WO2016084948A1 - Adhesive sheet - Google Patents

Adhesive sheet Download PDF

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Publication number
WO2016084948A1
WO2016084948A1 PCT/JP2015/083445 JP2015083445W WO2016084948A1 WO 2016084948 A1 WO2016084948 A1 WO 2016084948A1 JP 2015083445 W JP2015083445 W JP 2015083445W WO 2016084948 A1 WO2016084948 A1 WO 2016084948A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive sheet
resin
film
Prior art date
Application number
PCT/JP2015/083445
Other languages
French (fr)
Japanese (ja)
Inventor
山本　修平
松下　喜一郎
Original Assignee
日東電工株式会社
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
Priority claimed from JP2015164270A external-priority patent/JP6679239B2/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020177013531A priority Critical patent/KR102463777B1/en
Priority to US15/529,634 priority patent/US20170267897A1/en
Priority to CN201580064326.3A priority patent/CN107001871B/en
Publication of WO2016084948A1 publication Critical patent/WO2016084948A1/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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • the present invention relates to an adhesive sheet.
  • This application claims priority based on Japanese Patent Application No. 2014-242183 filed on November 28, 2014 and Japanese Patent Application No. 2015-164270 filed on August 21, 2015. The entire contents of these applications are hereby incorporated by reference.
  • a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive, hereinafter the same) is in a soft solid (viscoelastic body) state in the temperature range near room temperature and has a property of easily adhering to an adherend by pressure.
  • the pressure-sensitive adhesive is in the form of a pressure-sensitive adhesive sheet with a base material provided with a pressure-sensitive adhesive layer on at least one surface of the base material, for example, fixing various articles, surface protection of various articles, Alternatively, it is widely used for the purpose of obtaining a desired appearance such as decoration.
  • Patent document 1 is mentioned as a literature which discloses this kind of prior art.
  • the present invention has been created in view of the above circumstances, and provides a pressure-sensitive adhesive sheet that can exhibit high adhesive strength over time and has good air escape between the pressure-sensitive adhesive sheet and the adherend. With the goal.
  • an adhesive sheet comprising a film-like substrate and an adhesive layer provided on at least one surface of the film-like substrate.
  • the pressure-sensitive adhesive sheet includes a coat layer that partially covers the surface of the pressure-sensitive adhesive layer, whereby the surface of the pressure-sensitive adhesive layer has a coat layer placement portion and a coat layer non-placement portion.
  • positioning part in the said adhesive layer surface is 70% or more.
  • positioning part has a part extended linearly toward the other end from the one end of this adhesive layer, when the said adhesive layer surface is seen from upper direction.
  • the width of the linearly extending portion is in the range of 0.1 to 2 mm.
  • the adhesiveness As a general tendency, as the area of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet decreases, the adhesiveness also decreases in proportion thereto. Even when a coating layer is disposed on the adhesive surface of the adhesive sheet, the exposed area of the adhesive surface is reduced by the amount of the coating layer, and thus the same tendency is considered to be exhibited. In fact, also in the examples described later, when the area of the coating layer on the surface of the pressure-sensitive adhesive layer was increased and the exposed area of the pressure-sensitive adhesive layer was decreased, the initial adhesive force immediately after the bonding was reduced in proportion thereto. However, as a result of the study by the present inventors, it has been clarified that the adhesive force with time tends to be different from the initial adhesive force.
  • the original action of the coat layer which imparts air escape between the pressure-sensitive adhesive sheet and the adherend, may be impaired. Therefore, in the technology disclosed herein, when the pressure-sensitive adhesive layer surface is viewed from above, the coat layer is disposed so as to have a portion extending linearly from one end to the other end of the pressure-sensitive adhesive layer, and The width of the linearly extending portion is set within the range of 0.1 to 2 mm. Thereby, in the pressure-sensitive adhesive sheet capable of exhibiting a high adhesive strength with time, it is possible to realize good air escape properties.
  • the width of the linearly extending portion is preferably 0.2 mm or more (for example, 0.3 mm or more, more preferably 0.5 mm or more), and 1.2 mm or less (more preferably 0.7 mm or less, more preferably Is preferably 0.4 mm or less).
  • the time-dependent adhesive strength refers to the adhesive strength after 24 hours or more have passed since bonding to the adherend.
  • a plurality of linearly extending portions are disposed on the surface of the pressure-sensitive adhesive layer.
  • a plurality of linearly extending portions constituting a group among the plurality of linearly extending portions are arranged at intervals in the width direction thereof, whereby the coat layer arrangement portion is striped. Has a pattern.
  • the coat layer arrangement portion includes a first stripe pattern portion, and a second stripe pattern portion arranged so as to intersect the first stripe pattern portion.
  • the coat layer arrangement portion has a lattice pattern.
  • a plurality of linearly extending portions constituting one stripe pattern have a distance of 1.0 to 10 mm.
  • the interval between the linearly extending portions is more preferably 1.5 to 8 mm, and further preferably 2.5 to 5 mm.
  • the pressure-sensitive adhesive surface on which the coat layer is partially disposed exhibits a 180-degree peel strength after 24 hours of 13 N / 25 mm or more. According to the technique disclosed herein, the above-described peel strength can be realized in a configuration in which a coat layer is provided.
  • a pressure-sensitive adhesive sheet with a release liner comprising any of the pressure-sensitive adhesive sheets disclosed herein and a release liner for protecting the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet. And the surface at the side of the said adhesive layer among the surfaces of this release liner is formed smoothly.
  • a release liner for pressure-sensitive adhesive sheets comprising a peelable support having at least one surface that is a peelable surface.
  • a coat layer that can be transferred to the pressure-sensitive adhesive sheet is provided, whereby the peelable surface has a coat layer placement portion and a coat layer non-placement portion.
  • positioning part in the said peelable surface is 70% or more.
  • the coat layer has a portion extending linearly from one end to the other end of the peelable surface. The width of the linearly extending portion is in the range of 0.1 to 2 mm.
  • FIG. 2 is a cross-sectional view taken along line II-II in FIG. It is sectional drawing which shows typically the adhesive sheet with a peeling liner which concerns on one Embodiment. It is sectional drawing which shows typically the adhesive sheet with a peeling liner which concerns on other embodiment. It is sectional drawing which shows typically the peeling liner for adhesive sheets which concerns on one Embodiment.
  • the concept of the pressure-sensitive adhesive sheet in this specification includes what can be called pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, pressure-sensitive adhesive films, and the like.
  • the pressure-sensitive adhesive sheet disclosed herein may be in the form of a roll or a single sheet. Or the sheet
  • FIG. 1 is a top view schematically showing an adhesive sheet according to an embodiment
  • FIG. 2 is a cross-sectional view taken along the line II-II in FIG.
  • the pressure-sensitive adhesive sheet of this embodiment will be described with reference to the drawings.
  • the pressure-sensitive adhesive sheet 1 has a laminated structure of a film-like base material 10 and a pressure-sensitive adhesive layer 20.
  • the film-like substrate 10 supports the pressure-sensitive adhesive layer 20.
  • the surface 20 ⁇ / b> A on the pressure-sensitive adhesive layer 20 side constitutes a pressure-sensitive adhesive surface 1 ⁇ / b> A.
  • the other surface (surface on the film-like substrate 10 side) 1B of the pressure-sensitive adhesive sheet 1 is a non-adhesive surface.
  • the coat layer 30 is partially disposed on the surface 20A of the pressure-sensitive adhesive layer 20.
  • the pressure-sensitive adhesive layer surface 20 ⁇ / b> A is partially covered by the coat layer 30, and the coat layer placement portion 50 where the coat layer 30 is placed and the pressure-sensitive adhesive layer 20 where the coat layer 30 is not placed are arranged. And a coat layer non-arranged portion 51 exposed on the surface.
  • the coat layer 30 serves as a passage through which air or the like passes between the pressure-sensitive adhesive sheet 1 and the adherend when the pressure-sensitive adhesive sheet 1 is bonded to the adherend, and imparts air release properties.
  • the surface of the coat layer 30 may be flush with the pressure-sensitive adhesive layer surface 20A, or at least a part in the thickness direction may protrude from the pressure-sensitive adhesive layer surface 20A.
  • the coat layer arrangement part 50 presents a predetermined pattern (coat layer pattern) 60 when the pressure-sensitive adhesive layer surface 20A is viewed from above.
  • the coat layer arrangement portion 50 has a lattice pattern 60.
  • the lattice pattern 60 by the coat layer 30 is arranged so as to intersect the first stripe pattern portion 70 and the first stripe pattern portion 70 when the pressure-sensitive adhesive layer surface 20A is viewed from above.
  • the second stripe pattern portion 80 is formed.
  • the first stripe pattern portion 70 is composed of a plurality of long portions (band-like portions) 75A, 75B, 75C extending linearly from one end of the pressure-sensitive adhesive layer 20 to the other end.
  • the portions 75A, 75B, and 75C are arranged in parallel at intervals in the width direction.
  • the long portions 75 ⁇ / b> A, 75 ⁇ / b> B, and 75 ⁇ / b> C are arranged at angles at which the longitudinal direction intersects the end portions in the width direction of the pressure-sensitive adhesive sheet 1, and respectively reach the both ends of the pressure-sensitive adhesive layer 20. .
  • the “long portion” is used to mean a portion having a longitudinal direction and a width direction (a direction orthogonal to the longitudinal direction), and typically, regardless of whether it is linear or curved, It is a part extending in a band shape.
  • the long part can be rephrased as a part extending linearly.
  • the second stripe pattern portion 80 also has a plurality of long portions (band portions) 85 ⁇ / b> A, 85 ⁇ / b> B, 85 ⁇ / b> C that extend linearly from one end to the other end of the adhesive layer 20.
  • the plurality of long portions 85A, 85B, 85C are arranged in parallel in the width direction at intervals.
  • the long portions 85 ⁇ / b> A, 85 ⁇ / b> B, and 85 ⁇ / b> C are arranged at angles at which the longitudinal direction intersects the end portions in the width direction of the pressure-sensitive adhesive sheet 1, and respectively reach the both ends of the pressure-sensitive adhesive layer 20. .
  • the long portions 75A, 75B, 75C, 85A, 85B, and 85C are linear, but the present invention is not limited to this, and each long portion may extend in a curved shape.
  • the stripe pattern that can be formed by the plurality of long portions may be wavy.
  • the first stripe pattern portion 70 and the second stripe pattern portion 80 are the long portions 75A, 75B, 75C of the first stripe pattern portion 70 and the second stripe pattern portion 80.
  • the long portions 85A, 85B, and 85C intersect so as to be substantially orthogonal. Therefore, the long portions 75A, 75B, 75C of the first stripe pattern portion 70 and the long portions 85A, 85B, 85C of the second stripe pattern portion 80 partially overlap.
  • the lattice pattern typically refers to a pattern including two stripe pattern portions intersecting each other, and not only an orthorhombic lattice as in the present embodiment, but also a square lattice and a triangular lattice. And various other lattice shapes.
  • the crossing angle (acute angle side) of the two stripe pattern parts is within the range of 10 degrees to 90 degrees (preferably 45 degrees to 90 degrees, typically 60 degrees to 90 degrees). It can be set with.
  • the lattice pattern disclosed herein includes a pattern including a stripe-shaped pattern portion composed of a plurality of long portions that repeatedly bend, for example, a pattern such as a hexagonal lattice.
  • Such a pattern may be a pattern in which adjacent long portions are partially connected.
  • the coat layer arrangement portion preferably has one or more stripe pattern portions. Accordingly, the coat layer arrangement portion (typically a lattice pattern) may have a third stripe pattern portion.
  • the width (W1) of each of the long portions 75A, 75B, 75C, 85A, 85B, and 85C in the coat layer arrangement portion 50 is set within a range of 0.1 to 2 mm. Thereby, it is possible to achieve both high adhesive strength with time and good air escape.
  • the width W1 of the long part is preferably 0.2 mm or more, more preferably 0.3 mm or more, and still more preferably 0.5 mm or more, from the viewpoint of improving air escape. From the viewpoint of adhesive strength, appearance, etc., the width W1 of the long portion is preferably 1.2 mm or less, more preferably 1.0 mm or less, still more preferably 0.7 mm or less, particularly preferably 0.5 mm or less, Most preferably, it is 0.4 mm or less.
  • the interval W2 between the long portions 75A, 75B, and 75C constituting the first stripe pattern portion 70 is preferably set within a range of 1.0 to 10 mm.
  • the interval W2 between the long portions refers to the width of a portion existing between two adjacent long portions on the pressure-sensitive adhesive layer surface.
  • the distance W2 between the long portions is more preferably 1.5 mm or more, and further preferably 2.5 mm or more, from the viewpoint of improving the adhesive strength with time.
  • the interval W2 between the long portions may be about 8 mm or less (for example, 5 mm or less, typically 3 mm or less).
  • the intervals between the long portions 85A, 85B, and 85C constituting the second stripe pattern portion 80 are also preferably set within the range exemplified as the interval W2 between the long portions 75A, 75B, and 75C.
  • the interval W2 is preferably an equal interval.
  • the pitch of the long part is preferably in the range of 1 to 20 mm from the viewpoint of achieving a balance between high adhesive strength with time and air release.
  • the pitch of the long part is more preferably 1.5 mm or more, further preferably 2 mm or more (for example, 2.5 mm or more), more preferably 15 mm or less (for example, 12 mm or less), and further preferably 5 mm or less. is there.
  • the said pitch shall point out the distance (space
  • the pressure-sensitive adhesive sheet 1 is a pressure-sensitive adhesive with a release liner having a configuration in which the pressure-sensitive adhesive layer 20 is protected by a release liner 40 having at least a pressure-sensitive adhesive layer surface 20A side as a release surface, as shown in FIG. It may be in the form of a sheet 1.
  • the back surface of the film-like substrate 10 (the surface opposite to the surface on the pressure-sensitive adhesive layer 20 side) is a release surface, and the pressure-sensitive adhesive layer 20 is formed on the back surface by winding the pressure-sensitive adhesive sheet 1.
  • abutted and the adhesive layer 20 was protected by the back surface of the film-form base material 10 may be sufficient.
  • Such a single-sided adhesive sheet (single-sided adhesive sheet) having adhesiveness only on one side is, for example, a case where characteristics such as decoration and surface protection are required on the surface opposite to the adhesive surface. It is suitable when used as a paint substitute sheet.
  • the adhesive sheet disclosed here is a double-sided adhesive type adhesive sheet with a base material (double-sided adhesive sheet) shown in FIG. Non-peelable) are provided with pressure-sensitive adhesive layers 21 and 22, respectively, and the pressure-sensitive adhesive layers 21 and 22 are protected by release liners 41 and 42, at least the pressure-sensitive adhesive layer side being a release surface, respectively. It may have.
  • the coat layer 30 is partially disposed only on the surface of the pressure-sensitive adhesive layer 21, and no coat layer is provided on the surface of the pressure-sensitive adhesive layer 22.
  • the double-sided pressure-sensitive adhesive sheet is provided with a pressure-sensitive adhesive layer on each surface of the film-like substrate (both are non-peelable), and one of the pressure-sensitive adhesive layers has both surfaces separated from each other. You may have the structure protected by the release liner which has become.
  • This type of pressure-sensitive adhesive sheet has a configuration in which two pressure-sensitive adhesive layers are protected by one release liner by winding the pressure-sensitive adhesive sheet and bringing the other pressure-sensitive adhesive layer into contact with the back surface of the release liner.
  • the double-sided pressure-sensitive adhesive sheet is preferably used, for example, for joining and fixing.
  • the pressure-sensitive adhesive sheet disclosed herein has an area ratio of the coating layer non-arranged portion on the surface of the pressure-sensitive adhesive layer (which may also be the area ratio of the coat layer on the adhesive surface (sticky surface) of the pressure-sensitive adhesive sheet) of 70% or more. Characterized by being. Thereby, high adhesive strength with time can be ensured.
  • the area ratio is preferably 75% or more, more preferably 80% or more. From the viewpoint of obtaining good air escape properties, the area ratio is preferably 90% or less, more preferably 85% or less.
  • the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet (typically composed of the pressure-sensitive adhesive layer surface and the coat layer surface) has a 180 ° peel strength (hereinafter referred to as “24 hours”) after 24 hours of 13 N / 25 mm or more. Also referred to as “adhesive strength after elapse.”
  • the adhesive strength after 24 hours is preferably 14 N / 25 mm or more (for example, 16 N / 25 mm or more).
  • the adhesive strength after the lapse of 24 hours may be measured by the following method.
  • the adhesive surface of the measurement sample is made of a stainless steel plate (SUS304BA plate) in an environment of 23 ° C. and 50% RH. A 2 kg roller is reciprocated once on the surface and pressed. After leaving it in the same environment for 24 hours, using a universal tensile compression tester, in accordance with JIS Z 0237: 2000, under conditions of a tensile speed of 300 mm / min and a peel angle of 180 degrees, the peel strength (N / 25 mm). More specifically, it is measured by the method described in Examples described later.
  • the pressure-sensitive adhesive sheet is a transparent (including translucent) pressure-sensitive adhesive sheet.
  • a transparent (including translucent) pressure-sensitive adhesive sheet when bubbles or the like are mixed between the pressure-sensitive adhesive sheet and the adherend, the bubbles and the like are visually recognized through the pressure-sensitive adhesive sheet, and the appearance is easily impaired.
  • the technology disclosed herein generation of bubbles or the like between the pressure-sensitive adhesive sheet and the adherend is prevented, so that an excellent appearance can be obtained in a pressure-sensitive adhesive sheet having transparency.
  • the pressure-sensitive adhesive sheet may exhibit a total light transmittance of 80% or more (for example, 90% or more, typically 95% or more).
