG. 3, a shape having two or more end portions is used. It is preferable to do so.
  • the adhesive tape 11 has rectangular portions forming one end portion of the adhesive tape 11 by the number of the end portions of the adhesive tape 11, and one side of each rectangular portion has the adhesive tape 11 thereon.
  • the adhesive tape 11 can have a shape having two or more end portions by facing the center side and the other side (the side that becomes the end portion) toward the outside of the adhesive tape 11. More specifically, when the adhesive tape 11 has two end portions, the two rectangular portions are connected by connecting one side of the two rectangular portions, and as shown in FIG.
  • one side of the rectangular portion is connected toward the central portion of the adhesive tape 11, and the other side is formed to extend (spread) from the central portion toward the outside.
  • the above-mentioned rectangular portion of the adhesive tape 11 does not need to be strictly rectangular, and may be curved as long as it has a shape elongated in one direction as a whole. Further, the shape of the entire adhesive tape 11 may be curved or bent. Further, the width of the adhesive tape 11 may change in the longitudinal direction.
  • the adhesive tape 11 has a glueless portion 12 on at least one surface of the adhesive tape 11 on one end side.
  • the illustrated adhesive tape 11 has two end portions, and a glueless portion 12 is formed in a portion near one end portion (center side from the end portion).
  • the specific distance from the end of the end where the glueless portion 12 is formed can be arbitrarily set depending on the target to which the adhesive tape 11 is attached.
  • the glueless portion 12 is provided near one end of the plurality of end portions, but near the end of some of the plurality of end portions or of the plurality of end portions. Glueless portions 12 can be provided near all the ends.
  • the glueless portion 12 crosses the surface of the adhesive tape 11 from one end (edge) in the width direction (direction orthogonal to the longitudinal direction) to the other end (edge). Is formed in. Further, the glueless portion 12 is formed on one surface of the adhesive tape 11 in the illustrated example, but also on the other surface, similarly in the vicinity of the end portion, preferably in a plan view of the adhesive tape 11. Thus, it is possible to form the adhesive-free portion 12 on one surface and the adhesive-free portion 12 on the other surface so as to overlap each other, more preferably in the same range.
  • the function and effect of the adhesive tape 11 of the present embodiment will be described.
  • other members are also attached to the housing in the vicinity of the components attached using an adhesive tape. Then, in order to peel off the adhesive tape while avoiding the other members, the handle portion of the adhesive tape is pulled at an angle with respect to the sticking surface and peeled off, which may cause a load on the adhesive tape and may be torn off.
  • the adhesive tape 11 has a glueless portion 12 (particularly, among the glueless portions 12, the adhesive tape 11
  • the adhesive tape 11 When the adhesive tape 11 is peeled from the component at an angle with respect to the attachment surface by attaching the adhesive tape 11 such that the end side) is positioned at a portion of the attachment surface of the component that is adjacent to a corner that defines the attachment surface.
  • the adhesive-free portion 12 can relieve a large force at the beginning of elongation applied to the portion (corresponding to the glue-less portion 12) of the adhesive tape 11 that sticks to the vicinity of the corner of the component. Therefore, the load on the adhesive tape 11 can be reduced and tearing can be prevented.
  • the glueless portion 12 can be the same as the glueless portion 2 of the laminated film 1 according to the embodiment of the present invention described above.
  • the size of the glueless portion 12 in the adhesive tape can be arbitrary, but the length of the glueless portion 12 measured along the longitudinal direction is preferably 0.5 to 100 mm, and more preferably. It is 1 to 50 mm, more preferably 10 to 30 mm.
  • the glueless portion 12 can be easily attached by aligning with the corners of the parts, and when the adhesive tape 11 is peeled off, the handle portion of the adhesive tape 11 is angled. Even if it is pulled, the load on the adhesive tape 11 is reduced, and tearing can be effectively prevented.
  • the length of the glueless portion 12 may be sufficient to facilitate the peeling of the adhesive tape 11 at the beginning of its extension.
  • the adhesiveness of the adhesive tape 11 can be easily maintained by setting the length of the adhesive-free portion 12 along the longitudinal direction to 100 mm or less. Further, by setting the length to 100 mm or less, the glueless portion 12 does not become too large, and the influence on the adhesiveness of the adhesive tape 11 can be suppressed.
  • the end portion of the adhesive tape 11, specifically, the end portion side of the adhesive-free portion 12 can be used as the handle portion, and the handle portion has a handle portion.
  • the film 15 (which has not been subjected to the peeling treatment) may be attached to the surface of the adhesive tape 11, or the adhesive layer 14 may not be formed.
  • the pressure-sensitive adhesive layer 14 is not formed on the handle portion as in the case of the glueless portion 12, the length of the preferable glueless portion 12 measured along the longitudinal direction is the length of the handle portion. The length can be added.
  • Examples of the material of the film 15 include cellophane, polyethylene, polypropylene, nylon, polystyrene, polyimide, polyester, tetrafluoroethylene and the like.
  • polyester film which is inexpensive and has excellent workability
  • tetrafluoroethylene which has excellent slipperiness, are preferable.
  • the width of the adhesive tape 11 can be made arbitrary, but in particular, the end portion of the adhesive tape 11 on which the glueless portion 12 is formed has a length measured along the width direction of 0.5 to 100 mm. It is preferably, and more preferably 10 to 50 mm. When the length is 0.5 to 100 mm, the size of the adhesive tape 11 can be made easy to use while ensuring the adhesiveness. Further, the length of the entire adhesive tape 11 can be arbitrarily set depending on the object to be attached.
  • the structure of the adhesive tape 11 other than the glueless portion 12, specifically, the pressure-sensitive adhesive layer, the base material layer, and the like can be the same as the pressure-sensitive adhesive layer and the base material layer of the laminated film.
  • the adhesive tape 11 of the present embodiment is not particularly limited and can be produced, for example, by a known method. Specifically, the adhesive tape 11 first manufactures the laminated film as described above. Then, the adhesive film 11 can be obtained by cutting out the laminated film into a desired shape. The adhesive-free portion of the adhesive tape may be formed by removing the adhesive layer so as to have a desired shape and size for a laminated film or adhesive tape having an adhesive layer on the entire surface. Good.
  • the total thickness and adhesive strength of the adhesive tape 11 of the present embodiment can be the same as those of the laminated film described above.
  • the adhesive body of the present embodiment includes an adhesive tape 11 according to the above-described embodiment of the present invention, and a first adherend 16 attached on one surface of the adhesive tape 11. , A second adherend 17 attached on the other surface of the adhesive tape 11.
  • the portion of the adhesive tape 11 on the end side of the adhesive-free portion 12 is more than the first attaching surface of the first adherend 16 to which the adhesive tape 11 is attached.
  • the corner 18 is located on the outside and defines the first sticking surface on the glueless portion 12.
  • the adhesive body of the present embodiment when the adhesive tape 11 is peeled off at an angle to the sticking surface in order to remove the first adherend 16 from the second adherend 17, the load on the adhesive tape 11 is applied. Since it can be reduced, it is possible to prevent the adhesive tape 11 from being torn.
  • the first adherend 16 and the second adherend 17 are not particularly limited, and are used in various industrial fields such as OA equipment, IT/home electric appliances, automobiles, etc.
  • the body 17 is a housing for these products, and the first adherend 16 is a component such as a battery, an electronic component, or a structural component to be incorporated in those products.
  • the second adherend 17 can be fixed or temporarily fixed.
  • the first adherend 16 may be used as a label for displaying product information or the like, and the second adherend 17 may be used as a display unit for displaying the label.
  • the portion of the adhesive tape 11 on the end side of the adhesive-free portion 12 is more than the first attachment surface of the first adherend 16 to which the adhesive tape 11 is attached. It is located outside. As shown in FIG. 5, the portion of the adhesive tape 11 closer to the end than the non-adhesive portion 12 is the first attachment surface of the first adherend 16 and the second attachment to which the adhesive tape 11 is attached. It is a portion that is not sandwiched between the second sticking surface of the body 17, and can be used as a handle portion when the adhesive tape 11 is peeled off.
  • the corner 18 that defines the first attachment surface is located on the glueless portion 12.
  • the first 1 A corner 18 is located which defines the application surface.
  • the boundary and the corner 18 do not have to be exactly aligned, and the corner 18 may be located on the glueless portion 12 side of the boundary (adhesive).
  • the glueless portion 12 of the tape 11 may be located on the side surface of the first adherend 16).
  • the corner 18 and the end portion side are opposite to each other.
  • the distance from the boundary between the glueless portion 12 and the adhesive layer 14 is 1 mm or more. Is preferred.
  • the adhesive tape 11 is attached to the first attachment surface of the first adherend 16. At this time, the corner 18 defining the first sticking surface is pasted so as to be located at the glueless portion 12. Then, the first adherend 16 can be assembled by sticking it to the second adherend 17.
  • the adhesive tape 11 is attached to the second attachment surface of the second adherend 17. At this time, the glue-free portion 12 is pasted so as to be located at the position of the second pasting surface where the corner 18 that defines the first pasting surface is located.
  • the first adherend 16 is attached to the second adherend 17 so that the corner 18 of the first attachment surface of the first adherend 16 is located at the glueless portion 12 of the adhesive tape 11. Can be assembled.
  • the portion of the adhesive tape 11 that is closer to the end than the glueless portion 12 (in FIG. 5, the portion that is located along the side surface of the first adherend 16) is used.
  • the adhesive tape 11 is peeled off by pulling at an angle of 60 ° or more with respect to the sticking surface, and the first adherend 16 is removed from the second adherend 17.
  • the adhesive tape 11 of the present embodiment can be more preferably used.
  • the breaking elongation of the adhesive tape is determined by punching the adhesive tape into a dumbbell shape with a marked line length of 20 mm and a width of 10 mm, and swelling the adhesive with a solvent such as ethyl acetate, alcohol or toluene. Then, it is scraped off with a spatula etc. to obtain only the base layer of the adhesive tape, and the solvent is further dried with a dryer, and then the base layer is subjected to a Tensilon tensile tester under the conditions of a measurement atmosphere of 23° C. and 50% RH. It was measured by pulling in the length direction at a tensile speed of 300 mm / min.
  • the breaking strength of the base material layer is obtained by punching out an adhesive tape into a dumbbell shape having a marked line length of 20 mm and a width of 10 mm, and swelling the adhesive agent with a solvent such as ethyl acetate, alcohol or toluene. Then, scrape off with a spatula etc. to obtain only the base layer of the adhesive tape, further dry the solvent with a dryer, and then use the Tensilon tensile tester under the conditions of a measurement atmosphere of 23° C. and 50% RH. , Measured by pulling in the length direction at a tensile speed of 300 mm / min.
  • Adhesive Strength of Adhesive Layer With respect to the adhesive tape, one adhesive surface was backed with a polyester film (thickness 25 ⁇ m), and a tape sample was obtained with a size of 20 mm ⁇ 100 mm. A stainless steel plate was placed on the other adhesive surface of the tape sample, pressure-bonded one reciprocatingly using a 2 kg roller, and then left at 23 ° C. and 50% RH for 1 hour. Then, it was peeled off in a 180° direction at a peeling speed of 300 mm/min, and the adhesive force (N/20 mm) at that time was measured.
  • the thicknesses of the base material layer and the pressure-sensitive adhesive layer in the pressure-sensitive adhesive tape were measured at 10 points, and the arithmetic mean value was taken as the thickness of each layer.
  • the thickness of the base material layer and the pressure-sensitive adhesive layer is a length measured from the surface on one side to the surface on the other side of each layer along the laminating direction.
  • a first adherend described below is fixed to a second adherend described below using the adhesive tape having a length of 120 mm and a width of 20 mm obtained in Examples and Comparative Examples, and then the adhesive tape.
  • the easiness of peeling was evaluated.
  • an adhesive tape having a length of 120 mm and a width of 20 mm is prepared, and a portion of the adhesive tape having a length of 20 mm on the front end side is protruded as a handle portion, and a stainless steel plate which is a second adherend. Pasted on.
  • the corners forming the first sticking surface of the first adherend are formed on the adhesive tape so that the longitudinal direction of the adhesive tape is the longitudinal direction of the first adherend.
  • Example 1 In the case of an adhesive tape having no glue-free portion formed on its surface (Comparative Example 1), the adhesive tape was fixed to the stainless steel plate in the same manner as in Example 1 and the like. ⁇ : 10 out of 10 could be peeled off. ⁇ : 7 to 9 out of 10 pieces could be peeled off. ⁇ : 1 to 6 out of 10 could be peeled off. X: None of the 10 pieces could be peeled off.
  • Adhesiveness The first adherend (38 g) described below was fixed using the adhesive tape having a length of 120 mm and a width of 20 mm obtained in Examples and Comparative Examples, and then the adhesiveness of the adhesive tape was evaluated. did. Specifically, an adhesive tape having a length of 120 mm and a width of 20 mm was prepared, and the stainless steel plate (thickness: 1.5 mm, with the adhesive tape having a length of 20 mm on the tip side protruding as a handle portion) was prepared. The length was 150 mm, the width was 50 mm, and the weight was 85 g).
  • a battery obtained by the following method was used as the first adherend.
  • a battery packaging film for packaging a battery was obtained by the following method.
  • a polyethylene terephthalate resin and nylon 6 were extruded by a T-die method to prepare a co-extruded film, biaxially stretched in the MD and TD directions by a sequential stretching method, and then heat-treated at 200° C. to produce a resin film A.
  • the draw ratio was set to 3.4 times in the flow direction (MD) and 3.8 times in the width direction (TD).
  • the laminated structure of the resin film A is polyethylene terephthalate (5 ⁇ m) / nylon 6 (20 ⁇ m).
  • the polyethylene terephthalate resin layer is located on the opposite side of the base material layer from the sealant layer.
  • the adhesive layer A two-layer coextruded film composed of a sealant layer and a sealant layer was produced.
  • the two-layer coextrusion film prepared above is added to the metal layer of the laminate composed of the base material layer (resin film A)/adhesive layer (urethane resin adhesive)/metal layer (aluminum foil) prepared above.
  • Got The obtained laminated body was once cooled, then heated to 180° C. and heat-treated while maintaining the temperature for 1 minute to obtain a battery packaging film.
  • the obtained battery packaging film was cut into a predetermined shape, and a battery element such as a positive electrode, a negative electrode and an electrolyte was packaged.
  • the shape of the battery after packaging was a flat plate, with a thickness of 5 mm, a length of 100 mm, and a width of 50 mm.
  • the mass of the obtained battery was 38 g.
  • the resin composition of the base material layer is a mixture of a styrene-isoprene copolymer and a styrene-isoprene-styrene copolymer (hereinafter, may be referred to as “SIS”), and is represented by the following chemical formula (1). 25% by mass of the structural unit derived from styrene, and the ratio of the styrene-isoprene copolymer to the total amount of the resin composition (1) was 17% by mass.
  • SIS styrene-isoprene copolymer
  • the substrate layer S-1 was prepared by applying it on the above-mentioned product and drying it at 60 ° C. for 5 minutes.
  • the obtained base layer has a thickness of 50 ⁇ m, a breaking elongation of 1150% and a breaking strength of 18.6 MPa.
  • -Base material layer S-2 As the resin composition of the base material layer, an ester polyurethane compound (Mobilon film MF100T, manufactured by Nisshinbo Textile Co., Ltd.) was used, and the thickness after drying was 100 ⁇ m. A base material layer S-2 was prepared in the same manner. The base material layer S-2 has a thickness of 100 ⁇ m, a breaking elongation of 720%, and a breaking strength of 33.0 MPa.
  • -Base layer S-3 A polyethylene terephthalate film (Toray Industries, Inc., Lumirror S10 # 25) was used. The thickness is 25 ⁇ m, the elongation at break is 160%, and the strength at break is 230 MPa.
  • Adhesive layer] -Adhesive layer A-1 The pressure-sensitive adhesive of the pressure-sensitive adhesive layer was produced as follows. 75.94 parts by mass of n-butyl acrylate, 5 parts by mass of 2-ethylhexyl acrylate, 15 parts by mass of cyclohexyl acrylate, acrylic acid 4 in a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel. A mixture (1) was obtained by charging 0.06 parts by mass of 4-hydroxybutyl acrylate and 200 parts by mass of ethyl acetate and raising the temperature to 65 ° C. while blowing nitrogen under stirring.
  • a cross-linking agent (Bernock D-40, manufactured by DIC Corporation; trimethylolpropane adduct of tolylene diisocyanate, isocyanate group content of 7% by mass, non-volatile content) 40% by mass) 1.3 parts by mass was added, and the mixture was stirred and mixed so as to be uniform, and then filtered through a 100 mesh wire net to obtain a pressure-sensitive adhesive resin (1) having a solid content of 31.1% by mass.
  • a cross-linking agent (Bernock D-40, manufactured by DIC Corporation; trimethylolpropane adduct of tolylene diisocyanate, isocyanate group content of 7% by mass, non-volatile content) 40% by mass) 1.3 parts by mass was added, and the mixture was stirred and mixed so as to be uniform, and then filtered through a 100 mesh wire net to obtain a pressure-sensitive adhesive resin (1) having a solid content of 31.1% by mass.
  • filler 1 (aluminum hydroxide, BW153, manufactured by Nippon Light Metal Co., Ltd., volume average particle diameter: 18 ⁇ m, particle size distribution (D 90 / 30 parts by mass of D 10 ): 12.3) was added to obtain a pressure-sensitive adhesive (1).
  • the particle size distribution (D 90 /D 10 ) of the filler particles is converted into a particle size distribution by measuring the particle size of the filler particles by using a measuring machine (Microtrac) using a laser diffraction scattering method. It is the value obtained by doing.
  • the pressure-sensitive adhesive (1) was applied by a strip coating method using a die coater to a release liner (film binder 75E-0010GT, manufactured by Fujimori Industry Co., Ltd., so that the thickness after drying would be 50 ⁇ m).
  • the pressure-sensitive adhesive layer A-1 was prepared by applying the composition onto the above and drying at 80° C. for 3 minutes. At this time, as shown in FIG. 1, a glueless portion having a width of 10 mm was prepared without applying an adhesive.
  • the pressure-sensitive adhesive layer A-2 was produced in the same manner as the pressure-sensitive adhesive layer A-1 except that the width of the glueless portion was 5 mm.
  • the pressure-sensitive adhesive layer A-3 was prepared in the same manner as the pressure-sensitive adhesive layer A-1 except that the pressure-sensitive adhesive (1) was applied on the release liner with an applicator so that the thickness after drying was 25 ⁇ m.
  • the pressure-sensitive adhesive (2) was obtained in the same manner as the pressure-sensitive adhesive (1) except that the pressure-sensitive adhesive 1 did not contain a filler, and then the pressure-sensitive adhesive layer A-4 was prepared in the same manner as the pressure-sensitive adhesive layer A-1.
  • the pressure-sensitive adhesive layer A-3 was prepared in the same manner as the pressure-sensitive adhesive layer A-1 except that the pressure-sensitive adhesive (1) was applied on a release liner with an applicator so that the thickness after drying was 10 ⁇ m.
  • -Adhesive layer A-6 The pressure-sensitive adhesive (1) is applied onto a release liner by an applicator so that the thickness after drying becomes 50 ⁇ m, and dried at 80° C. for 3 minutes to obtain a pressure-sensitive adhesive layer in which no glue-free portion is formed. Agent layer A-6 was prepared.
  • Examples 1 to 6 and Comparative Examples 1 and 2 The pressure-sensitive adhesive layer and the base material layer manufactured as described above were used in combination shown in Table 1 to manufacture a rectangular pressure-sensitive adhesive tape as shown in FIG. Specifically, after peeling off the release liner of the base material layer, the pressure-sensitive adhesive layers formed on the release liner are attached to both sides of the base material layer, and the pressure is applied at 0.2 MPa to laminate the adhesive tape.
  • the obtained adhesive tape had a total thickness of 200 ⁇ m, a length of 120 mm, a width of 20 mm, and a handle portion at the end of the adhesive tape (length measured along the longitudinal direction of the adhesive tape) was 20 mm. Met.
  • the above-mentioned evaluation was carried out for each of the obtained adhesive tapes, and the results are shown in Table 1.
  • the adhesive tape has a glueless portion on at least one surface on one end side, the breaking elongation of the base material layer is 200 to 3000%, and the breaking strength is 1.5.
  • the adhesive tapes of Examples 1 to 6 having a temperature of about 80 MPa were able to reduce the load on the adhesive tape and prevent tearing even when the adhesive tape was peeled off at an angle with respect to the sticking surface. Further, as can be seen by comparing Examples 1 and 4, it can be seen that the pressure-sensitive adhesive tape is more easily peeled off when the pressure-sensitive adhesive of the pressure-sensitive adhesive layer contains the filler.
  • the adhesive tape of Comparative Example 1 having no glueless portion has a large load when the adhesive tape starts to stretch when the adhesive tape is peeled off at an angle to the sticking surface, and is adhesive.
  • the tape was torn.
  • the adhesive tape of Comparative Example 2 in which the breaking elongation and breaking strength of the base material layer are out of the predetermined ranges when the adhesive tape is peeled off at an angle to the sticking surface, the adhesive tape does not stretch and the load is one. I was torn because I concentrated on the club.
  • a laminated film, an adhesive tape and an adhesive body capable of reducing the load on the adhesive tape and preventing tearing even when the adhesive tape is peeled off at an angle with respect to the sticking surface. be able to.

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

Abstract

The purpose of the present invention is to provide a lamination film capable of preventing tearing, even when an adhesive tape oriented at a certain angle with respect to an affixed surface is to be peeled, by reducing the stress on the adhesive tape. This lamination film is provided with a base material layer and adhesive agent layers disposed on both surfaces of the base material layer. The lamination film is characterized in that: on at least one of the surfaces of the lamination film, a glue-free part in which the adhesive agent layers do not exist; and that the base material layer has a rupture elongation of 200-3000% and a rupture strength of 1.5-80 MPa.

Description

積層フィルム、粘着テープおよび接着体Laminated film, adhesive tape and adhesive
　本発明は、積層フィルム、粘着テープおよび接着体に関する。 The present invention relates to laminated films, adhesive tapes and adhesives.
　粘着テープは、作業性に優れ、且つ、接着信頼性が高いので、接合手段として、ＯＡ機器、ＩＴ・家電製品、自動車等の各産業分野で、部品固定用途や、部品の仮固定用途、製品情報を表示するラベル用途等に広範に使用されている（例えば特許文献１）。 Since the adhesive tape has excellent workability and high adhesion reliability, it can be used as a joining means in various industrial fields such as OA equipment, IT/home appliances, automobiles, etc. for fixing parts, temporarily fixing parts, and products. It is widely used for labels that display information (for example, Patent Document 1).
特開２００１－８９７２６号公報Japanese Unexamined Patent Publication No. 2001-89726
　ところで、近年、環境保護の観点から、これら家電や自動車等の各種の産業分野において、使用済み製品のリサイクル、リユースの要請が高まっている。各種製品をリサイクル、リユースする際には、当該使用済み製品を解体し、製品中の各部品を取り外すこととなるが、各部品を取り外すときには、部品の固定やラベルに使用されている粘着テープを剥離する作業が必要となる。しかし、当該粘着テープは製品中の各所に設けられており、より簡易に除去可能となることにより作業コストの低減が要望されている。
　具体的には、近年の高性能化にともない各種製品において、部品が高密度に実装されるようになってきている。このような製品において、各部品を筐体や他の部品等（以下、単に筐体と称す）に固定する際、図６に示すように、筐体２１と部品２０との間に粘着テープ２２が設けられる。しかし、上述のようにリサイクル等するため製品を解体する場合には、部品２０を取り外すために、当該粘着テープ２２の取手部分を引っ張って粘着テープを剥がすことを要するが、従来では粘着テープを剥がせないことがあった。
　より具体的には、高密度に部品を実装する機器では、例えばゴム基材を有する粘着テープを用いて貼り付けた部品に近接して、他の部材も筐体に取り付けられている。そして、当該他の部材を避けて粘着テープを剥がすためには、当該粘着テープの取手部分を貼付け面に対して高角度（例えば６０°以上）の方向に引っ張って剥がすこととなり、このように高い角度で引っ張ると粘着テープに負荷がかかり、ちぎれることがあった。そして、このように粘着テープを容易に除去できないことにより、作業コストが増大する要因となっていた。 By the way, in recent years, from the viewpoint of environmental protection, demands for recycling and reuse of used products are increasing in various industrial fields such as home appliances and automobiles. When recycling and reusing various products, the used products are disassembled and each part in the product is removed. When removing each part, the adhesive tape used for fixing the parts and labeling is used. Work to peel off is required. However, the pressure-sensitive adhesive tape is provided in various places in the product, and it is desired to reduce the work cost because it can be removed more easily.