  • the haze value of an adhesive sheet is 10% or less (for example, 5% or less).
  • the total light transmittance and haze value are measured using a commercially available transmissometer (for example, trade name “HAZEMETER HM-150”, manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K 7136: 2000. do it.
  • the total light transmittance and haze value of a film-like substrate described later are also measured by the same method.
  • the total thickness of the pressure-sensitive adhesive sheet (including the pressure-sensitive adhesive layer and the base material but not including the release liner) disclosed herein is not particularly limited, and is suitably in the range of about 2 to 1000 ⁇ m.
  • the thickness is preferably 5 to 500 ⁇ m (for example, 10 to 300 ⁇ m, typically 30 to 100 ⁇ m).
  • the pressure-sensitive adhesive sheet having a limited total thickness can be advantageous in terms of reducing the size, weight, and resource saving of the product to which the pressure-sensitive adhesive sheet is applied.
  • a resin film, paper, cloth, rubber film, foam film, metal foil, a composite or laminate of these, and the like can be used.
  • a resin film layer is included from a viewpoint of sticking property or an external appearance property.
  • the inclusion of the resin film layer is advantageous from the viewpoint of dimensional stability, thickness accuracy, workability, tensile strength, and the like.
  • resin films examples include polyolefin resin films such as polyethylene (PE), polypropylene (PP), and ethylene / propylene copolymers; polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; Vinyl chloride resin film; vinyl acetate resin film; polyimide resin film; polyamide resin film; fluorine resin film; cellophane; Preferable examples include resin films formed from PE, PP, and PET. Among the resin films, a polyester film is more preferable, and a PET film is more preferable among them.
  • the film-like substrate may have a single layer structure or may have a multilayer structure of two layers or three or more layers.
  • the film-like base material is a base material (foam-containing base material) provided with a foam film.
  • the foam film refers to a film-like structure provided with a portion having bubbles (bubble structure).
  • the foam-containing base material may be a single-layer structure composed of a foam film, or a multilayer in which at least one of two or more multilayer structures is composed of a foam film (foam layer). It may be a structure.
  • a foam containing base material the composite base material with which the foam film (foam layer) and the non-foam film (non-foam layer) were laminated
  • Non-foamed film refers to a film-like structure that has not undergone intentional treatment (for example, bubble introduction treatment) to make a foam, and a film that does not substantially have a bubble structure.
  • a typical example of a non-foam film is a resin film (for example, a polyester-based resin film such as PET) having an expansion ratio of less than 1.1 times (for example, less than 1.05 times, typically less than 1.01 times).
  • the film-like substrate includes two or more foam layers, the materials and structures of these foam layers may be the same or different.
  • the contact bonding layer may be arrange
  • the average cell diameter of the foam film is not particularly limited, but is usually suitably 10 ⁇ m to 200 ⁇ m, preferably 20 ⁇ m to 180 ⁇ m, and more preferably 30 ⁇ m to 150 ⁇ m.
  • the average cell diameter is 10 ⁇ m or more, the impact absorbability tends to be improved.
  • the average cell diameter is 200 ⁇ m or less, the handleability and waterproofness (water-stopping property) tend to be improved.
  • the average cell diameter ( ⁇ m) of the foam film can be determined by taking an enlarged image of the foam cross section and analyzing the image using a commercially available low vacuum scanning electron microscope.
  • the number of bubbles to be analyzed may be about 10-20.
  • As the low vacuum scanning electron microscope for example, a trade name “S-3400N scanning electron microscope” manufactured by Hitachi High-Tech Science Systems, Inc. can be used.
  • the density (apparent density) of the foam film is not particularly limited, but is usually suitably 0.01 g / cm 3 or more, preferably 0.01 to 0.7 g / cm 3 , Preferably, it is 0.02 to 0.5 g / cm 3 .
  • the density is not particularly limited, but is usually suitably 0.01 g / cm 3 or more, preferably 0.01 to 0.7 g / cm 3 , Preferably, it is 0.02 to 0.5 g / cm 3 .
  • the density (apparent density) of the foam film is measured according to the method described in JIS K 7222: 1999. Specifically, a foam film is punched into a size of 100 mm ⁇ 100 mm to prepare a sample, and the dimension of the sample is measured. Further, the thickness of the sample is measured using a 1/100 dial gauge having a measurement terminal diameter of 20 mm. The volume of the foam film sample is calculated from these values. Further, the weight of the sample is measured with an upper pan balance having a minimum scale of 0.01 g or more. From these values, the apparent density (g / cm 3 ) of the foam film can be determined.
  • the 50% compressive load of the foam film is not particularly limited. From the viewpoint of impact resistance, it is appropriate that the foam film exhibits a 50% compressive load of 0.1 N / cm 2 or more. When the 50% compression load is equal to or greater than the predetermined value, for example, even when the foam film is thin (for example, about 100 ⁇ m thick), sufficient resistance when compressed (to push back when compressed) Force), and good impact resistance can be maintained.
  • the 50% compressive load is preferably 0.2 N / cm 2 or more, more preferably 0.5 N / cm 2 or more.
  • the 50% compression load is suitably 8 N / cm 2 or less, preferably 6 N / cm 2 or less, more preferably 3 N / cm 2 or less.
  • the 50% compression load (hardness) of the foam film is measured according to JIS K 6767: 1999. Specifically, the foam film is cut out to 100 mm ⁇ 100 mm, laminated so that the total thickness is 2 mm or more, and this is used as a measurement sample. When the sample was compressed at a speed of 10 mm / min using a compression tester at room temperature, and the compression rate reached 50% (compressed to 50% of the initial thickness) The value after 10 seconds holding (repulsive stress: N / cm 2 ) is recorded as a 50% compression load. About other conditions (for example, a jig
  • the cell structure of the foam constituting the foam film disclosed herein is not particularly limited.
  • the cell structure may be any of an open cell structure, a closed cell structure, and a semi-continuous semi-closed cell structure. From the viewpoint of impact absorption, an open cell structure and a semi-open semi-closed cell structure are preferable.
  • the material of the foam film is not particularly limited.
  • the foam film can be formed from a material that typically includes a polymer component (eg, a thermoplastic polymer).
  • a foam film formed of a foam of a plastic material (plastic foam) is preferable.
  • the plastic material for forming the plastic foam (meaning including rubber material) is not particularly limited, and can be appropriately selected from known plastic materials.
  • Plastic materials typically thermoplastic polymers
  • the main component of the polymer component contained in the film-like substrate or the foam film may be hereinafter referred to as “base polymer”.
  • foams include polyolefin resin foams such as PE foams and PP foams; polyester resin foams such as PET foams, polyethylene naphthalate foams, polybutylene terephthalate foams, etc. Body; Polyvinyl chloride resin foam such as polyvinyl chloride foam; Vinyl acetate resin foam; Acrylic resin foam; Polyphenylene sulfide resin foam; Polyamide (nylon) resin foam; Amide resin foams such as wholly aromatic polyamide (aramid) resin foams; Polyimide resin foams; Polyetheretherketone (PEEK) foams; Polystyrene ether foams such as polystyrene foams And urethane resin foams such as polyurethane resin foam; and the like. Further, as the foam, a rubber-based resin foam such as a polychloroprene rubber foam may be used.
  • a rubber-based resin foam such as a polychloroprene rubber foam may be used as a polychloroprene
  • an acrylic resin foam (acrylic resin foam) is used as the foam.
  • the acrylic resin foam refers to a foam containing an acrylic polymer as a base polymer.
  • the definition of the acrylic polymer in the present specification is as described below.
  • the alkyl (meth) acrylate constituting the acrylic polymer is one kind of alkyl (meth) acrylate having a chain alkyl group having 1 to 20 carbon atoms (preferably 1 to 8, typically 1 to 4). Or 2 or more types are used preferably.
  • Preferable examples of the alkyl (meth) acrylate include ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
  • the amount of the alkyl (meth) acrylate as the main monomer is suitably 70% by weight or more, preferably 75% by weight or more (for example, 80% by weight or more) in the total monomer components of the acrylic polymer.
  • the amount of the alkyl (meth) acrylate is suitably 98% by weight or less, preferably 97% by weight or less (for example, 96% by weight or less) in all monomer components.
  • the secondary monomer copolymerizable with the main monomer, alkyl (meth) acrylate can be useful for introducing a crosslinking point into the acrylic polymer or increasing the cohesive strength of the acrylic polymer.
  • a secondary monomer for example, a carboxy group-containing monomer, a hydroxyl group-containing monomer, an acid anhydride group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a functional group-containing monomer such as a monomer having a nitrogen atom-containing ring 1 type (s) or 2 or more types can be used.
  • the secondary monomer may also be a vinyl ester monomer such as vinyl acetate, an aromatic vinyl compound such as styrene, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, and the like.
  • the amount of the submonomer is suitably 0.5% by weight or more, preferably 1% by weight or more in the total monomer component of the acrylic polymer.
  • the amount of the submonomer is suitably 30% by weight or less, preferably 10% by weight or less, based on all monomer components.
  • the monomer component constituting the acrylic polymer is used as a sub-monomer. It is preferable that a nitrogen atom-containing monomer is contained. As a result, bubbles are likely to be generated during foaming, and when the foam is formed (typically, when the resin composition is dried), the viscosity of the composition increases and the bubbles are retained in the foam. The effect of being easy can be exhibited.
  • nitrogen atom-containing monomer examples include cyano group-containing monomers such as acrylonitrile and methacrylonitrile; lactam ring-containing monomers such as N-vinyl-2-pyrrolidone; (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, Amide group-containing monomers such as N-methylolacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and diacetoneacrylamide; These can be used alone or in combination of two or more. Of these, cyano group-containing monomers such as acrylonitrile and lactam ring-containing monomers such as N-vinyl-2-pyrrolidone are preferred.
  • the amount of the nitrogen atom-containing monomer is suitably 2% by weight or more, preferably 3% by weight or more (for example, 4% by weight or more) in the total monomer components of the acrylic polymer.
  • the amount of the nitrogen atom-containing monomer is suitably 30% by weight or less, preferably 25% by weight or less (for example, 20% by weight or less) in all monomer components.
  • the method for obtaining the acrylic polymer is not particularly limited.
  • a method for synthesizing the acrylic polymer such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, active energy ray polymerization method (for example, UV polymerization method).
  • Various known polymerization methods can be appropriately employed.
  • a monomer mixture is dissolved or dispersed in a suitable polymerization solvent (toluene, ethyl acetate, water, etc.), and a polymerization operation is performed using a polymerization initiator such as an azo polymerization initiator or a peroxide initiator.
  • a desired acrylic polymer can be obtained.
  • An acrylic resin foam (emulsion-type acrylic resin foam) obtained by an emulsion polymerization method is preferably used in terms of foamability and environmental aspects.
  • the acrylic resin foam-forming composition preferably contains a cross-linking agent from the viewpoint of increasing the cohesive strength.
  • the type of the crosslinking agent is not particularly limited, and one or more of various crosslinking agents can be appropriately selected and used.
  • the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a melamine crosslinking agent, and a metal oxide crosslinking agent. Of these, oxazoline-based crosslinking agents are preferred.
  • the amount of the crosslinking agent used is not particularly limited, and is from about 10 parts by weight or less (for example, about 0.005 to 10 parts by weight, preferably about 0.01 to 5 parts by weight) with respect to 100 parts by weight of the acrylic polymer. It is appropriate to select.
  • a polyolefin resin foam (polyolefin resin foam) is used as the foam.
  • plastic material constituting the polyolefin foam various known or commonly used polyolefin resins can be used without particular limitation.
  • polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), metallocene catalyst type linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene- A vinyl acetate copolymer etc. are mentioned.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • HDPE high density polyethylene
  • metallocene catalyst type linear low density polyethylene polypropylene
  • ethylene-propylene copolymer ethylene- A vinyl acetate copolymer etc.
  • Such polyolefin resin can be used individually by 1 type or in combination of 2 or more types as appropriate.
  • a polyethylene foam film substantially composed of a polyethylene resin foam examples thereof include a polypropylene-based foam film substantially composed of a foam.
  • the polyethylene-based resin refers to a resin having ethylene as a main monomer (that is, a main component of the monomer), and other than HDPE, LDPE, LLDPE, etc., the ethylene copolymerization ratio exceeds 50% by weight.
  • -Propylene copolymer, ethylene-vinyl acetate copolymer, etc. may be included.
  • a polypropylene resin refers to a resin having propylene as a main monomer.
  • a polypropylene-based foam film can be preferably employed.
  • the foaming method of the foam film is not particularly limited, and methods such as a chemical method and a physical method can be used alone or in combination depending on the purpose and operability.
  • a physical foaming method is preferable from the viewpoint of contamination and the like.
  • a foaming method in which a low-boiling compound such as hydrocarbon or a foaming agent such as thermal expansion microspheres is contained in the film-forming material, and bubbles are formed from the foaming agent, a gas such as air mechanically And the like, a solvent removal foaming method using removal of a solvent such as water, a foaming method using a supercritical fluid, and the like.
  • a method of forming a foam film by injecting an inert gas (for example, oxygen dioxide) into a polymer for forming a foam film under pressure and reducing the pressure can be preferably employed.
  • an inert gas for example, oxygen dioxide
  • the average cell diameter can be easily limited to a predetermined value or less, and the foam film can be easily reduced in density.
  • a foam film is produced.
  • the formation of the foam film is not particularly limited.
  • a foaming method in which a gas such as air is mechanically mixed is employed, a resin composition containing bubbles (for example, an emulsion type resin composition) is then used.
  • a foam film can be obtained by applying on a substrate or release paper and drying.
  • the drying preferably includes a preliminary drying step of 50 ° C. or more and lower than 125 ° C. and a main drying step of 125 ° C. to 200 ° C. from the viewpoint of bubble stability and the like.
  • a film-like foam may be continuously formed using a calendar, an extruder, a conveyor belt casting, or the like, and a method of foam-molding a kneaded product of the foam-forming material may be employed.
  • the surface layer portion may be removed by slicing and adjusted to have a desired thickness and foam characteristics.
  • the thermoplastic polymer that can be included in the foam film may include a thermoplastic elastomer that exhibits properties as a rubber at room temperature and exhibits thermoplasticity at a high temperature.
  • a thermoplastic elastomer such as ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, polybutene, polyisobutylene, chlorinated polyethylene; styrene -Styrene elastomers such as butadiene-styrene copolymers; thermoplastic polyester elastomers; thermoplastic polyurethane elastomers; thermoplastic acrylic elastomers; Among them, a thermoplastic elastomer having a glass transition temperature of room temperature or lower (for example, 20 ° C. or lower) is preferably used.
  • foam film forming materials for example, emulsion type acrylic resin compositions
  • foaming agents such as anionic surfactants and cationic surfactants.
  • Various surfactants such as an agent, a nonionic surfactant, and an amphoteric surfactant can be used. Hydrocarbon or fluorine surfactants may be used.
  • anionic surfactants are preferred from the viewpoint of finer bubble diameter and bubble stability, and fatty acid ammonium (typically higher fatty acid ammonium) surfactants such as ammonium stearate are more preferred.
  • the said surfactant can be used individually by 1 type or in combination of 2 or more types.
  • the surfactant content is preferably about 0.1 to 10 parts by weight (eg 0.5 to 8 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film.
  • the foaming agent in this specification includes not only an agent exhibiting a foaming action but also a bubble stabilizer such as a bubble diameter adjusting agent for reducing the bubble diameter and a foam stabilizer.
  • the foam film-forming material is an aqueous dispersion (for example, an acrylic emulsion)
  • a silicone compound as the foaming agent.
  • the silicone compound a silicone compound having a siloxane bond of 2000 or less is preferable.
  • the silicone compound include silicone oil, modified silicone oil, and silicone resin. Of these, dimethyl silicone oil and methylphenyl silicone oil are preferable.
  • a silicone-modified polymer for example, silicone-modified acrylic polymer, silicone-modified urethane polymer, etc.
  • the content of the silicone compound is 0.01 to 5 parts by weight (eg 0.05 to 4 parts by weight, typically 0.1 to 3 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film. It is preferable to set the degree.
  • the foam film-forming material may contain a thickener.
  • the thickener is not particularly limited, and examples thereof include an acrylic acid thickener, a urethane thickener, and a polyvinyl alcohol thickener. Of these, polyacrylic acid thickeners and urethane thickeners are preferred.
  • the content of the thickener is preferably about 0.1 to 10 parts by weight (for example, 0.1 to 5 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film.
  • the foam film When a foam-containing substrate is used as the film-like substrate, the foam film preferably contains a cell nucleating agent such as a metal hydroxide (for example, magnesium hydroxide).
  • a cell nucleating agent such as a metal hydroxide (for example, magnesium hydroxide).
  • the cell nucleating agent may be a metal oxide, composite oxide, metal carbonate, metal sulfate or the like.
  • the content of the cell nucleating agent is preferably about 0.5 to 125 parts by weight (for example, 1 to 120 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film.
  • the foam film contains a gas permeation inhibitor such as fatty acid amide from the viewpoint of suppressing the permeation of gas components from the foam during the formation of bubbles. It is preferable.
  • the fatty acid amide is more preferably one having a bisamide structure.
  • the gas permeation inhibitor may be a fatty acid metal salt.
  • the content of the gas permeation inhibitor is about 0.5 to 10 parts by weight (for example, 0.7 to 8 parts by weight, typically 1 to 6 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film. It is preferable to do.
  • the film-like substrate may contain a softening agent for the purpose of imparting desired fluidity to the film-forming material and improving properties such as flexibility.
  • a softening agent for the purpose of imparting desired fluidity to the film-forming material and improving properties such as flexibility.
  • properties such as film stretchability and expansion ratio can be preferably adjusted.
  • hydrocarbon softeners such as liquid paraffin, paraffin wax, microwax and polyethylene wax, ester softeners such as stearic acid monoglyceride, and fatty acid softeners can be preferably used. .
  • the content of the softening agent is 0.5 to 50 parts by weight (for example, 0.8 to 40 parts by weight, typically 1 to 30 parts) with respect to 100 parts by weight of the base polymer of the film-like substrate (for example, foam film). Part by weight) is preferable.
  • an arbitrary rust inhibitor may be included to prevent corrosion of the metal member adjacent to the foam film.
  • an azole ring-containing compound is preferable.
  • an azole ring-containing compound it is possible to achieve both high levels of metal corrosion prevention and adhesion to an adherend.
  • compounds in which the azole ring forms a condensed ring with an aromatic ring such as a benzene ring are preferred, and benzotriazole compounds and benzothiazole compounds are particularly preferred.
  • the content of the rust inhibitor is preferably about 0.2 to 5 parts by weight (for example, 0.3 to 2 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film.
  • the film-like substrate has transparency (including translucency).
  • the pressure-sensitive adhesive sheet having such a film-like substrate when bubbles or the like are mixed between the pressure-sensitive adhesive sheet and the adherend, the bubbles are visually recognized through the pressure-sensitive adhesive sheet, and the appearance is easily impaired. According to the technique disclosed herein, generation of bubbles or the like between the pressure-sensitive adhesive sheet and the adherend is prevented, so that excellent appearance can be obtained in a configuration including a transparent substrate.
  • the film-like substrate may exhibit a total light transmittance of 80% or more (for example, 90% or more, typically 95% or more).
  • the haze value of a film-form base material is 10% or less (for example, 5% or less).
  • the film-like substrate (for example, a resin film) may be colored black, white, or other colors by including various colorants (for example, pigments) in order to impart desired designability and optical characteristics. Carbon black is preferred as the black colorant.
  • a filler inorganic filler, organic filler, etc.
  • an anti-aging agent for example, an antioxidant, an ultraviolet absorber, as necessary.
  • various additives such as an antistatic agent, a lubricant and a plasticizer may be further blended.
  • the surface (back surface) opposite to the surface on which the pressure-sensitive adhesive layer is provided is formed smoothly among the surfaces of the film-like substrate.
  • the smooth surface can be the outer surface of the pressure-sensitive adhesive sheet, when the pressure-sensitive adhesive sheet having the smooth surface is used as, for example, a decorative sheet or a surface protective sheet, a better appearance (design) can be provided.
  • the arithmetic average surface roughness on the back surface of the film-like substrate is 1 ⁇ m or less (for example, about 0.05 to 0.75 ⁇ m, typically about 0 from the viewpoint of adhesive properties and appearance (design). .1 to 0.5 ⁇ m).
  • the arithmetic average surface roughness is measured using a general surface roughness measuring device (for example, a non-contact three-dimensional surface shape measuring device manufactured by Veeco, model “Wyko NT-3300”). be able to.
  • the back surface of the film-like substrate (the side opposite to the surface on which the adhesive layer is provided)
  • the surface may be subjected to a release treatment with a release treatment agent such as a silicone-based, long-chain alkyl-based, or fluorine-based material, if necessary.
  • a release treatment agent such as a silicone-based, long-chain alkyl-based, or fluorine-based material
  • the peeling treatment effects such as easy rewinding of the wound body obtained by winding the pressure-sensitive adhesive sheet into a roll shape can be obtained.
  • the surface of the film-like base material which has been conventionally known, such as corona discharge treatment, primer coating, etc. May be given.
  • the thickness of the film-like substrate is not particularly limited and can be appropriately selected depending on the purpose. In general, the thickness is usually 1 ⁇ m or more (for example, about 2 to 500 ⁇ m), and 5 to 500 ⁇ m (for example, 10 to 200 ⁇ m, typically 15 to 100 ⁇ m). Is preferred. Limiting the thickness of the film-like substrate is advantageous in terms of reducing the thickness, reducing the size, reducing the weight, and saving resources of the pressure-sensitive adhesive sheet.
  • the thickness of the foam-containing substrate (for example, the foam film substrate) can be appropriately set according to the strength, flexibility, purpose of use, etc. of the pressure-sensitive adhesive sheet. . From the viewpoint of impact absorption and the like, it is appropriate that the thickness of the foam-containing substrate is 30 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 60 ⁇ m or more (for example, 80 ⁇ m or more). From the viewpoint of reducing the thickness of the pressure-sensitive adhesive sheet, reducing the size, reducing the weight, saving resources, and the like, it is usually appropriate to set the thickness of the foam-containing substrate to 1 mm or less.
  • the foam film disclosed herein By using the foam film disclosed herein, an excellent shock absorbing function can be exhibited even when the thickness is about 350 ⁇ m or less (more preferably 250 ⁇ m or less, for example, 180 ⁇ m or less).
  • the thickness of the foam film (which may be a foam layer) in the foam-containing substrate can also be preferably selected from the range exemplified as the thickness of the above-mentioned foam-containing substrate.
  • the pressure-sensitive adhesive layer disclosed herein typically exhibits a soft solid (viscoelastic body) state in a temperature range near room temperature, and is a material (pressure-sensitive adhesive) that has a property of easily adhering to an adherend by pressure. ).
  • the adhesive here is generally complex elastic modulus E * (1 Hz) as defined in “C. A. Dahlquist,“ Adhesion: Fundamental and Practice ”, McLaren & Sons, (1966) P. 143”. ⁇ 10 ⁇ 7 > dyne / cm ⁇ 2 > material (typically a material having the above properties at 25 [deg.] C.).
  • the pressure-sensitive adhesive layer disclosed herein is a known acrylic polymer, rubber polymer, polyester polymer, urethane polymer, polyether polymer, silicone polymer, polyamide polymer, fluorine polymer, etc. in the field of pressure sensitive adhesive. 1 type, or 2 types or more may be included as a base polymer. From the viewpoint of adhesive properties (for example, peel strength and repulsion resistance) and molecular design, an acrylic polymer can be preferably used. In other words, the pressure-sensitive adhesive layer is preferably an acrylic pressure-sensitive adhesive layer containing an acrylic polymer as a base polymer.
  • the “base polymer” of the pressure-sensitive adhesive refers to the main component of the polymer component contained in the pressure-sensitive adhesive (typically a component included in an amount exceeding 50% by weight).
  • the acrylic polymer for example, a polymer of a monomer raw material that includes alkyl (meth) acrylate as a main monomer and may further include a submonomer copolymerizable with the main monomer is preferable.
  • the main monomer means a component occupying more than 50% by weight of the monomer composition in the monomer raw material.
  • alkyl (meth) acrylate for example, a compound represented by the following formula (1) can be preferably used.
  • CH 2 C (R 1 ) COOR 2 (1)
  • R 1 in the above formula (1) is a hydrogen atom or a methyl group.
  • R 2 is a chain alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of the number of carbon atoms may be represented as “C 1-20 ”).
  • an alkyl (meth) acrylate in which R 2 is a chain alkyl group of C 1-12 eg, C 2-10 , typically C 4-8 ) is preferable.
  • alkyl (meth) acrylate in which R 2 is a C 1-20 chain alkyl group can be used singly or in combination of two or more.
  • Preferred alkyl (meth) acrylates include n-butyl acrylate and 2-ethylhexyl acrylate.
  • the secondary monomer copolymerizable with the main monomer, alkyl (meth) acrylate can be useful for introducing a crosslinking point into the acrylic polymer or increasing the cohesive strength of the acrylic polymer.
  • a submonomer for example, one or two functional group-containing monomers such as a carboxy group-containing monomer, a hydroxyl group-containing monomer, an acid anhydride group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, and a monomer having a nitrogen atom-containing ring The above can be used.
  • the secondary monomer may also be a vinyl ester monomer such as vinyl acetate, an aromatic vinyl compound such as styrene, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, and the like.
  • a vinyl ester monomer such as vinyl acetate, an aromatic vinyl compound such as styrene, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, and the like.
  • an acrylic polymer obtained by copolymerizing a carboxy group-containing monomer and a hydroxyl group-containing monomer as the submonomer is preferable.
  • the carboxy group-containing monomer include acrylic acid and methacrylic acid.
  • the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate.
  • the amount of the submonomer is suitably 0.5% by weight or more, preferably 1% by weight or more, based on the total monomer components of the acrylic polymer. Further, the amount of the submonomer is suitably 30% by weight or less, preferably 10% by weight or less (for example, 5% by weight or less) in the total monomer components.
  • the content of the carboxy group-containing monomer is, among all monomer components used for the synthesis of the acrylic polymer, from the viewpoint of coexistence of adhesive force and cohesive force. It is preferably in the range of about 0.1 to 10% by weight (eg 0.2 to 8% by weight, typically 0.5 to 5% by weight).
  • the content of the hydroxyl group-containing monomer is approximately 0 out of all monomer components used for the synthesis of the acrylic polymer from the viewpoint of achieving both cohesion and cohesion. It is preferably within the range of 0.001 to 10% by weight (eg 0.01 to 5% by weight, typically 0.02 to 2% by weight). Further, when a vinyl ester monomer such as vinyl acetate is copolymerized as the submonomer, the content of the vinyl ester monomer is about 30% in the total monomer components used for the synthesis of the acrylic polymer. % Or less (typically 0.01 to 30% by weight, for example 0.1 to 10% by weight).
  • the method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for acrylic polymers, such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization, are appropriately employed. be able to. Active energy ray irradiation polymerization performed by irradiation with UV or the like may be employed.
  • a monomer mixture is dissolved or dispersed in a suitable polymerization solvent (toluene, ethyl acetate, water, etc.), and a polymerization operation is performed using a polymerization initiator such as an azo polymerization initiator or a peroxide initiator.
  • a desired acrylic polymer can be obtained.
  • the weight average molecular weight (Mw) of the acrylic polymer disclosed herein is preferably in the range of 10 ⁇ 10 4 or more and 100 ⁇ 10 4 or less from the viewpoint of balancing the adhesive force and the cohesive force in a balanced manner.
  • Mw means the value of standard polystyrene conversion obtained by GPC (gel permeation chromatography).
  • the pressure-sensitive adhesive composition preferably contains a crosslinking agent from the viewpoint of increasing the cohesive force.
  • the type of the crosslinking agent is not particularly limited, and one or more conventionally known crosslinking agents can be appropriately selected and used.
  • Preferable examples of the crosslinking agent include isocyanate crosslinking agents and epoxy crosslinking agents.
  • the amount of the crosslinking agent used is not particularly limited, and is, for example, about 10 parts by weight or less (for example, about 0.005 to 10 parts by weight, preferably about 0.01 to 5 parts by weight) with respect to 100 parts by weight of the acrylic polymer. You can choose from a range.
  • the pressure-sensitive adhesive layer disclosed herein may have a composition containing a tackifier.
  • the tackifier is not particularly limited, for example, rosin tackifier resin, terpene tackifier resin, hydrocarbon tackifier resin, epoxy tackifier resin, polyamide tackifier resin, elastomer tackifier resin, Various tackifying resins such as a phenolic tackifying resin and a ketone tackifying resin can be used. Such tackifier resin can be used individually by 1 type or in combination of 2 or more types.
  • the softening point (softening temperature) of the tackifier resin is preferably about 60 ° C. or higher (preferably about 80 ° C. or higher, typically 100 ° C. or higher). Thereby, the adhesive sheet with higher adhesive force can be realized.
  • the upper limit of the softening point of the tackifying resin is not particularly limited, and can be about 180 ° C. or lower (for example, about 140 ° C. or lower).
  • the softening point of the tackifier resin here is defined as a value measured by a softening point test method (ring ball method) defined in any of JIS K5902: 2006 and JIS K2207: 2006.
  • the amount of the tackifier used is not particularly limited, and can be appropriately set according to the target tack performance (adhesive strength, etc.).
  • the tackifier is approximately 10 to 100 parts by weight (more preferably 20 to 80 parts by weight, more preferably 30 to 60 parts by weight) with respect to 100 parts by weight of the base polymer (preferably an acrylic polymer) based on the solid content. (Part by weight) is preferably used.
  • the pressure-sensitive adhesive composition may be a leveling agent, a crosslinking aid, a plasticizer, a softener, a filler, an antistatic agent, an anti-aging agent, an ultraviolet absorber, an antioxidant, a light stabilizer, etc., if necessary.
  • Various additives common in the field of pressure-sensitive adhesive compositions can be contained. About such various additives, a conventionally well-known thing should just be used by a conventional method.
  • the pressure-sensitive adhesive layer disclosed herein may be a pressure-sensitive adhesive layer formed from a water-based, solvent-type, hot-melt type, active energy ray-curable pressure-sensitive adhesive composition, or the like.
  • the water-based pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in a form containing a pressure-sensitive adhesive (pressure-sensitive adhesive layer forming component) in a water-based solvent (water-based solvent), and is typically dispersed in water.
  • a type pressure-sensitive adhesive composition a composition in which at least a part of the pressure-sensitive adhesive is dispersed in water
  • a solvent-type adhesive composition means the adhesive composition of the form which contains an adhesive in an organic solvent.
  • a water-based pressure-sensitive adhesive composition is preferable from the viewpoint of reducing environmental burden, and a solvent-type pressure-sensitive adhesive composition is preferably used from the viewpoint of adhesive properties and the like.
  • the pressure-sensitive adhesive layer disclosed herein can be formed by a conventionally known method.
  • a method (direct method) of forming a pressure-sensitive adhesive layer by directly applying (typically applying) the pressure-sensitive adhesive composition to a substrate and drying it can be preferably employed.
  • a method for forming a pressure-sensitive adhesive layer on the surface by applying a pressure-sensitive adhesive composition to a surface having a peelable property (peeling surface) and drying it, and transferring the pressure-sensitive adhesive layer to a substrate May be adopted.
  • peelable property peelable property
  • transfer method May be adopted as the release surface, the surface of the release liner, the back surface of the substrate after the release treatment, or the like.
  • the pressure-sensitive adhesive composition is applied using a known or conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, die coater, bar coater, knife coater, spray coater, etc. be able to.
  • the pressure-sensitive adhesive composition may be applied by impregnation or curtain coating.
  • the pressure-sensitive adhesive composition is preferably dried under heating.
  • the drying temperature can be, for example, about 40 to 150 ° C., and is usually preferably about 60 to 130 ° C.
  • After drying the pressure-sensitive adhesive composition it may be further aged for the purpose of adjusting component migration in the pressure-sensitive adhesive layer, progress of the crosslinking reaction, relaxation of strain that may exist in the base material or pressure-sensitive adhesive layer, etc. Good.
  • the thickness of the pressure-sensitive adhesive layer disclosed herein is not particularly limited and can be appropriately selected depending on the purpose. Usually, from the viewpoint of productivity such as drying efficiency and adhesive properties, it is appropriate to be about 0.5 to 200 ⁇ m, and about 2 to 200 ⁇ m (for example, 5 to 100 ⁇ m, typically 10 to 50 ⁇ m). It is preferable to do. Limiting the thickness of the pressure-sensitive adhesive layer is advantageous in terms of reducing the thickness of the pressure-sensitive adhesive sheet, reducing the size, reducing the weight, and saving resources. When the technique disclosed here is implemented in the form of a double-sided pressure-sensitive adhesive sheet having pressure-sensitive adhesive layers on both sides of the substrate, the thickness of each pressure-sensitive adhesive layer may be the same or different.
  • the coat layer that partially covers the surface of the pressure-sensitive adhesive layer is not particularly limited as long as it can impart air bleedability.
  • a preferred example of the coating layer material is a resin material. From the viewpoint of appearance, a coat layer formed from a transparent or translucent resin material is preferable.
  • the resin material that can constitute the coating layer examples include polyurethane resins, phenol resins, epoxy resins, polyamide resins, urea melamine resins, silicone resins, polysilazane resins, fluorine resins, phenoxy resins, methacrylic resins.
  • vinyl, polyvinylidene chloride, polycarbonate, celluloses, polyacetal and the like examples of these resins may be one type or two or more types of resins selected from various types of resins such as thermosetting resins, ultraviolet curable resins, electron beam curable resins, and two-component mixed resins.
  • the coating layer disclosed herein includes a filler, an antioxidant, an antioxidant, an ultraviolet absorber, a crosslinking agent, a lubricant, a colorant (pigment, dye, etc.), an antistatic agent, a fluidity modifier (thixotropic agent, Various additives such as thickeners and film-forming aids may be included as necessary.
  • the coat layer is preferably non-adhesive or weakly adhesive. Thereby, good air escape properties are preferably realized.
  • that the coating layer is non-tacky or weakly tacky means that the 180 ° peel strength of the coating layer is less than 3 N / 25 mm (typically less than 1 N / 25 mm, and the adhesive force is too low to be measured. Including the case.)
  • the 180 degree peel strength of the coat layer is measured by the following method. That is, for a measurement sample obtained by cutting a pressure-sensitive adhesive sheet having a coating layer on the entire surface of the pressure-sensitive adhesive layer into a size of 25 mm in width and 100 mm in length, the coating layer of the measurement sample is used at 23 ° C.
  • the method for arranging the coat layer on the surface of the pressure-sensitive adhesive layer is not particularly limited.
  • the following method can be adopted.
  • the composition for forming a coat layer is prepared by dissolving or dispersing in a suitable solvent as necessary.
  • the composition is also referred to as a peelable support (also referred to as “coat layer transfer film”, typically a release liner). Apply to the surface and cure.