Specifically, with the increasing performance in recent years, in various products, parts have been mounted at high density. In such a product, when each component is fixed to a housing or other parts (hereinafter, simply referred to as a housing), as shown in FIG. 6, the adhesive tape 22 is between the housing 21 and the component 20. Is provided. However, when disassembling the product for recycling or the like as described above, in order to remove the part 20, it is necessary to pull the handle portion of the adhesive tape 22 to peel off the adhesive tape, but conventionally, the adhesive tape is peeled off. There was something I couldn't do.
More specifically, in a device for mounting components at high density, other members are also attached to the housing in close proximity to the components attached using, for example, an adhesive tape having a rubber base material. Then, in order to peel off the adhesive tape while avoiding the other members, the handle portion of the adhesive tape is pulled in a direction of a high angle (for example, 60 ° or more) with respect to the sticking surface to peel off, which is high. Pulling at an angle puts a load on the adhesive tape, which could tear it. In addition, since the adhesive tape cannot be easily removed in this manner, it has been a factor of increasing the work cost.
　そこで、本発明は、上記の課題に鑑みてなされた発明であり、上記のように当該粘着テープを貼付け面に対して角度をつけて剥がす際にも、粘着テープへの負荷を低減しちぎれを防止することができる、積層フィルム、粘着テープおよび接着体を提供することを目的とする。 Therefore, the present invention has been made in view of the above problems, and even when the adhesive tape is peeled off at an angle with respect to the sticking surface as described above, the load on the adhesive tape is reduced to prevent tearing. It is an object of the present invention to provide a laminated film, an adhesive tape and an adhesive which can be prevented.
　本発明者らは、上記従来技術の課題を解決するため鋭意検討を行った結果、図６に示すように粘着テープ２２を用いて部品２０を筐体２１等に固定した場合において、粘着テープ２２を貼付け面に対して角度をつけて部品２０から剥がす際、粘着テープ２２の引張を開始したときに、粘着テープ２２の中でも部品２０の角２３付近に貼り付く部分に、その伸び始めに大きな力が加わること、粘着テープ２２の外表面のうちの部品２０の角２３付近に接する部分が、粘着テープの伸び始めに滑らかに伸びると、粘着テープ２２への負荷を低減できること、の知見を得、本願発明に至った。
　すなわち、本願発明は以下の通りである。 As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors have found that when the component 20 is fixed to the housing 21 or the like using the adhesive tape 22 as shown in FIG. When the adhesive tape 22 is pulled from the component 20 at an angle with respect to the attachment surface, when the adhesive tape 22 is pulled, a large force is applied to the portion of the adhesive tape 22 that is attached to the vicinity of the corner 23 of the component 20 at the beginning of its extension. It was found that the load on the adhesive tape 22 can be reduced if the portion of the outer surface of the adhesive tape 22 in contact with the corner 23 of the component 20 extends smoothly at the beginning of the extension of the adhesive tape. The present invention has been achieved.
That is, the invention of the present application is as follows.
〔１〕基材層と、当該基材層の両面に粘着剤層とを備える積層フィルムであって、
　前記積層フィルムの少なくとも一方の表面上に前記粘着剤層が存在しない糊無し部を有し、
　前記基材層は、破断伸度が２００～３０００％であり、破断強度が１．５～８０ＭＰａであることを特徴とする、積層フィルム。
〔２〕前記粘着剤層の粘着剤がフィラーを含有する、上記〔１〕に記載の積層フィルム。
〔３〕基材層と、当該基材層の両面に粘着剤層とを備える粘着テープであって、
　前記粘着テープの１つの端部側の少なくとも一方の表面上に前記粘着剤層が存在しない糊無し部を有し、
　前記基材層は、破断伸度が２００～３０００％であり、破断強度が１．５～８０ＭＰａであることを特徴とする、粘着テープ。
〔４〕前記粘着テープの長手方向に沿って測った前記糊無し部の長さは、０．５～１００ｍｍである、上記〔３〕に記載の粘着テープ。
〔５〕前記粘着剤層の粘着剤がフィラーを含有する、上記〔３〕または〔４〕に記載の粘着テープ。
〔６〕上記〔３〕～〔５〕のいずれかに記載の粘着テープと、当該粘着テープの一方の表面上に貼り付けられた第１被着体と、当該粘着テープの他方の表面上に貼り付けられた第２被着体とを備える接着体であって、
　前記粘着テープのうち前記糊無し部よりも端部側の部分が、当該粘着テープが貼り付けられた第１被着体の第１貼付け面よりも外側に位置し、
　前記糊無し部上に前記第１貼付け面を画定する角が位置することを特徴とする、接着体。 [1] A laminated film provided with a base material layer and adhesive layers on both sides of the base material layer.
It has a glueless portion on at least one surface of the laminated film in which the pressure-sensitive adhesive layer does not exist.
A laminated film, wherein the base material layer has a breaking elongation of 200 to 3000% and a breaking strength of 1.5 to 80 MPa.
[2] The laminated film according to the above [1], wherein the pressure-sensitive adhesive of the pressure-sensitive adhesive layer contains a filler.
[3] An adhesive tape provided with a base material layer and adhesive layers on both sides of the base material layer.
It has a glueless portion on the surface of at least one end side of the adhesive tape in which the adhesive layer is not present.
The adhesive tape, wherein the base material layer has a breaking elongation of 200 to 3000% and a breaking strength of 1.5 to 80 MPa.
[4] The adhesive tape according to the above [3], wherein the length of the glueless portion measured along the longitudinal direction of the adhesive tape is 0.5 to 100 mm.
[5] The adhesive tape according to the above [3] or [4], wherein the adhesive in the pressure-sensitive adhesive layer contains a filler.
[6] On the adhesive tape according to any one of the above [3] to [5], the first adherend attached on one surface of the adhesive tape, and on the other surface of the adhesive tape. An adhesive body comprising a pasted second adherend,
A portion of the adhesive tape on the end side of the adhesive-free portion is located outside the first attaching surface of the first adherend to which the adhesive tape is attached,
An adhesive body, characterized in that an angle defining the first attachment surface is located on the glueless portion.
　本発明は、粘着テープを貼付け面に対して角度をつけて剥がす際にも、粘着テープへの負荷を低減しちぎれを防止することができる、積層フィルム、粘着テープおよび接着体を提供することができる。 The present invention can provide a laminated film, an adhesive tape, and an adhesive that can reduce the load on the adhesive tape and prevent tearing even when the adhesive tape is peeled off at an angle to the sticking surface. it can.
本発明の一実施形態に係る積層フィルムを示す平面図である。It is a top view which shows the laminated film which concerns on one Embodiment of this invention. 図１の積層フィルムの変形例を示す平面図である。It is a top view which shows the modification of the laminated film of FIG. 本発明の一実施形態に係る粘着テープを示す斜視図である。It is a perspective view which shows the adhesive tape which concerns on one Embodiment of this invention. 図３に示す粘着テープの変形例を示す斜視図である。It is a perspective view which shows the modification of the adhesive tape shown in FIG. 被着体を図３の粘着テープを用いて貼り付けた状態を示す、当該粘着テープの断面図である。It is sectional drawing of the said adhesive tape which shows the state which adhered the adherend using the adhesive tape of FIG. 従来の粘着テープを用いて部品を筐体に貼り付けた状態を示す図である。It is a figure which shows the state which the component was attached to the housing using the conventional adhesive tape.
　以下、図面を参照しつつ、本発明の実施形態（以下、「本実施形態」という。）を詳細に説明するが、本発明は本実施形態に限定されるものではない。
《積層フィルム》
　本実施形態の積層フィルム１は、図１に示すように、基材層と、当該基材層の両面に粘着剤層４とを備え、積層フィルム１の少なくとも一方の表面上に粘着剤層４が存在しない糊無し部２を有し、基材層は、破断伸度が２００～３０００％であり、破断強度が１．５～８０ＭＰａであることを特徴とする。
　本実施形態の積層フィルム１によれば、積層フィルム１から得た粘着テープを貼付け面に対して角度をつけて剥がす際にも、粘着テープへの負荷を低減しちぎれを防止することができる。具体的には、積層フィルム１から、粘着テープの１つの端部側の表面上に糊無し部２を有するように切り抜き、次いで、得られた粘着テープを用いて部品等の被着体を例えば筐体等に固定する際、図５に示すように、部品等の角（粘着テープが貼り付けられる貼付け面を画定する角）が当該糊無し部２上に位置するように貼り付ける。そして、このように固定した後、部品を筐体から取り外すために粘着テープを剥がす際、粘着テープを貼付け面に対して角度をつけて剥がすこととなっても、粘着テープの伸び始めに粘着テープの糊無し部２が滑らかに伸びることとなるので、粘着テープへの負荷を低減しちぎれを防止することができる。 Hereinafter, embodiments of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings, but the present invention is not limited to the present embodiment.
《Laminated film》
As shown in FIG. 1, the laminated film 1 of the present embodiment includes a base material layer and pressure-sensitive adhesive layers 4 on both surfaces of the base material layer, and the pressure-sensitive adhesive layer 4 is provided on at least one surface of the laminated film 1. Is present, the base material layer has a breaking elongation of 200 to 3000% and a breaking strength of 1.5 to 80 MPa.
According to the laminated film 1 of the present embodiment, even when the adhesive tape obtained from the laminated film 1 is peeled off at an angle with respect to the sticking surface, the load on the adhesive tape can be reduced and tearing can be prevented. Specifically, the laminated film 1 is cut out so as to have the glueless portion 2 on the surface of one end side of the adhesive tape, and then the adherend such as a part is cut out using the obtained adhesive tape, for example. When fixing to a housing or the like, as shown in FIG. 5, the components are attached so that the corners (the corners that define the attachment surface to which the adhesive tape is attached) are located on the glueless portion 2. Then, after fixing in this way, when the adhesive tape is peeled off to remove the part from the housing, even if the adhesive tape is peeled off at an angle to the sticking surface, the adhesive tape starts to stretch. Since the non-adhesive portion 2 of the above will smoothly expand, it is possible to reduce the load on the adhesive tape and prevent tearing.
　ここで、本実施形態において、積層フィルム１は、図１に示すように、粘着テープを製造するためのフィルムであり、具体的には、積層フィルム１を、例えば図中の破線３で示すように、粘着テープの１つの端部側の表面上に糊無し部２が存在するように切り抜くことで、複数の粘着テープを製造することができる。 Here, in the present embodiment, the laminated film 1 is a film for producing an adhesive tape as shown in FIG. 1, and specifically, the laminated film 1 is shown by a broken line 3 in the drawing, for example. In addition, a plurality of adhesive tapes can be manufactured by cutting out the adhesive tape so that the glueless portion 2 is present on the surface of one end side of the adhesive tape.
　積層フィルム１の表面上の糊無し部２の、積層フィルム１の平面視での形状や大きさは、当該積層フィルム１により作製される粘着テープの形状、大きさ等により変化し得、特に限定されず任意にすることができる。
　一方、糊無し部２は、任意の形状をとることができるが、一の方向（図１の例では、ＴＤ方向）に沿って測った長さが少なくとも０．５ｍｍであり、当該一の方向に直交する方向（図１の例では、ＭＤ方向）に沿って測った長さが少なくとも０．５ｍｍであることが好ましい。また、より好ましくは、糊無し部２は、一の方向に沿って測った長さが少なくとも３ｍｍであり、当該一の方向に直交する方向に沿って測った長さが少なくとも３ｍｍである。
　糊無し部２をこのような大きさにすることにより、本実施形態の積層フィルム１を用いて、所望の粘着テープを作製することができる。
　なお、積層フィルム１は、一の方向の長さが０．５ｍｍ以上であり、当該方向に直交する方向の長さが０．５ｍｍ以上である糊無し部２に対して、当該一の方向に隣接する、少なくとも３０ｍｍの長さの範囲内においては、粘着剤層４が実質的に全面に存在することが好ましい。これにより、積層フィルム１より得られる粘着テープに糊無し部２を設けても、粘着テープの粘着力を確保しやすくすることができる。なお、ここでの「実質的に全面に存在する」とは、糊無し部２に対して一の方向に隣接する、少なくとも３０ｍｍの長さの範囲内に、粘着剤層４でない部分がわずかに点在していても、全体として粘着力が同等であると認められる程度である場合には許容されるものとする。また、より好ましくは、当該範囲内において、全面に粘着剤層４が存在することである。 The shape and size of the adhesive-free portion 2 on the surface of the laminated film 1 in plan view of the laminated film 1 may vary depending on the shape, size, etc. of the adhesive tape produced by the laminated film 1, and is particularly limited. Instead, it can be arbitrary.
On the other hand, the glueless portion 2 can have any shape, but the length measured along one direction (TD direction in the example of FIG. 1) is at least 0.5 mm, and the one direction It is preferable that the length measured along the direction orthogonal to (in the example of FIG. 1, the MD direction) is at least 0.5 mm. Further, more preferably, the glueless portion 2 has a length measured along one direction of at least 3 mm, and a length measured along a direction orthogonal to the one direction is at least 3 mm.
A desired adhesive tape can be produced by using the laminated film 1 of the present embodiment by making the glueless portion 2 have such a size.
The laminated film 1 has a length of 0.5 mm or more in one direction and a length of 0.5 mm or more in a direction orthogonal to the direction with respect to the glueless portion 2 in the one direction. Within the adjacent, at least 30 mm length range, it is preferred that the pressure-sensitive adhesive layer 4 is substantially present over the entire surface. Thereby, even if the adhesive-free portion 2 is provided on the adhesive tape obtained from the laminated film 1, the adhesive force of the adhesive tape can be easily secured. In addition, "substantially present on the entire surface" here means that there is a slight portion other than the adhesive layer 4 within a length range of at least 30 mm, which is adjacent to the glueless portion 2 in one direction. Even if they are scattered, it is permissible if the adhesive strength is considered to be the same as a whole. Further, more preferably, the pressure-sensitive adhesive layer 4 is present on the entire surface within the range.
　本実施形態において、図１に示すように、糊無し部２は、積層フィルム１の表面上に複数あってもよい。例えば、積層フィルム１の平面視で、糊無し部２を複数存在させる場合において、図１に示すようにそれぞれの糊無し部２をＭＤ方向に延在するようにしたり、また、図示は省略するが、ＴＤ方向に延在するようにしたり、さらにＭＤ方向やＴＤ方向に対して傾斜する方向に延在するようにしたりしてもよい。図１に示すように、積層フィルム１の表面において、糊無し部２が延在するよう形成されている場合、図１に示すように、糊無し部２が粘着テープの中でも中央側ではなく、端部側に位置するように、図１中の破線３で示す位置で積層フィルム１を切り出すことにより、複数の所望の粘着テープを製造することができる。また、図１の例では、１つの粘着テープとなる範囲において、糊無し部２よりも端部側の部分に粘着剤層４が存在しており、この範囲を切り出すことにより得られる粘着テープの端部側の部分にも粘着剤層４が存在することとなる。糊無し部２の例えば幅を広くすることにより、積層フィルム１を切り出すことにより得られる粘着テープの端部側の部分に粘着剤層４が存在しないものとすることもできる。
　また、本実施形態において、図２に示すように、積層フィルム１の平面視で、積層フィルム１の表面の糊無し部２を海状にし、粘着剤層４を島状にすることにより、糊無し部２と粘着剤層４とを海島状にすることもできる（なお、逆に糊無し部２を島状、粘着剤層４を海状にすることもできる）。積層フィルム１の粘着剤層４を島状にした場合には、例えば図２中の破線３で示す位置で積層フィルム１を切り出すことにより、複数（図示では３つ以上）の端部を有する粘着テープを得ることができる。
　なお、図１に示す例では、積層フィルム１から矩形状粘着テープを、図２に示す例では、積層フィルム１から３つ以上の端部を有する粘着テープを製造しているが、積層フィルム１から製造される粘着テープの形状および大きさ等は、任意にすることができる。 In the present embodiment, as shown in FIG. 1, a plurality of glueless portions 2 may be provided on the surface of the laminated film 1. For example, when a plurality of glueless portions 2 are present in a plan view of the laminated film 1, each glueless portion 2 may be extended in the MD direction as shown in FIG. 1, or the illustration is omitted. However, it may extend in the TD direction, or may extend in a direction inclined with respect to the MD direction and the TD direction. As shown in FIG. 1, when the glueless portion 2 is formed to extend on the surface of the laminated film 1, as shown in FIG. 1, the glueless portion 2 is not on the center side of the adhesive tape, A plurality of desired adhesive tapes can be manufactured by cutting out the laminated film 1 at the position shown by the broken line 3 in FIG. 1 so as to be located on the end side. Further, in the example of FIG. 1, the adhesive layer 4 is present in a portion on the end side of the non-adhesive portion 2 in the range of one adhesive tape, and the adhesive tape obtained by cutting out this range is The pressure-sensitive adhesive layer 4 also exists on the end side portion. By increasing the width of the glueless portion 2, for example, it is possible that the pressure-sensitive adhesive layer 4 does not exist in the portion on the end side of the pressure-sensitive adhesive tape obtained by cutting out the laminated film 1.
In addition, in the present embodiment, as shown in FIG. 2, when the laminated film 1 is viewed in a plan view, the non-adhesive portion 2 on the surface of the laminated film 1 has a sea-like shape and the adhesive layer 4 has an island-like shape. The non-coated portion 2 and the pressure-sensitive adhesive layer 4 may be formed in a sea-island shape (conversely, the glue-less portion 2 may be formed in an island shape and the pressure-sensitive adhesive layer 4 may be formed in a sea shape). When the pressure-sensitive adhesive layer 4 of the laminated film 1 is formed into an island shape, for example, by cutting out the laminated film 1 at the position indicated by the broken line 3 in FIG. 2, the adhesive has a plurality of (three or more in the drawing) ends. You can get the tape.
In the example shown in FIG. 1, a rectangular adhesive tape is manufactured from the laminated film 1, and in the example shown in FIG. 2, an adhesive tape having three or more ends is manufactured from the laminated film 1. The shape and size of the adhesive tape manufactured from can be arbitrary.
　本実施形態の積層フィルム１において、糊無し部２は、図示の例では積層フィルム１の一方の表面上に形成されているが、他方側の表面上にも、好ましくは積層フィルム１の平面視で一方の表面上の糊無し部２と他方の表面上の糊無し部２が重複するように、より好ましくは同じ位置に、形成することができる。
　また、本実施形態において、糊無し部２とは、積層フィルム１の表面を形成する粘着剤層４が形成されていない部分である。糊無し部２は、積層フィルム１の基材層が露出する部分とすることができるが、粘着剤層の厚さの１０％以下の厚さで粘着剤が存在することは許容されるものとする。 In the laminated film 1 of the present embodiment, the glueless portion 2 is formed on one surface of the laminated film 1 in the illustrated example, but is also preferably on the surface of the other side in a plan view of the laminated film 1. Thus, it is possible to form the glueless portion 2 on one surface and the glueless portion 2 on the other surface so that they overlap each other, more preferably at the same position.
Further, in the present embodiment, the glueless portion 2 is a portion where the pressure-sensitive adhesive layer 4 forming the surface of the laminated film 1 is not formed. The glueless portion 2 can be a portion where the base material layer of the laminated film 1 is exposed, but it is permissible that the adhesive is present at a thickness of 10% or less of the thickness of the adhesive layer. To do.
　ここで、積層フィルム１を構成する基材層、粘着剤層４について以下説明する。
－基材層－
　本実施形態の積層フィルム１は、図５の積層フィルムより得られる粘着テープ１１に示すように、粘着剤層１４の担体としての基材層１３を有している。
　本実施形態における積層フィルム１の基材層は、破断伸度が２００～３０００％であり、破断強度が１．５～８０ＭＰａである。 Here, the base material layer and the pressure-sensitive adhesive layer 4 constituting the laminated film 1 will be described below.
-Base material layer-
The laminated film 1 of the present embodiment has a base material layer 13 as a carrier of an adhesive layer 14, as shown in an adhesive tape 11 obtained from the laminated film of FIG.
The base material layer of the laminated film 1 in the present embodiment has a breaking elongation of 200 to 3000% and a breaking strength of 1.5 to 80 MPa.
　本実施形態における基材層の材料としては、基材層１３が上記の破断伸度および破断強度を有すれば特に限定されないが、例えば、ビニル芳香族ブロック共重合体（Ａ）を含有することが好ましい。基材層の材料に使用できるビニル芳香族ブロック共重合体（Ａ）としては、芳香族ビニル化合物と共役ジエン化合物とのブロック共重合体から選ばれる１種又は２種以上の共重合体が使用でき、前記芳香族ビニル化合物がスチレンであるスチレン系共重合体が好ましい。また、前記共役ジエン化合物としてはイソプレン、ブタジエン、エチレンブチレン、エチレンプロピレンが好ましい。なかでも、前記ブロック共重合体（Ａ）としては、スチレン－イソプレン共重合体、スチレン－ブタジエン共重合体、スチレン－エチレンブチレン共重合体、スチレン－エチレンプロピレン共重合体などのジブロック共重合体、スチレン－イソプレン－スチレン共重合体、スチレン－ブタジエン－スチレン共重合体などのトリブロック共重合体から選ばれる１種又は２種以上の共重合体が好ましく、スチレン－イソプレン共重合体、スチレン－ブタジエン共重合体、スチレン－エチレンブチレン共重合体、スチレン－イソプレン－スチレン共重合体、スチレン－ブタジエン－スチレン共重合体、スチレン－エチレンブチレン共重合体から選ばれる１種又は２種以上の共重合体がより好ましく、スチレン－イソプレン共重合体、スチレン－イソプレン－スチレン共重合体が特に好ましい。 The material of the base material layer in the present embodiment is not particularly limited as long as the base material layer 13 has the above-mentioned elongation at break and breaking strength, but for example, it contains a vinyl aromatic block copolymer (A). Is preferable. As the vinyl aromatic block copolymer (A) that can be used as the material of the base material layer, one or more copolymers selected from block copolymers of an aromatic vinyl compound and a conjugated diene compound are used. A styrene copolymer in which the aromatic vinyl compound is styrene is preferable. Further, as the conjugated diene compound, isoprene, butadiene, ethylene butylene and ethylene propylene are preferable. Among them, the block copolymer (A) is a diblock copolymer such as a styrene-isoprene copolymer, a styrene-butadiene copolymer, a styrene-ethylenebutylene copolymer, a styrene-ethylenepropylene copolymer. One or more copolymers selected from triblock copolymers such as styrene-isoprene-styrene copolymers and styrene-butadiene-styrene copolymers are preferable. Styrene-isoprene copolymers, styrene- One or more copolymers selected from butadiene copolymer, styrene-ethylene butylene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-ethylene butylene copolymer Copolymers are more preferable, and styrene-isoprene copolymer and styrene-isoprene-styrene copolymer are particularly preferable.
　本実施形態における基材層の材料に含まれるビニル芳香族ブロック共重合体（Ａ）の割合は、当該材料を１００質量％とするときに、５０～１００質量％であることが好ましく、６０～１００質量％であることがより好ましく、６５～１００質量％であることが更に好ましく、７０～１００質量％であることがより一層好ましい。当該範囲であることで、スチレン系共重合体の持つ優れた破断伸度や破断応力を得ることができる。また、本実施形態における基材層の材料には、ビニル芳香族ブロック共重合体（Ａ）以外に、ポリオレフィンやポリカーボネートなどの各種熱可塑性樹脂が使用することができ、一種または複数種同時に使用することができる。 The ratio of the vinyl aromatic block copolymer (A) contained in the material of the base material layer in the present embodiment is preferably 50 to 100% by mass, and 60 to 100% by mass when the material is 100% by mass. It is more preferably 100% by mass, further preferably 65 to 100% by mass, and even more preferably 70 to 100% by mass. Within such a range, the excellent breaking elongation and breaking stress of the styrene-based copolymer can be obtained. In addition to the vinyl aromatic block copolymer (A), various thermoplastic resins such as polyolefin and polycarbonate can be used as the material of the base material layer in the present embodiment, and one kind or plural kinds thereof are used at the same time. be able to.