  • the peelable support body surface in which the coating layer was formed is contact
  • a desired coat layer pattern such as a grid pattern can be preferably formed by employing a method such as offset printing, silk screen printing, letterpress printing, flexographic printing, gravure printing, or ink jet printing. From the viewpoint of air escape, gravure printing is more preferable.
  • the coating layer may be partially disposed on the surface of the pressure-sensitive adhesive layer by applying the composition for forming a coating layer directly to the surface of the pressure-sensitive adhesive layer and curing it by a technique such as ultraviolet curing.
  • the thickness of the coat layer is not particularly limited as long as it is designed so as to obtain a desired air escape property.
  • the thickness of the pressure-sensitive adhesive layer is not more than half (for example, 1 / 3 or less, typically 1/5 or less).
  • the thickness of the coat layer is preferably 0.1 ⁇ m or more (for example, 0.5 ⁇ m or more, typically 1 ⁇ m or more) from the viewpoint of air bleeding.
  • the thickness of the coat layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less (eg, 3 ⁇ m or less, typically 2 ⁇ m or less).
  • the thickness of a coating layer can be grasped
  • TEM transmission electron microscope
  • the technique disclosed herein is preferably implemented in the form of a pressure-sensitive adhesive sheet with a release liner provided with a release liner that protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet.
  • a conventional release paper or the like can be used as the release liner, and is not particularly limited.
  • a low-adhesiveness of a release liner having a release treatment layer on the surface of a liner substrate such as a resin film such as PET or paper, or a fluorine-based polymer (polytetrafluoroethylene, etc.) or a polyolefin resin (PE, PP, etc.)
  • a release liner made of a material can be used.
  • the release treatment layer may be formed, for example, by surface-treating the liner base material with a release treatment agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.
  • the peelable surface (the surface on the side in contact with the adhesive surface of the pressure-sensitive adhesive sheet) of the release liner (release film) is formed smoothly.
  • a coat layer is partially formed on the peelable surface of such a release liner, and the surface of the pressure-sensitive adhesive layer is brought into contact with the surface of the release liner on which the coat layer is partially formed so that the coat layer is the surface of the pressure-sensitive adhesive layer.
  • the release liner also serves as a coat layer transfer film (release film)
  • a coat layer is partially formed on the peelable surface of the release liner as described above, and an adhesive layer is further formed on the peelable surface on which the coat layer is formed so as to cover the coat layer.
  • the formed pressure-sensitive adhesive layer is transferred to the surface of the film-like substrate.
  • the arithmetic average surface roughness of the release surface of the release liner is 1 ⁇ m or less (eg, about 0.05 to 0.75 ⁇ m, typically about 0.1 to 0.5 ⁇ m). Is preferred.
  • the release liner used for the production of the pressure-sensitive adhesive sheet disclosed herein may be a release liner 110 with a coat layer including a peelable support 120 having a peelable surface 120A as shown in FIG.
  • the peelable support 120 may have a release treatment layer on at least one surface of the liner substrate, or may be a support made of a low adhesive material.
  • a coat layer 30 that can be transferred to an adhesive sheet is provided on the peelable surface 120A of the peelable support 120. That is, the coat layer 30 is disposed on the peelable surface 120A in a state where it can be separated by the adhesive force of the pressure-sensitive adhesive.
  • the configuration of the coat layer (shape, arrangement state, arrangement relationship, size, pattern, etc.) provided on the peelable surface of the peelable support is the configuration of the coat layer that partially covers the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet described above. Therefore, the structure and relative relationship (including the area ratio of the coat layer non-arranged part) of the coat layer disposition part and the coat layer non-arrangement part on the peelable surface are also included in the adhesive. Since it is basically the same as the configuration and relative relationship (including the area ratio of the coat layer non-arranged part) of the coat layer arrangement part and the coat layer non-arrangement part on the surface of the agent layer, description thereof is omitted.
  • the thickness (total thickness) of the release liner is not particularly limited, but is preferably about 10 to 500 ⁇ m (for example, 15 to 100 ⁇ m) from the viewpoints of release workability, handleability, strength, and the like.
  • the pressure-sensitive adhesive sheet disclosed herein can efficiently prevent generation of bubbles and the like between the adherend and the adherend. Therefore, in any pasting method of manual pasting (hand pasting) or pasting (automatic pasting) using an automatic pasting machine or the like, the pasting property is improved. For example, in the case of pasting by hand, the dependence on the individual skill can be reduced, so that advantages such as improvement and stabilization of pasting efficiency and pasting quality can be obtained. In addition, when pasting by automatic pasting, it is possible to realize a reduction in pasting failure such as mixing of bubbles and a reduction in pasting work.
  • bubbles may be generated between the pressure-sensitive adhesive sheet and the adherend not only at the time of pasting but also as time passes after pasting.
  • a relatively high temperature eg, 35 ° C. or higher
  • the above-mentioned bubbles and the like are generated between the adhesive sheet and the adherend.
  • the appearance may be deteriorated.
  • the inside of a factory in summer, the outdoors, the inside of an electronic device, and the like are likely to be in a high temperature state as described above. According to the technology disclosed herein, generation of bubbles and the like can be prevented even when used in applications exposed to the high temperature environment as described above.
  • the pressure-sensitive adhesive sheet disclosed herein can be preferably used for applications to be applied to the surface of various articles by taking advantage of the characteristics described above.
  • it can be used as various decorative sheets, surface protective sheets, fixing sheets for printing plates such as flexographic printing, light shielding sheets, and the like.
  • a decorative sheet typically a paint substitute sheet
  • it is also suitable as a covering sheet used for the purpose of improving the smoothness of the outer surface of the chassis and for covering non-uniform portions such as screw holes on the surfaces of various members inside an electronic device such as a television.
  • a covering sheet it is possible to reduce the appearance unevenness on the outer surface of the adherend and make the dimensional accuracy uniform.
  • it can be preferably used as an exterior sheet of a battery pack in which appearance is important.
  • a surface protective sheet for a portable electronic device for example, a mobile phone, a smartphone, a tablet computer, a notebook computer, etc.
  • a bonding and fixing application in a liquid crystal display device of the portable electronic device for example, a display unit of the portable electronic device
  • a protection panel (lens) fixing application for example, a key module member fixing application of a cellular phone, and the like.
  • the pressure-sensitive adhesive sheet When used in the portable electronic device, the pressure-sensitive adhesive sheet may have a frame shape (frame shape), a band shape (strip shape), or the like depending on the purpose or the like.
  • frame shape frame shape
  • band shape strip shape
  • “portable” means that it is not sufficient to be able to carry it alone, but to have a portability that allows an individual (standard adult) to carry it relatively easily. Shall mean.
  • a pressure-sensitive adhesive sheet comprising a film-like substrate and a pressure-sensitive adhesive layer provided on at least one surface of the film-like substrate, A coating layer partially covering the pressure-sensitive adhesive layer surface, whereby the pressure-sensitive adhesive layer surface has a coating layer disposition portion and a coating layer non-disposition portion;
  • the area ratio of the coating layer non-arranged portion on the pressure-sensitive adhesive layer surface is 70% or more,
  • the coat layer arrangement portion has a portion extending linearly from one end of the pressure-sensitive adhesive layer to the other when the pressure-sensitive adhesive layer surface is viewed from above,
  • the pressure-sensitive adhesive sheet has a width of the linearly extending portion within a range of 0.1 to 2 mm.
  • a plurality of linearly extending portions are disposed on the pressure-sensitive adhesive layer surface, Among the plurality of linearly extending portions, the plurality of linearly extending portions constituting a group are arranged at intervals in the width direction, whereby the coat layer arranging portion has a stripe pattern.
  • the coat layer arrangement portion includes a first stripe pattern portion and a second stripe pattern portion arranged to intersect the first stripe pattern portion, whereby the coat layer arrangement is performed.
  • the adhesive sheet according to (2), wherein the part has a lattice pattern.
  • the interval between a plurality of linearly extending portions constituting one stripe pattern is in the range of 1.0 to 10 mm, according to (2) or (3) above Adhesive sheet.
  • the pressure-sensitive adhesive layer contains an acrylic polymer in a proportion exceeding 50% by weight of the polymer component contained in the pressure-sensitive adhesive layer,
  • R 1 is a hydrogen atom or a methyl group.
  • R 2 is a chain alkyl group having 1 to 20 carbon atoms.
  • the acrylic polymer is an acrylic polymer obtained by copolymerizing at least one submonomer selected from the group consisting of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate.
  • the acrylic polymer is copolymerized with a carboxy group-containing monomer, and a copolymerization ratio of the carboxy group-containing monomer is 0.1 to about 0.1 to about all monomer components used in the synthesis of the acrylic polymer.
  • the pressure-sensitive adhesive sheet according to any one of (6) to (9), wherein the pressure-sensitive adhesive sheet is 10% by weight.
  • the acrylic polymer is copolymerized with a hydroxyl group-containing monomer, The pressure-sensitive adhesive sheet according to any one of the above (6) to (10), wherein the copolymerization ratio of the hydroxyl group-containing monomer is 0.001 to 10% by weight in the total monomer components used in the synthesis of the acrylic polymer. .
  • the pressure-sensitive adhesive sheet according to any one of (6) to (11), wherein the pressure-sensitive adhesive layer contains an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent.
  • the pressure-sensitive adhesive layer contains a tackifying resin having a softening point of 100 ° C. to 140 ° C. in a ratio of 30 to 60 parts by weight with respect to 100 parts by weight of the acrylic polymer,
  • the tackifier resin is at least one selected from the group consisting of a rosin tackifier resin, a terpene tackifier resin, and a hydrocarbon tackifier resin, according to any one of the above (6) to (12).
  • Adhesive sheet is at least one selected from the group consisting of a rosin tackifier resin, a terpene tackifier resin, and a hydrocarbon tackifier resin, according to any one of the above (6) to (12).
  • the pressure-sensitive adhesive sheet according to any one of (1) to (13), wherein the coat layer is made of a transparent resin.
  • the coating layer is made of polyurethane resin, phenol resin, epoxy resin, polyamide resin, urea melamine resin, silicone resin, polysilazane resin, fluorine resin, phenoxy resin, methacrylic resin, acrylic resin.
  • the film-like substrate is a polyolefin resin film, a polyester resin film, a vinyl chloride resin film, a vinyl acetate resin film, a polyimide resin film, a polyamide resin film, a fluorine resin film, or a cellophane film.
  • a release liner for a pressure-sensitive adhesive sheet comprising a peelable support, wherein at least one surface is a peelable surface, On the peelable surface of the peelable support, a coat layer that can be transferred to the pressure-sensitive adhesive sheet is provided, whereby the peelable surface has a coat layer placement portion and a coat layer non-placement portion.
  • the area ratio of the coat layer non-arranged portion on the peelable surface is 70% or more,
  • the coat layer has a portion extending linearly from one end to the other end of the peelable surface, A release liner in which the width of the linearly extending portion is in the range of 0.1 to 2 mm.
  • Mw of the obtained acrylic polymer was about 440,000.
  • 30 parts of polymerized rosin pentaerythritol ester made by Arakawa Chemical Industries, trade name “Pencel D-125”, softening point 125 ° C.
  • an isocyanate-based crosslinking agent trade name “Coronate L”, manufactured by Nippon Polyurethane Industry Co., Ltd.
  • a coat layer forming material (urethane-based: two-component mixed curable ink) was applied to the peelable surface of a 75 ⁇ m-thick release film (trade name “FMN-75WD (C1-CA1)” manufactured by Fujiko) by gravure printing Then, a coat layer (coating thickness 1.5 ⁇ m, transparent) having a lattice pattern was formed.
  • a 75 ⁇ m thick PET film substrate (trade name “Lumirror”, manufactured by Toray Industries, Inc.) is prepared, and the pressure-sensitive adhesive composition is dried on the corona discharge treated surface of the PET substrate so that the thickness after drying is 15 ⁇ m. And dried at 100 ° C. for 3 minutes to form an adhesive layer on one side of the PET film substrate.
  • the surface of the pressure-sensitive adhesive layer was brought into contact with the surface of the release layer-coated release film obtained above to transfer the coat layer to the surface of the pressure-sensitive adhesive layer.
  • the release film was used for protecting the pressure-sensitive adhesive layer surface as it was.
  • a lattice pattern comprising the coating layer shown in FIG. 1 is formed on the surface of the pressure-sensitive adhesive layer of this pressure-sensitive adhesive sheet.
  • the width (line width) of the long portion of the coating layer arrangement portion is 2 mm, and the interval is 8 mm. It was.
  • Example 1B A pressure-sensitive adhesive sheet according to this example was produced in the same manner as in Example 1A, except that the interval between the long portions of the coat layer arrangement portion was changed to 13 mm.
  • Example 1C A pressure-sensitive adhesive sheet according to this example was prepared in the same manner as Example 1A except that the coat layer was not formed.
  • the adhesive sheet which concerns on each example SUS180 degree peel strength (adhesive force) was evaluated. Specifically, for a measurement sample obtained by cutting the pressure-sensitive adhesive sheet into a size of 25 mm in width and 100 mm in length, the adhesive surface of the measurement sample is made of a stainless steel plate (SUS304BA plate) in an environment of 23 ° C. and 50% RH. A 2 kg roller was reciprocated once on the surface and pressed. After leaving this in the same environment for 30 minutes, 24 hours or 72 hours, using a universal tensile compression tester in accordance with JIS Z 0237: 2000 under conditions of a tensile speed of 300 mm / minute and a peeling angle of 180 degrees.
  • SUS180 degree peel strength adheresive force
  • the peel strength (N / 25 mm) was measured. The measurement was performed three times for each example and each condition (elapsed time after pressure bonding), and the average value was adopted. Further, assuming that the 180 degree peel strength value in Example 1C where the area ratio of the coat layer non-arranged portion is 100% is 100%, the 180 degree peel strength values in Examples 1A and 1B are shown as relative values (%). The degree of decrease in adhesive strength accompanying the decrease in area of the part was evaluated. The results are shown in Table 1 together with the area ratio (%) of the coating layer non-arranged part.
  • Example 1A in which the area ratio of the coating layer non-arranged portion is 64%, the adhesive force does not increase with time.
  • the proportional relationship such as the initial adhesive strength is broken, and the area ratio of the coating layer non-arranged portion is 75%, and the value is significantly lower than the value expected from the result in Example 1C of 100%. It was. From this result, it can be seen that, in the configuration in which the coat layer is partially disposed on the surface of the pressure-sensitive adhesive layer, in order to obtain a high adhesive strength with time, the area ratio of the coat layer non-arranged portion needs to be 70% or more.
  • Example 2A to Example 2J The width (mm) and interval (mm) of the long part of the coat layer arrangement part were set to the values shown in Table 2, and pressure-sensitive adhesive sheets according to each example were produced in the same manner as in Example 1A.
  • Table 2 shows the 180-degree peel strength (N / 25 mm) after 24 hours measured for each example. The measuring method is as described above. Note that Example 2A, Example 2I, and Example 2J have the same configurations as Example 1B, Example 1A, and Example 1C, respectively.
  • the area ratio of the coating layer non-arranged portion on the surface of the pressure-sensitive adhesive layer is 70% or more, and the width of the long portion of the coating layer disposed portion is in the range of 0.1 to 2 mm.
  • the pressure-sensitive adhesive sheets according to 2A to Example 2H showed high adhesive strength with time (180-degree peel strength after 24 hours), and good air bleeding between the pressure-sensitive adhesive sheet and the adherend. Furthermore, the pressure-sensitive adhesive sheets according to Examples 2C to 2H were excellent in appearance because the coating layer was hardly visible when viewed from the adherend side and the pressure-sensitive adhesive sheet side after being bonded to the adherend.
  • the pressure-sensitive adhesive sheets according to Examples 2C to 2G were excellent in appearance and achieved both a good balance between high adhesive strength with time and air release.
  • Example 2E Example 2F
  • Example 2G the appearance properties of Example 2E, Example 2F, and Example 2G were particularly excellent.
  • the adhesive strength with time was lower than in Examples 2A to 2H.
  • Example 2J in which no coat layer was disposed, air bubbles remained between the adhesive sheet and the adherend.
  • Adhesive sheet 1A Adhesive surface 10 Film-like base material 20,21,22 Adhesive layer 20A Adhesive layer surface 30 Coat layer 40,41,42 Release liner 50 Coat layer arrangement part 51 Coat layer non-arrangement part 60 Coat Layer pattern (lattice pattern) 70 1st stripe pattern part 75A, 75B, 75C long part (part extended linearly) 80 Second stripe pattern portion 85A, 85B, 85C Long portion (portion extending linearly) 110 Release liner with coat layer 120 Peelable support 120A Peelable surface

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Abstract

Provided is an adhesive sheet which is capable of exhibiting high adhesive strength over time, and with which excellent air release properties between the adhesive sheet and an adherend are achieved. According to the present invention, provided is an adhesive sheet provided with: a film-like base material; and an adhesive layer provided to at least one surface of the film-like base material. The adhesive sheet is provided with a coating layer which partially covers the surface of the adhesive layer. Accordingly, the surface of the adhesive layer is provided with a section where the coating layer is provided and sections where the coating layer is not provided. Furthermore, the area ratio of the sections where the coating layer is not provided on the surface of the adhesive layer is at least 70%. Moreover, when the surface of the adhesive layer is viewed from above, the section where the coating layer is provided has segments which extend linearly from one end to another end of the adhesive layer. The width of the segments which extend linearly is in the range of 0.1-2 mm.

Description

粘着シートAdhesive sheet
　本発明は、粘着シートに関する。
　本出願は、２０１４年１１月２８日に出願された日本国特許出願２０１４－２４２１８３号および２０１５年８月２１日に出願された日本国特許出願２０１５－１６４２７０号に基づく優先権を主張しており、それら出願の全内容は本明細書中に参照として組み入れられている。 The present invention relates to an adhesive sheet.