　スチレン系共重合体としては、前記スチレン－イソプレン共重合体とスチレン－イソプレン－スチレン共重合体の全質量に対して、下記化学式（１）で示される構造単位を１３質量％～６０質量％の範囲で有するものを使用することが好ましく、１５～５０質量％の範囲で有するものを使用することがより好ましく、１６～４５質量％の範囲で有するものを使用することが更に好ましく、１７～３５質量％の範囲で有するものを使用することがより一層好ましい。これにより、破断伸度や破断応力が好適な範囲で得られ易くなる。 As the styrene-based copolymer, 13% by mass to 60% by mass of the structural unit represented by the following chemical formula (1) is based on the total mass of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer. It is preferable to use one having a range of 15 to 50% by mass, more preferably one having a range of 15 to 50% by mass, and further preferably to use one having a range of 16 to 45% by mass. It is even more preferable to use one having a mass in the range of%. This makes it easier to obtain the breaking elongation and breaking stress in a suitable range.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　前記スチレン系共重合体としては、構造の異なる共重合体を２種以上含有するものを使用し、スチレン－イソプレン共重合体とスチレン－イソプレン－スチレン共重合体とを組み合わせ含有するものを使用することができる。
　前記スチレン系共重合体は、前記スチレン－イソプレン共重合体とスチレン－イソプレン－スチレン共重合体の合計質量に対して、前記スチレン－イソプレン共重合体を０質量％～８０質量％の範囲で含有するものを使用することが好ましく、０質量％～７０質量％の範囲で含有するものを使用することがより好ましく、０質量％～５０質量％の範囲で含有するものを使用することが更に好ましく、０質量％～３０質量％の範囲で使用することがより一層好ましい。前記範囲とすることで、優れた破断伸度や破断応力を維持しながら熱耐久性との両立が可能となる。 As the styrene-based copolymer, one containing two or more kinds of copolymers having different structures is used, and one containing a combination of a styrene-isoprene copolymer and a styrene-isoprene-styrene copolymer is used. be able to.
The styrene-based copolymer contains the styrene-isoprene copolymer in a range of 0% by mass to 80% by mass based on the total mass of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer. It is more preferable to use those which are contained in the range of 0% by mass to 70% by mass, more preferably those contained in the range of 0% by mass to 50% by mass. It is even more preferable to use it in the range of 0% by mass to 30% by mass. Within the above range, it is possible to achieve both thermal durability while maintaining excellent breaking elongation and breaking stress.
　また、前記スチレン－イソプレン共重合体としては、ゲルパーミエーションクロマトグラフ（ＧＰＣ）を用い標準ポリスチレン換算で測定された重量平均分子量（ゲルパーミエーションクロマトグラフィー、東ソー社製ＳＣ－８０２０、高分子量カラムＴＳＫｇｅｌＧＭＨＨＲ－Ｈ、溶媒：テトラヒドロフラン）が１万～８０万の範囲であるものを使用することが好ましく、３万～５０万の範囲であるものを使用することがより好ましく、５万～３０万の範囲であるものを使用することがよりいっそう好ましい。前記範囲であることで、加熱流動性や溶剤希釈時の相溶性を確保できるため製造工程における作業性が良好でありながら、熱耐久性を備えた粘着テープを得るうえでより好ましい。 Further, as the styrene-isoprene copolymer, the weight average molecular weight (gel permeation chromatography, SC-8020 manufactured by Toso Co., Ltd., high molecular weight column TSKgelGMHR) measured in terms of standard polystyrene using a gel permeation chromatograph (GPC). -H, solvent: tetrahydrofuran) is preferably in the range of 10,000 to 800,000, more preferably in the range of 30,000 to 500,000, and more preferably in the range of 50,000 to 300,000. It is even more preferable to use one that is. Within the above range, the heating fluidity and the compatibility at the time of solvent dilution can be ensured, so that the workability in the manufacturing process is good, and it is more preferable for obtaining an adhesive tape having heat durability.
　前記スチレン系共重合体は、例えば、線状構造や分岐構造または多分岐構造などの単一構造のものを使用することが出来るが、異なる構造のものを混合して使用することも可能である。線状構造が豊富なスチレン系共重合体は本実施形態の積層フィルム１に優れた破断伸度を与える。一方、分岐構造や多分岐構造でありながら分子末端にスチレンブロックを配したものは擬似的架橋構造を取ることができ、優れた凝集力を与えることができる。このため、必要な機械特性にあわせて混合して使用することが好ましい。 The styrene-based copolymer may have a single structure such as a linear structure, a branched structure or a multi-branched structure, but may have a mixture of different structures. .. The styrene-based copolymer rich in linear structure gives the laminated film 1 of the present embodiment an excellent breaking elongation. On the other hand, those having a branched structure or a multi-branched structure with a styrene block arranged at the terminal of the molecule can have a pseudo cross-linked structure and can give excellent cohesive force. For this reason, it is preferable to mix and use it according to required mechanical characteristics.
　前記スチレン－イソプレン－スチレン共重合体の製造方法は特に限定されることは無く、従来既知の製造方法が適用できる。例えば、アニオンリビング重合法によりスチレンブロックおよびイソプレンブロックを逐次重合する方法や、リビング性活性末端を有するブロック共重合体を製造した後にカップリング剤と反応させてカップリングしたブロック共重合体を製造する方法がある。 The method for producing the styrene-isoprene-styrene copolymer is not particularly limited, and conventionally known production methods can be applied. For example, a method of sequentially polymerizing a styrene block and an isoprene block by an anionic living polymerization method, or a block copolymer having a living active terminal is produced and then reacted with a coupling agent to produce a coupled block copolymer. There is a way.
　前記スチレン－イソプレン共重合体の製造方法は特に限定されることは無く、従来既知の製造方法が適用できる。例えば、アニオンリビング重合法によりスチレンブロックおよびイソプレンブロックを逐次重合する方法がある。 The method for producing the styrene-isoprene copolymer is not particularly limited, and conventionally known production methods can be applied. For example, there is a method of sequentially polymerizing a styrene block and an isoprene block by an anionic living polymerization method.
　前記スチレン－イソプレン共重合体とスチレン－イソプレン－スチレン共重合体の混合物の製造方法は特に限定されることは無く、従来既知の製造方法が適用できる。例えば、上記で製造したスチレン－イソプレン共重合体とスチレン－イソプレン－スチレン共重合体を混合して使用する方法がある。また、ひとつの重合工程で同時に混合物として製造することも可能である。より具体的な一態様としては、アニオンリビング重合法により、まず、第一に、重合溶媒中、アニオン重合開始剤を用いてスチレン単量体を重合して、リビング性の活性末端を有するポリスチレンブロックを形成する。次いで、第二に、ポリスチレンブロックのリビング性の活性末端からイソプレンを重合して、リビング性の活性末端を有するスチレン－イソプレンジブロック共重合体を得る。引き続き、第三に、当該リビング性の活性末端を有するスチレン－イソプレンジブロック共重合体の一部とカップリング剤とを反応し、カップリングしたスチレン－イソプレン－スチレンブロック共重合体を形成する。そして、第四に、前記のリビング性の活性末端を有するスチレン－イソプレンジブロック共重合体の残部を重合停止剤で、そのリビング性の活性末端を失活させてスチレン－イソプレンジブロック共重合体を形成させる。 The method for producing the mixture of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer is not particularly limited, and conventionally known production methods can be applied. For example, there is a method in which the styrene-isoprene copolymer produced above and the styrene-isoprene-styrene copolymer are mixed and used. It is also possible to produce them as a mixture at the same time in one polymerization step. As a more specific embodiment, by the anion living polymerization method, first, in a polymerization solvent, a styrene monomer is polymerized using an anionic polymerization initiator to form a polystyrene block having a living active terminal. To form. Then, secondly, isoprene is polymerized from the living active end of the polystyrene block to obtain a styrene-isoprene diene block copolymer having a living active end. Subsequently, thirdly, a part of the styrene-isoprene diene block copolymer having a living active terminal is reacted with a coupling agent to form a coupled styrene-isoprene-styrene block copolymer. And fourthly, the rest of the styrene-isoprene diene block copolymer having a living active end is deactivated with a polymerization terminator to deactivate the living active end of the styrene-isoprene diene block copolymer. To form.
－－粘着付与樹脂－－
　また、本実施形態において、前記基材層には、粘着剤層４との密着性を高めることや耐熱性を高める目的で粘着付与樹脂を使用することができる。中でも、軟化点が８０℃以上の粘着付与樹脂が好適に使用でき、軟化点は９０℃以上であることがより好ましく、１００℃以上であることが更に好ましく、１１０℃以上であることがよりいっそう好ましい。前記軟化点は、ＪＩＳＫ２２０７に規定の方法（乾球式）で測定された値を指す。 －－Adhesive-imparting resin －－
Further, in the present embodiment, a tackifying resin can be used in the base material layer for the purpose of enhancing the adhesiveness with the pressure-sensitive adhesive layer 4 and enhancing the heat resistance. Among them, a tackifier resin having a softening point of 80 ° C. or higher can be preferably used, and the softening point is more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and even more preferably 110 ° C. or higher. preferable. The softening point refers to a value measured by a method (dry-bulb type) specified in JIS K2207.
　前記粘着付与樹脂としては、例えば常温（２３℃）で固体状のものを使用することが好ましく、Ｃ５系石油樹脂、Ｃ５系／Ｃ９系石油樹脂、脂環族系石油樹脂等の石油樹脂を使用することができる。
　前記石油樹脂は、スチレン－イソプレンブロック共重合体やスチレン－イソプレンブロック－スチレン共重合体を構成するポリイソプレン構造と相溶しやすく、その結果、粘着テープの初期接着力と熱耐久性とをより一層向上させることができる。
　前記Ｃ５系石油樹脂としては、脂肪族系石油樹脂を使用することができ、例えば、エスコレッツ１２０２、１３０４、１４０１（東燃化学合同会社製）、ウイングタック９５（グッドイヤー・タイヤ・アンド・ラバー・カンパニー製）、クイントンＫ１００、Ｒ１００、Ｆ１００（日本ゼオン株式会社製）、ピコタック９５、ピコペール１００（理化ハーキュレス製）等を使用することができる。 As the tackifier resin, for example, a solid resin at room temperature (23 ° C.) is preferably used, and petroleum resins such as C5 petroleum resin, C5 / C9 petroleum resin, and alicyclic petroleum resin are used. can do.
The petroleum resin is easily compatible with the polyisoprene structure constituting the styrene-isoprene block copolymer or the styrene-isoprene block-styrene copolymer, and as a result, the initial adhesive strength and heat durability of the pressure-sensitive adhesive tape are improved. It can be further improved.
As the C5 petroleum resin, an aliphatic petroleum resin can be used, for example, Escolets 1202, 1304, 1401 (manufactured by Tonen Chemical Corporation), Wing Tuck 95 (manufactured by Goodyear Tire and Rubber Company). ), Quinton K100, R100, F100 (manufactured by Zeon Corporation), PicoTac 95, Picopel 100 (manufactured by Rika Hercules) and the like can be used.
　前記Ｃ５系／Ｃ９系石油樹脂としては、前記したＣ５系石油樹脂と、Ｃ９系石油樹脂との共重合体を使用することができ、例えば、エスコレッツ２１０１（トーネックス製）、クイントンＧ１１５（日本ゼオン製）、ハーコタック１１４９（理化ハーキュレス製）等を使用することができる。
　前記脂環族系石油樹脂としては、前記したＣ９系石油樹脂に水素添加して得られるが、例えば、エスコレッツ５３００（トーネックス製）、アルコンＰ－１００（荒川化学工業製）、リガライトＲ１０１（理化ファインテク製）等を使用することができる。 As the C5 / C9 petroleum resin, a copolymer of the C5 petroleum resin and the C9 petroleum resin can be used. For example, Escolets 2101 (manufactured by Tonex) and Quinton G115 (manufactured by Zeon Corporation). ), Harcotac 1149 (manufactured by Rika Hercules) and the like can be used.
The alicyclic petroleum resin is obtained by hydrogenating the C9 petroleum resin described above. For example, Escolets 5300 (manufactured by Tonex), Archon P-100 (manufactured by Arakawa Chemical Industries), Rigalite R101 (Rika Fine). Tech) and the like can be used.
　前記粘着付与樹脂としては、前記Ｃ５系石油樹脂、Ｃ５系／Ｃ９系石油樹脂、及び脂環族系石油樹脂以外に、例えば、重合ロジン系樹脂、Ｃ９系石油樹脂、テルペン系樹脂、ロジン系樹脂、テルペン－フェノール樹脂、スチレン樹脂、クマロン－インデン樹脂、キシレン樹脂、フェノール樹脂等を使用することができる。
　なかでも、前記粘着付与樹脂としては、前記Ｃ５系石油樹脂と重合ロジン系樹脂とを組み合わせて使用することが、より一層優れた初期接着性と熱耐久性とを両立するうえで好ましい。 Examples of the tackifier resin include polymerized rosin-based resin, C9-based petroleum resin, terpene-based resin, and rosin-based resin, in addition to the C5-based petroleum resin, C5-based / C9-based petroleum resin, and alicyclic petroleum resin. , Terpene-phenol resin, styrene resin, coumarone-indene resin, xylene resin, phenol resin and the like can be used.
Above all, it is preferable to use the C5 petroleum resin and the polymerized rosin resin in combination as the tackifying resin, in order to achieve both excellent initial adhesiveness and thermal durability.
　前記粘着付与樹脂は、前記スチレン－イソプレン共重合体やスチレン－イソプレン－スチレン共重合体の全量に対して０質量％～１００質量％の範囲で使用することが好ましく、０質量％～７０質量％の範囲で使用することがより好ましく、０質量％～５０質量％の範囲で使用することが更に好ましく、０質量％～３０質量％の範囲で使用することがよりいっそう好ましい。上記範囲で使用することで、粘着剤層４と基材層の界面密着性を高めながら粘着テープの優れた破断伸度や熱耐久性とを両立させ易くなる。 The tackifying resin is preferably used in the range of 0% by mass to 100% by mass, and 0% by mass to 70% by mass, based on the total amount of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer. Is more preferably used in the range of 0% by mass to 50% by mass, further preferably in the range of 0% by mass to 30% by mass. By using it in the above range, it becomes easy to achieve both excellent breaking elongation and thermal durability of the adhesive tape while enhancing the interfacial adhesion between the pressure-sensitive adhesive layer 4 and the base material layer.
－－その他の成分－－
　また、本実施形態において、前記樹脂基材には、特性を損なわない範囲で必要に応じて、その他のポリマー成分、架橋剤、老化防止剤、紫外線吸収剤、充填剤、重合禁止剤、表面調整剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、酸化防止剤、レベリング剤、有機顔料、無機顔料、顔料分散剤、シリカビーズ、有機ビーズなどの添加剤；酸化ケイ素、酸化アルミニウム、酸化チタン、ジルコニア、五酸化アンチモンなどの無機系充填剤などを含有するものを使用することができる。 －－Other ingredients －－
Further, in the present embodiment, the resin substrate, if necessary, other polymer components, a cross-linking agent, an antioxidant, an ultraviolet absorber, a filler, a polymerization inhibitor, a surface adjustment, as long as the characteristics are not impaired. Agents, antistatic agents, antifoaming agents, viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads, etc. Additives; those containing inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide and the like can be used.
－－基材層の特性－－
　前記基材は、その厚さが１０～２４９０μｍであることが好ましく、３０～３００μｍであることがより好ましく、６０～２００μｍであることが更に好ましく、７０μｍ～１５０μｍであることがよりいっそう好ましい。前記基材の厚さが上記範囲であることで、被着体の歪みに対して粘着テープが追従し易く高い接着強度を得易く、粘着テープを引き伸ばしながら剥離する際に必要な応力が大きくなりすぎないため好ましい。 --Characteristics of base layer ---
The base material preferably has a thickness of 10 to 2490 μm, more preferably 30 to 300 μm, further preferably 60 to 200 μm, and further preferably 70 μm to 150 μm. When the thickness of the base material is within the above range, the adhesive tape can easily follow the strain of the adherend and obtain high adhesive strength, and the stress required for peeling while stretching the adhesive tape becomes large. It is preferable because it is not too much.
　また、前記基材層の破断伸度は２００～３０００％であり、６５０～２８００％であることが好ましく、７００～２７００％であることがより好ましく、７５０～２６００％であることがさらに好ましい。前記基材層の破断伸度が前記範囲の下限以上であることで、前記粘着テープが強固に被着体に接着している場合でも粘着テープを剥離する際の粘着テープを引き伸ばすための応力が大きくなり過ぎず、引き剥がし工程においても粘着テープが過剰に伸びすぎることなく容易に引き剥がすことが出来る。また、前記基材層の破断伸度が前記範囲の上限以下であることで粘着テープを剥離する際の粘着テープの引き伸ばし距離が長くなりすぎず小スペースでの作業が可能となるため好ましい。 The breaking elongation of the base material layer is 200 to 3000%, preferably 650 to 2800%, more preferably 700 to 2700%, and further preferably 750 to 2600%. The breaking elongation of the base material layer is at least the lower limit of the range, the stress for stretching the pressure-sensitive adhesive tape when peeling the pressure-sensitive adhesive tape even when the pressure-sensitive adhesive tape is firmly adhered to the adherend It does not become too large, and the adhesive tape can be easily peeled off without being excessively stretched even in the peeling step. Further, it is preferable that the breaking elongation of the base material layer is equal to or less than the upper limit of the above range because the stretching distance of the pressure-sensitive adhesive tape at the time of peeling the pressure-sensitive adhesive tape is not too long and the work can be performed in a small space.
　また、前記基材層の破断強度は１．５～８０ＭＰａであり、２．０～６０ＭＰａであることが好ましく、２．５～５０ＭＰａであることがより好ましく、３．０～４０ＭＰａであることがさらに好ましい。前記基材層の破断強度が前記範囲の下限以上であることで、粘着テープを引き伸ばして剥がす際にも粘着テープが千切れてしまうことが抑制でき、粘着テープを伸長させるための荷重が過剰になり過ぎないため引き剥がしによる剥離作業が容易になる。また、粘着テープを引き伸ばして変形させる際に必要な力は粘着テープの厚みにも依存することになる。例えば、厚みが厚く破断強度が高い粘着テープを引き伸ばして剥離しようとした場合には、十分に引き伸ばすことが出来ず剥離することができない。 The breaking strength of the base material layer is 1.5 to 80 MPa, preferably 2.0 to 60 MPa, more preferably 2.5 to 50 MPa, and further preferably 3.0 to 40 MPa. More preferred. When the breaking strength of the base material layer is at least the lower limit of the above range, it is possible to prevent the adhesive tape from being torn even when the adhesive tape is stretched and peeled off, and the load for stretching the adhesive tape becomes excessive. Since it does not become too much, the peeling work by peeling becomes easy. Further, the force required for stretching and deforming the adhesive tape also depends on the thickness of the adhesive tape. For example, when an adhesive tape having a large thickness and a high breaking strength is stretched to be peeled, it cannot be sufficiently stretched and cannot be peeled.
　前記基材層の２５％伸長時応力は０．１５～１０．０ＭＰａであることが好ましく、０．２５～７．０ＭＰａであることがより好ましく、０．３５～５．０ＭＰａであることが更に好ましく、０．４５～２．０ＭＰａであることがよりいっそう好ましい。粘着テープの２５％伸長時応力が前記範囲にあることで、粘着テープに好適な接着強度を得ることができ、剥離する工程でも比較的容易に引き剥がすことが可能となる。上記範囲を下回る場合、硬質な被着体同士を固定していながら粘着テープのせん断方向への荷重が生じた場合に粘着テープが剥がれてしまう懸念が生じる。また、上記範囲を上回る場合には、粘着テープの引き剥がし工程において、粘着テープを伸長させるために必要な力が過大となってしまう。 The stress at 25% elongation of the base material layer is preferably 0.15 to 10.0 MPa, more preferably 0.25 to 7.0 MPa, and further preferably 0.35 to 5.0 MPa. It is more preferably 0.45 to 2.0 MPa. When the 25% elongation stress of the adhesive tape is within the above range, the adhesive strength suitable for the adhesive tape can be obtained, and the adhesive tape can be peeled off relatively easily even in the peeling step. If it is less than the above range, there is a concern that the adhesive tape may be peeled off when a load is applied to the adhesive tape in the shearing direction while fixing the hard adherends to each other. On the other hand, if it exceeds the above range, the force necessary for extending the adhesive tape in the peeling step of the adhesive tape becomes excessive.
　前記基材層の５０％伸長時応力は０．１５～１０．５ＭＰａであることが好ましく、０．２５～７．５ＭＰａであることがより好ましく、０．３５～５．０ＭＰａであることが更に好ましく、０．５～２．５ＭＰａであることがよりいっそう好ましい。粘着テープの５０％伸長時応力が前記範囲にあることで、粘着テープに好適な接着強度を得ることができ、剥離する工程でも比較的容易に引き剥がすことが可能となる。上記範囲を下回る場合、硬質な被着体同士を固定していながら粘着テープのせん断方向への荷重が生じた場合に粘着テープが剥がれてしまう懸念が生じる。また、上記範囲を上回る場合には、粘着テープの引き剥がし工程において、粘着テープを伸長させるために必要な力が過大となってしまう。 The stress at 50% elongation of the base material layer is preferably 0.15 to 10.5 MPa, more preferably 0.25 to 7.5 MPa, and further preferably 0.35 to 5.0 MPa. It is preferably 0.5 to 2.5 MPa, and even more preferably 0.5 to 2.5 MPa. When the stress at 50% elongation of the pressure-sensitive adhesive tape is within the above range, the adhesive strength suitable for the pressure-sensitive adhesive tape can be obtained, and the adhesive tape can be relatively easily peeled even in the peeling step. If it is less than the above range, the adhesive tape may be peeled off when a load is applied in the shearing direction of the adhesive tape while fixing the hard adherends to each other. On the other hand, if it exceeds the above range, the force necessary for extending the adhesive tape in the peeling step of the adhesive tape becomes excessive.
　前記基材層の５０％伸長時応力は２５％伸長時応力の１００～１６０％であることが好ましく、１０３～１５０％であることがより好ましく、１０５～１４０％であることが更に好ましく、１１０～１３０％であることがよりいっそう好ましい。
粘着テープの５０％伸長時応力が粘着テープの２５％伸長時応力に対して前記範囲にあることで、粘着テープの剥離時に引き剥がすために必要な応力が安定させることが可能となる。 The 50% elongation stress of the base material layer is preferably 100 to 160% of the 25% elongation stress, more preferably 103 to 150%, further preferably 105 to 140%, 110. It is even more preferable that it is ˜130%.
When the 50% elongation stress of the adhesive tape is within the above range with respect to the 25% elongation stress of the adhesive tape, it is possible to stabilize the stress required for peeling when the adhesive tape is peeled off.
　前記基材層の貯蔵弾性率Ｅ’（２３℃）は１．０×１０４～１．０×１０８Ｐａであることが好ましく、５．０×１０４～５．０×１０７Ｐａであることがより好ましく、１．０×１０５～１．０×１０７Ｐａであることが更に好ましく、３．０×１０５～７．０×１０６Ｐａであることがよりいっそう好ましい。基材層の破断点応力が前記範囲にあることで、被着体の歪などに対して追従し易く優れた接着強度が得られ易くなり、粘着テープの寸法安定性も確保することが出来るため好適な貼付作業性が得られる。 The storage elastic modulus E'(23 ° C.) of the base material layer is preferably 1.0 × 10 4 to 1.0 × 10 8 Pa, preferably 5.0 × 10 4 to 5.0 × 10 7 Pa. It is more preferably 1.0 × 10 5 to 1.0 × 10 7 Pa, and even more preferably 3.0 × 10 5 to 7.0 × 10 6 Pa. When the breaking point stress of the base material layer is within the above range, it is easy to follow the strain of the adherend and obtain excellent adhesive strength, and the dimensional stability of the adhesive tape can be ensured. Suitable sticking workability can be obtained.
　前記基材層としては、粘着剤層４との密着性をより一層向上させることを目的として、プライマー層が設けられたもの、サンドブラスト法や溶剤処理法などによる表面の凹凸化処理、コロナ放電処理、クロム酸処理、火炎処理、熱風処理、オゾン処理、紫外線照射処理、酸化処理などの表面処理が施されたものを使用することができる。 As the base material layer, a primer layer is provided for the purpose of further improving the adhesion with the pressure-sensitive adhesive layer 4, surface roughening treatment by a sand blast method or a solvent treatment method, corona discharge treatment , Chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, oxidation treatment and other surface treatments can be used.