This application claims priority based on Japanese Patent Application No. 2014-242183 filed on November 28, 2014 and Japanese Patent Application No. 2015-164270 filed on August 21, 2015. The entire contents of these applications are hereby incorporated by reference.
　一般に、粘着剤（感圧接着剤ともいう。以下同じ。）は室温付近の温度域において柔らかい固体（粘弾性体）の状態を呈し、圧力により簡単に被着体に接着する性質を有する。このような性質を活かして、粘着剤は、基材の少なくとも一方の表面に粘着剤層を設けた基材付き粘着シートの形態で、例えば、各種物品を固定したり、各種物品の表面保護、あるいは装飾など所望の外観を得る等の目的で広く利用されている。この種の従来技術を開示する文献として、特許文献１が挙げられる。 Generally, a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive, hereinafter the same) is in a soft solid (viscoelastic body) state in the temperature range near room temperature and has a property of easily adhering to an adherend by pressure. Taking advantage of such properties, the pressure-sensitive adhesive is in the form of a pressure-sensitive adhesive sheet with a base material provided with a pressure-sensitive adhesive layer on at least one surface of the base material, for example, fixing various articles, surface protection of various articles, Alternatively, it is widely used for the purpose of obtaining a desired appearance such as decoration. Patent document 1 is mentioned as a literature which discloses this kind of prior art.
日本国特許出願公開２０００－１６０１１７号公報Japanese Patent Application Publication No. 2000-160117
　従来の粘着シートでは、粘着シートを被着体に貼り付けるときに、粘着シートと被着体との間に空気等の流動性異物が残り、この異物が気泡等（空気だまり等）となって外観品質の低下を引き起こす場合がある。上記のような気泡等は接着力の低下など粘着特性に悪影響を及ぼす点でも望ましくない。このような気泡等の発生を予防し、または発生した気泡等を除去する性質（以下「空気抜け性」ともいう。）を付与することを目的として、粘着剤層の表面に非粘着性層を部分的に積層する技術が提案されている（特許文献１）。しかし、特許文献１に記載の技術では、粘着剤層表面に占める非粘着性層の面積割合が高いため、接着力が低下傾向となるなど粘着特性への影響に十分に対応したものではなかった。特に、貼り合わせ後、継続して高い接着力が要求される用途においては、信頼性の高い接着手段とならないことが本発明者らの検討によって明らかとなった。 In the conventional pressure-sensitive adhesive sheet, when the pressure-sensitive adhesive sheet is attached to the adherend, fluid foreign matters such as air remain between the pressure-sensitive adhesive sheet and the adherend, and the foreign matters become bubbles or the like (air traps or the like). It may cause deterioration in appearance quality. Such bubbles and the like are also undesirable in that they adversely affect the adhesive properties such as a decrease in adhesive strength. A non-adhesive layer is provided on the surface of the pressure-sensitive adhesive layer for the purpose of preventing the generation of such air bubbles or imparting the property of removing the generated air bubbles (hereinafter also referred to as “air venting”). A technique of partially laminating has been proposed (Patent Document 1). However, in the technique described in Patent Document 1, since the area ratio of the non-adhesive layer occupying the surface of the adhesive layer is high, the adhesive force tends to decrease and the effect on the adhesive properties is not sufficiently dealt with. . In particular, the present inventors have clarified that it is not a highly reliable adhesive means in applications where high adhesive strength is continuously required after bonding.
　本発明は、上記の事情に鑑みて創出されたものであり、高い経時接着力を示すことができ、かつ粘着シートと被着体との間における空気抜け性が良好な粘着シートを提供することを目的とする。 The present invention has been created in view of the above circumstances, and provides a pressure-sensitive adhesive sheet that can exhibit high adhesive strength over time and has good air escape between the pressure-sensitive adhesive sheet and the adherend. With the goal.
　本発明によると、フィルム状基材と、該フィルム状基材の少なくとも一方の表面に設けられた粘着剤層と、を備える粘着シートが提供される。この粘着シートは、前記粘着剤層表面を部分的に覆うコート層を備え、これによって、該粘着剤層表面はコート層配置部とコート層非配置部とを有する。また、前記粘着剤層表面における前記コート層非配置部の面積割合は７０％以上である。さらに、前記コート層配置部は、前記粘着剤層表面を上方から見たときに、該粘着剤層の一端から他端に向かって線状に延びる部分を有する。そして、前記線状に延びる部分の幅は０．１～２ｍｍの範囲内である。 According to the present invention, there is provided an adhesive sheet comprising a film-like substrate and an adhesive layer provided on at least one surface of the film-like substrate. The pressure-sensitive adhesive sheet includes a coat layer that partially covers the surface of the pressure-sensitive adhesive layer, whereby the surface of the pressure-sensitive adhesive layer has a coat layer placement portion and a coat layer non-placement portion. Moreover, the area ratio of the said coating layer non-arrangement | positioning part in the said adhesive layer surface is 70% or more. Furthermore, the said coating layer arrangement | positioning part has a part extended linearly toward the other end from the one end of this adhesive layer, when the said adhesive layer surface is seen from upper direction. The width of the linearly extending portion is in the range of 0.1 to 2 mm.
　一般的傾向として、粘着シートは、その粘着面の面積が小さくなると、それに比例して接着性も低下する。粘着シートの粘着面にコート層を配置した場合にも、コート層の被覆分だけ粘着面の露出面積は減少するため、同様の傾向を示すと考えられる。実際、後述の実施例においても、粘着剤層表面におけるコート層の面積が大きくなり粘着剤層の露出面積が減少すると、それに比例するように貼り合わせ直後の初期接着力は低下した。ところが、本発明者らの検討の結果、経時接着力については上記初期接着力とは異なる傾向を示すことが明らかになった。具体的には、コート層を粘着剤層表面に部分的に配置した構成において、粘着剤層表面におけるコート層非配置部の面積割合を７０％未満とした場合には、貼り合わせ直後からの接着力上昇が発現し難く、上記面積割合が７０％以上の場合と比べて経時接着力の不足傾向が増大することが判明した（後述の実施例参照）。そこで、ここに開示される技術では、上記コート層非配置部の面積割合を７０％以上として高い経時接着力を得る。しかし当然のことながら、コート層非配置部の面積を大きくすると、コート層配置部の面積は相対的に小さくなる。そのため、粘着シートと被着体との間に空気抜け性を付与するというコート層本来の作用が損なわれかねない。そこで、ここに開示される技術では、粘着剤層表面を上方から見たときに、粘着剤層の一端から他端に向かって線状に延びる部分を有するようにコート層を配置し、かつ当該線状に延びる部分の幅を０．１～２ｍｍの範囲内に設定する。これにより、高い経時接着力を示すことが可能な粘着シートにおいて、良好な空気抜け性を実現することができる。上記線状に延びる部分の幅は、０．２ｍｍ以上（例えば０．３ｍｍ以上、さらには０．５ｍｍ以上）とすることが好ましく、また１．２ｍｍ以下（より好ましくは０．７ｍｍ以下、さらに好ましくは０．４ｍｍ以下）とすることが好ましい。なお、この明細書において経時接着力とは、被着体への貼り合わせから２４時間以上経過した後の接着力を指すものとする。 As a general tendency, as the area of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet decreases, the adhesiveness also decreases in proportion thereto. Even when a coating layer is disposed on the adhesive surface of the adhesive sheet, the exposed area of the adhesive surface is reduced by the amount of the coating layer, and thus the same tendency is considered to be exhibited. In fact, also in the examples described later, when the area of the coating layer on the surface of the pressure-sensitive adhesive layer was increased and the exposed area of the pressure-sensitive adhesive layer was decreased, the initial adhesive force immediately after the bonding was reduced in proportion thereto. However, as a result of the study by the present inventors, it has been clarified that the adhesive force with time tends to be different from the initial adhesive force. Specifically, in the configuration in which the coat layer is partially disposed on the surface of the pressure-sensitive adhesive layer, when the area ratio of the coat layer non-arranged portion on the surface of the pressure-sensitive adhesive layer is less than 70%, adhesion immediately after bonding is performed. It was found that an increase in force was difficult to occur and the tendency of insufficient adhesive force with time was increased as compared with the case where the area ratio was 70% or more (see Examples described later). Therefore, in the technique disclosed herein, a high adhesive strength with time is obtained by setting the area ratio of the coating layer non-arranged portion to 70% or more. However, as a matter of course, when the area of the coat layer non-arrangement portion is increased, the area of the coat layer arrangement portion is relatively decreased. Therefore, the original action of the coat layer, which imparts air escape between the pressure-sensitive adhesive sheet and the adherend, may be impaired. Therefore, in the technology disclosed herein, when the pressure-sensitive adhesive layer surface is viewed from above, the coat layer is disposed so as to have a portion extending linearly from one end to the other end of the pressure-sensitive adhesive layer, and The width of the linearly extending portion is set within the range of 0.1 to 2 mm. Thereby, in the pressure-sensitive adhesive sheet capable of exhibiting a high adhesive strength with time, it is possible to realize good air escape properties. The width of the linearly extending portion is preferably 0.2 mm or more (for example, 0.3 mm or more, more preferably 0.5 mm or more), and 1.2 mm or less (more preferably 0.7 mm or less, more preferably Is preferably 0.4 mm or less). In addition, in this specification, the time-dependent adhesive strength refers to the adhesive strength after 24 hours or more have passed since bonding to the adherend.
　ここに開示される粘着シートの好ましい一態様では、前記粘着剤層表面には、前記線状に延びる部分が複数配置されている。また、前記複数の線状に延びる部分のうち一群を構成する複数の線状に延びる部分は、その幅方向にて間隔をおいて配置されており、これによって、前記コート層配置部はストライプ状パターンを有する。このように構成することで、ストライプ状パターンを構成する複数の線状に延びる部分を通じて、被着体表面と粘着面との間に留まろうとする空気等は効率よく除去される。 In a preferred embodiment of the pressure-sensitive adhesive sheet disclosed herein, a plurality of linearly extending portions are disposed on the surface of the pressure-sensitive adhesive layer. In addition, a plurality of linearly extending portions constituting a group among the plurality of linearly extending portions are arranged at intervals in the width direction thereof, whereby the coat layer arrangement portion is striped. Has a pattern. By comprising in this way, the air etc. which are going to stay between a to-be-adhered body surface and an adhesive surface are efficiently removed through the several linearly-extending part which comprises a striped pattern.
　ここに開示される粘着シートの好ましい一態様では、前記コート層配置部は、第１ストライプ状パターン部と、該第１ストライプ状パターン部と交差するように配置された第２ストライプ状パターン部とを含み、これによって、前記コート層配置部は格子状パターンを有する。このように構成することで、被着体表面と粘着面との間に留まろうとする空気等は効率よく除去される。 In a preferred embodiment of the pressure-sensitive adhesive sheet disclosed herein, the coat layer arrangement portion includes a first stripe pattern portion, and a second stripe pattern portion arranged so as to intersect the first stripe pattern portion. Thereby, the coat layer arrangement portion has a lattice pattern. By comprising in this way, the air etc. which are going to stay between a to-be-adhered body surface and an adhesion surface are removed efficiently.
　ここに開示される粘着シートの好ましい一態様では、前記コート層配置部において、一のストライプ状パターンを構成する複数の線状に延びる部分の間隔は１．０～１０ｍｍの範囲内である。このように構成することで、高い経時接着力と空気抜け性とがバランスよく両立される。上記線状に延びる部分の間隔は、より好ましくは１．５～８ｍｍ、さらに好ましくは２．５～５ｍｍである。 In a preferred embodiment of the pressure-sensitive adhesive sheet disclosed herein, in the coat layer disposition portion, a plurality of linearly extending portions constituting one stripe pattern have a distance of 1.0 to 10 mm. By comprising in this way, the high adhesive force with passage of time and the air release property are balanced. The interval between the linearly extending portions is more preferably 1.5 to 8 mm, and further preferably 2.5 to 5 mm.
　ここに開示される粘着シートの好ましい一態様では、前記コート層が部分的に配置された粘着性表面は、１３Ｎ／２５ｍｍ以上の２４時間経過後１８０度剥離強度を示す。ここに開示される技術によると、コート層を設ける構成において、上記の剥離強度を実現することができる。 In a preferred embodiment of the pressure-sensitive adhesive sheet disclosed herein, the pressure-sensitive adhesive surface on which the coat layer is partially disposed exhibits a 180-degree peel strength after 24 hours of 13 N / 25 mm or more. According to the technique disclosed herein, the above-described peel strength can be realized in a configuration in which a coat layer is provided.
　また、本発明によると、ここに開示されるいずれかの粘着シートと、該粘着シートの粘着剤層表面を保護する剥離ライナーと、を備える剥離ライナー付き粘着シートが提供される。そして、この剥離ライナーの表面のうち前記粘着剤層側の表面は、平滑に形成されている。このように構成することで、粘着特性が向上する傾向がある。また、ここに開示される技術によると、上記構成を採用して、剥離ライナーをコート層転写用フィルムとして利用する場合に、良好なコート層転写性を実現することができる。 Also, according to the present invention, there is provided a pressure-sensitive adhesive sheet with a release liner comprising any of the pressure-sensitive adhesive sheets disclosed herein and a release liner for protecting the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet. And the surface at the side of the said adhesive layer among the surfaces of this release liner is formed smoothly. By comprising in this way, there exists a tendency for an adhesive characteristic to improve. Moreover, according to the technique disclosed here, when the above configuration is adopted and the release liner is used as a coat layer transfer film, good coat layer transferability can be realized.
　また、本発明によると、少なくとも一方の表面が剥離性表面である剥離性支持体を備える粘着シート用剥離ライナーが提供される。この剥離ライナーの前記剥離性支持体の剥離性表面上には、粘着シートに転写可能なコート層が設けられており、これによって、該剥離性表面はコート層配置部とコート層非配置部とを有する。また、前記剥離性表面における前記コート層非配置部の面積割合は７０％以上である。さらに、前記コート層は、前記剥離性表面の一端から他端に向かって線状に延びる部分を有する。そして、前記線状に延びる部分の幅は０．１～２ｍｍの範囲内である。このような剥離ライナーを用いて粘着シートの粘着剤層表面にコート層を転写することで、高い経時接着力と良好な空気抜け性とを高度に両立した粘着シートを好ましく実現することができる。 Further, according to the present invention, there is provided a release liner for pressure-sensitive adhesive sheets comprising a peelable support having at least one surface that is a peelable surface. On the peelable surface of the peelable support of the release liner, a coat layer that can be transferred to the pressure-sensitive adhesive sheet is provided, whereby the peelable surface has a coat layer placement portion and a coat layer non-placement portion. Have Moreover, the area ratio of the said coating layer non-arrangement | positioning part in the said peelable surface is 70% or more. Further, the coat layer has a portion extending linearly from one end to the other end of the peelable surface. The width of the linearly extending portion is in the range of 0.1 to 2 mm. By transferring the coat layer to the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet using such a release liner, a pressure-sensitive adhesive sheet having a high degree of both high adhesive strength with time and good air detachability can be preferably realized.
一実施形態に係る粘着シートを模式的に示す上面図である。It is a top view which shows typically the adhesive sheet which concerns on one Embodiment. 図１のII－II線における断面図である。FIG. 2 is a cross-sectional view taken along line II-II in FIG. 一実施形態に係る剥離ライナー付き粘着シートを模式的に示す断面図である。It is sectional drawing which shows typically the adhesive sheet with a peeling liner which concerns on one Embodiment. 他の実施形態に係る剥離ライナー付き粘着シートを模式的に示す断面図である。It is sectional drawing which shows typically the adhesive sheet with a peeling liner which concerns on other embodiment. 一実施形態に係る粘着シート用剥離ライナーを模式的に示す断面図である。It is sectional drawing which shows typically the peeling liner for adhesive sheets which concerns on one Embodiment.
　以下、本発明の好適な実施形態を説明する。なお、本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、本明細書に記載された発明の実施についての教示と出願時の技術常識とに基づいて当業者に理解され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。また、以下の図面において、同じ作用を奏する部材・部位には同じ符号を付して説明することがあり、重複する説明は省略または簡略化することがある。また、図面に記載の実施形態は、本発明を明瞭に説明するために模式化されており、製品として実際に提供される本発明の粘着シートのサイズや縮尺を必ずしも正確に表したものではない。 Hereinafter, preferred embodiments of the present invention will be described. Note that matters other than the matters specifically mentioned in the present specification and necessary for the implementation of the present invention are based on the teachings on the implementation of the invention described in the present specification and the common general technical knowledge at the time of filing. Can be understood by those skilled in the art. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field. Further, in the following drawings, members / parts having the same action may be described with the same reference numerals, and overlapping descriptions may be omitted or simplified. In addition, the embodiment described in the drawings is schematically illustrated for clearly explaining the present invention, and does not necessarily accurately represent the size and scale of the pressure-sensitive adhesive sheet of the present invention that is actually provided as a product. .
　また、本明細書における粘着シートの概念には、粘着テープ、粘着ラベル、粘着フィルム等と称され得るものが包含される。また、ここに開示される粘着シートは、ロール状であってもよく、枚葉状であってもよい。あるいは、さらに種々の形状に加工された形態のシートであってもよい。 Further, the concept of the pressure-sensitive adhesive sheet in this specification includes what can be called pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, pressure-sensitive adhesive films, and the like. Further, the pressure-sensitive adhesive sheet disclosed herein may be in the form of a roll or a single sheet. Or the sheet | seat of the form processed into the various shape further may be sufficient.