　前記基材層の製造方法としては、押し出し成型によるキヤスト法、一軸延伸法、逐次二次延伸法、同時二軸延伸法、インフレーション法、チューブ法、さらに、カレンダー法、溶液法などがある。中でも押し出し成型によるキヤスト法、一軸延伸法、逐次二次延伸法、同時二軸延伸法、インフレーション法、チューブ法による製造方法が好適に使用でき、本実施形態の積層フィルム１に必要な機械的強度に合わせて選択すればよい。 As the method for producing the base material layer, there are a cast method by extrusion molding, a uniaxial stretching method, a sequential secondary stretching method, a simultaneous biaxial stretching method, an inflation method, a tube method, a calender method, a solution method and the like. Among them, the cast method by extrusion molding, the uniaxial stretching method, the sequential secondary stretching method, the simultaneous biaxial stretching method, the inflation method, the tube method can be preferably used, and the mechanical strength required for the laminated film 1 of the present embodiment can be suitably used. It may be selected according to.
　前記基材層は、単層構造、２層や３層またはそれ以上の複層構造であっても良い。複層構造の場合、少なくとも1つの層は前記した樹脂組成を有する層であることで必要な機械特性を発揮させ易いため好ましい。また、例えば、ポリプロピレンなどの熱可塑性樹脂と前記スチレン－イソプレン－スチレン共重合体を共押出する方法で３層構造の基材層を得ることができる。これは、本実施形態の積層フィルム１について、例えば適度な寸法安定性やコシを持たせたい場合には好適な構成として使用できる場合がある。 The base material layer may have a single-layer structure, a double-layer structure, a three-layer structure, or a multi-layer structure of two or more layers. In the case of a multi-layer structure, it is preferable that at least one layer is a layer having the above-mentioned resin composition because it is easy to exhibit necessary mechanical properties. Further, for example, a base material layer having a three-layer structure can be obtained by a method of coextruding a thermoplastic resin such as polypropylene and the styrene-isoprene-styrene copolymer. This may be used as a suitable configuration for the laminated film 1 of the present embodiment, for example, when it is desired to have appropriate dimensional stability and elasticity.
－粘着剤層－
　本実施形態において、粘着剤層４の粘着剤は、特に限定されないが、基材層と良好な密着性を有するものを使用でき、例えば、アクリル系粘着剤、ウレタン系粘着剤、ゴム系粘着剤、シリコーン系粘着剤などが挙げられる。また、本実施形態において、粘着剤層４の粘着剤として水分散性のエマルジョン型粘着剤も使用することができる。
　本実施形態においては、比較的強い粘着力が得やすいことからアクリル系粘着剤が好ましい。 -Adhesive layer-
In the present embodiment, the pressure-sensitive adhesive of the pressure-sensitive adhesive layer 4 is not particularly limited, but one having good adhesion to the base material layer can be used, for example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive. , Silicone-based adhesives and the like. Further, in the present embodiment, a water-dispersible emulsion type pressure-sensitive adhesive can also be used as the pressure-sensitive adhesive of the pressure-sensitive adhesive layer 4.
In the present embodiment, an acrylic pressure-sensitive adhesive is preferable because a relatively strong adhesive force can be easily obtained.
－－アクリル系粘着剤－－
　アクリル系粘着剤としては、特に限定されないが例えば、（メタ）アクリル酸アルキルエステル単量体を単量体単位として含む少なくとも１種のアクリル系重合体を含む。（メタ）アクリル酸アルキルエステル単量体としては、例えばアルキル基の炭素数が２～１４個である（メタ）アクリル酸アルキルエステルであり、例としては、特に限定されないが、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸イソアミル、アクリル酸ヘキシル、アクリル酸オクチル、アクリル酸２－エチルヘキシル、アクリル酸イソオクチル、アクリル酸イソノリル、アクリル酸イソデシル、メタクリル酸ブチル、メタクリル酸ヘキシル、メタクリル酸イソデシル、メタクリル酸ラウリル等が挙げられる。
　なお、本明細書において、「（メタ）アクリル酸アルキルエステル」とはアクリル酸アルキルエステル又はメタクリル酸アルキルエステルを意味する。 --- Acrylic adhesive ---
The acrylic pressure-sensitive adhesive is not particularly limited, but includes, for example, at least one acrylic polymer containing a (meth)acrylic acid alkyl ester monomer as a monomer unit. The (meth)acrylic acid alkyl ester monomer is, for example, a (meth)acrylic acid alkyl ester having an alkyl group with 2 to 14 carbon atoms, and examples thereof include, but are not limited to, ethyl acrylate and acryl. Propyl acrylate, butyl acrylate, isobutyl acrylate, isoamyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isonolyl acrylate, isodecyl acrylate, butyl methacrylate, hexyl methacrylate, methacryl Examples thereof include isodecyl acid acid and lauryl methacrylate.
In addition, in this specification, "(meth)acrylic acid alkyl ester" means acrylic acid alkyl ester or methacrylic acid alkyl ester.
　アクリル系重合体には、側鎖に水酸基、カルボキシル基、アミノ基などの極性基を有するアクリル酸エステルやその他のビニル系単量体を０．１～１５質量％の範囲で共重合することが好ましい。また、アクリル酸単位を２～１０質量％の範囲で共重合することが、粘着性に優れ好ましい。
　これによりこれら単量体由来の構成単位がアクリル系重合体中で架橋点となり、粘着成分の硬さを調整し目的の粘着力を発現させることができる。 The acrylic polymer may be copolymerized with an acrylic acid ester having a polar group such as a hydroxyl group, a carboxyl group, or an amino group in the side chain or another vinyl-based monomer in the range of 0.1 to 15% by mass. preferable. Further, it is preferable to copolymerize the acrylic acid unit in the range of 2 to 10% by mass because of its excellent adhesiveness.
As a result, the structural units derived from these monomers serve as crosslinking points in the acrylic polymer, and the hardness of the pressure-sensitive adhesive component can be adjusted to develop the desired adhesive strength.
　アクリル系重合体は、溶液重合法、塊状重合法、懸濁重合法、乳化重合法、紫外線照射法、電子線照射法によって共重合させることにより得ることができる。アクリル系重合体の重量平均分子量は塗工性と粘着物性を両立するため、４０万～１４０万が好ましく、更に好ましくは、６０万～１２０万である。前記重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）による標準ポリスチレン換算である。測定条件として、カラムはＴＳＫｇｅｌ　ＧＭＨＸＬ［東ソー製］を用い、カラム温度４０℃、溶離液はテトラヒドロフラン、流量は１．０ｍＬ／分とし、標準ポリスチレンはＴＳＫ標準ポリスチレンを用いる。 The acrylic polymer can be obtained by copolymerization by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, an ultraviolet irradiation method, or an electron beam irradiation method. The weight average molecular weight of the acrylic polymer is preferably 400,000 to 1,400,000, and more preferably 600,000 to 1,200,000 in order to achieve both coating properties and adhesive properties. The weight average molecular weight is converted to standard polystyrene by gel permeation chromatography (GPC). As the measurement conditions, TSKgel GMHXL [manufactured by Tosoh] is used as the column, the column temperature is 40 ° C., the eluent is tetrahydrofuran, the flow rate is 1.0 mL / min, and TSK standard polystyrene is used as the standard polystyrene.
　さらに粘着剤の凝集力をあげるために、架橋剤を添加するのが好ましい。架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、キレート系架橋剤等があげられる。特に粘着剤層４を設ける場合は、イソシアネート系架橋剤またはエポキシ系架橋剤を使用するのが好ましい。架橋剤の添加量としては、粘着剤層４のゲル分率が２５～８０％になるよう調整するのが好ましい。さらに好ましいゲル分率は、３０～７０％である。そのなかでも３５～６０％が最も好ましい。ゲル分率が２５％以上であると粘着剤が適度な凝集力をもつため、打鍵試験でズレが生じにくい。一方、ゲル分率が８０％以下であると粘着剤が硬くなりすぎず、基板等の被着体への接着力が良好である。ゲル分率は、養生後の粘着剤層４の組成物をトルエン中に浸漬し、２４時間放置後に残った不溶分の乾燥後の質量を測定し、元の質量に対する百分率で表す。 It is preferable to add a cross-linking agent in order to further increase the cohesive force of the pressure-sensitive adhesive. Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and chelate-based cross-linking agents. In particular, when the pressure-sensitive adhesive layer 4 is provided, it is preferable to use an isocyanate-based cross-linking agent or an epoxy-based cross-linking agent. The amount of the cross-linking agent added is preferably adjusted so that the gel fraction of the pressure-sensitive adhesive layer 4 is 25 to 80%. A more preferred gel fraction is 30-70%. Among them, 35 to 60% is the most preferable. When the gel fraction is 25% or more, the adhesive has an appropriate cohesive force, so that deviation is unlikely to occur in the keystroke test. On the other hand, when the gel fraction is 80% or less, the adhesive does not become too hard and the adhesive force to the adherend such as a substrate is good. The gel fraction is expressed as a percentage with respect to the original mass by measuring the mass of the insoluble matter remaining after immersing the composition of the adhesive layer 4 after curing in toluene and leaving it for 24 hours.
－－ゴム系粘着剤－－
　ゴム系粘着剤としては、天然ゴムやその変性物等の天然ゴム系重合体、合成ゴム系重合体、ビニル芳香族ブロック共重合体（Ｂ）等のゴム系ポリマーの１種または２種以上を含む。
　また、ゴム系粘着剤としては、ビニル芳香族ブロック共重合体（Ｂ）を含有するものが好ましい。なかでも、芳香族ビニル化合物と共役ジエン化合物とのブロック共重合体から選ばれる１種又は２種以上の共重合体が使用でき、前記芳香族ビニル化合物がスチレンであるスチレン系共重合体が好ましい。また、前記共役ジエン化合物としてはイソプレン、ブタジエン、エチレンブチレン、エチレンプロピレンが好ましい。なかでも、前記ブロック共重合体（Ｂ）としては、スチレン－イソプレン共重合体、スチレン－ブタジエン共重合体、スチレン－エチレンブチレン共重合体、スチレン－エチレンプロピレン共重合体などのジブロック共重合体、スチレン－イソプレン－スチレン共重合体、スチレン－ブタジエン－スチレン共重合体などのトリブロック共重合体から選ばれる１種又は２種以上の共重合体が好ましく、スチレン－イソプレン共重合体、スチレン－ブタジエン共重合体、スチレン－エチレンブチレン共重合体、スチレン－イソプレン－スチレン共重合体、スチレン－ブタジエン－スチレン共重合体から選ばれる１種又は２種以上の共重合体がより好ましく、スチレン－イソプレン共重合体、スチレン－イソプレン－スチレン共重合体から選ばれる１種又は２種以上の共重合体が特に好ましい。 ---Rubber adhesive ---
As the rubber-based pressure-sensitive adhesive, one or more of natural rubber-based polymers such as natural rubber and its modified products, synthetic rubber-based polymers, and rubber-based polymers such as vinyl aromatic block copolymer (B) are used. Including.
Further, as the rubber-based pressure-sensitive adhesive, those containing a vinyl aromatic block copolymer (B) are preferable. Among them, one or more copolymers selected from block copolymers of an aromatic vinyl compound and a conjugated diene compound can be used, and a styrene copolymer in which the aromatic vinyl compound is styrene is preferable. .. Further, as the conjugated diene compound, isoprene, butadiene, ethylene butylene and ethylene propylene are preferable. Among them, the block copolymer (B) is a diblock copolymer such as a styrene-isoprene copolymer, a styrene-butadiene copolymer, a styrene-ethylenebutylene copolymer, and a styrene-ethylenepropylene copolymer. , One or more copolymers selected from triblock copolymers such as styrene-isoprene-styrene copolymer and styrene-butadiene-styrene copolymer are preferable, and styrene-isoprene copolymer and styrene- One or more copolymers selected from a butadiene copolymer, a styrene-ethylenebutylene copolymer, a styrene-isoprene-styrene copolymer, and a styrene-butadiene-styrene copolymer are more preferable, and styrene-isoprene. One or more copolymers selected from copolymers and styrene-isoprene-styrene copolymers are particularly preferable.
　前記ビニル芳香族ブロック共重合体としては、前記スチレン－イソプレン共重合体とスチレン－イソプレン－スチレン共重合体の全質量に対して、下記化学式（２）で示される構造単位を１０質量％～８０質量％の範囲で有するものを使用することが好ましく、１２～６０質量％の範囲で有するものを使用することがより好ましく、１５～４０質量％の範囲で有するものを使用することが更に好ましく１７～３５質量％の範囲で有するものを使用することがよりいっそう好ましい。これにより、優れた接着性と耐熱性を得ることができる。 The vinyl aromatic block copolymer contains 10% by mass to 80% by mass of the structural unit represented by the following chemical formula (2) with respect to the total mass of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer. It is preferable to use one having a range of 12 to 60% by mass, more preferably 12 to 60% by mass, and still more preferably one having a range of 15 to 40% by mass. It is even more preferable to use one having a range of about 35% by mass. Thereby, excellent adhesiveness and heat resistance can be obtained.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　前記ビニル芳香族ブロック共重合体としては、構造の異なる共重合体を２種以上含有するものを使用することができ、スチレン－イソプレン共重合体とスチレン－イソプレン－スチレン共重合体とを組み合わせ含有するものを使用することが出来る。
　前記スチレン系樹脂は、前記スチレン－イソプレン共重合体とスチレン－イソプレン－スチレン共重合体の合計質量に対して、前記スチレン－イソプレン共重合体を０質量％～８０質量％の範囲で含有するものを使用することが好ましく、０質量％～７７質量％の範囲で含有するものを使用することが更に好ましく、０質量％～７５質量％の範囲で含有するものを使用することが特に好ましく、０質量％～７０質量％の範囲で使用することがよりいっそう好ましい。前記範囲とすることで、本実施形態の積層フィルム１に優れた接着性能と熱耐久性とを両立させることができる。 As the vinyl aromatic block copolymer, one containing two or more kinds of copolymers having different structures can be used, and a styrene-isoprene copolymer and a styrene-isoprene-styrene copolymer are contained in combination. You can use what you do.
The styrene-based resin contains the styrene-isoprene copolymer in the range of 0% by mass to 80% by mass based on the total mass of the styrene-isoprene copolymer and the styrene-isoprene-styrene copolymer. Is preferably used, more preferably those contained in the range of 0% by mass to 77% by mass, particularly preferably those contained in the range of 0% by mass to 75% by mass, and It is even more preferable to use it in the range of from 70% by mass to 70% by mass. Within the above range, the laminated film 1 of the present embodiment can have both excellent adhesive performance and thermal durability.
　また、前記スチレン－イソプレン共重合体としては、ゲルパーミエーションクロマトグラフ（ＧＰＣ）を用い標準ポリスチレン換算で測定された重量平均分子量（ゲルパーミエーションクロマトグラフィー、東ソー社製ＳＣ－８０２０、高分子量カラムＴＳＫｇｅｌＧＭＨＨＲ－Ｈ、溶媒：テトラヒドロフラン）が１万～８０万の範囲であるものを使用することが好ましく、３万～５０万の範囲であるものを使用することがより好ましく、５万～３０万の範囲であるものを使用することがよりいっそう好ましい。前記範囲であることで、加熱流動性や溶剤希釈時の相溶性を確保できるため製造工程における作業性が良好でありながら、熱耐久性を備えた積層フィルム１を得るうえでより好ましい。 Further, as the styrene-isoprene copolymer, the weight average molecular weight (gel permeation chromatography, SC-8020 manufactured by Toso Co., Ltd., high molecular weight column TSKgelGMHR) measured in terms of standard polystyrene using a gel permeation chromatograph (GPC). -H, solvent: tetrahydrofuran) is preferably in the range of 10,000 to 800,000, more preferably in the range of 30,000 to 500,000, and more preferably in the range of 50,000 to 300,000. It is even more preferable to use one that is. Within the above range, it is more preferable to obtain a laminated film 1 having thermal durability while having good workability in the manufacturing process because heat fluidity and compatibility at the time of solvent dilution can be ensured.
　前記スチレン系共重合体は、例えば、線状構造や分岐構造または多分岐構造などの単一構造のものを使用することが出来るが、異なる構造のものを混合して使用することも可能である。線状構造が豊富なスチレン系樹脂を粘着剤層４に使用した際は本実施形態の積層フィルム１に優れた接着性能を与える。一方、分岐構造や多分岐構造でありながら分子末端にスチレンブロックを配したものは擬似的架橋構造を取ることができ、優れた凝集力を与えることができるため、高い保持力を与えることができる。これらは必要な特性にあわせて混合して使用することが好ましい。 The styrene-based copolymer may have a single structure such as a linear structure, a branched structure or a multi-branched structure, but may have a mixture of different structures. .. When a styrene-based resin having abundant linear structures is used for the pressure-sensitive adhesive layer 4, the laminated film 1 of this embodiment has excellent adhesive performance. On the other hand, a branched structure or a multi-branched structure having a styrene block at the terminal of the molecule can have a pseudo cross-linking structure and can give excellent cohesive force, and thus can give high holding power. .. These are preferably mixed and used according to the required characteristics.
　前記スチレン－イソプレン－スチレン共重合体の製造方法は特に限定されることは無く、従来既知の製造方法が適用でき、前記基材層に関する記載と同様の方法で製造することができる。 The method for producing the styrene-isoprene-styrene copolymer is not particularly limited, and a conventionally known production method can be applied, and the production method can be the same as that described for the base material layer.
－－粘着付与樹脂－－
　さらに本実施形態において、粘着剤層４の粘着力を向上させるため、粘着付与樹脂を添加するのが好ましい。本実施形態の積層フィルム１の粘着剤層４に添加する粘着付与樹脂は、ロジンやロジンのエステル化物等のロジン系樹脂；ジテルペン重合体やα－ピネン－フェノール共重合体等のテルペン系樹脂；脂肪族系（Ｃ５系）や芳香族系（Ｃ９）等の石油樹脂；その他、スチレン系樹脂、フェノール系樹脂、キシレン樹脂等が挙げられる。また、前記アクリル共重合体以外のアクリル樹脂を粘着付与樹脂として添加してもよい。 －－Adhesive-imparting resin －－
Further, in the present embodiment, it is preferable to add a tackifier resin in order to improve the adhesive strength of the pressure-sensitive adhesive layer 4. The tackifying resin added to the pressure-sensitive adhesive layer 4 of the laminated film 1 of the present embodiment is a rosin-based resin such as rosin or an esterification product of rosin; a terpene-based resin such as a diterpene polymer or an α-pinene-phenol copolymer; Examples include petroleum resins such as aliphatic (C5) and aromatic (C9) resins; styrene resins, phenol resins, xylene resins and the like. Further, an acrylic resin other than the acrylic copolymer may be added as a tackifier resin.
　粘着付与樹脂の添加量としては、粘着剤樹脂がアクリル系重合体である場合は、アクリル系重合体１００質量部に対して１０～６０質量部を添加するのが好ましい。接着性を重視する場合は、２０～５０質量部を添加するのが最も好ましい。また、粘着剤樹脂がゴム系の樹脂である場合は、ゴム系の樹脂１００質量部に対して、粘着付与樹脂を８０～１５０質量部添加するのが好ましい。なお、一般的に粘着剤樹脂がシリコーン系の樹脂である場合は、粘着付与樹脂を添加しない。 When the pressure-sensitive adhesive resin is an acrylic polymer, it is preferable to add 10 to 60 parts by mass with respect to 100 parts by mass of the acrylic polymer. When importance is attached to the adhesiveness, it is most preferable to add 20 to 50 parts by mass. When the pressure-sensitive adhesive resin is a rubber-based resin, it is preferable to add 80 to 150 parts by mass of the tackifier resin to 100 parts by mass of the rubber-based resin. In addition, generally, when the pressure-sensitive adhesive resin is a silicone-based resin, the tackifying resin is not added.
　なお、粘着剤がビニル芳香族ブロック共重合体（Ｂ）を含む場合において、粘着剤に含有させることが可能な粘着付与樹脂としては、軟化点が８０℃以上の粘着付与樹脂を使用することが好ましい。これにより、優れた初期接着性と熱耐久性とを備えた粘着剤及び粘着テープを得ることができる。前記軟化点は、ＪＩＳＫ２２０７に規定の方法（乾球式）で測定された値を指す。 When the pressure-sensitive adhesive contains the vinyl aromatic block copolymer (B), a tackifier resin having a softening point of 80° C. or higher can be used as the tackifier resin that can be contained in the pressure-sensitive adhesive. preferable. This makes it possible to obtain a pressure-sensitive adhesive and a pressure-sensitive adhesive tape having excellent initial adhesiveness and thermal durability. The softening point refers to a value measured by a method (dry bulb method) specified in JIS K2207.
　粘着付与樹脂としては、例えば常温（２３℃）で固体状のものを使用することが好ましく、Ｃ５系石油樹脂、Ｃ５系／Ｃ９系石油樹脂、脂環族系石油樹脂等の石油樹脂を使用することができる。前記石油樹脂は、スチレン系樹脂を構成するポリイソプレン構造と相溶しやすく、その結果、粘着剤及び粘着テープの初期接着力と熱耐久性とをより一層向上させることができる。
　前記Ｃ５系石油樹脂としては、脂肪族系石油樹脂を使用することができ、例えば、エスコレッツ１２０２、１３０４、１４０１（東燃化学合同会社製）、ウイングタック９５（グッドイヤー・タイヤ・アンド・ラバー・カンパニー製）、クイントンＫ１００、Ｒ１００、Ｆ１００（日本ゼオン株式会社製）、ピコタック９５、ピコペール１００（理化ハーキュレス製）等を使用することができる。 As the tackifying resin, it is preferable to use a solid resin at room temperature (23° C.), for example, a C5 petroleum resin, a C5/C9 petroleum resin, an alicyclic petroleum resin, or the like. be able to. The petroleum resin is easily compatible with the polyisoprene structure constituting the styrene-based resin, and as a result, the initial adhesive strength and thermal durability of the pressure-sensitive adhesive and pressure-sensitive adhesive tape can be further improved.
As the C5 petroleum resin, an aliphatic petroleum resin can be used, for example, Escolets 1202, 1304, 1401 (manufactured by Tonen Chemical Corporation), Wing Tuck 95 (manufactured by Goodyear Tire and Rubber Company). ), Quinton K100, R100, F100 (manufactured by Zeon Corporation), PicoTac 95, Picopel 100 (manufactured by Rika Hercules) and the like can be used.
　前記Ｃ５系／Ｃ９系石油樹脂としては、前記したＣ５系石油樹脂と、Ｃ９系石油樹脂との共重合体を使用することができ、例えば、エスコレッツ２１０１（トーネックス製）、クイントンＧ１１５（日本ゼオン製）、ハーコタック１１４９（理化ハーキュレス製）等を使用することができる。
　前記脂環族系石油樹脂としては、前記したＣ９系石油樹脂に水素添加して得られるが、例えば、エスコレッツ５３００（トーネックス製）、アルコンＰ－１００（荒川化学工業製）、リガライトＲ１０１（理化ファインテク製）等を使用することができる。 As the C5 / C9 petroleum resin, a copolymer of the C5 petroleum resin and the C9 petroleum resin can be used. For example, Escolets 2101 (manufactured by Tonex) and Quinton G115 (manufactured by Zeon Corporation). ), Harcotac 1149 (manufactured by Rika Hercules) and the like can be used.
The alicyclic petroleum resin is obtained by hydrogenating the C9 petroleum resin described above. For example, Escolets 5300 (manufactured by Tonex), Archon P-100 (manufactured by Arakawa Chemical Industries), Rigalite R101 (Rika Fine). Tech) and the like can be used.
　前記軟化点が８０℃以上の粘着付与樹脂としては、前記Ｃ５系石油樹脂、Ｃ５系／Ｃ９系石油樹脂、及び脂環族系石油樹脂以外に、例えば、重合ロジン系樹脂、Ｃ９系石油樹脂、テルペン系樹脂、ロジン系樹脂、テルペン－フェノール樹脂、スチレン樹脂、クマロン－インデン樹脂、キシレン樹脂、フェノール樹脂等を使用することができる。
　なかでも、前記軟化点が８０℃以上の粘着付与樹脂としては、前記Ｃ５系石油樹脂と重合ロジン系樹脂とを組み合わせ使用することが、より一層優れた初期接着性と熱耐久性とを両立するうえで好ましい。
　前記軟化点が８０℃以上の粘着付与樹脂は、前記スチレン系樹脂の全量に対して３質量％～１００質量％の範囲で使用することが好ましく、５質量％～８０質量％の範囲で使用することがより好ましく、５質量％～８０質量％の範囲で使用することが、より一層優れた接着性と優れた熱耐久性とを両立した粘着剤及び粘着テープを得るうえでより好ましい。 Examples of the tackifier resin having a softening point of 80 ° C. or higher include polymerized rosin-based resin and C9-based petroleum resin, in addition to the C5-based petroleum resin, C5-based / C9-based petroleum resin, and alicyclic petroleum resin. A terpene resin, a rosin resin, a terpene-phenol resin, a styrene resin, a coumarone-indene resin, a xylene resin, a phenol resin or the like can be used.
Among them, as the tackifying resin having a softening point of 80° C. or higher, it is possible to use a combination of the C5 petroleum resin and the polymerized rosin resin in combination to further improve the initial adhesiveness and the thermal durability. It is preferable above.
The tackifier resin having a softening point of 80 ° C. or higher is preferably used in the range of 3% by mass to 100% by mass with respect to the total amount of the styrene-based resin, and is used in the range of 5% by mass to 80% by mass. It is more preferable, and it is more preferable to use it in the range of 5% by mass to 80% by mass in order to obtain an adhesive and an adhesive tape having both further excellent adhesiveness and excellent thermal durability.
　また、定温環境での貼付性や初期接着性を得る目的で、前記軟化点が８０℃以上の粘着付与樹脂と組み合わせて、軟化点が－５℃以下の粘着付与樹脂を使用することも出来る。前記流動点は、ＪＩＳＫ２２６９に規定される方法に準拠した方法で測定された値を指す。
　前記軟化点が－５℃以下の粘着付与樹脂としては、室温で液状の粘着付与樹脂を使用することが好ましい。このような室温で液状の粘着付与樹脂は、公知の上記粘着付与樹脂の中から選択することが好ましい。
　前記軟化点が－５℃以下の粘着付与樹脂としては、例えば、プロセスオイル、ポリエステル、ポリブテン等の液状ゴム等を使用することができ、なかでもポリブテンを使用することが、より一層優れた初期接着性を発現させるうえで好ましい。 Further, in order to obtain the sticking property in the constant temperature environment and the initial adhesiveness, a tackifying resin having a softening point of −5° C. or lower can be used in combination with the tackifying resin having a softening point of 80° C. or higher. The pour point refers to a value measured by a method according to the method defined in JIS K2269.
As the tackifier resin having a softening point of −5 ° C. or lower, it is preferable to use a tackifier resin that is liquid at room temperature. Such a tackifying resin which is liquid at room temperature is preferably selected from the above known tackifying resins.
As the tackifying resin having a softening point of −5° C. or lower, for example, liquid oils such as process oil, polyester, polybutene and the like can be used, and among them, polybutene is more excellent in initial adhesion. It is preferable for expressing the sex.
　前記軟化点が－５℃以下の粘着付与樹脂は、前記粘着付与樹脂の全量に対して０質量％～４０質量％の範囲で使用することが好ましく、０質量％～３０質量％の範囲で使用することがより好ましい。
　前記軟化点が－５℃以下の粘着付与樹脂としては、前記スチレン系樹脂の全量に対して０質量％～４０質量％の範囲で使用することが好ましく、０質量％～３０質量％の範囲で使用することが、初期接着力を向上させ良好に接着することができ、かつ、十分な熱耐久性を得ることができる。 The tackifying resin having a softening point of −5° C. or lower is preferably used in the range of 0% by mass to 40% by mass, and is used in the range of 0% by mass to 30% by mass with respect to the total amount of the tackifying resin. It is more preferable to do so.
The tackifying resin having a softening point of -5°C or lower is preferably used in the range of 0% by mass to 40% by mass, and in the range of 0% by mass to 30% by mass, based on the total amount of the styrene resin. By using it, the initial adhesive strength can be improved, good adhesion can be obtained, and sufficient thermal durability can be obtained.
　前記軟化点が８０℃以上の粘着付与樹脂及び前記軟化点が－５℃以下の粘着付与樹脂の質量割合は、５～５０の範囲であることが好ましく、１０～３０の範囲であることが、優れた初期接着性と優れた保持力とを両立した粘着剤及び粘着テープを得るうえでより好ましい。 The mass ratio of the tackifier resin having a softening point of 80 ° C. or higher and the tackifier resin having a softening point of −5 ° C. or lower is preferably in the range of 5 to 50, and preferably in the range of 10 to 30. It is more preferable for obtaining a pressure-sensitive adhesive and a pressure-sensitive adhesive tape that have both excellent initial adhesiveness and excellent holding power.
　前記スチレン系樹脂と前記粘着付与樹脂とは、［スチレン系樹脂／粘着付与樹脂］で表される質量比が０．５～１０．０となる範囲で組み合わせ使用することが好ましく、０．６～９．０となる範囲で使用することが、初期接着力を向上することができ、かつ、優れた熱耐久性を得ることができる。また、前記質量比［スチレン系樹脂／粘着付与樹脂］は、１よりも大きいことが、例えば被着体の曲面部等に貼付した際に粘着テープの反発力に起因した剥がれを防止（耐反発性）するうえで好ましい。 The styrene resin and the tackifier resin are preferably used in combination in a range where the mass ratio represented by [styrene resin / tackifier resin] is 0.5 to 10.0, and is 0.6 to 10.0. By using it in the range of 9.0, the initial adhesive strength can be improved and excellent thermal durability can be obtained. The mass ratio [styrene-based resin/tackifying resin] is preferably larger than 1 to prevent peeling due to the repulsive force of the adhesive tape when attached to a curved surface of an adherend (repulsion resistance). It is preferable in terms of
－－フィラー粒子－－
　本実施形態において、粘着剤層４の粘着剤は、フィラー粒子を含有することが好ましい。
　粘着剤がフィラー粒子を含むことにより、粘着シートを伸長した際にフィラー粒子が粘着剤層４から露出し、これにより粘着剤層４と被着体との接着面積が小さくなるため、粘着シートの伸長方向が貼付対象（以下、「被着体」と称することもある）の貼付面に対して垂直方向（「９０°方向」と称することもある）等の高角度であっても容易に伸長剥離することができる。 ---Filler particles---
In the present embodiment, the pressure-sensitive adhesive of the pressure-sensitive adhesive layer 4 preferably contains filler particles.
When the pressure-sensitive adhesive contains filler particles, the filler particles are exposed from the pressure-sensitive adhesive layer 4 when the pressure-sensitive adhesive sheet is elongated, and the adhesive area between the pressure-sensitive adhesive layer 4 and the adherend becomes small, so that the pressure-sensitive adhesive sheet Easily extends even if the extension direction is a high angle such as a direction perpendicular to the attachment surface of the attachment target (hereinafter, also referred to as "adherent") (also sometimes referred to as "90° direction") It can be peeled off.
　フィラー粒子の種類としては、特に制限はなく、本発明の効果を損なわない範囲で適宜選択することができ、無機フィラー粒子であってもよく、有機フィラー粒子であってもよい。これらは、１種単独で使用してもよく、２種以上を併用してもよい。 The type of filler particles is not particularly limited and may be appropriately selected within a range that does not impair the effects of the present invention, and may be inorganic filler particles or organic filler particles. These may be used alone or in combination of two or more.
　無機フィラー粒子の具体例としては、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム、酸化ケイ素、酸化マグネシウム、酸化亜鉛、酸化チタン、酸化ジルコニウム、酸化鉄、炭化ケイ素、窒化ホウ素、窒化アルミニウム、窒化チタン、窒化ケイ素、ホウ素化チタン、カーボン、ニッケル、銅、アルミニウム、チタン、金、銀、水酸化ジルコニウム、塩基性炭酸マグネシウム、ドロマイト、ハイドロタルサイト、水酸化カルシウム、水酸化バリウム、酸化スズ、酸化スズの水和物、硼砂、ホウ酸亜鉛、メタホウ酸亜鉛、メタホウ酸バリウム、炭酸亜鉛、炭酸マグネシウム－カルシウム、炭酸カルシウム、炭酸バリウム、酸化モリブデン、酸化アンチモン、赤リン、マイカ、クレイ、カオリン、タルク、ゼオライト、ウォラストナイト、スメクタイト、シリカ（石英、ヒュームドシリカ、沈降性シリカ、無水ケイ酸、溶融シリカ、結晶性シリカ、超微粉無定型シリカ等）、チタン酸カリウム、硫酸マグネシウム、セピオライト、ゾノライト、ホウ酸アルミニウム、硫酸バリウム、チタン酸バリウム、酸化ジルコニア、セリウム、錫、インジウム、炭素、イオウ、テリウム、コバルト、モリブデン、ストロンチウム、クロム、バリウム、鉛、酸化錫、酸化インジウム、ダイヤモンド、マグネシウム、白金、亜鉛、マンガン、ステンレスなどが挙げられる。これらの中でも、水酸化アルミニウム、ニッケルなどが好ましい。
　また、無機フィラーは、粘着剤への分散性向上のため、シランカップリング処理、ステアリン酸処理などの表面処理を施したものであってもよい。 Specific examples of the inorganic filler particles include aluminum hydroxide, magnesium hydroxide, aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, titanium oxide, zirconium oxide, iron oxide, silicon carbide, boron nitride, aluminum nitride, titanium nitride, and the like. Of silicon nitride, titanium boronite, carbon, nickel, copper, aluminum, titanium, gold, silver, zirconium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, tin oxide, tin oxide Hydrate, borax, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium-calcium carbonate, calcium carbonate, barium carbonate, molybdenum oxide, antimony oxide, red phosphorus, mica, clay, kaolin, talc, zeolite , Wollastonite, smectite, silica (quartz, fumed silica, precipitated silica, silicic acid anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.), potassium titanate, magnesium sulfate, sepiolite, zonolite, boro Aluminum oxide, barium sulfate, barium titanate, zirconia oxide, cerium, tin, indium, carbon, sulfur, thallium, cobalt, molybdenum, strontium, chromium, barium, lead, tin oxide, indium oxide, diamond, magnesium, platinum, zinc , Manganese, stainless steel and the like. Among these, aluminum hydroxide, nickel and the like are preferable.
Further, the inorganic filler may be subjected to a surface treatment such as silane coupling treatment or stearic acid treatment in order to improve dispersibility in the pressure-sensitive adhesive.
　有機フィラー粒子の具体例としては、ポリスチレン系フィラー、ベンゾグアナミン系フィラー、ポリエチレン系フィラー、ポリプロピレン系フィラー、シリコーン系フィラー、尿素－ホルマリン系フィラー、スチレン／メタクリル酸共重合体、シリコン系フィラー、フッ素系フィラー、アクリル系フィラー、ポリカーボネート系フィラー、ポリウレタン系フィラー、ポリアミド系フィラー、エポキシ樹脂系フィラー、熱硬化樹脂系中空フィラーなどが挙げられる。 Specific examples of the organic filler particles include polystyrene filler, benzoguanamine filler, polyethylene filler, polypropylene filler, silicone filler, urea-formalin filler, styrene/methacrylic acid copolymer, silicon filler, fluorine filler. , Acrylic filler, polystyrene filler, polyurethane filler, polyamide filler, epoxy resin filler, thermosetting resin hollow filler and the like.
　フィラー粒子の形状としては、特に制限はなく、目的に応じて適宜選択することができ、規則的な形状であってもよく、不規則な形状であってもよい。フィラー粒子の形状の具体例としては、多角形状、立方体状、楕円状、球状、針状、平板状、鱗片状などが挙げられる。これらの形状のフィラー粒子は、１種単独で使用してもよく、２種以上を併用してもよい。また、これらの形状のフィラー粒子が凝集したものであってもよい。これらの中でも、フィラー粒子の形状としては、楕円状、球状、多角形状が好ましい。フィラー粒子形状が、楕円状や球状、多角形状であると、粘着シートを伸長した際に、粘着剤層４の被着体に対する滑りが良好であり、粘着シートの伸長方向が被着体の貼付面に対して９０°方向であっても容易に伸長剥離することができる。 The shape of the filler particles is not particularly limited and may be appropriately selected depending on the intended purpose, and may be a regular shape or an irregular shape. Specific examples of the shape of the filler particles include a polygonal shape, a cubic shape, an elliptical shape, a spherical shape, a needle shape, a flat plate shape, and a scale shape. The filler particles having these shapes may be used alone or in combination of two or more. Further, the filler particles having these shapes may be aggregated. Among these, the shape of the filler particles is preferably elliptical, spherical, or polygonal. When the filler particle shape is elliptical, spherical, or polygonal, the adhesive layer 4 slides well to the adherend when the adhesive sheet is stretched, and the adhesive sheet is stretched in the direction of attachment of the adherend. It can be easily stretched and peeled even in the 90 ° direction with respect to the surface.
　フィラー粒子の粒度分布（Ｄ９０／Ｄ１０）としては、特に制限はなく、目的に応じて適宜選択することができるが、２．５～２０が好ましく、耐衝撃性の点で、２．５～１５がより好ましく、２．５～５が更に好ましい。フィラー粒子の粒度分布（Ｄ９０／Ｄ１０）が前記好ましい範囲内であると、粘着シートの伸長方向が被着体の貼付面に対して９０°方向であっても容易に伸長剥離でき、粘着シートの基材の厚みが薄い場合であっても千切れにくく、かつ、耐衝撃性、せん断接着力、及び割裂接着力に優れる。一方、フィラー粒子の粒度分布（Ｄ９０／Ｄ１０）が、２．５未満であると、粘着シートの伸長方向が被着体の貼付面に対して９０°方向である場合の伸長剥離性を損なうことがあり、２０を超えると、耐衝撃性、せん断接着力、割裂接着力等の接着性能を損なうことがある。
　フィラー粒子の粒度分布（Ｄ９０／Ｄ１０）は、例えば、レーザー回折散乱法を用いた測定機（マイクロトラック）を使用することにより前記フィラー粒子の粒子径を測定して、粒度分布に換算することで得られる。 The particle size distribution (D 90 /D 10 ) of the filler particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2.5 to 20 and is 2.5 in terms of impact resistance. -15 are more preferable, and 2.5-5 are further preferable. When the particle size distribution (D 90 /D 10 ) of the filler particles is within the above-mentioned preferred range, the pressure-sensitive adhesive sheet can be easily stretched and peeled even if the stretching direction is 90° with respect to the sticking surface of the adherend, and the sticking Even when the base material of the sheet is thin, it is difficult to be torn and is excellent in impact resistance, shear adhesive strength, and split adhesive strength. On the other hand, when the particle size distribution (D 90 / D 10 ) of the filler particles is less than 2.5, the stretch peelability when the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the sticking surface of the adherend. If it exceeds 20, the adhesive properties such as impact resistance, shear adhesive strength and split adhesive strength may be impaired.
The particle size distribution (D 90 /D 10 ) of the filler particles is converted into a particle size distribution by measuring the particle size of the filler particles by using a measuring machine (Microtrac) using a laser diffraction scattering method. It can be obtained by.
　前記フィラー粒子の体積平均粒径としては、特に制限はなく、目的に応じて適宜選択することができるが、３μｍ～２５μｍが好ましく、５μｍ～２０μｍがより好ましく、５μｍ～１４μｍが更に好ましい。前記フィラー粒子の体積平均粒径が前記好ましい範囲内であると、前記粘着シートの伸長方向が被着体の貼付面に対して９０°方向であっても容易に伸長剥離でき、前記粘着シートの基材の厚みが薄い場合であっても千切れにくく、かつ、耐衝撃性、せん断接着力、及び割裂接着力に優れる。一方、前記フィラー粒子の体積平均粒径が、３μｍ未満であると、前記粘着シートの伸長方向が被着体の貼付面に対して９０°方向である場合に伸長剥離し難くなることがあり、２５μｍを超えると、耐衝撃性、せん断接着力、割裂接着力等の接着性能を損なうことがある。
　フィラー粒子の体積平均粒径は、例えば、レーザー回折散乱法を用いた測定機（マイクロトラック）を使用することにより測定することができる。 The volume average particle diameter of the filler particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm to 25 μm, more preferably 5 μm to 20 μm, still more preferably 5 μm to 14 μm. When the volume average particle diameter of the filler particles is within the preferable range, the pressure-sensitive adhesive sheet can be easily stretched and peeled even if the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the attachment surface of the adherend. Even when the base material is thin, it is not easily torn, and is excellent in impact resistance, shear adhesive strength, and split adhesive strength. On the other hand, if the volume average particle diameter of the filler particles is less than 3 μm, it may be difficult to stretch and peel the pressure-sensitive adhesive sheet when the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the attachment surface of the adherend. If it exceeds 25 μm, the adhesive performance such as impact resistance, shear adhesive strength, and split adhesive strength may be impaired.
The volume average particle diameter of the filler particles can be measured, for example, by using a measuring machine (Microtrac) using a laser diffraction scattering method.
　フィラー粒子の体積平均粒径と、後述する粘着剤層４の平均厚みとの比率としては、特に制限はなく、目的に応じて適宜選択することができるが、［フィラー粒子の体積平均粒径／粘着剤層の平均厚み］で表される、粘着剤層４の平均厚みに対するフィラー粒子の体積平均粒径との比率が、５／１００以上であることが好ましく、５／１００～９５／１００であることがより好ましく、１０／１００～７５／１００が更に好ましく、２０／１００～６０／１００が特に好ましい。当該比率が好ましい範囲内にあると、粘着シートの伸長方向が被着体の貼付面に対して９０°方向であっても容易に伸長剥離でき、粘着シートの基材の厚みが薄い場合であっても千切れにくい。また、当該比率が前記特に好ましい範囲内にあると、粘着シートの伸長方向が被着体の貼付面に対して９０°方向であっても容易に伸長剥離でき、粘着シートの基材の厚みが薄い場合であっても千切れにくく、かつ、耐衝撃性、せん断接着力、割裂接着力等の接着性能もより優れる点で有利である。一方、当該比率が５／１００未満であると、粘着シートの伸長方向が被着体の貼付面に対して９０°方向である場合の伸長剥離性を損なうことがあり、９５／１００を超えると、耐衝撃性、せん断接着力、割裂接着力等の接着性能を損なうことがある。 The ratio between the volume average particle diameter of the filler particles and the average thickness of the pressure-sensitive adhesive layer 4 described below is not particularly limited and can be appropriately selected according to the purpose. The average thickness of the pressure-sensitive adhesive layer] is preferably 5/100 or more, and the ratio of the volume average particle diameter of the filler particles to the average thickness of the pressure-sensitive adhesive layer 4 is preferably 5/100 to 95/100. More preferably, 10/100 to 75/100 is more preferable, and 20/100 to 60/100 is particularly preferable. When the ratio is within the preferred range, the pressure-sensitive adhesive sheet can be easily stretched and peeled even when the stretching direction is 90° with respect to the attaching surface of the adherend, and the thickness of the base material of the pressure-sensitive adhesive sheet is small. But it's hard to tear. Further, when the ratio is within the particularly preferable range, the adhesive sheet can be easily stretched and peeled even when the stretched direction is 90° with respect to the attaching surface of the adherend, and the thickness of the base material of the adhesive sheet is Even if it is thin, it is not easily torn, and it is advantageous in that it has better adhesive performance such as impact resistance, shear adhesive force, and split adhesive force. On the other hand, when the ratio is less than 5/100, the stretch releasability may be impaired in the case where the stretching direction of the pressure-sensitive adhesive sheet is 90° with respect to the sticking surface of the adherend, and when it exceeds 95/100. , Impact resistance, shear adhesive strength, split adhesive strength, and other adhesive performance may be impaired.
　粘着剤層４におけるフィラー粒子の含有量は、粘着剤１００質量％に対して、９～５０質量％であることが好ましく、１３～３４質量％であることがより好ましく、１７～３０質量％であることがさらに好ましい。粘着剤１００質量％に対するフィラー粒子の含有量が９質量％未満であると、粘着シートの伸長方向が被着体の貼付面に対して９０°方向である場合に伸長剥離できず、また粘着シートの千切れが生じ、粘着シートが伸長せず剥離することができない。また、粘着剤１００質量％に対するフィラー粒子の含有量が５０質量％を超えると、粘着シートが伸長せず、被着体に粘着剤組成物が残留し、耐衝撃性が悪くなり、また、せん断接着力や割裂接着力が弱くなることがある。一方、粘着剤１００質量％に対するフィラー粒子の含有量が９～５０質量％であると、粘着シートの伸長方向が被着体の貼付面に対して９０°方向であっても容易に伸長剥離でき、粘着シートの基材の厚みが薄い場合であっても千切れにくく、かつ、耐衝撃性、せん断接着力、及び割裂接着力に優れる。
　粘着剤層４における前記フィラー粒子の含有量は、粘着剤を調製する際に、適宜調製することができる。 The content of the filler particles in the pressure-sensitive adhesive layer 4 is preferably 9 to 50% by mass, more preferably 13 to 34% by mass, and 17 to 30% by mass with respect to 100% by mass of the pressure-sensitive adhesive. It is more preferable to have. When the content of the filler particles is less than 9% by mass relative to 100% by mass of the pressure-sensitive adhesive, the pressure-sensitive adhesive sheet cannot be stretch-peeled when the stretching direction is 90° to the sticking surface of the adherend, and the pressure-sensitive adhesive sheet The adhesive sheet does not stretch and cannot be peeled off. Further, when the content of the filler particles with respect to 100% by weight of the adhesive is more than 50% by weight, the adhesive sheet does not elongate, the adhesive composition remains on the adherend, the impact resistance is deteriorated, and the shear resistance is reduced. Adhesive strength and split adhesive strength may be weakened. On the other hand, when the content of the filler particles with respect to 100% by mass of the pressure-sensitive adhesive is 9 to 50% by mass, the pressure-sensitive adhesive sheet can be easily stretched and peeled even if the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the sticking surface of the adherend. Even if the thickness of the base material of the pressure-sensitive adhesive sheet is small, it is hard to be torn and is excellent in impact resistance, shear adhesive strength, and split adhesive strength.
The content of the filler particles in the pressure-sensitive adhesive layer 4 can be appropriately adjusted when preparing the pressure-sensitive adhesive.
　粘着剤層４全体の体積に対するフィラー粒子の体積比は、４％～４０％であるが、５％～３０％が好ましく、５％～２０％がより好ましく、５％～１５％が更に好ましい。
い。フィラー粒子の体積比が、４％未満であると、粘着シートの伸長方向が被着体の貼付面に対して９０°方向である場合に伸長剥離できず、また粘着シートの千切れが生じ、粘着シートが伸長せず剥離することができない。また、フィラー粒子の体積比が、４０％を超えると、粘着シートが伸長せず、被着体に粘着剤が残留し、耐衝撃性が悪くなり、また、せん断接着力や割裂接着力が弱くなることがある。一方、フィラー粒子の体積比が４％～４０％であると、粘着シートの伸長方向が被着体の貼付面に対して９０°方向であっても容易に伸長剥離でき、粘着シートの基材の厚みが薄い場合であっても千切れにくく、かつ、耐衝撃性、せん断接着力、及び割裂接着力に優れる。
　粘着剤層４に対するフィラー粒子の体積比は、下記式（１）～（３）より算出することができる。
　　粘着剤樹脂＊１の質量Ａ（ｇ）／粘着剤樹脂＊１の密度Ａ（ｇ／ｃｍ３）＝粘着剤樹脂＊１の体積Ａ（ｃｍ３）　・・・式（１）
　　フィラー粒子の質量Ｂ（ｇ）／フィラー粒子の密度Ｂ（ｇ／ｃｍ３）＝フィラー粒子の体積Ｂ（ｃｍ３）　・・・式（２）
　　フィラー粒子の体積Ｂ（ｃｍ３）／（粘着剤樹脂＊１の体積Ａ（ｃｍ３）＋フィラー粒子の体積Ｂ（ｃｍ３））×１００＝フィラー粒子の体積比（％）　・・・式（３）
　　なお、上記式（１）及び（３）において、＊１で表される粘着剤樹脂は、必要に応じてその他の成分を含んでいてもよい。
　　前記密度は、ＪＩＳ　Ｚ　８８０４に準拠して測定した値である。 The volume ratio of the filler particles to the total volume of the pressure-sensitive adhesive layer 4 is 4% to 40%, preferably 5% to 30%, more preferably 5% to 20%, still more preferably 5% to 15%.
Yes. When the volume ratio of the filler particles is less than 4%, the adhesive sheet cannot be stretch-peeled when the extending direction is 90° to the adherend surface of the adherend, and the adhesive sheet is torn. The adhesive sheet does not stretch and cannot be peeled off. When the volume ratio of the filler particles exceeds 40%, the pressure-sensitive adhesive sheet does not expand, the pressure-sensitive adhesive remains on the adherend, the impact resistance deteriorates, and the shear adhesive strength and split adhesive strength are weakened. May be. On the other hand, when the volume ratio of the filler particles is 4% to 40%, the pressure-sensitive adhesive sheet can be easily stretched and peeled even if the stretch direction of the pressure-sensitive adhesive sheet is 90 ° with respect to the attachment surface of the adherend, and the base material of the pressure-sensitive adhesive sheet can be easily stretched and peeled off. Even if the thickness is small, it is not easily torn, and is excellent in impact resistance, shear adhesive strength, and split adhesive strength.