　図１は一実施形態に係る粘着シートを模式的に示す上面図であり、図２は図１のII－II線における断面図である。図面を参照しながら、この実施形態の粘着シートについて説明する。 FIG. 1 is a top view schematically showing an adhesive sheet according to an embodiment, and FIG. 2 is a cross-sectional view taken along the line II-II in FIG. The pressure-sensitive adhesive sheet of this embodiment will be described with reference to the drawings.
　図１，２に示すように、この実施形態に係る粘着シート１は、フィルム状基材１０と粘着剤層２０との積層構造を有する。フィルム状基材１０は、粘着剤層２０を支持している。粘着シート１において、粘着剤層２０側の表面２０Ａは粘着性表面１Ａを構成している。粘着シート１の他方の表面（フィルム状基材１０側の表面）１Ｂは非粘着性の表面である。 1 and 2, the pressure-sensitive adhesive sheet 1 according to this embodiment has a laminated structure of a film-like base material 10 and a pressure-sensitive adhesive layer 20. The film-like substrate 10 supports the pressure-sensitive adhesive layer 20. In the pressure-sensitive adhesive sheet 1, the surface 20 </ b> A on the pressure-sensitive adhesive layer 20 side constitutes a pressure-sensitive adhesive surface 1 </ b> A. The other surface (surface on the film-like substrate 10 side) 1B of the pressure-sensitive adhesive sheet 1 is a non-adhesive surface.
　粘着剤層２０の表面２０Ａには、コート層３０が部分的に配置されている。換言すると、粘着剤層表面２０Ａは、コート層３０によって部分的に覆われており、コート層３０が配置されたコート層配置部５０と、コート層３０が配置されておらず粘着剤層２０が表面に露出したコート層非配置部５１と、を有する。このコート層３０は、粘着シート１の被着体への貼り合わせ時に、粘着シート１と被着体との間で空気等が通る通路となり、空気抜け性を付与する。なお、コート層３０は、その表面が粘着剤層表面２０Ａと面一であってもよく、粘着剤層表面２０Ａに対して厚さ方向の少なくとも一部が突出していてもよい。 The coat layer 30 is partially disposed on the surface 20A of the pressure-sensitive adhesive layer 20. In other words, the pressure-sensitive adhesive layer surface 20 </ b> A is partially covered by the coat layer 30, and the coat layer placement portion 50 where the coat layer 30 is placed and the pressure-sensitive adhesive layer 20 where the coat layer 30 is not placed are arranged. And a coat layer non-arranged portion 51 exposed on the surface. The coat layer 30 serves as a passage through which air or the like passes between the pressure-sensitive adhesive sheet 1 and the adherend when the pressure-sensitive adhesive sheet 1 is bonded to the adherend, and imparts air release properties. The surface of the coat layer 30 may be flush with the pressure-sensitive adhesive layer surface 20A, or at least a part in the thickness direction may protrude from the pressure-sensitive adhesive layer surface 20A.
　コート層配置部５０は、粘着剤層表面２０Ａを上方から見たときに所定のパターン（コート層パターン）６０を呈している。この実施形態では、コート層配置部５０は格子状パターン６０を呈している。コート層３０による格子状パターン６０は、具体的には、粘着剤層表面２０Ａを上方から見たときに、第１ストライプ状パターン部７０と、第１ストライプ状パターン部７０と交差するように配置された第２ストライプ状パターン部８０とからなる。 The coat layer arrangement part 50 presents a predetermined pattern (coat layer pattern) 60 when the pressure-sensitive adhesive layer surface 20A is viewed from above. In this embodiment, the coat layer arrangement portion 50 has a lattice pattern 60. Specifically, the lattice pattern 60 by the coat layer 30 is arranged so as to intersect the first stripe pattern portion 70 and the first stripe pattern portion 70 when the pressure-sensitive adhesive layer surface 20A is viewed from above. The second stripe pattern portion 80 is formed.
　第１ストライプ状パターン部７０は、粘着剤層２０の一端から他端に向かって直線状に延びる複数の長尺部（帯状部分）７５Ａ，７５Ｂ，７５Ｃから構成されており、これら複数の長尺部７５Ａ，７５Ｂ，７５Ｃは、その幅方向にて間隔をおいて平行に配置されている。この実施形態では、長尺部７５Ａ，７５Ｂ，７５Ｃは、その長手方向が粘着シート１の幅方向の端部と交差する角度で配置されており、それぞれ粘着剤層２０の両端に到達している。なお、この明細書において「長尺部」は、長手方向と幅方向（長手方向に直交する方向）とを有する部分という意味で用いられ、典型的には、直線状、曲線状にかかわらず、帯状に延びる部分である。長尺部は、線状に延びる部分と言い換えることが可能である。 The first stripe pattern portion 70 is composed of a plurality of long portions (band-like portions) 75A, 75B, 75C extending linearly from one end of the pressure-sensitive adhesive layer 20 to the other end. The portions 75A, 75B, and 75C are arranged in parallel at intervals in the width direction. In this embodiment, the long portions 75 </ b> A, 75 </ b> B, and 75 </ b> C are arranged at angles at which the longitudinal direction intersects the end portions in the width direction of the pressure-sensitive adhesive sheet 1, and respectively reach the both ends of the pressure-sensitive adhesive layer 20. . In this specification, the “long portion” is used to mean a portion having a longitudinal direction and a width direction (a direction orthogonal to the longitudinal direction), and typically, regardless of whether it is linear or curved, It is a part extending in a band shape. The long part can be rephrased as a part extending linearly.
　第２ストライプ状パターン部８０も、第１ストライプ状パターン部７０と同様に、粘着剤層２０の一端から他端に向かって直線状に延びる複数の長尺部（帯状部分）８５Ａ，８５Ｂ，８５Ｃから構成されており、これら複数の長尺部８５Ａ，８５Ｂ，８５Ｃは、その幅方向にて間隔をおいて平行に配置されている。この実施形態では、長尺部８５Ａ，８５Ｂ，８５Ｃは、その長手方向が粘着シート１の幅方向の端部と交差する角度で配置されており、それぞれ粘着剤層２０の両端に到達している。なお、この実施形態では、長尺部７５Ａ，７５Ｂ，７５Ｃ，８５Ａ，８５Ｂ，８５Ｃは直線状であるが、これに限定されず、各長尺部は曲線状に延びるものであってもよい。その場合、複数の長尺部が形成し得るストライプ状パターンは波状等であり得る。 Similarly to the first stripe pattern portion 70, the second stripe pattern portion 80 also has a plurality of long portions (band portions) 85 </ b> A, 85 </ b> B, 85 </ b> C that extend linearly from one end to the other end of the adhesive layer 20. The plurality of long portions 85A, 85B, 85C are arranged in parallel in the width direction at intervals. In this embodiment, the long portions 85 </ b> A, 85 </ b> B, and 85 </ b> C are arranged at angles at which the longitudinal direction intersects the end portions in the width direction of the pressure-sensitive adhesive sheet 1, and respectively reach the both ends of the pressure-sensitive adhesive layer 20. . In this embodiment, the long portions 75A, 75B, 75C, 85A, 85B, and 85C are linear, but the present invention is not limited to this, and each long portion may extend in a curved shape. In this case, the stripe pattern that can be formed by the plurality of long portions may be wavy.
　また、この実施形態では、第１ストライプ状パターン部７０と第２ストライプ状パターン部８０とは、第１ストライプ状パターン部７０の長尺部７５Ａ，７５Ｂ，７５Ｃと第２ストライプ状パターン部８０の長尺部８５Ａ，８５Ｂ，８５Ｃとがほぼ直交するように交差している。したがって、第１ストライプ状パターン部７０の長尺部７５Ａ，７５Ｂ，７５Ｃと第２ストライプ状パターン部８０の長尺部８５Ａ，８５Ｂ，８５Ｃとは、部分的に重なっている。 Further, in this embodiment, the first stripe pattern portion 70 and the second stripe pattern portion 80 are the long portions 75A, 75B, 75C of the first stripe pattern portion 70 and the second stripe pattern portion 80. The long portions 85A, 85B, and 85C intersect so as to be substantially orthogonal. Therefore, the long portions 75A, 75B, 75C of the first stripe pattern portion 70 and the long portions 85A, 85B, 85C of the second stripe pattern portion 80 partially overlap.
　なお、本明細書において格子状パターンとは、典型的には、互いに交差する２つのストライプ状パターン部を含むパターンを指し、本実施形態のような斜方格子だけでなく、正方格子、三角格子等の各種の格子形状を包含する。長尺部が直線状の場合、２つのストライプ状パターン部の交差角度（鋭角側）は、１０度～９０度（好ましく４５度～９０度、典型的には６０度～９０度）の範囲内で設定され得る。また、ここに開示される格子状パターンには、屈曲を繰り返す複数の長尺部から構成されるストライプ状パターン部を含むパターン、例えば六角格子のようなパターンも包含されるものとする。そのようなパターンは、隣りあう長尺部同士が一部で接続したものであり得る。空気抜け性の観点から、コート層配置部は、１または２以上のストライプ状パターン部を有することが好ましい。したがって、コート層配置部（典型的には格子状パターン）は、第３のストライプ状パターン部を有するものであり得る。 In the present specification, the lattice pattern typically refers to a pattern including two stripe pattern portions intersecting each other, and not only an orthorhombic lattice as in the present embodiment, but also a square lattice and a triangular lattice. And various other lattice shapes. When the long part is linear, the crossing angle (acute angle side) of the two stripe pattern parts is within the range of 10 degrees to 90 degrees (preferably 45 degrees to 90 degrees, typically 60 degrees to 90 degrees). It can be set with. In addition, the lattice pattern disclosed herein includes a pattern including a stripe-shaped pattern portion composed of a plurality of long portions that repeatedly bend, for example, a pattern such as a hexagonal lattice. Such a pattern may be a pattern in which adjacent long portions are partially connected. From the viewpoint of air release, the coat layer arrangement portion preferably has one or more stripe pattern portions. Accordingly, the coat layer arrangement portion (typically a lattice pattern) may have a third stripe pattern portion.
　コート層配置部５０における各長尺部７５Ａ，７５Ｂ，７５Ｃ，８５Ａ，８５Ｂ，８５Ｃの幅（Ｗ１）は、０．１～２ｍｍの範囲内で設定される。これにより、高い経時接着力と良好な空気抜け性とを両立することができる。上記長尺部の幅Ｗ１は、空気抜け性向上の観点から、好ましくは０．２ｍｍ以上、より好ましくは０．３ｍｍ以上、さらに好ましくは０．５ｍｍ以上である。接着力や外観等の観点からは、上記長尺部の幅Ｗ１は、好ましくは１．２ｍｍ以下、より好ましくは１．０ｍｍ以下、さらに好ましくは０．７ｍｍ以下、特に好ましくは０．５ｍｍ以下、最も好ましくは０．４ｍｍ以下である。 The width (W1) of each of the long portions 75A, 75B, 75C, 85A, 85B, and 85C in the coat layer arrangement portion 50 is set within a range of 0.1 to 2 mm. Thereby, it is possible to achieve both high adhesive strength with time and good air escape. The width W1 of the long part is preferably 0.2 mm or more, more preferably 0.3 mm or more, and still more preferably 0.5 mm or more, from the viewpoint of improving air escape. From the viewpoint of adhesive strength, appearance, etc., the width W1 of the long portion is preferably 1.2 mm or less, more preferably 1.0 mm or less, still more preferably 0.7 mm or less, particularly preferably 0.5 mm or less, Most preferably, it is 0.4 mm or less.
　コート層配置部５０において第１ストライプ状パターン部７０を構成する長尺部７５Ａ，７５Ｂ，７５Ｃの間隔Ｗ２は１．０～１０ｍｍの範囲内に設定することが好ましい。これにより、長尺部の幅が上記の範囲内とされた構成において、高い経時接着力と空気抜け性とがバランスよく両立される傾向が高まる。ここで長尺部の間隔Ｗ２とは、粘着剤層表面において隣りあう２つの長尺部の間に存在する部分の幅を指す。上記長尺部の間隔Ｗ２は、経時接着力向上等の観点から、より好ましくは１．５ｍｍ以上、さらに好ましくは２．５ｍｍ以上である。上記長尺部の間隔Ｗ２は、８ｍｍ以下（例えば５ｍｍ以下、典型的には３ｍｍ以下）程度であってもよい。第２ストライプ状パターン部８０を構成する長尺部８５Ａ，８５Ｂ，８５Ｃの間隔も、上記長尺部７５Ａ，７５Ｂ，７５Ｃの間隔Ｗ２として例示した範囲内から好ましく設定される。上記間隔Ｗ２は等間隔であることが好ましい。 In the coat layer arrangement portion 50, the interval W2 between the long portions 75A, 75B, and 75C constituting the first stripe pattern portion 70 is preferably set within a range of 1.0 to 10 mm. Thereby, in the configuration in which the width of the long portion is within the above range, the tendency that high adhesive strength with time and air bleedability are compatible with each other is increased. Here, the interval W2 between the long portions refers to the width of a portion existing between two adjacent long portions on the pressure-sensitive adhesive layer surface. The distance W2 between the long portions is more preferably 1.5 mm or more, and further preferably 2.5 mm or more, from the viewpoint of improving the adhesive strength with time. The interval W2 between the long portions may be about 8 mm or less (for example, 5 mm or less, typically 3 mm or less). The intervals between the long portions 85A, 85B, and 85C constituting the second stripe pattern portion 80 are also preferably set within the range exemplified as the interval W2 between the long portions 75A, 75B, and 75C. The interval W2 is preferably an equal interval.
　長尺部のピッチは、高い経時接着力と空気抜け性とをバランスよく両立する観点から、１～２０ｍｍの範囲内とすることが好ましい。上記長尺部のピッチは、より好ましくは１．５ｍｍ以上、さらに好ましくは２ｍｍ以上（例えば２．５ｍｍ以上）であり、より好ましくは１５ｍｍ以下（例えば１２ｍｍ以下）であり、さらに好ましくは５ｍｍ以下である。なお、上記ピッチは、上記長尺部の幅方向の中心線間の距離（間隔）を指すものとする。 The pitch of the long part is preferably in the range of 1 to 20 mm from the viewpoint of achieving a balance between high adhesive strength with time and air release. The pitch of the long part is more preferably 1.5 mm or more, further preferably 2 mm or more (for example, 2.5 mm or more), more preferably 15 mm or less (for example, 12 mm or less), and further preferably 5 mm or less. is there. In addition, the said pitch shall point out the distance (space | interval) between the centerlines of the width direction of the said elongate part.
　粘着シート１は、使用前においては、図３に示すように、粘着剤層２０が、少なくとも粘着剤層表面２０Ａ側が剥離面となっている剥離ライナー４０によって保護された構成を有する剥離ライナー付き粘着シート１の形態であり得る。あるいはまた、フィルム状基材１０の背面（粘着剤層２０側の表面とは反対側の面）が剥離面となっており、粘着シート１を巻回することにより該背面に粘着剤層２０が当接して、粘着剤層２０がフィルム状基材１０の背面で保護された構成であってもよい。このような片面のみが接着性を有する片面接着性の粘着シート（片面粘着シート）は、例えば、粘着性表面とは反対側の表面に装飾性、表面保護性等の特性が要求される場合や、塗料代替シートとして用いられる場合に好適である。 As shown in FIG. 3, the pressure-sensitive adhesive sheet 1 is a pressure-sensitive adhesive with a release liner having a configuration in which the pressure-sensitive adhesive layer 20 is protected by a release liner 40 having at least a pressure-sensitive adhesive layer surface 20A side as a release surface, as shown in FIG. It may be in the form of a sheet 1. Alternatively, the back surface of the film-like substrate 10 (the surface opposite to the surface on the pressure-sensitive adhesive layer 20 side) is a release surface, and the pressure-sensitive adhesive layer 20 is formed on the back surface by winding the pressure-sensitive adhesive sheet 1. The structure which contact | abutted and the adhesive layer 20 was protected by the back surface of the film-form base material 10 may be sufficient. Such a single-sided adhesive sheet (single-sided adhesive sheet) having adhesiveness only on one side is, for example, a case where characteristics such as decoration and surface protection are required on the surface opposite to the adhesive surface. It is suitable when used as a paint substitute sheet.
　また、ここに開示される粘着シートが、図４に示す両面接着タイプの基材付き粘着シート（両面粘着シート）の場合には、粘着シート２は、フィルム状基材１０の各面（いずれも非剥離性）に粘着剤層２１，２２がそれぞれ設けられ、それらの粘着剤層２１，２２が、少なくとも該粘着剤層側が剥離面となっている剥離ライナー４１，４２によってそれぞれ保護された構成を有するものであり得る。なお、この粘着シート２では、粘着剤層２１の表面にのみコート層３０が部分的に配置されており、粘着剤層２２の表面にはコート層は設けられていない。あるいは、特に図示しないが、両面粘着シートは、フィルム状基材の各面（いずれも非剥離性）にそれぞれ粘着剤層が設けられ、それらのうち一方の粘着剤層が、両面が剥離面となっている剥離ライナーにより保護された構成を有していてもよい。この種の粘着シートは、該粘着シートを巻回して他方の粘着剤層を剥離ライナーの裏面に当接させることにより、２つの粘着剤層が１つの剥離ライナーによって保護された構成となる。上記両面粘着シートは、例えば接合固定用途等に好ましく利用される。 Moreover, when the adhesive sheet disclosed here is a double-sided adhesive type adhesive sheet with a base material (double-sided adhesive sheet) shown in FIG. Non-peelable) are provided with pressure-sensitive adhesive layers 21 and 22, respectively, and the pressure-sensitive adhesive layers 21 and 22 are protected by release liners 41 and 42, at least the pressure-sensitive adhesive layer side being a release surface, respectively. It may have. In the pressure-sensitive adhesive sheet 2, the coat layer 30 is partially disposed only on the surface of the pressure-sensitive adhesive layer 21, and no coat layer is provided on the surface of the pressure-sensitive adhesive layer 22. Alternatively, although not particularly illustrated, the double-sided pressure-sensitive adhesive sheet is provided with a pressure-sensitive adhesive layer on each surface of the film-like substrate (both are non-peelable), and one of the pressure-sensitive adhesive layers has both surfaces separated from each other. You may have the structure protected by the release liner which has become. This type of pressure-sensitive adhesive sheet has a configuration in which two pressure-sensitive adhesive layers are protected by one release liner by winding the pressure-sensitive adhesive sheet and bringing the other pressure-sensitive adhesive layer into contact with the back surface of the release liner. The double-sided pressure-sensitive adhesive sheet is preferably used, for example, for joining and fixing.