The volume ratio of the filler particles to the pressure-sensitive adhesive layer 4 can be calculated from the following formulas (1) to (3).
Adhesive resin * 1 mass A (g) / adhesive resin * 1 Density A (g / cm 3) = adhesive resin * 1 volume A (cm 3) · · · Equation (1)
Mass B(g) of filler particles/density B(g/cm 3 ) of filler particles=volume B(cm 3 ) of filler particles Equation (2)
Filler particle volume B (cm 3 ) / (Adhesive resin * 1 volume A (cm 3 ) + Filler particle volume B (cm 3 )) x 100 = Filler particle volume ratio (%) ... 3)
In addition, in the above formulas (1) and (3), the pressure-sensitive adhesive resin represented by *1 may include other components as necessary.
The density is a value measured according to JIS Z 8804.
－－他の成分－－
　また、本実施形態において、必要に応じて、他の公知慣用の添加剤を添加することができる。具体的には、粘着剤の添加剤として、特性を損なわない範囲で必要に応じて、その他のポリマー成分、架橋剤、老化防止剤、紫外線吸収剤、充填剤、重合禁止剤、表面調整剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、酸化防止剤、レベリング剤、有機顔料、無機顔料、顔料分散剤、可塑剤、軟化剤、難燃剤、金属不活性剤、有機ビーズなどの添加剤；酸化ケイ素、酸化アルミニウム、酸化チタン、ジルコニア、五酸化アンチモンなどの無機系充填剤などを含有するものを使用することができる。 ---Other ingredients---
Further, in the present embodiment, other known and commonly used additives can be added, if necessary. Specifically, as an additive for a pressure-sensitive adhesive, other polymer components, cross-linking agents, anti-aging agents, ultraviolet absorbers, fillers, polymerization inhibitors, surface conditioners, as necessary, as long as the properties are not impaired. Antistatic agent, defoaming agent, viscosity modifier, light resistance stabilizer, weather resistance stabilizer, heat resistance stabilizer, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, plasticizer, softener, flame retardant, Additives such as metal deactivators and organic beads; those containing inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be used.
－－粘着剤層の粘着剤の特性－－
　本実施形態において、粘着剤の周波数１Ｈｚでの動的粘弾性スペクトルの損失正接は７０℃下で０．５～０．８であることが好ましい。さらに好ましくは、０．５５～０．７５である。０．５以上であれば耐剥がれ性に優れ、０．８以下であれば、高温時における粘着剤の印刷部への染み出しが少なくなりやすい。 --- Characteristics of the adhesive in the adhesive layer---
In this embodiment, the loss tangent of the dynamic viscoelastic spectrum of the adhesive at a frequency of 1 Hz is preferably 0.5 to 0.8 at 70°C. More preferably, it is 0.55 to 0.75. When it is 0.5 or more, the peeling resistance is excellent, and when it is 0.8 or less, the pressure-sensitive adhesive is less likely to seep to the printed portion at high temperature.
　粘着剤層４の厚みは特に限定されるものではないが、５～１００μｍが好ましく、より好ましくは５～７５μｍであり、さらに好ましくは１０～６０μｍである。この範囲にあることで接着性とテープの薄型化の両立がしやすい。 The thickness of the pressure-sensitive adhesive layer 4 is not particularly limited, but is preferably 5 to 100 μm, more preferably 5 to 75 μm, and further preferably 10 to 60 μm. Within this range, it is easy to achieve both adhesiveness and thin tape.
　本実施形態の積層フィルムの粘着剤層４は、５０％伸長時応力が０．０５～１０．５ＭＰａであるが、０．０７～７．５ＭＰａであることがより好ましく、０．１～５．５ＭＰａであることが更に好ましく、０．１５～３．５ＭＰａであることがよりいっそう好ましい。粘着剤層４の５０％伸長時応力が前記範囲にあることで、粘着テープの優れた接着性と剥離性を得ることが出来る。即ち、被着体の歪などに対して追従し易く優れた接着強度が得られ易く、粘着テープの剥離工程で粘着剤層４が被着体に残留してしまうことが抑制できる。 The pressure-sensitive adhesive layer 4 of the laminated film of the present embodiment has a stress at 50% elongation of 0.05 to 10.5 MPa, more preferably 0.07 to 7.5 MPa, and 0.1 to 5. It is more preferably 5 MPa, and even more preferably 0.15 to 3.5 MPa. When the 50% elongation stress of the pressure-sensitive adhesive layer 4 is within the above range, excellent adhesiveness and peelability of the pressure-sensitive adhesive tape can be obtained. That is, it is possible to easily follow the strain of the adherend and to obtain excellent adhesive strength, and it is possible to prevent the pressure-sensitive adhesive layer 4 from remaining on the adherend in the peeling step of the pressure-sensitive adhesive tape.
　本実施形態の積層フィルム１の粘着剤層４は、貯蔵弾性率Ｇ’（２３℃）が１．０×１０５～１．０×１０７Ｐａであるが、１．０×１０５～８．０×１０６Ｐａが好ましく、１．０×１０５～５．０×１０６Ｐａがより好ましく、１．０×１０５～４．０×１０６Ｐａが更に好ましく、１．０×１０５～３．０×１０６Ｐａが最も好ましい。粘着剤層４の貯蔵弾性率Ｇ’（２３℃）が前記範囲にあることで、粘着テープの優れた接着性と剥離性を得ることが出来、特に、高温や高湿環境下で使用された後にも粘着テープの剥離工程で粘着剤層４が被着体に残留してしまうことが抑制できる。 The adhesive layer 4 of the laminated film 1 of the present embodiment has a storage elastic modulus G′ (23° C.) of 1.0×10 5 to 1.0×10 7 Pa, but 1.0×10 5 to 8 .0 × 10 6 Pa is preferable, 1.0 × 10 5 to 5.0 × 10 6 Pa is more preferable, 1.0 × 10 5 to 4.0 × 10 6 Pa is more preferable, and 1.0 × 10 Most preferably, it is 5 to 3.0×10 6 Pa. When the storage elastic modulus G′ (23° C.) of the pressure-sensitive adhesive layer 4 is in the above range, excellent adhesiveness and releasability of the pressure-sensitive adhesive tape can be obtained, and the adhesive tape was used particularly in a high temperature and high humidity environment. It is possible to prevent the adhesive layer 4 from remaining on the adherend in the process of peeling the adhesive tape later.
　前記粘着剤層４の厚みは、基材層の厚みに対して１／２～１／５００であることが好ましく、１／３～１／３００であることがより好ましく、１／５～１／２００であることが更に好ましく、１／１０～１／５０であることがよりいっそう好ましい。粘着テープの粘着剤層４と基材層の厚み比率が上記範囲にあることで、粘着テープの優れた接着性と剥離性を得ることが出来る。本実施形態の積層フィルム１において、粘着剤層４の凝集力は基材層の凝集力よりも低くなるため、上記範囲よりも粘着剤層４が厚い場合には、粘着テープの剥離工程で粘着剤層４のみが被着体に残存してしまう可能性がある。また、上記範囲よりも粘着剤層４が薄い場合には、被着体の表面が凹凸形状などの場合に粘着剤層４が追従できずに顕著に接着強度が低下してしまう懸念がある。 The thickness of the pressure-sensitive adhesive layer 4 is preferably 1/2 to 1/500, more preferably 1/3 to 1/300, and 1/5 to 1/300 with respect to the thickness of the base material layer. It is more preferably 200, and even more preferably 1/10 to 1/50. When the thickness ratio of the pressure-sensitive adhesive layer 4 and the base material layer of the pressure-sensitive adhesive tape is within the above range, excellent adhesiveness and peelability of the pressure-sensitive adhesive tape can be obtained. In the laminated film 1 of the present embodiment, the cohesive force of the pressure-sensitive adhesive layer 4 becomes lower than the cohesive force of the base material layer. Therefore, when the pressure-sensitive adhesive layer 4 is thicker than the above range, the pressure-sensitive adhesive tape is adhered in the peeling step. Only the agent layer 4 may remain on the adherend. When the pressure-sensitive adhesive layer 4 is thinner than the above range, there is a concern that the pressure-sensitive adhesive layer 4 cannot follow when the surface of the adherend is uneven and the adhesive strength is significantly reduced.
　本実施形態の積層フィルム１に使用する粘着剤層４の破断点応力は、０．５～２５．０ＭＰａであることが好ましく、０．８～２０．０ＭＰａであることがより好ましく、１．０～１７．０ＭＰａであることが更に好ましく、１．２～１５．０ＭＰａであることがよりいっそう好ましい。前記粘着剤層４の破断点応力が前記範囲にあることで、優れた粘着性が発揮でき、本実施形態の積層フィルム１を引き伸ばして剥離する際に被着体上に粘着剤成分が残留し難いため好ましい。 The stress at break of the pressure-sensitive adhesive layer 4 used in the laminated film 1 of the present embodiment is preferably 0.5 to 25.0 MPa, more preferably 0.8 to 20.0 MPa, and 1.0 It is more preferably ˜17.0 MPa, even more preferably 1.2 to 15.0 MPa. When the stress at break of the pressure-sensitive adhesive layer 4 is in the above range, excellent adhesiveness can be exhibited, and the pressure-sensitive adhesive component remains on the adherend when the laminated film 1 of the present embodiment is stretched and peeled off. It is difficult and preferable.
－積層フィルムの製造方法－
　本実施形態の積層フィルム１は、特に限定されなく例えば、公知の方法により製造することができる。具体的には、積層フィルム１は、離型フィルム（離型ライナー）の表面に粘着剤を塗布し乾燥等することによって、離型フィルムの両面の粘着剤層（即ち、粘着剤が形成された離型フィルムを２枚作製する）を形成する。この際、少なくとも一方の離型フィルムの表面上に粘着剤層を形成する際には、例えばグラビア印刷法やダイコート法やコンマコート法により、離型フィルム上に粘着剤を塗布しない部分を形成して、粘着剤層中に糊無し部２を形成する。次いで、準備した基材層の両表面に対し、上記の離型フィルムを有する状態の粘着剤層を貼り合わせ、必要に応じて加圧等することで積層フィルム１を得ることができる。 -Manufacturing method of laminated film-
The laminated film 1 of the present embodiment is not particularly limited and can be produced, for example, by a known method. Specifically, in the laminated film 1, a pressure-sensitive adhesive layer is applied to the surface of a release film (release liner) and dried to form a pressure-sensitive adhesive layer on both sides of the release film (that is, the pressure-sensitive adhesive is formed). Two release films are prepared). At this time, when forming the pressure-sensitive adhesive layer on the surface of at least one of the release films, for example, by a gravure printing method, a die coating method or a comma coating method, a portion not coated with the pressure-sensitive adhesive is formed on the release film. Then, the glueless portion 2 is formed in the adhesive layer. Next, the laminated film 1 can be obtained by laminating the pressure-sensitive adhesive layer having the above-mentioned release film on both surfaces of the prepared base material layer and applying pressure or the like as necessary.
　本実施形態の積層フィルム１において、上記の製造方法に記載したように、粘着剤層４の保護のため離型フィルムが積層されていてもよい。離型フィルムとしては、特に限定されないが例えば、ポリエチレン、ポリプロピレン、ポリエステルフィルムなどの合成樹脂フィルム、紙、不織布、布、発泡シートや金属箔、およびこれらのラミネート体などの基材層の少なくとも片面または両面に、粘着剤からの剥離性を高めるためのシリコーン系処理、長鎖アルキル系処理、フッ素系処理などの剥離処理が施されたものを使用することができる。 In the laminated film 1 of the present embodiment, a release film may be laminated for protecting the pressure-sensitive adhesive layer 4, as described in the above manufacturing method. The release film is not particularly limited, but for example, at least one side of a synthetic resin film such as polyethylene, polypropylene, polyester film, paper, non-woven fabric, cloth, foam sheet or metal foil, and a base material layer such as a laminate thereof or It is possible to use those whose both surfaces have been subjected to a release treatment such as a silicone-based treatment, a long-chain alkyl-based treatment, or a fluorine-based treatment for enhancing the releasability from the adhesive.
－積層フィルムの特性－
　本実施形態の積層フィルム１は、その総厚さが５０～３０００μｍであることが好ましく、より好ましくは７０～５００μｍであり、１００～３００μｍであることがさらに好ましい。 -Characteristics of laminated film-
The laminated film 1 of the present embodiment preferably has a total thickness of 50 to 3000 μm, more preferably 70 to 500 μm, and even more preferably 100 to 300 μm.
　本実施形態の積層フィルム１は、後述の実施例に記載の方法により測定した粘着力が１～５０Ｎ／２０ｍｍであることが好ましく、より好ましくは１０～３０Ｎ／２０ｍｍであり、さらに好ましくは１５～２５Ｎ／２０ｍｍである。上記範囲にすることで、解体時のテープのちぎれにくさと粘着性を両立しやすい。 The laminated film 1 of the present embodiment preferably has an adhesive strength of 1 to 50 N / 20 mm, more preferably 10 to 30 N / 20 mm, still more preferably 15 to 20 mm, as measured by the method described in Examples described later. It is 25N / 20mm. When the content is in the above range, it is easy to achieve both good tear resistance and adhesiveness at the time of disassembling.
　《粘着テープ》
　本実施形態の粘着テープ１１は、図３、５に示すように、基材層１３と、当該基材層１３の両面に粘着剤層１４とを備えている。また、粘着テープ１１は、粘着テープ１１の１つの端部側の少なくとも一方の表面上に粘着剤層１４が存在しない糊無し部１２を有し、基材層１３は、破断伸度が２００～３０００％であり、破断強度が１．５～８０ＭＰａである。本実施形態の粘着テープ１１は、このような構成を有することにより、粘着テープ１１を貼付け面に対して角度をつけて剥がす際にも、粘着テープ１１への負荷を低減しちぎれを防止することができる。 "Adhesive tape"
As shown in FIGS. 3 and 5, the pressure-sensitive adhesive tape 11 of the present embodiment includes a base material layer 13 and pressure-sensitive adhesive layers 14 on both surfaces of the base material layer 13. Further, the adhesive tape 11 has a glueless portion 12 on which the adhesive layer 14 does not exist on at least one surface of the adhesive tape 11 on one end side, and the base material layer 13 has a breaking elongation of 200 to It is 3000% and the breaking strength is 1.5 to 80 MPa. By having such a configuration, the adhesive tape 11 of the present embodiment reduces the load on the adhesive tape 11 and prevents tearing even when the adhesive tape 11 is peeled off at an angle with respect to the sticking surface. You can
　ここで、本実施形態の粘着テープ１１において、その形状は、粘着テープ１１を貼り付ける対象によって任意にすることができるが、例えば、図３に示すように、端部を２つ以上有する形状とすることが好ましい。具体的には、粘着テープ１１が、粘着テープ１１中の１つの端部を構成する矩形状部分を、粘着テープ１１の端部の数分有し、それぞれの矩形状部分の一方側が粘着テープ１１の中央側に向き、それぞれの他方側（端部となる側）が粘着テープ１１の外側に向くことで、粘着テープ１１について端部を２つ以上有する形状とすることができる。より具体的には、粘着テープ１１の端部が２つである場合には、２つの矩形状部分の一方側同士がつながり合うことで２つの矩形部分が一続きになり、図３のように全体として直線状となる（この場合、全体としても矩形となる）。また、端部が３つ以上である場合には、矩形状部分の一方側を粘着テープ１１の中央部分に向けてそれぞれつなげ、他方側を中央部分から外側に向けて延びる（広がる）形状とすることで、例えばＹ字状（図４）などの形状とすることができる。なお、粘着テープ１１の上記の矩形状部分は、厳密に矩形である必要はなく、全体として一方の方向に長い形状となっていれば湾曲していてもよい。また、粘着テープ１１全体の形状としても湾曲していたり、折れ曲がっていたりしてもよい。さらに、粘着テープ１１の幅は長手方向で変化してもよい。 Here, in the pressure-sensitive adhesive tape 11 of the present embodiment, its shape can be arbitrary depending on the object to which the pressure-sensitive adhesive tape 11 is attached, but for example, as shown in FIG. 3, a shape having two or more end portions is used. It is preferable to do so. Specifically, the adhesive tape 11 has rectangular portions forming one end portion of the adhesive tape 11 by the number of the end portions of the adhesive tape 11, and one side of each rectangular portion has the adhesive tape 11 thereon. The adhesive tape 11 can have a shape having two or more end portions by facing the center side and the other side (the side that becomes the end portion) toward the outside of the adhesive tape 11. More specifically, when the adhesive tape 11 has two end portions, the two rectangular portions are connected by connecting one side of the two rectangular portions, and as shown in FIG. It becomes linear as a whole (in this case, it becomes rectangular as a whole). When there are three or more end portions, one side of the rectangular portion is connected toward the central portion of the adhesive tape 11, and the other side is formed to extend (spread) from the central portion toward the outside. This makes it possible to form a shape such as a Y shape (FIG. 4). The above-mentioned rectangular portion of the adhesive tape 11 does not need to be strictly rectangular, and may be curved as long as it has a shape elongated in one direction as a whole. Further, the shape of the entire adhesive tape 11 may be curved or bent. Further, the width of the adhesive tape 11 may change in the longitudinal direction.
　本実施形態において、粘着テープ１１は、図３に示すように、粘着テープ１１の１つの端部側の少なくとも一方の表面上に糊無し部１２を有している。具体的には、図示の粘着テープ１１は、２つの端部を有しており、そのうち１つの端部付近（端部よりも中央側）の部分に糊無し部１２が形成されている。なお、具体的な、糊無し部１２が形成される端部の端からの距離は、粘着テープ１１を貼り付ける対象によって任意にすることができる。このように糊無し部１２を端より離間して形成することにより端部側を、粘着テープ１１を剥がす際の取手部分とすることができる。また、図示の例では複数の端部のうち１つの端部付近に糊無し部１２を設けているが、複数の端部のうち一部の端部付近に、または複数の端部のうちの全ての端部付近に、糊無し部１２を設けることもできる。 In the present embodiment, as shown in FIG. 3, the adhesive tape 11 has a glueless portion 12 on at least one surface of the adhesive tape 11 on one end side. Specifically, the illustrated adhesive tape 11 has two end portions, and a glueless portion 12 is formed in a portion near one end portion (center side from the end portion). The specific distance from the end of the end where the glueless portion 12 is formed can be arbitrarily set depending on the target to which the adhesive tape 11 is attached. By forming the glueless portion 12 away from the end in this way, the end portion side can be used as a handle portion when the adhesive tape 11 is peeled off. Further, in the illustrated example, the glueless portion 12 is provided near one end of the plurality of end portions, but near the end of some of the plurality of end portions or of the plurality of end portions. Glueless portions 12 can be provided near all the ends.
　本実施形態の粘着テープ１１において、糊無し部１２は、粘着テープ１１の表面上に、幅方向（長手方向に直交する方向）の一方の端（縁）から他方の端（縁）まで横切るように形成されている。また、糊無し部１２は、図示の例では粘着テープ１１の一方の表面上に形成されているが、他方側の表面上にも、同様に端部付近に、好ましくは粘着テープ１１の平面視で一方の表面上の糊無し部１２と他方の表面上の糊無し部１２が重複するように、より好ましくは同じ範囲に、形成することができる。 In the adhesive tape 11 of the present embodiment, the glueless portion 12 crosses the surface of the adhesive tape 11 from one end (edge) in the width direction (direction orthogonal to the longitudinal direction) to the other end (edge). Is formed in. Further, the glueless portion 12 is formed on one surface of the adhesive tape 11 in the illustrated example, but also on the other surface, similarly in the vicinity of the end portion, preferably in a plan view of the adhesive tape 11. Thus, it is possible to form the adhesive-free portion 12 on one surface and the adhesive-free portion 12 on the other surface so as to overlap each other, more preferably in the same range.
　ここで、本実施形態の粘着テープ１１による作用効果を説明する。
　従来、高密度に部品を実装する機器では、粘着テープを用いて貼り付けた部品に近接して、他の部材も筐体に取り付けられていた。そして、当該他の部材を避けて粘着テープを剥がすためには、当該粘着テープの取手部分を貼付け面に対して角度をつけて引っ張って剥がすこととなり、粘着テープに負荷がかかり、ちぎれることがあった。
　これに対して、本実施形態の粘着テープ１１を用いて部品を筐体等に固定する場合において、当該粘着テープ１１の糊無し部１２（特に、糊無し部１２のなかでも、粘着テープ１１の端部側）が、部品の貼付け面のうち、貼付け面を区画する角に隣接する部分に位置するように貼り付けることで、粘着テープ１１を貼付け面に対して角度をつけて部品から剥がす際、粘着テープ１１の中でも部品の角付近に貼り付く部分（糊無し部１２に相当）に加わる、その伸び始めの大きな力を、糊無し部１２が緩和することができる。したがって、粘着テープ１１への負荷を低減しちぎれを防止することができる。 Here, the function and effect of the adhesive tape 11 of the present embodiment will be described.
Conventionally, in a device in which components are mounted at high density, other members are also attached to the housing in the vicinity of the components attached using an adhesive tape. Then, in order to peel off the adhesive tape while avoiding the other members, the handle portion of the adhesive tape is pulled at an angle with respect to the sticking surface and peeled off, which may cause a load on the adhesive tape and may be torn off. It was
On the other hand, when the component is fixed to the housing or the like using the adhesive tape 11 of the present embodiment, the adhesive tape 11 has a glueless portion 12 (particularly, among the glueless portions 12, the adhesive tape 11 When the adhesive tape 11 is peeled from the component at an angle with respect to the attachment surface by attaching the adhesive tape 11 such that the end side) is positioned at a portion of the attachment surface of the component that is adjacent to a corner that defines the attachment surface. The adhesive-free portion 12 can relieve a large force at the beginning of elongation applied to the portion (corresponding to the glue-less portion 12) of the adhesive tape 11 that sticks to the vicinity of the corner of the component. Therefore, the load on the adhesive tape 11 can be reduced and tearing can be prevented.
　ところで、本実施形態の粘着テープ１では、糊無し部１２は、上述した本発明の実施形態に係る積層フィルム１の糊無し部２と同様にすることができる。粘着テープにおける糊無し部１２の大きさは、任意にすることができるが、糊無し部１２は、長手方向に沿って測った長さが０．５～１００ｍｍであることが好ましく、より好ましくは１～５０ｍｍであり、さらに好ましくは１０～３０ｍｍである。当該長さを０．５ｍｍ以上にすることにより、糊無し部１２を部品の角に合わせて貼り合わせしやすくなるとともに、粘着テープ１１を取り剥がす際、粘着テープ１１の取手部分を角度をつけて引っ張っても、粘着テープ１１への負荷が低減され、ちぎれを有効に防止することができる。
　また、粘着テープ１１の取手部分を角度をつけて引っ張る際、粘着テープ１１の引張を開始したときに、粘着テープ１１の中でも部品の角付近に貼り付く部分に、その伸び始めにより大きな力が加わることから、糊無し部１２の長さは、粘着テープ１１の伸び始めに剥離しやすくするのに足りる長さがあればよい。そして、糊無し部１２を長手方向に沿って測った長さは１００ｍｍ以下とすることにより、粘着テープ１１の粘着性を維持しやすい。また、当該長さを１００ｍｍ以下にすることにより、糊無し部１２が大きくなりすぎず、粘着テープ１１の粘着性への影響を抑えることができる。 By the way, in the adhesive tape 1 of the present embodiment, the glueless portion 12 can be the same as the glueless portion 2 of the laminated film 1 according to the embodiment of the present invention described above. The size of the glueless portion 12 in the adhesive tape can be arbitrary, but the length of the glueless portion 12 measured along the longitudinal direction is preferably 0.5 to 100 mm, and more preferably. It is 1 to 50 mm, more preferably 10 to 30 mm. By setting the length to 0.5 mm or more, the glueless portion 12 can be easily attached by aligning with the corners of the parts, and when the adhesive tape 11 is peeled off, the handle portion of the adhesive tape 11 is angled. Even if it is pulled, the load on the adhesive tape 11 is reduced, and tearing can be effectively prevented.
Further, when the handle portion of the adhesive tape 11 is pulled at an angle, when pulling of the adhesive tape 11 is started, a large force is applied to the portion of the adhesive tape 11 that sticks near the corner of the component due to the start of its extension. Therefore, the length of the glueless portion 12 may be sufficient to facilitate the peeling of the adhesive tape 11 at the beginning of its extension. The adhesiveness of the adhesive tape 11 can be easily maintained by setting the length of the adhesive-free portion 12 along the longitudinal direction to 100 mm or less. Further, by setting the length to 100 mm or less, the glueless portion 12 does not become too large, and the influence on the adhesiveness of the adhesive tape 11 can be suppressed.