　＜粘着シートの特性等＞
　ここに開示される粘着シートは、その粘着剤層表面におけるコート層非配置部の面積割合（粘着シートの接着面（粘着性表面）におけるコート層の面積割合でもあり得る。）が７０％以上であることによって特徴づけられる。これにより、高い経時接着力を確保することができる。上記面積割合は、好ましくは７５％以上、より好ましくは８０％以上である。良好な空気抜け性を得る観点からは、上記面積割合は、好ましくは９０％以下、より好ましくは８５％以下である。 <Characteristics of adhesive sheet>
The pressure-sensitive adhesive sheet disclosed herein has an area ratio of the coating layer non-arranged portion on the surface of the pressure-sensitive adhesive layer (which may also be the area ratio of the coat layer on the adhesive surface (sticky surface) of the pressure-sensitive adhesive sheet) of 70% or more. Characterized by being. Thereby, high adhesive strength with time can be ensured. The area ratio is preferably 75% or more, more preferably 80% or more. From the viewpoint of obtaining good air escape properties, the area ratio is preferably 90% or less, more preferably 85% or less.
　好ましい一態様では、粘着シートの粘着性表面（典型的には粘着剤層表面とコート層表面とから構成される）は、１３Ｎ／２５ｍｍ以上の２４時間経過後１８０度剥離強度（以下「２４時間経過後接着力」ともいう。）を示す。上記粘着シートによると、良好な空気等抜け性を有しつつ、所定以上の経時接着力を発揮することができる。上記２４時間経過後接着力は１４Ｎ／２５ｍｍ以上（例えば１６Ｎ／２５ｍｍ以上）であることが好ましい。なお、上記２４時間経過後接着力は、下記の方法で測定すればよい。具体的には、粘着シートを幅２５ｍｍ、長さ１００ｍｍのサイズにカットした測定サンプルにつき、２３℃、５０％ＲＨの環境下にて、上記測定サンプルの粘着性表面をステンレス鋼板（ＳＵＳ３０４ＢＡ板）の表面に、２ｋｇのローラを１往復させて圧着する。これを同環境下に２４時間放置した後、万能引張圧縮試験機を使用して、ＪＩＳ　Ｚ　０２３７：２０００に準じて、引張速度３００ｍｍ／分、剥離角度１８０度の条件で、剥離強度（Ｎ／２５ｍｍ）を測定する。より具体的には、後述の実施例に記載の方法で測定される。 In a preferred embodiment, the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet (typically composed of the pressure-sensitive adhesive layer surface and the coat layer surface) has a 180 ° peel strength (hereinafter referred to as “24 hours”) after 24 hours of 13 N / 25 mm or more. Also referred to as “adhesive strength after elapse.” According to the pressure-sensitive adhesive sheet, it is possible to exert a predetermined time-dependent adhesive force while having good air detachability. The adhesive strength after 24 hours is preferably 14 N / 25 mm or more (for example, 16 N / 25 mm or more). The adhesive strength after the lapse of 24 hours may be measured by the following method. Specifically, for a measurement sample obtained by cutting the pressure-sensitive adhesive sheet into a size of 25 mm in width and 100 mm in length, the adhesive surface of the measurement sample is made of a stainless steel plate (SUS304BA plate) in an environment of 23 ° C. and 50% RH. A 2 kg roller is reciprocated once on the surface and pressed. After leaving it in the same environment for 24 hours, using a universal tensile compression tester, in accordance with JIS Z 0237: 2000, under conditions of a tensile speed of 300 mm / min and a peel angle of 180 degrees, the peel strength (N / 25 mm). More specifically, it is measured by the method described in Examples described later.
　好ましい一態様では、粘着シートは透明性（半透明を包含する。）の粘着シートである。このような粘着シートでは、粘着シートと被着体との間に気泡等が混入すると、粘着シート越しに当該気泡等が視認されて外観性が損なわれやすい。ここに開示される技術によると、粘着シートと被着体との間における気泡等の発生が防止されるので、透明性を有する粘着シートにおいて優れた外観性が得られる。具体的には、上記粘着シートは８０％以上（例えば９０％以上、典型的には９５％以上）の全光線透過率を示すものであり得る。また、粘着シートのヘイズ値は１０％以下（例えば５％以下）であることが好ましい。上記全光線透過率およびヘイズ値は、ＪＩＳ　Ｋ　７１３６：２０００に準拠して、市販の透過率計（例えば、商品名「ＨＡＺＥＭＥＴＥＲ　ＨＭ－１５０」、村上色彩技術研究所社製）を使用して測定すればよい。後述のフィルム状基材の全光線透過率およびヘイズ値も同様の方法で測定される。 In a preferred embodiment, the pressure-sensitive adhesive sheet is a transparent (including translucent) pressure-sensitive adhesive sheet. In such a pressure-sensitive adhesive sheet, when bubbles or the like are mixed between the pressure-sensitive adhesive sheet and the adherend, the bubbles and the like are visually recognized through the pressure-sensitive adhesive sheet, and the appearance is easily impaired. According to the technology disclosed herein, generation of bubbles or the like between the pressure-sensitive adhesive sheet and the adherend is prevented, so that an excellent appearance can be obtained in a pressure-sensitive adhesive sheet having transparency. Specifically, the pressure-sensitive adhesive sheet may exhibit a total light transmittance of 80% or more (for example, 90% or more, typically 95% or more). Moreover, it is preferable that the haze value of an adhesive sheet is 10% or less (for example, 5% or less). The total light transmittance and haze value are measured using a commercially available transmissometer (for example, trade name “HAZEMETER HM-150”, manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K 7136: 2000. do it. The total light transmittance and haze value of a film-like substrate described later are also measured by the same method.
　ここに開示される粘着シート（粘着剤層と基材とを含むが、剥離ライナーは含まない。）の総厚さは特に限定されず、凡そ２～１０００μｍの範囲とすることが適当であり、好ましくは５～５００μｍ（例えば１０～３００μｍ、典型的には３０～１００μｍ）である。総厚さが制限された粘着シートは、該粘着シートが適用される製品の小型化、軽量化、省資源化等の点で有利なものとなり得る。 The total thickness of the pressure-sensitive adhesive sheet (including the pressure-sensitive adhesive layer and the base material but not including the release liner) disclosed herein is not particularly limited, and is suitably in the range of about 2 to 1000 μm. The thickness is preferably 5 to 500 μm (for example, 10 to 300 μm, typically 30 to 100 μm). The pressure-sensitive adhesive sheet having a limited total thickness can be advantageous in terms of reducing the size, weight, and resource saving of the product to which the pressure-sensitive adhesive sheet is applied.
　＜フィルム状基材＞
　ここに開示されるフィルム状基材としては、例えば、樹脂フィルム、紙、布、ゴムフィルム、発泡体フィルム、金属箔、これらの複合体や積層体等を用いることができる。なかでも、貼り付け性や外観性の観点から、樹脂フィルム層を含むことが好ましい。樹脂フィルム層を含むことは、寸法安定性、厚さ精度、加工性、引張強度等の観点からも有利である。樹脂フィルムの例としては、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、エチレン・プロピレン共重合体等のポリオレフィン系樹脂フィルム；ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂フィルム；塩化ビニル系樹脂フィルム；酢酸ビニル系樹脂フィルム；ポリイミド系樹脂フィルム；ポリアミド系樹脂フィルム；フッ素系樹脂フィルム；セロハン；等が挙げられる。好適例としては、ＰＥ、ＰＰ、ＰＥＴから形成された樹脂フィルムが挙げられる。樹脂フィルムのなかでは、ポリエステルフィルムがより好ましく、そのなかでもＰＥＴフィルムがさらに好ましい。フィルム状基材は、単層構造であってもよく、２層または３層以上の多層構造を有してもよい。 <Film substrate>
As the film-like substrate disclosed herein, for example, a resin film, paper, cloth, rubber film, foam film, metal foil, a composite or laminate of these, and the like can be used. Especially, it is preferable that a resin film layer is included from a viewpoint of sticking property or an external appearance property. The inclusion of the resin film layer is advantageous from the viewpoint of dimensional stability, thickness accuracy, workability, tensile strength, and the like. Examples of resin films include polyolefin resin films such as polyethylene (PE), polypropylene (PP), and ethylene / propylene copolymers; polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; Vinyl chloride resin film; vinyl acetate resin film; polyimide resin film; polyamide resin film; fluorine resin film; cellophane; Preferable examples include resin films formed from PE, PP, and PET. Among the resin films, a polyester film is more preferable, and a PET film is more preferable among them. The film-like substrate may have a single layer structure or may have a multilayer structure of two layers or three or more layers.
　好ましい一態様では、フィルム状基材は、発泡体フィルムを備える基材（発泡体含有基材）である。これによって、粘着シートに衝撃吸収機能が付与される。ここで発泡体フィルムとは、気泡（気泡構造）を有する部分を備えたフィルム状構造体をいう。発泡体含有基材は、発泡体フィルムから構成された単層構造体であってもよく、２層以上の多層構造のうちの少なくとも１層が発泡体フィルム（発泡体層）で構成された多層構造体であってもよい。発泡体含有基材の構成例としては、発泡体フィルム（発泡体層）と非発泡体フィルム（非発泡体層）とが積層された複合基材が挙げられる。非発泡体フィルム（非発泡体層）とは、発泡体とするための意図的な処理（例えば気泡導入処理）を行っていないフィルム状構造体をいい、気泡構造を実質的に有しないフィルムをいう。非発泡体フィルムの典型例としては、発泡倍率が１．１倍未満（例えば１．０５倍未満、典型的には１．０１倍未満）の樹脂フィルム（例えばＰＥＴ等のポリエステル系樹脂フィルム）が挙げられる。フィルム状基材が２層以上の発泡体層を含む場合、それらの発泡体層の材質や構造は、同一であってもよく異なってもよい。また、発泡体フィルムが発泡体層を含む多層構造を有する場合、各層の間には層間密着性向上の観点から接着層が配置されていてもよい。 In a preferred embodiment, the film-like base material is a base material (foam-containing base material) provided with a foam film. Thereby, an impact absorbing function is imparted to the adhesive sheet. Here, the foam film refers to a film-like structure provided with a portion having bubbles (bubble structure). The foam-containing base material may be a single-layer structure composed of a foam film, or a multilayer in which at least one of two or more multilayer structures is composed of a foam film (foam layer). It may be a structure. As a structural example of a foam containing base material, the composite base material with which the foam film (foam layer) and the non-foam film (non-foam layer) were laminated | stacked is mentioned. Non-foamed film (non-foamed layer) refers to a film-like structure that has not undergone intentional treatment (for example, bubble introduction treatment) to make a foam, and a film that does not substantially have a bubble structure. Say. A typical example of a non-foam film is a resin film (for example, a polyester-based resin film such as PET) having an expansion ratio of less than 1.1 times (for example, less than 1.05 times, typically less than 1.01 times). Can be mentioned. When the film-like substrate includes two or more foam layers, the materials and structures of these foam layers may be the same or different. Moreover, when a foam film has a multilayer structure containing a foam layer, the contact bonding layer may be arrange | positioned from a viewpoint of an interlayer adhesive improvement between each layer.
　上記発泡体フィルムの平均気泡径は特に限定されないが、通常は１０μｍ～２００μｍであることが適当であり、好ましくは２０μｍ～１８０μｍであり、さらに好ましくは３０μｍ～１５０μｍである。平均気泡径を１０μｍ以上とすることにより、衝撃吸収性が向上する傾向がある。一方、平均気泡径を２００μｍ以下とすることにより、取扱い性や防水性（止水性）が向上する傾向がある。 The average cell diameter of the foam film is not particularly limited, but is usually suitably 10 μm to 200 μm, preferably 20 μm to 180 μm, and more preferably 30 μm to 150 μm. When the average cell diameter is 10 μm or more, the impact absorbability tends to be improved. On the other hand, when the average cell diameter is 200 μm or less, the handleability and waterproofness (water-stopping property) tend to be improved.
　発泡体フィルムの平均気泡径（μｍ）は、市販の低真空走査電子顕微鏡を用いて、発泡体断面の拡大画像を取り込み、画像解析することにより求めることができる。解析する気泡数は１０～２０個程度とすればよい。低真空走査電子顕微鏡としては、例えば、日立ハイテクサイエンスシステムズ社製の商品名「Ｓ－３４００Ｎ型走査電子顕微鏡」を用いることができる。 The average cell diameter (μm) of the foam film can be determined by taking an enlarged image of the foam cross section and analyzing the image using a commercially available low vacuum scanning electron microscope. The number of bubbles to be analyzed may be about 10-20. As the low vacuum scanning electron microscope, for example, a trade name “S-3400N scanning electron microscope” manufactured by Hitachi High-Tech Science Systems, Inc. can be used.
　上記発泡体フィルムの密度（見掛け密度）は、特に限定されないが、通常は０．０１ｇ／ｃｍ３以上とすることが適当であり、好ましくは０．０１～０．７ｇ／ｃｍ３であり、さらに好ましくは０．０２～０．５ｇ／ｃｍ３である。密度を０．０１ｇ／ｃｍ３以上とすることにより、発泡体フィルムの強度（ひいては粘着シートの強度）が向上し、耐衝撃性や取扱性が向上する傾向にある。一方、密度を０．７ｇ／ｃｍ３以下とすることにより、柔軟性が低下し過ぎず、段差追従性が向上する傾向にある。 The density (apparent density) of the foam film is not particularly limited, but is usually suitably 0.01 g / cm 3 or more, preferably 0.01 to 0.7 g / cm 3 , Preferably, it is 0.02 to 0.5 g / cm 3 . By setting the density to 0.01 g / cm 3 or more, the strength of the foam film (and consequently the strength of the pressure-sensitive adhesive sheet) is improved, and impact resistance and handleability tend to be improved. On the other hand, by setting the density to 0.7 g / cm 3 or less, the flexibility does not deteriorate too much and the step following ability tends to be improved.
　発泡体フィルムの密度（見掛け密度）は、ＪＩＳ　Ｋ　７２２２：１９９９に記載の方法に準拠して測定される。具体的には、発泡体フィルムを１００ｍｍ×１００ｍｍのサイズに打抜いて試料を作製し、当該試料の寸法を測定する。また、測定端子の直径が２０ｍｍである１／１００ダイヤルゲージを用いて試料の厚さを測定する。これらの値から発泡体フィルム試料の体積を算出する。また、上記試料の重量を最小目盛り０．０１ｇ以上の上皿天秤にて測定する。これらの値から発泡体フィルムの見掛け密度（ｇ／ｃｍ３）を求めることができる。 The density (apparent density) of the foam film is measured according to the method described in JIS K 7222: 1999. Specifically, a foam film is punched into a size of 100 mm × 100 mm to prepare a sample, and the dimension of the sample is measured. Further, the thickness of the sample is measured using a 1/100 dial gauge having a measurement terminal diameter of 20 mm. The volume of the foam film sample is calculated from these values. Further, the weight of the sample is measured with an upper pan balance having a minimum scale of 0.01 g or more. From these values, the apparent density (g / cm 3 ) of the foam film can be determined.
　上記発泡体フィルムの５０％圧縮荷重は特に限定されない。耐衝撃性の観点からは、発泡体フィルムは０．１Ｎ／ｃｍ２以上の５０％圧縮荷重を示すことが適当である。５０％圧縮荷重が所定値以上であることにより、例えば発泡体フィルムが薄厚（例えば１００μｍ程度の厚さ）の場合にも、圧縮された際に十分な抵抗（圧縮された際に押し戻そうとする力）を示し、良好な耐衝撃性を保つことができる。上記５０％圧縮荷重は、好ましくは０．２Ｎ／ｃｍ２以上であり、より好ましくは０．５Ｎ／ｃｍ２以上である。また、柔軟性と耐衝撃性とをバランスよく両立する観点から、上記５０％圧縮荷重は、８Ｎ／ｃｍ２以下であることが適当であり、好ましくは６Ｎ／ｃｍ２以下であり、より好ましくは３Ｎ／ｃｍ２以下である。 The 50% compressive load of the foam film is not particularly limited. From the viewpoint of impact resistance, it is appropriate that the foam film exhibits a 50% compressive load of 0.1 N / cm 2 or more. When the 50% compression load is equal to or greater than the predetermined value, for example, even when the foam film is thin (for example, about 100 μm thick), sufficient resistance when compressed (to push back when compressed) Force), and good impact resistance can be maintained. The 50% compressive load is preferably 0.2 N / cm 2 or more, more preferably 0.5 N / cm 2 or more. In addition, from the viewpoint of achieving a good balance between flexibility and impact resistance, the 50% compression load is suitably 8 N / cm 2 or less, preferably 6 N / cm 2 or less, more preferably 3 N / cm 2 or less.