　また、本実施形態の粘着テープ１１では、上述のように粘着テープ１１の端部、具体的には糊無し部１２よりも端部側を取手部分とすることができ、当該取手部分には、後述するように、粘着テープ１１の表面にフィルム１５（剥離処理をしていない）を貼り合わせたり、または、粘着剤層１４を形成しないようにしたりすることができる。取手部分において糊無し部１２と同様に粘着剤層１４を形成しないようにする場合には、上記の好ましい糊無し部１２の、長手方向に沿って測った長さは、当該取手部分の長さを加えた長さとすることができる。
　当該フィルム１５の材質としては、セロファン、ポリエチレン、ポリプロピレン、ナイロン、ポリスチレン、ポリイミド、ポリエステル、テトラフルオロエチレン等があげられる。そのなかでも、安価で加工性に優れるポリエステルフィルムや、滑り性に優れるテトラフルオロエチレンが好ましい。 Further, in the adhesive tape 11 of the present embodiment, as described above, the end portion of the adhesive tape 11, specifically, the end portion side of the adhesive-free portion 12 can be used as the handle portion, and the handle portion has a handle portion. As will be described later, the film 15 (which has not been subjected to the peeling treatment) may be attached to the surface of the adhesive tape 11, or the adhesive layer 14 may not be formed. When the pressure-sensitive adhesive layer 14 is not formed on the handle portion as in the case of the glueless portion 12, the length of the preferable glueless portion 12 measured along the longitudinal direction is the length of the handle portion. The length can be added.
Examples of the material of the film 15 include cellophane, polyethylene, polypropylene, nylon, polystyrene, polyimide, polyester, tetrafluoroethylene and the like. Among them, polyester film, which is inexpensive and has excellent workability, and tetrafluoroethylene, which has excellent slipperiness, are preferable.
　また、粘着テープ１１の幅は、任意にすることができるが、特に粘着テープ１１の糊無し部１２が形成された端部は、幅方向に沿って測った長さが０．５～１００ｍｍであることが好ましく、より好ましくは１０～５０ｍｍである。
　当該長さが、０．５～１００ｍｍであることにより、粘着テープ１１の粘着性を確保しつつ使用しやすい大きさとすることができる。
　また、粘着テープ１１全体の長さは、その貼り合わせる対象によって任意にすることができる。 The width of the adhesive tape 11 can be made arbitrary, but in particular, the end portion of the adhesive tape 11 on which the glueless portion 12 is formed has a length measured along the width direction of 0.5 to 100 mm. It is preferably, and more preferably 10 to 50 mm.
When the length is 0.5 to 100 mm, the size of the adhesive tape 11 can be made easy to use while ensuring the adhesiveness.
Further, the length of the entire adhesive tape 11 can be arbitrarily set depending on the object to be attached.
　なお、粘着テープ１１の糊無し部１２以外の構成、具体的には、粘着剤層、基材層等は、積層フィルムの粘着剤層、基材層と同様にすることができる。 The structure of the adhesive tape 11 other than the glueless portion 12, specifically, the pressure-sensitive adhesive layer, the base material layer, and the like can be the same as the pressure-sensitive adhesive layer and the base material layer of the laminated film.
－粘着テープの製造方法－
　本実施形態の粘着テープ１１は、特に限定されなく例えば、公知の方法により製造することができる。具体的には、粘着テープ１１は、まず上述のような積層フィルムを製造する。そして、積層フィルムを所望の形状に切り抜くことで粘着テープ１１を得ることができる。
　なお、粘着テープの糊無し部の形成は、粘着剤層を全面に有する積層フィルムや粘着テープについて、所望の形状、大きさになるように粘着剤層を取り除いて糊無し部を形成してもよい。 -Manufacturing method of adhesive tape-
The adhesive tape 11 of the present embodiment is not particularly limited and can be produced, for example, by a known method. Specifically, the adhesive tape 11 first manufactures the laminated film as described above. Then, the adhesive film 11 can be obtained by cutting out the laminated film into a desired shape.
The adhesive-free portion of the adhesive tape may be formed by removing the adhesive layer so as to have a desired shape and size for a laminated film or adhesive tape having an adhesive layer on the entire surface. Good.
－粘着テープの特性－
　本実施形態の粘着テープ１１の総厚さや粘着力は、上述した積層フィルムと同様にすることができる。 -Characteristics of adhesive tape-
The total thickness and adhesive strength of the adhesive tape 11 of the present embodiment can be the same as those of the laminated film described above.
《接着体》
　本実施形態の接着体は、図５に示すように、上記の本発明の実施形態に係る粘着テープ１１と、当該粘着テープ１１の一方の表面上に貼り付けられた第１被着体１６と、当該粘着テープ１１の他方の表面上に貼り付けられた第２被着体１７とを備える。また、本実施形態の接着体は、粘着テープ１１のうち糊無し部１２よりも端部側の部分が、当該粘着テープ１１が貼り付けられた第１被着体１６の第１貼付け面よりも外側に位置し、糊無し部１２上に前記第１貼付け面を画定する角１８が位置している。
　本実施形態の接着体によれば、第１被着体１６を第２被着体１７から取り外すために粘着テープ１１を貼付け面に対して角度をつけて剥がす際、粘着テープ１１への負荷を低減することができるので、粘着テープ１１のちぎれを防止することができる。 《Adhesive body》
As shown in FIG. 5, the adhesive body of the present embodiment includes an adhesive tape 11 according to the above-described embodiment of the present invention, and a first adherend 16 attached on one surface of the adhesive tape 11. , A second adherend 17 attached on the other surface of the adhesive tape 11. In the adhesive body of the present embodiment, the portion of the adhesive tape 11 on the end side of the adhesive-free portion 12 is more than the first attaching surface of the first adherend 16 to which the adhesive tape 11 is attached. The corner 18 is located on the outside and defines the first sticking surface on the glueless portion 12.
According to the adhesive body of the present embodiment, when the adhesive tape 11 is peeled off at an angle to the sticking surface in order to remove the first adherend 16 from the second adherend 17, the load on the adhesive tape 11 is applied. Since it can be reduced, it is possible to prevent the adhesive tape 11 from being torn.
　ここで、第１被着体１６および第２被着体１７は、特に限定されなく、例えば、ＯＡ機器、ＩＴ・家電製品、自動車等の各産業分野で用いられるものであり、第２被着体１７はそれら製品の筐体であり、第１被着体１６はそれら製品に組み込む電池、電子部品、構造部品等の部品である場合が挙げられ、粘着テープ１１により第１被着体１６および第２被着体１７を固定または仮固定することができる。または、例えば、第１被着体１６を製品情報等を表示するラベルとし、第２被着体１７をラベルを表示するための表示部とすることもできる。 Here, the first adherend 16 and the second adherend 17 are not particularly limited, and are used in various industrial fields such as OA equipment, IT/home electric appliances, automobiles, etc. The body 17 is a housing for these products, and the first adherend 16 is a component such as a battery, an electronic component, or a structural component to be incorporated in those products. The second adherend 17 can be fixed or temporarily fixed. Alternatively, for example, the first adherend 16 may be used as a label for displaying product information or the like, and the second adherend 17 may be used as a display unit for displaying the label.
　また、本実施形態の接着体では、粘着テープ１１のうち糊無し部１２よりも端部側の部分が、当該粘着テープ１１が貼り付けられた第１被着体１６の第１貼付け面よりも外側に位置している。粘着テープ１１のうち糊無し部１２よりも端部側の部分は、図５に示すように、第１被着体１６の第１貼付け面と、粘着テープ１１が貼り付けられた第２被着体１７の第２貼付け面とで挟まれていない部分であり、粘着テープ１１を取り剥がす際の取手部分とすることができる。 Further, in the adhesive body of the present embodiment, the portion of the adhesive tape 11 on the end side of the adhesive-free portion 12 is more than the first attachment surface of the first adherend 16 to which the adhesive tape 11 is attached. It is located outside. As shown in FIG. 5, the portion of the adhesive tape 11 closer to the end than the non-adhesive portion 12 is the first attachment surface of the first adherend 16 and the second attachment to which the adhesive tape 11 is attached. It is a portion that is not sandwiched between the second sticking surface of the body 17, and can be used as a handle portion when the adhesive tape 11 is peeled off.
　また、本実施形態の接着体では、図５に示すように、糊無し部１２上に第１貼付け面を画定する角１８が位置している。具体的には、図示の例では、糊無し部１２と粘着テープ１１の端部側の部分との境界（糊無し部１２のうち、粘着テープ１１の端部側の端部）上に、第１貼付け面を画定する角１８が位置している。
　しかし、本実施形態では、図示の例のように、境界と角１８とが厳密に一致している必要はなく、角１８が境界よりも糊無し部１２側に位置していてもよい（粘着テープ１１の糊無し部１２が第１被着体１６の側面に位置していてもよい）。角１８が境界よりも糊無し部１２側に位置する場合には、糊無し部１２による粘着テープ１１のちぎれ防止の効果を十分に得る観点から、角１８と、端部側とは逆側の糊無し部１２および粘着剤層１４の境界との距離（換言すれば、平面視で、第１被着体１６の第１貼付け面と糊無し部１２とが重複する長さ）は、１ｍｍ以上であることが好ましい。 Further, in the adhesive body of the present embodiment, as shown in FIG. 5, the corner 18 that defines the first attachment surface is located on the glueless portion 12. Specifically, in the illustrated example, on the boundary between the glueless portion 12 and the end side portion of the adhesive tape 11 (of the glueless portion 12, the end portion of the adhesive tape 11 on the end side), the first 1 A corner 18 is located which defines the application surface.
However, in the present embodiment, as in the illustrated example, the boundary and the corner 18 do not have to be exactly aligned, and the corner 18 may be located on the glueless portion 12 side of the boundary (adhesive). The glueless portion 12 of the tape 11 may be located on the side surface of the first adherend 16). When the corner 18 is located closer to the adhesive-free portion 12 side than the boundary, from the viewpoint of sufficiently obtaining the effect of preventing the adhesive tape 11 from being torn by the adhesive-free portion 12, the corner 18 and the end portion side are opposite to each other. The distance from the boundary between the glueless portion 12 and the adhesive layer 14 (in other words, the length in which the first attachment surface of the first adherend 16 and the glueless portion 12 overlap each other in plan view) is 1 mm or more. Is preferred.
　ここで、本実施形態の接着体の組み立て方法は、まず、第１被着体１６の第１貼付け面に対して粘着テープ１１を貼る。この際、第１貼付け面を画定する角１８が糊無し部１２に位置するように貼る。次いで、第１被着体１６を第２被着体１７へ貼り合わせることにより、組み立てることができる。
　或いは、上記の方法に代えて、まず、第２被着体１７の第２貼付け面に対して粘着テープ１１を貼る。この際、糊無し部１２が、第１貼付け面を画定する角１８が位置することとなる第２貼付け面の位置に位置するように貼る。次いで、第１被着体１６の第１貼付け面の角１８が粘着テープ１１の糊無し部１２に位置するように、第１被着体１６を第２被着体１７へ貼り合わせることにより、組み立てることができる。 Here, in the method for assembling the adhesive body of the present embodiment, first, the adhesive tape 11 is attached to the first attachment surface of the first adherend 16. At this time, the corner 18 defining the first sticking surface is pasted so as to be located at the glueless portion 12. Then, the first adherend 16 can be assembled by sticking it to the second adherend 17.
Alternatively, instead of the above method, first, the adhesive tape 11 is attached to the second attachment surface of the second adherend 17. At this time, the glue-free portion 12 is pasted so as to be located at the position of the second pasting surface where the corner 18 that defines the first pasting surface is located. Next, the first adherend 16 is attached to the second adherend 17 so that the corner 18 of the first attachment surface of the first adherend 16 is located at the glueless portion 12 of the adhesive tape 11. Can be assembled.
　また、本実施形態の接着体の解体方法は、粘着テープ１１のうち糊無し部１２よりも端部側の部分（図５では、第１被着体１６の側面に沿って位置する部分）を、貼付け面に対して６０°以上の角度をつけて引っ張ることにより粘着テープ１１を剥ぎ取り、第１被着体１６を第２被着体１７から取り外す。なお、粘着テープ１１の端部側の部分を引っ張る角度が、貼付け面に対して７５°以上の角度の場合には、本実施形態の粘着テープ１１がより好適に用いることができる。 In addition, in the method for disassembling the adhesive body of the present embodiment, the portion of the adhesive tape 11 that is closer to the end than the glueless portion 12 (in FIG. 5, the portion that is located along the side surface of the first adherend 16) is used. The adhesive tape 11 is peeled off by pulling at an angle of 60 ° or more with respect to the sticking surface, and the first adherend 16 is removed from the second adherend 17. In addition, when the angle of pulling the end portion side of the adhesive tape 11 is an angle of 75° or more with respect to the attaching surface, the adhesive tape 11 of the present embodiment can be more preferably used.
　以上、図面を参照して本発明の実施形態を説明したが、本発明の粘着テープおよび接着体は、上記の例に限定されることは無く、適宜変更を加えることができる。 Although the embodiments of the present invention have been described above with reference to the drawings, the pressure-sensitive adhesive tape and the adhesive body of the present invention are not limited to the above examples, and can be appropriately modified.
　以下、実施例により本発明を更に詳細に説明するが、本発明は下記の実施例になんら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
＜測定及び評価方法＞
　各実施例および比較例で得られた粘着テープの測定及び評価は、次の方法に基づいて行った。 <Measurement and evaluation method>
The measurement and evaluation of the adhesive tape obtained in each Example and Comparative Example were carried out based on the following method.
（１）基材層の破断伸度
　粘着テープの破断伸度は、粘着テープを標線長さ２０ｍｍ、幅１０ｍｍのダンベル状に打ち抜き、酢酸エチルやアルコールやトルエン等の溶剤で粘着剤を膨潤させて、スパチラ等でこそぎ落して粘着テープの基材層だけを得、さらにドライヤーで溶剤を乾燥させ、次いで、基材層を測定雰囲気２３℃、５０％ＲＨの条件で、テンシロン引張試験機を用い、引張速度３００ｍｍ／ｍｉｎで長さ方向に引っ張ることで測定した。 (1) Breaking elongation of the base material layer The breaking elongation of the adhesive tape is determined by punching the adhesive tape into a dumbbell shape with a marked line length of 20 mm and a width of 10 mm, and swelling the adhesive with a solvent such as ethyl acetate, alcohol or toluene. Then, it is scraped off with a spatula etc. to obtain only the base layer of the adhesive tape, and the solvent is further dried with a dryer, and then the base layer is subjected to a Tensilon tensile tester under the conditions of a measurement atmosphere of 23° C. and 50% RH. It was measured by pulling in the length direction at a tensile speed of 300 mm / min.
（２）基材層の破断強度
　基材層の破断強度は、粘着テープを標線長さ２０ｍｍ、幅１０ｍｍのダンベル状に打ち抜き、酢酸エチルやアルコールやトルエン等の溶剤で粘着剤を膨潤させて、スパチラ等でこそぎ落して粘着テープの基材層だけを得、さらにドライヤーで溶剤を乾燥させ、次いで、基材層を測定雰囲気２３℃、５０％ＲＨの条件で、テンシロン引張試験機を用い、引張速度３００ｍｍ／ｍｉｎで長さ方向に引っ張ることで測定した。 (2) Breaking strength of base material layer The breaking strength of the base material layer is obtained by punching out an adhesive tape into a dumbbell shape having a marked line length of 20 mm and a width of 10 mm, and swelling the adhesive agent with a solvent such as ethyl acetate, alcohol or toluene. Then, scrape off with a spatula etc. to obtain only the base layer of the adhesive tape, further dry the solvent with a dryer, and then use the Tensilon tensile tester under the conditions of a measurement atmosphere of 23° C. and 50% RH. , Measured by pulling in the length direction at a tensile speed of 300 mm / min.
（３）粘着剤層の粘着力
　粘着テープについて、一方の粘着面を、ポリエステルフィルム（厚さ２５μｍ）を用いてバッキングし、その大きさを２０ｍｍ×１００ｍｍとしてテープサンプルを得た。当該テープサンプルの他方の粘着面にステンレス板を載せ、２ｋｇローラーを用いて１往復加圧貼付し、ついで、２３℃、５０％ＲＨの条件下で一時間放置した。その後、剥離速度３００ｍｍ／ｍｉｎで１８０°方向に引き剥がし、その際の粘着力（Ｎ／２０ｍｍ）を測定した。 (3) Adhesive Strength of Adhesive Layer With respect to the adhesive tape, one adhesive surface was backed with a polyester film (thickness 25 μm), and a tape sample was obtained with a size of 20 mm × 100 mm. A stainless steel plate was placed on the other adhesive surface of the tape sample, pressure-bonded one reciprocatingly using a 2 kg roller, and then left at 23 ° C. and 50% RH for 1 hour. Then, it was peeled off in a 180° direction at a peeling speed of 300 mm/min, and the adhesive force (N/20 mm) at that time was measured.
（４）基材層および粘着剤層の厚さ
　粘着テープを液体窒素中に１分間浸漬した後、ピンセットを用いて液体窒素中で、粘着テープの幅方向を折り目として折り曲げて割り、該粘着テープの厚さ方向の割断面観察用の切片を作製した。前記切片をデシケータ内で常温に戻した後、前記割断面に対して電子線が垂直に入射するように試料台に固定し、電子顕微鏡（Ｍｉｎｉｓｃｏｐｅ（登録商標）　ＴＭ３０３０Ｐｌｕｓ、日立ハイテクノロジー株式会社製）を用いて、前記割断面の観察を行った。電子顕微鏡のスケールを元に、前記粘着テープにおける基材層および粘着剤層の厚さを１０箇所測定し、その算術平均値を各層の厚さとした。なお、基材層および粘着剤層の厚さは、それぞれの層の一方側の表面から他方側の表面までを積層方向に沿って測った長さである。 (4) Thickness of base material layer and pressure-sensitive adhesive layer After immersing the pressure-sensitive adhesive tape in liquid nitrogen for 1 minute, the pressure-sensitive adhesive tape is folded in liquid nitrogen using tweezers with the width direction of the pressure-sensitive adhesive as a fold line to divide the pressure-sensitive adhesive tape. A section for observing a fractured surface in the thickness direction of was prepared. After returning the section to room temperature in a desiccator, the section was fixed on a sample table so that an electron beam was vertically incident on the fractured surface, and an electron microscope (Miniscope (registered trademark) TM3030Plus, manufactured by Hitachi High Technology Co., Ltd.) The fractured surface was observed using. Based on the scale of an electron microscope, the thicknesses of the base material layer and the pressure-sensitive adhesive layer in the pressure-sensitive adhesive tape were measured at 10 points, and the arithmetic mean value was taken as the thickness of each layer. In addition, the thickness of the base material layer and the pressure-sensitive adhesive layer is a length measured from the surface on one side to the surface on the other side of each layer along the laminating direction.
（５）剥離性
　後述の第１被着体を、実施例および比較例により得た長さ１２０ｍｍ×幅２０ｍｍの粘着テープを用いて後述の第２被着体に固定させた後、当該粘着テープの剥がしやすさについて評価した。具体的には、長さ１２０ｍｍ×幅２０ｍｍの粘着テープを準備し、当該粘着テープを、先端側の長さ２０ｍｍの部分を取手部分としてはみ出させた状態で、第２被着体であるステンレス板に貼った。ついで、第１被着体を、粘着テープ上に、粘着テープの長手方向が第１被着体の長手方向になるような向きで、第１被着体の第１貼付け面を形成する角が、当該粘着テープの取手部分と糊無し部との境界に位置するように貼り付けた。さらに、５ｋｇの荷重ローラーで１往復圧着した後、２３℃に１時間または８５℃に５００時間放置し、その後、取手部分をつかみ、第１被着体の第１貼付け面に対して９０°の方向（テープ面と垂直の方向）に引き出した。実施例、比較例の粘着テープを、固定して２３℃に１時間放置した場合、また固定して８５℃５００時間放置した場合について、１０個の試験片を評価してちぎれがなく剥がすことができるかを評価した。なお、糊無し部が表面に形成されていない粘着テープの場合（比較例１）も実施例１等と同様な方法でステンレス板に固定した。
　◎：１０個中１０個が剥がすことができた。
　〇：１０個中７～９個が剥がすことができた。
　△：１０個中１～６個が剥がすことができた。
　×：１０個中１個も剥がすことができなかった。 (5) Peelability A first adherend described below is fixed to a second adherend described below using the adhesive tape having a length of 120 mm and a width of 20 mm obtained in Examples and Comparative Examples, and then the adhesive tape. The easiness of peeling was evaluated. Specifically, an adhesive tape having a length of 120 mm and a width of 20 mm is prepared, and a portion of the adhesive tape having a length of 20 mm on the front end side is protruded as a handle portion, and a stainless steel plate which is a second adherend. Pasted on. Next, the corners forming the first sticking surface of the first adherend are formed on the adhesive tape so that the longitudinal direction of the adhesive tape is the longitudinal direction of the first adherend. , It was attached so as to be located at the boundary between the handle portion and the glueless portion of the adhesive tape. Furthermore, after pressing back and forth once with a load roller of 5 kg, it is left at 23° C. for 1 hour or at 85° C. for 500 hours, then the grip portion is grasped and the angle is 90° with respect to the first attaching surface of the first adherend. Direction (direction perpendicular to the tape surface). When the pressure-sensitive adhesive tapes of Examples and Comparative Examples were fixed and left at 23° C. for 1 hour, and fixed and left at 85° C. for 500 hours, 10 test pieces could be evaluated and peeled without tearing. I evaluated whether it could be done. In the case of an adhesive tape having no glue-free portion formed on its surface (Comparative Example 1), the adhesive tape was fixed to the stainless steel plate in the same manner as in Example 1 and the like.
⊚: 10 out of 10 could be peeled off.
◯: 7 to 9 out of 10 pieces could be peeled off.
Δ: 1 to 6 out of 10 could be peeled off.
X: None of the 10 pieces could be peeled off.
（６）接着性
　後述の第１被着体（３８ｇ）を、実施例および比較例により得た長さ１２０ｍｍ×幅２０ｍｍの粘着テープを用いて固定させた後、当該粘着テープの接着性について評価した。具体的には、長さ１２０ｍｍ×幅２０ｍｍの粘着テープを準備し、当該粘着テープを、先端側の長さ２０ｍｍの部分を取手部分としてはみ出させた状態で、ステンレス板（厚さ１．５ｍｍ、長さ１５０ｍｍ、幅５０ｍｍ、重さ８５ｇ）に貼った。そして、１時間後に２３℃で１．５ｍの高さから上記の貼り合わせた試験片をコンクリート板に自由落下させ、第１被着体が第２被着体から外れないかを評価した。
　尚、落下のさせ方はステンレスの平面がコンクリート板に落ちるように落下させた。
　◎：１０個中１０個とも剥がれなかった。
　〇：１０個中８～９個が剥がれなかった。
　×：１０個中１～７個が剥がれた。 (6) Adhesiveness The first adherend (38 g) described below was fixed using the adhesive tape having a length of 120 mm and a width of 20 mm obtained in Examples and Comparative Examples, and then the adhesiveness of the adhesive tape was evaluated. did. Specifically, an adhesive tape having a length of 120 mm and a width of 20 mm was prepared, and the stainless steel plate (thickness: 1.5 mm, with the adhesive tape having a length of 20 mm on the tip side protruding as a handle portion) was prepared. The length was 150 mm, the width was 50 mm, and the weight was 85 g). Then, one hour later, the above-mentioned bonded test pieces were freely dropped onto a concrete plate from a height of 1.5 m at 23 ° C., and it was evaluated whether or not the first adherend was removed from the second adherend.
The method of dropping was such that the flat surface of stainless steel fell on the concrete plate.
⊚: None of the 10 pieces were peeled off.
◯: 8 to 9 out of 10 pieces were not peeled off.
X: 1 to 7 out of 10 were peeled off.
　続いて、実施例、比較例で用いた各材料等は下記のとおりである。 Subsequently, the materials used in the examples and comparative examples are as follows.
















































〔第１被着体〕
　第１被着体は下記の方法により得た電池を用いた。
　まず、電池を包装する電池用包装フィルムを次の方法により得た。ポリエチレンテレフタレート樹脂とナイロン６をＴダイ法により押出して共押出フィルムを作製し、逐次延伸法でＭＤ、ＴＤ方向に二軸延伸した後、２００℃で熱処理することにより、樹脂フィルムＡを製造した。延伸倍率は、流れ方向（ＭＤ）３．４倍、幅方向（ＴＤ）３．８倍の条件とした。樹脂フィルムＡの積層構造は、ポリエチレンテレフタレート（５μｍ）／ナイロン６（２０μｍ）である。
　次に、ガラス転移点０℃、重量平均分子量２０×１０3、水酸基等量１．２個／ｍｏｌのポリオール化合物とトルエンジイソシアネート（ＴＤＩ）のトリメチロールプロパン（ＴＭＰ）アダクト体を主成分とする芳香族イソシアネートを１：３の比率で混合したウレタン樹脂系接着剤を用いて、樹脂フィルムＡと、アルミニウム箔２０μｍ（８０２１材、引張破断強度１００ＭＰａ、引張破断伸度１０％、０．２％耐力７０ＭＰａ）を積層した。尚、接着剤の厚みは３μｍであった。またポリエチレンテレフタレート樹脂層が基材層のシーラント層とは反対側に位置するようにした。
　別途、接着層を構成する酸変性ポリプロピレン樹脂（不飽和カルボン酸でグラフト変性した不飽和カルボン酸グラフト変性ランダムポリプロピレン）と、シーラント層を構成するポリプロピレン（ランダムコポリマー）を共押出しすることにより、接着層とシーラント層からなる２層共押出しフィルムを作製した。次いで、前記で作製した基材層（樹脂フィルムＡ）／接着層（ウレタン樹脂系接着剤）／金属層（アルミニウム箔）からなる積層体の金属層に、前記で作製した２層共押出しフィルムの接着層が接するように重ねあわせ、金属層が１２０℃となるように加熱してサーマルラミネーションを行うことにより、基材層／接着層／金属層／接着層／シーラント層が順に積層された積層体を得た。得られた積層体を一旦冷却した後に、１８０℃になるまで加熱し、１分間その温度を保持して熱処理を施すことにより、電池用包装フィルムを得た。
　次いで、得られた電池用包装フィルムを所定の形状に切り出し、正極、負極、電解質等の電池素子を包装した。包装後の電池の形状は、平板状であり、厚さ５ｍｍ、長さ１００ｍｍ、幅５０ｍｍであった。また得られた電池の質量は３８ｇであった。















































[First adherend]
A battery obtained by the following method was used as the first adherend.
First, a battery packaging film for packaging a battery was obtained by the following method. A polyethylene terephthalate resin and nylon 6 were extruded by a T-die method to prepare a co-extruded film, biaxially stretched in the MD and TD directions by a sequential stretching method, and then heat-treated at 200° C. to produce a resin film A. The draw ratio was set to 3.4 times in the flow direction (MD) and 3.8 times in the width direction (TD). The laminated structure of the resin film A is polyethylene terephthalate (5 μm) / nylon 6 (20 μm).
Next, aroma to the glass transition temperature 0 ° C., a weight average molecular weight 20 × 10 3, trimethylolpropane (TMP) adducts of hydroxyl equivalents 1.2 pieces / mol of polyol compound and toluene diisocyanate (TDI) as the main component Using a urethane resin adhesive mixed with group isocyanate at a ratio of 1: 3, resin film A and aluminum foil 20 μm (8021 material, tensile breaking strength 100 MPa, tensile breaking elongation 10%, 0.2% strength 70 MPa) ) Was laminated. The thickness of the adhesive was 3 μm. Further, the polyethylene terephthalate resin layer is located on the opposite side of the base material layer from the sealant layer.
Separately, by coextruding the acid-modified polypropylene resin (unsaturated carboxylic acid graft-modified random polypropylene graft-modified with unsaturated carboxylic acid) that constitutes the adhesive layer and the polypropylene (random copolymer) that constitutes the sealant layer, the adhesive layer A two-layer coextruded film composed of a sealant layer and a sealant layer was produced. Then, the two-layer coextrusion film prepared above is added to the metal layer of the laminate composed of the base material layer (resin film A)/adhesive layer (urethane resin adhesive)/metal layer (aluminum foil) prepared above. A laminate in which a base material layer/adhesive layer/metal layer/adhesive layer/sealant layer are laminated in this order by stacking them so that the adhesive layers are in contact with each other and performing thermal lamination by heating the metal layer to 120° C. Got The obtained laminated body was once cooled, then heated to 180° C. and heat-treated while maintaining the temperature for 1 minute to obtain a battery packaging film.
Next, the obtained battery packaging film was cut into a predetermined shape, and a battery element such as a positive electrode, a negative electrode and an electrolyte was packaged. The shape of the battery after packaging was a flat plate, with a thickness of 5 mm, a length of 100 mm, and a width of 50 mm. The mass of the obtained battery was 38 g.
〔第２被着体〕
　第２被着体は、厚さ１．５ｍｍ、長さ１５０ｍｍ、幅５０ｍｍ、重さ８５ｇのステンレス板を用いた。 [Second adherend]
As the second adherend, a stainless plate having a thickness of 1.5 mm, a length of 150 mm, a width of 50 mm and a weight of 85 g was used.
〔基材層〕
・基材層Ｓ－１：
　基材層の樹脂組成物としては、スチレン－イソプレン共重合体及びスチレン－イソプレン－スチレン共重合体の混合物（以下、「ＳＩＳ」と称することがある）であり、下記化学式（１）で表されるスチレン由来の構造単位２５質量％、及び樹脂組成物（１）の全量に対するスチレン－イソプレン共重合体の割合が１７質量％のものを使用した。次に、得られた樹脂組成物にトルエンを添加して均一になる様に攪拌し、アプリケーターにより乾燥後の厚さが５０μｍになるように離型ライナー（フィルムバイナ７５Ｅ‐００１０ＧＴ、藤森工業株式会社製、以下同様）上に塗布し、６０℃にて５分間乾燥させることによって基材層Ｓ－１を作製した。得られた基剤層の厚さは、５０μｍであり、破断伸度が１１５０％であり、破断強度が１８．６ＭＰａである。 [Base material layer]
-Base material layer S-1:
The resin composition of the base material layer is a mixture of a styrene-isoprene copolymer and a styrene-isoprene-styrene copolymer (hereinafter, may be referred to as “SIS”), and is represented by the following chemical formula (1). 25% by mass of the structural unit derived from styrene, and the ratio of the styrene-isoprene copolymer to the total amount of the resin composition (1) was 17% by mass. Next, toluene is added to the obtained resin composition and the mixture is stirred so as to be uniform, and a release liner (Film Vineer 75E-0010GT, Fujimori Industry Co., Ltd.) is used so that the thickness after drying is 50 μm by an applicator. The substrate layer S-1 was prepared by applying it on the above-mentioned product and drying it at 60 ° C. for 5 minutes. The obtained base layer has a thickness of 50 μm, a breaking elongation of 1150% and a breaking strength of 18.6 MPa.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
・基材層Ｓ－２：
　基材層の樹脂組成物として、エステル系ポリウレタン化合物（モビロンフィルムＭＦ１００Ｔ、日清紡テキスタイル株式会社製）を使用し、乾燥後の厚さが１００μｍになるようにした以外、基材層Ｓ－１と同様にして基材層Ｓ－２を作製した。当該基材層Ｓ－２の厚さが１００μｍであり、破断伸度が７２０％であり、破断強度が３３．０ＭＰａである。 -Base material layer S-2:
As the resin composition of the base material layer, an ester polyurethane compound (Mobilon film MF100T, manufactured by Nisshinbo Textile Co., Ltd.) was used, and the thickness after drying was 100 μm. A base material layer S-2 was prepared in the same manner. The base material layer S-2 has a thickness of 100 μm, a breaking elongation of 720%, and a breaking strength of 33.0 MPa.
・基材層Ｓ－３：
　ポリエチレンテレフタレート製フィルム（東レ社製、ルミラーＳ１０＃２５）を用いた。厚さが２５μｍであり、破断伸度が１６０％であり、破断強度が２３０ＭＰａである。 -Base layer S-3:
A polyethylene terephthalate film (Toray Industries, Inc., Lumirror S10 # 25) was used. The thickness is 25 μm, the elongation at break is 160%, and the strength at break is 230 MPa.
〔粘着剤層〕
・粘着剤層Ａ－１：
　粘着剤層の粘着剤は、次のようにして製造した。攪拌機、還流冷却管、窒素導入管、温度計、及び滴下漏斗を備えた反応容器に、ｎ－ブチルアクリレート７５．９４質量部、２－エチルヘキシルアクリレート５質量部、シクロヘキシルアクリレート１５質量部、アクリル酸４質量部、４－ヒドロキシブチルアクリレート０．０６質量部、及び酢酸エチル２００質量部を仕込み、攪拌下、窒素を吹き込みながら６５℃まで昇温させて混合物（１）を得た。次に、得られた混合物（１）に、予め酢酸エチルに溶解した２，２’－アゾビスイソブチロニトリル溶液４質量部（固形分２．５質量％）を添加し、攪拌下、６５℃で１０時間ホールドして混合物（２）を得た。次に、混合物（２）を酢酸エチル９８質量部で希釈し、２００メッシュ金網でろ過することによって、質量平均分子量１６０万（ポリスチレン換算）のアクリル共重合体溶液（１）溶液を得た。次に、アクリル共重合体溶液（１）１００質量部に対して、重合ロジンエステル系粘着付与樹脂（Ｄ－１２５、荒川化学工業株式会社）５質量部と石油系粘着付与樹脂（ＦＴＲ（登録商標）６１２５、三井化学株式会社製）１５質量部とを混合攪拌したのち、酢酸エチルを加えることによって固形分３１質量％の粘着剤の樹脂溶液（１）を得た。次に、粘着剤の樹脂溶液（１）１００質量部に対し、架橋剤（バーノックＤ－４０、ＤＩＣ株式会社製；トリレンジイソシアネートのトリメチロールプロパンアダクト体、イソシアネート基含有率７質量％、不揮発分４０質量％）１．３質量部を添加し、均一になるよう攪拌混合した後、１００メッシュ金網で濾過することによって固形分３１．１質量％の粘着剤樹脂（１）を得た。
　次に、得られた粘着剤樹脂（１）の固形分１００質量部に対して、フィラー１（水酸化アルミニウム、ＢＷ１５３、日本軽金属株式会社製、体積平均粒径：１８μｍ、粒度分布（Ｄ９０／Ｄ１０）：１２．３）を３０質量部添加し、粘着剤（１）を得た。
　なお、前記フィラー粒子の粒度分布（Ｄ９０／Ｄ１０）は、レーザー回折散乱法を用いた測定機（マイクロトラック）を使用することにより前記フィラー粒子の粒子径を測定して、粒度分布に換算することで得られた値である。
　続いて、粘着剤（１）を、ダイコーターを用いたストライプ塗工法により、乾燥後の厚さが５０μｍになるように離型ライナー（フィルムバイナ７５Ｅ‐００１０ＧＴ、藤森工業株式会社製、以下同様）上に塗布し、８０℃３分間乾燥させることによって粘着剤層Ａ－１を作製した。この際、図１に示すように、粘着剤を塗布しないようにして幅１０ｍｍの糊無し部を作製した。 [Adhesive layer]
-Adhesive layer A-1:
The pressure-sensitive adhesive of the pressure-sensitive adhesive layer was produced as follows. 75.94 parts by mass of n-butyl acrylate, 5 parts by mass of 2-ethylhexyl acrylate, 15 parts by mass of cyclohexyl acrylate, acrylic acid 4 in a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel. A mixture (1) was obtained by charging 0.06 parts by mass of 4-hydroxybutyl acrylate and 200 parts by mass of ethyl acetate and raising the temperature to 65 ° C. while blowing nitrogen under stirring. Next, 4 parts by mass (solid content 2.5% by mass) of a 2,2'-azobisisobutyronitrile solution previously dissolved in ethyl acetate was added to the obtained mixture (1), and under stirring, 65 The mixture was held at ° C. for 10 hours to obtain the mixture (2). Next, the mixture (2) was diluted with 98 parts by mass of ethyl acetate and filtered through a 200-mesh wire net to obtain an acrylic copolymer solution (1) having a mass average molecular weight of 1.6 million (polystyrene equivalent). Next, with respect to 100 parts by mass of the acrylic copolymer solution (1), 5 parts by mass of a polymerized rosin ester-based tackifying resin (D-125, Arakawa Chemical Industry Co., Ltd.) and a petroleum-based tackifying resin (FTR (registered trademark) ) 6125, manufactured by Mitsui Chemicals, Inc.) 15 parts by mass was mixed and stirred, and then ethyl acetate was added to obtain a resin solution (1) of a pressure-sensitive adhesive having a solid content of 31% by mass. Next, based on 100 parts by mass of the resin solution (1) of the adhesive, a cross-linking agent (Bernock D-40, manufactured by DIC Corporation; trimethylolpropane adduct of tolylene diisocyanate, isocyanate group content of 7% by mass, non-volatile content) 40% by mass) 1.3 parts by mass was added, and the mixture was stirred and mixed so as to be uniform, and then filtered through a 100 mesh wire net to obtain a pressure-sensitive adhesive resin (1) having a solid content of 31.1% by mass.
Next, with respect to 100 parts by mass of the solid content of the obtained pressure-sensitive adhesive resin (1), filler 1 (aluminum hydroxide, BW153, manufactured by Nippon Light Metal Co., Ltd., volume average particle diameter: 18 μm, particle size distribution (D 90 / 30 parts by mass of D 10 ): 12.3) was added to obtain a pressure-sensitive adhesive (1).
The particle size distribution (D 90 /D 10 ) of the filler particles is converted into a particle size distribution by measuring the particle size of the filler particles by using a measuring machine (Microtrac) using a laser diffraction scattering method. It is the value obtained by doing.
Subsequently, the pressure-sensitive adhesive (1) was applied by a strip coating method using a die coater to a release liner (film binder 75E-0010GT, manufactured by Fujimori Industry Co., Ltd., so that the thickness after drying would be 50 μm). The pressure-sensitive adhesive layer A-1 was prepared by applying the composition onto the above and drying at 80° C. for 3 minutes. At this time, as shown in FIG. 1, a glueless portion having a width of 10 mm was prepared without applying an adhesive.
・粘着剤層Ａ－２：
　糊無し部の幅を５ｍｍとした以外、粘着剤層Ａ－１と同様にして粘着剤層Ａ－２を作製した。 -Adhesive layer A-2:
The pressure-sensitive adhesive layer A-2 was produced in the same manner as the pressure-sensitive adhesive layer A-1 except that the width of the glueless portion was 5 mm.
・粘着剤層Ａ－３：
　粘着剤（１）をアプリケーターにより乾燥後の厚さが２５μｍになるように離型ライナー上に塗布した以外、粘着剤層Ａ－１と同様にして粘着剤層Ａ－３を作製した。 -Adhesive layer A-3:
The pressure-sensitive adhesive layer A-3 was prepared in the same manner as the pressure-sensitive adhesive layer A-1 except that the pressure-sensitive adhesive (1) was applied on the release liner with an applicator so that the thickness after drying was 25 μm.
・粘着剤層Ａ－４：
　粘着剤１にフィラーを含有させない以外、粘着剤（１）と同様にして粘着剤（２）を得、次いで、粘着剤層Ａ－１と同様にして粘着剤層Ａ－４を作製した。 -Adhesive layer A-4:
The pressure-sensitive adhesive (2) was obtained in the same manner as the pressure-sensitive adhesive (1) except that the pressure-sensitive adhesive 1 did not contain a filler, and then the pressure-sensitive adhesive layer A-4 was prepared in the same manner as the pressure-sensitive adhesive layer A-1.
・粘着剤層Ａ－５：
　粘着剤（１）をアプリケーターにより乾燥後の厚さが１０μｍになるように離型ライナー上に塗布した以外、粘着剤層Ａ－１と同様にして粘着剤層Ａ－３を作製した。 -Adhesive layer A-5:
The pressure-sensitive adhesive layer A-3 was prepared in the same manner as the pressure-sensitive adhesive layer A-1 except that the pressure-sensitive adhesive (1) was applied on a release liner with an applicator so that the thickness after drying was 10 μm.
・粘着剤層Ａ－６：
　粘着剤（１）をアプリケーターにより乾燥後の厚さが５０μｍになるように離型ライナー上に塗布し、８０℃３分間乾燥させることによって、糊無し部が形成されていない粘着剤層である粘着剤層Ａ－６を作製した。 -Adhesive layer A-6:
The pressure-sensitive adhesive (1) is applied onto a release liner by an applicator so that the thickness after drying becomes 50 μm, and dried at 80° C. for 3 minutes to obtain a pressure-sensitive adhesive layer in which no glue-free portion is formed. Agent layer A-6 was prepared.
　続いて、実施例、比較例を説明する。 Next, Examples and Comparative Examples will be described.
〔実施例１～６、比較例１、２〕
　上記のように作製した粘着剤層、基材層について、表１に示す組み合わせで用いて、図３に示すような矩形状の粘着テープを作製した。具体的には、基材層の離型ライナーを剥離後、基材層の両面に離型ライナー上に形成された粘着剤層を貼り合わせ、０．２ＭＰａで加圧しラミネートすることによって、粘着テープを作製した。得られた粘着テープは、全体の厚さが２００μｍ、長さが１２０ｍｍ、幅が２０ｍｍ、粘着テープの端部の取手部分の長さ（粘着テープの長手方向に沿って測った長さ）が２０ｍｍであった。
　得られた各粘着テープについて上記の評価を行い、その結果を表１に示す。 [Examples 1 to 6 and Comparative Examples 1 and 2]
The pressure-sensitive adhesive layer and the base material layer manufactured as described above were used in combination shown in Table 1 to manufacture a rectangular pressure-sensitive adhesive tape as shown in FIG. Specifically, after peeling off the release liner of the base material layer, the pressure-sensitive adhesive layers formed on the release liner are attached to both sides of the base material layer, and the pressure is applied at 0.2 MPa to laminate the adhesive tape. Was produced. The obtained adhesive tape had a total thickness of 200 μm, a length of 120 mm, a width of 20 mm, and a handle portion at the end of the adhesive tape (length measured along the longitudinal direction of the adhesive tape) was 20 mm. Met.
The above-mentioned evaluation was carried out for each of the obtained adhesive tapes, and the results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

　表１に示すように、粘着テープの１つの端部側の少なくとも一方の表面上に糊無し部を有し、基材層の破断伸度が２００～３０００％であり、破断強度が１．５～８０ＭＰａである実施例１～６の粘着テープは、粘着テープを貼付け面に対して角度をつけて剥がす際にも、粘着テープへの負荷を低減しちぎれを防止することができた。また、実施例１、４を対比してわかるように、粘着剤層の粘着剤がフィラーを含有することでより粘着テープを剥がしやすくなることがわかる。
　一方、表１に示すように、糊無し部を有しない比較例１の粘着テープは、粘着テープを貼付け面に対して角度をつけて剥がす際、粘着テープが伸び始めときの負荷が大きく、粘着テープがちぎれた。また、基材層の破断伸度、破断強度が所定の範囲外である比較例２の粘着テープは、粘着テープを貼付け面に対して角度をつけて剥がす際、粘着テープが伸びず負荷が一部に集中したため、ちぎれた。 As shown in Table 1, the adhesive tape has a glueless portion on at least one surface on one end side, the breaking elongation of the base material layer is 200 to 3000%, and the breaking strength is 1.5. The adhesive tapes of Examples 1 to 6 having a temperature of about 80 MPa were able to reduce the load on the adhesive tape and prevent tearing even when the adhesive tape was peeled off at an angle with respect to the sticking surface. Further, as can be seen by comparing Examples 1 and 4, it can be seen that the pressure-sensitive adhesive tape is more easily peeled off when the pressure-sensitive adhesive of the pressure-sensitive adhesive layer contains the filler.
On the other hand, as shown in Table 1, the adhesive tape of Comparative Example 1 having no glueless portion has a large load when the adhesive tape starts to stretch when the adhesive tape is peeled off at an angle to the sticking surface, and is adhesive. The tape was torn. Further, in the adhesive tape of Comparative Example 2 in which the breaking elongation and breaking strength of the base material layer are out of the predetermined ranges, when the adhesive tape is peeled off at an angle to the sticking surface, the adhesive tape does not stretch and the load is one. I was torn because I concentrated on the club.
　本発明によれば、粘着テープを貼付け面に対して角度をつけて剥がす際にも、粘着テープへの負荷を低減しちぎれを防止することができる、積層フィルム、粘着テープおよび接着体を提供することができる。 According to the present invention, there is provided a laminated film, an adhesive tape and an adhesive body capable of reducing the load on the adhesive tape and preventing tearing even when the adhesive tape is peeled off at an angle with respect to the sticking surface. be able to.
１：積層フィルム
２：糊無し部
３：破線
４：粘着剤層
１１：粘着テープ
１２：糊無し部
１３：基材層
１４：粘着剤層
１５：フィルム
１６：第１被着体
１７：第２被着体
１８：角
２０：電池
２１：筐体
２２：粘着テープ
２３：角 1: Laminated film 2: No glue part 3: Broken line 4: Adhesive layer 11: Adhesive tape 12: No glue part 13: Base material layer 14: Adhesive layer 15: Film 16: First adherend 17: Second Substrate 18: Corner 20: Battery 21: Housing 22: Adhesive tape 23: Corner

Claims (6)

  1. 　基材層と、当該基材層の両面に粘着剤層とを備える積層フィルムであって、
    　前記積層フィルムの少なくとも一方の表面上に前記粘着剤層が存在しない糊無し部を有し、
    　前記基材層は、破断伸度が２００～３０００％であり、破断強度が１．５～８０ＭＰａであることを特徴とする、積層フィルム。     A substrate layer, a laminated film comprising a pressure-sensitive adhesive layer on both sides of the substrate layer,
    It has a glueless portion on at least one surface of the laminated film in which the pressure-sensitive adhesive layer does not exist.
    A laminated film, wherein the base material layer has a breaking elongation of 200 to 3000% and a breaking strength of 1.5 to 80 MPa.
  2. 　前記粘着剤層の粘着剤がフィラーを含有する、請求項１に記載の積層フィルム。 The laminated film according to claim 1, wherein the adhesive of the adhesive layer contains a filler.
  3. 　基材層と、当該基材層の両面に粘着剤層とを備える粘着テープであって、
    　前記粘着テープの１つの端部側の少なくとも一方の表面上に前記粘着剤層が存在しない糊無し部を有し、
    　前記基材層は、破断伸度が２００～３０００％であり、破断強度が１．５～８０ＭＰａであることを特徴とする、粘着テープ。     An adhesive tape provided with a base material layer and adhesive layers on both sides of the base material layer.
    It has a glueless portion on the surface of at least one end side of the adhesive tape in which the adhesive layer is not present.
    The adhesive tape, wherein the base material layer has a breaking elongation of 200 to 3000% and a breaking strength of 1.5 to 80 MPa.
  4. 　前記粘着テープの長手方向に沿って測った前記糊無し部の長さは、０．５～１００ｍｍである、請求項３に記載の粘着テープ。 The adhesive tape according to claim 3, wherein the length of the glueless portion measured along the longitudinal direction of the adhesive tape is 0.5 to 100 mm.
  5. 　前記粘着剤層の粘着剤がフィラーを含有する、請求項３または４に記載の粘着テープ。 The adhesive tape according to claim 3 or 4, wherein the adhesive of the adhesive layer contains a filler.
  6. 　請求項３～５のいずれかに記載の粘着テープと、当該粘着テープの一方の表面上に貼り付けられた第１被着体と、当該粘着テープの他方の表面上に貼り付けられた第２被着体とを備える接着体であって、
    　前記粘着テープのうち前記糊無し部よりも端部側の部分が、当該粘着テープが貼り付けられた第１被着体の第１貼付け面よりも外側に位置し、
    　前記糊無し部上に前記第１貼付け面を画定する角が位置することを特徴とする、接着体。     The adhesive tape according to any one of claims 3 to 5, a first adherend adhered on one surface of the adhesive tape, and a second adherend adhered on the other surface of the adhesive tape. An adhesive body including an adherend,
    A portion of the adhesive tape on the end side of the adhesive-free portion is located outside the first attaching surface of the first adherend to which the adhesive tape is attached,
    An adhesive body, characterized in that an angle defining the first attachment surface is located on the glueless portion.
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