　発泡体フィルムの５０％圧縮荷重（硬さ）は、ＪＩＳ　Ｋ　６７６７：１９９９に準拠して測定される。具体的には、発泡体フィルムを１００ｍｍ×１００ｍｍに切り抜き、総厚さが２ｍｍ以上になるように積層し、これを測定サンプルとする。室温条件にて、圧縮試験機を用いて上記測定サンプルに対して１０ｍｍ／分の速度で圧縮を行い、圧縮率が５０％に達したところ（初期厚さに対して厚さが５０％まで圧縮された時点）で、１０秒保持した後の値（反発応力：Ｎ／ｃｍ２）を５０％圧縮荷重として記録する。その他の条件（例えば治具や計算方法等）については、ＪＩＳ　Ｋ　６７６７：１９９９に準じればよい。 The 50% compression load (hardness) of the foam film is measured according to JIS K 6767: 1999. Specifically, the foam film is cut out to 100 mm × 100 mm, laminated so that the total thickness is 2 mm or more, and this is used as a measurement sample. When the sample was compressed at a speed of 10 mm / min using a compression tester at room temperature, and the compression rate reached 50% (compressed to 50% of the initial thickness) The value after 10 seconds holding (repulsive stress: N / cm 2 ) is recorded as a 50% compression load. About other conditions (for example, a jig | tool, a calculation method, etc.), what is necessary is just to follow JISK6767: 1999.
　ここに開示される発泡フィルムを構成する発泡体の気泡構造は特に制限されない。気泡構造としては、連続気泡構造、独立気泡構造、半連続半独立気泡構造のいずれであってもよい。衝撃吸収性の観点からは、連続気泡構造、半連続半独立気泡構造が好ましい。 The cell structure of the foam constituting the foam film disclosed herein is not particularly limited. The cell structure may be any of an open cell structure, a closed cell structure, and a semi-continuous semi-closed cell structure. From the viewpoint of impact absorption, an open cell structure and a semi-open semi-closed cell structure are preferable.
　発泡体フィルムの材質は特に制限されない。発泡体フィルムは、典型的にはポリマー成分（例えば熱可塑性ポリマー）を含む材料から形成され得る。通常は、プラスチック材料の発泡体（プラスチック発泡体）により形成された発泡体フィルムが好ましい。プラスチック発泡体を形成するためのプラスチック材料（ゴム材料を包含する意味である。）は、特に制限されず、公知のプラスチック材料のなかから適宜選択することができる。プラスチック材料（典型的には熱可塑性ポリマー）は１種を単独でまたは２種以上を適宜組み合わせて用いることができる。なお、フィルム状基材や発泡体フィルムに含まれるポリマー成分の主成分（典型的には、５０重量％を超えて含まれる成分）を、以下「ベースポリマー」ということがある。 The material of the foam film is not particularly limited. The foam film can be formed from a material that typically includes a polymer component (eg, a thermoplastic polymer). Usually, a foam film formed of a foam of a plastic material (plastic foam) is preferable. The plastic material for forming the plastic foam (meaning including rubber material) is not particularly limited, and can be appropriately selected from known plastic materials. Plastic materials (typically thermoplastic polymers) can be used singly or in appropriate combination of two or more. In addition, the main component of the polymer component contained in the film-like substrate or the foam film (typically, the component contained in excess of 50% by weight) may be hereinafter referred to as “base polymer”.
　発泡体の具体例としては、ＰＥ製発泡体、ＰＰ製発泡体等のポリオレフィン製樹脂発泡体；ＰＥＴ製発泡体、ポリエチレンナフタレート製発泡体、ポリブチレンテレフタレート製発泡体等のポリエステル系樹脂製発泡体；ポリ塩化ビニル製発泡体等のポリ塩化ビニル系樹脂製発泡体；酢酸ビニル系樹脂製発泡体；アクリル系樹脂製発泡体；ポリフェニレンスルフィド樹脂製発泡体；ポリアミド（ナイロン）樹脂製発泡体、全芳香族ポリアミド（アラミド）樹脂製発泡体等のアミド系樹脂製発泡体；ポリイミド系樹脂製発泡体；ポリエーテルエーテルケトン（ＰＥＥＫ）製発泡体；ポリスチレン製発泡体等のスチレン系樹脂製発泡体；ポリウレタン樹脂製発泡体等のウレタン系樹脂製発泡体；等が挙げられる。また、発泡体として、ポリクロロプレンゴム製発泡体等のゴム系樹脂製発泡体を用いてもよい。 Specific examples of foams include polyolefin resin foams such as PE foams and PP foams; polyester resin foams such as PET foams, polyethylene naphthalate foams, polybutylene terephthalate foams, etc. Body; Polyvinyl chloride resin foam such as polyvinyl chloride foam; Vinyl acetate resin foam; Acrylic resin foam; Polyphenylene sulfide resin foam; Polyamide (nylon) resin foam; Amide resin foams such as wholly aromatic polyamide (aramid) resin foams; Polyimide resin foams; Polyetheretherketone (PEEK) foams; Polystyrene ether foams such as polystyrene foams And urethane resin foams such as polyurethane resin foam; and the like. Further, as the foam, a rubber-based resin foam such as a polychloroprene rubber foam may be used.
　好ましい一態様では、発泡体としてアクリル系樹脂発泡体（アクリル系樹脂製発泡体）が用いられる。ここでアクリル系樹脂発泡体とは、アクリル系ポリマーをベースポリマーとして含む発泡体のことをいう。本明細書におけるアクリル系ポリマーの定義は後述のとおりである。アクリル系ポリマーを構成するアルキル（メタ）アクリレートとしては、炭素原子数１～２０（好ましくは１～８、典型的には１～４）の鎖状アルキル基を有するアルキル（メタ）アクリレートの１種または２種以上が好ましく用いられる。アルキル（メタ）アクリレートの好適例としては、エチルアクリレート、ｎ－ブチルアクリレートおよび２－エチルヘキシルアクリレートが挙げられる。主モノマーとしてのアルキル（メタ）アクリレートの量は、アクリル系ポリマーの全モノマー成分中の７０重量％以上とすることが適当であり、好ましくは７５重量％以上（例えば８０重量％以上）である。また、上記アルキル（メタ）アクリレートの量は、全モノマー成分中の９８重量％以下が適当であり、好ましくは９７重量％以下（例えば９６重量％以下）である。 In a preferred embodiment, an acrylic resin foam (acrylic resin foam) is used as the foam. Here, the acrylic resin foam refers to a foam containing an acrylic polymer as a base polymer. The definition of the acrylic polymer in the present specification is as described below. The alkyl (meth) acrylate constituting the acrylic polymer is one kind of alkyl (meth) acrylate having a chain alkyl group having 1 to 20 carbon atoms (preferably 1 to 8, typically 1 to 4). Or 2 or more types are used preferably. Preferable examples of the alkyl (meth) acrylate include ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate. The amount of the alkyl (meth) acrylate as the main monomer is suitably 70% by weight or more, preferably 75% by weight or more (for example, 80% by weight or more) in the total monomer components of the acrylic polymer. The amount of the alkyl (meth) acrylate is suitably 98% by weight or less, preferably 97% by weight or less (for example, 96% by weight or less) in all monomer components.
　主モノマーであるアルキル（メタ）アクリレートと共重合性を有する副モノマーは、アクリル系ポリマーに架橋点を導入したり、アクリル系ポリマーの凝集力を高めたりするために役立ち得る。副モノマーとして、例えばカルボキシ基含有モノマー、水酸基含有モノマー、酸無水物基含有モノマー、アミド基含有モノマー、アミノ基含有モノマー、シアノ基含有モノマー、窒素原子含有環を有するモノマー等の官能基含有モノマーの１種または２種以上を使用することができる。副モノマーはまた、酢酸ビニル等のビニルエステル系モノマー、スチレン等の芳香族ビニル化合物、スルホン酸基含有モノマー、リン酸基含有モノマー等であり得る。上記副モノマーの量は、アクリル系ポリマーの全モノマー成分中の０．５重量％以上とすることが適当であり、好ましくは１重量％以上である。また、副モノマーの量は、全モノマー成分中の３０重量％以下が適当であり、好ましくは１０重量％以下である。 The secondary monomer copolymerizable with the main monomer, alkyl (meth) acrylate, can be useful for introducing a crosslinking point into the acrylic polymer or increasing the cohesive strength of the acrylic polymer. As a secondary monomer, for example, a carboxy group-containing monomer, a hydroxyl group-containing monomer, an acid anhydride group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a functional group-containing monomer such as a monomer having a nitrogen atom-containing ring 1 type (s) or 2 or more types can be used. The secondary monomer may also be a vinyl ester monomer such as vinyl acetate, an aromatic vinyl compound such as styrene, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, and the like. The amount of the submonomer is suitably 0.5% by weight or more, preferably 1% by weight or more in the total monomer component of the acrylic polymer. The amount of the submonomer is suitably 30% by weight or less, preferably 10% by weight or less, based on all monomer components.
　エマルション型の樹脂組成物を使用し、撹拌など機械的に空気等の気体を混入させる発泡方法を採用して発泡体を形成する場合には、アクリル系ポリマーを構成するモノマー成分に、副モノマーとして窒素原子含有モノマーが含まれていることが好ましい。これにより、発泡時には気泡が発生しやすく、また、発泡体形成時（典型的には、上記樹脂組成物の乾燥時）には、上記組成物の粘度が上昇して発泡体内に気泡が保持されやすいという作用が発揮され得る。 When using an emulsion type resin composition and adopting a foaming method in which a gas such as air is mechanically mixed, such as stirring, to form a foam, the monomer component constituting the acrylic polymer is used as a sub-monomer. It is preferable that a nitrogen atom-containing monomer is contained. As a result, bubbles are likely to be generated during foaming, and when the foam is formed (typically, when the resin composition is dried), the viscosity of the composition increases and the bubbles are retained in the foam. The effect of being easy can be exhibited.
　上記窒素原子含有モノマーとしては、例えば、アクリロニトリル、メタクリロニトリル等のシアノ基含有モノマー；Ｎ－ビニル－２－ピロリドン等のラクタム環含有モノマー；（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、ジアセトンアクリルアミド等のアミド基含有モノマー；等が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。なかでも、アクリロニトリル等のシアノ基含有モノマー、Ｎ－ビニル－２－ピロリドン等のラクタム環含有モノマーが好ましい。 Examples of the nitrogen atom-containing monomer include cyano group-containing monomers such as acrylonitrile and methacrylonitrile; lactam ring-containing monomers such as N-vinyl-2-pyrrolidone; (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, Amide group-containing monomers such as N-methylolacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and diacetoneacrylamide; These can be used alone or in combination of two or more. Of these, cyano group-containing monomers such as acrylonitrile and lactam ring-containing monomers such as N-vinyl-2-pyrrolidone are preferred.
　上記窒素原子含有モノマーの量は、アクリル系ポリマーの全モノマー成分中の２重量％以上とすることが適当であり、好ましくは３重量％以上（例えば４重量％以上）である。また、上記窒素原子含有モノマーの量は、全モノマー成分中の３０重量％以下が適当であり、好ましくは２５重量％以下（例えば２０重量％以下）である。 The amount of the nitrogen atom-containing monomer is suitably 2% by weight or more, preferably 3% by weight or more (for example, 4% by weight or more) in the total monomer components of the acrylic polymer. The amount of the nitrogen atom-containing monomer is suitably 30% by weight or less, preferably 25% by weight or less (for example, 20% by weight or less) in all monomer components.
　アクリル系ポリマーを得る方法は特に限定されず、溶液重合法、エマルション重合法、塊状重合法、懸濁重合法、活性エネルギー線重合法（例えばＵＶ重合法）等の、アクリル系ポリマーの合成手法として知られている各種の重合方法を適宜採用することができる。例えば、適当な重合溶媒（トルエン、酢酸エチル、水等）中にモノマー混合物を溶解または分散させ、アゾ系重合開始剤や過酸化物系開始剤等の重合開始剤を用いて重合操作を行うことにより、所望のアクリル系ポリマーを得ることができる。起泡性や環境面から、エマルション重合法により得られたアクリル系樹脂発泡体（エマルション型アクリル系樹脂発泡体）が好ましく用いられる。 The method for obtaining the acrylic polymer is not particularly limited. As a method for synthesizing the acrylic polymer, such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, active energy ray polymerization method (for example, UV polymerization method). Various known polymerization methods can be appropriately employed. For example, a monomer mixture is dissolved or dispersed in a suitable polymerization solvent (toluene, ethyl acetate, water, etc.), and a polymerization operation is performed using a polymerization initiator such as an azo polymerization initiator or a peroxide initiator. Thus, a desired acrylic polymer can be obtained. An acrylic resin foam (emulsion-type acrylic resin foam) obtained by an emulsion polymerization method is preferably used in terms of foamability and environmental aspects.
　アクリル系樹脂発泡体形成用組成物は、凝集力を高める観点から架橋剤を含むことが好ましい。架橋剤の種類は特に制限されず、各種架橋剤の１種または２種以上を適宜選択して用いることができる。架橋剤の好適例としては、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、カルボジイミド系架橋剤、メラミン系架橋剤、金属酸化物系架橋剤が挙げられる。なかでも、オキサゾリン系架橋剤が好ましい。架橋剤の使用量は特に制限されず、アクリル系ポリマー１００重量部に対して凡そ１０重量部以下（例えば凡そ０．００５～１０重量部、好ましくは凡そ０．０１～５重量部）の範囲から選択することが適当である。 The acrylic resin foam-forming composition preferably contains a cross-linking agent from the viewpoint of increasing the cohesive strength. The type of the crosslinking agent is not particularly limited, and one or more of various crosslinking agents can be appropriately selected and used. Preferable examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a melamine crosslinking agent, and a metal oxide crosslinking agent. Of these, oxazoline-based crosslinking agents are preferred. The amount of the crosslinking agent used is not particularly limited, and is from about 10 parts by weight or less (for example, about 0.005 to 10 parts by weight, preferably about 0.01 to 5 parts by weight) with respect to 100 parts by weight of the acrylic polymer. It is appropriate to select.
　他の好ましい一態様では、発泡体としてポリオレフィン系樹脂発泡体（ポリオレフィン製樹脂発泡体）が用いられる。上記ポリオレフィン系発泡体を構成するプラスチック材料としては、公知または慣用の各種のポリオレフィン系樹脂を特に限定なく用いることができる。例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、メタロセン触媒系直鎖状低密度ポリエチレン等のポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体、エチレン－酢酸ビニル共重合体等が挙げられる。このようなポリオレフィン系樹脂は、１種を単独でまたは２種以上を適宜組み合わせて用いることができる。 In another preferred embodiment, a polyolefin resin foam (polyolefin resin foam) is used as the foam. As the plastic material constituting the polyolefin foam, various known or commonly used polyolefin resins can be used without particular limitation. For example, polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), metallocene catalyst type linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene- A vinyl acetate copolymer etc. are mentioned. Such polyolefin resin can be used individually by 1 type or in combination of 2 or more types as appropriate.
　ここに開示される技術における発泡体フィルムの好適例としては、耐衝撃性や防水性等の観点から、ポリエチレン系樹脂の発泡体から実質的に構成されるポリエチレン系発泡体フィルム、ポリプロピレン系樹脂の発泡体から実質的に構成されるポリプロピレン系発泡体フィルム等が挙げられる。ここで、ポリエチレン系樹脂とは、エチレンを主モノマー（すなわち、モノマーのなかの主成分）とする樹脂を指し、ＨＤＰＥ、ＬＤＰＥ、ＬＬＤＰＥ等のほか、エチレンの共重合割合が５０重量％を超えるエチレン－プロピレン共重合体やエチレン－酢酸ビニル共重合体等を包含し得る。同様に、ポリプロピレン系樹脂とは、プロピレンを主モノマーとする樹脂を指す。ここに開示される技術における発泡体フィルムとしては、ポリプロピレン系発泡体フィルムを好ましく採用し得る。 As a suitable example of the foam film in the technology disclosed herein, from the viewpoint of impact resistance, waterproofness, etc., a polyethylene foam film substantially composed of a polyethylene resin foam, a polypropylene resin Examples thereof include a polypropylene-based foam film substantially composed of a foam. Here, the polyethylene-based resin refers to a resin having ethylene as a main monomer (that is, a main component of the monomer), and other than HDPE, LDPE, LLDPE, etc., the ethylene copolymerization ratio exceeds 50% by weight. -Propylene copolymer, ethylene-vinyl acetate copolymer, etc. may be included. Similarly, a polypropylene resin refers to a resin having propylene as a main monomer. As the foam film in the technology disclosed herein, a polypropylene-based foam film can be preferably employed.
　発泡体フィルムの発泡方法は、特に限定されず、目的や操作性等に応じて化学的手法、物理的手法等の手法を単独でまたは組み合わせて採用することができる。汚染性等の観点から物理的発泡法が好ましい。具体的には、炭化水素等の低沸点化合物や熱膨張微小球等の発泡剤をフィルム形成材料中に含有させておき、当該発泡剤から気泡を形成する発泡方法、機械的に空気等の気体を混入させる発泡方法、水等の溶媒の除去を利用した溶媒除去発泡法、超臨界流体を利用した発泡法等が挙げられる。また例えば、発泡体フィルム形成用ポリマー中に加圧条件下で不活性ガス（例えば二酸化酸素）を注入し、それを減圧することで発泡体フィルムを形成する方法も好ましく採用され得る。この方法によると、平均気泡径を所定以下に制限しやすく、かつ発泡体フィルムを低密度化しやすい。 The foaming method of the foam film is not particularly limited, and methods such as a chemical method and a physical method can be used alone or in combination depending on the purpose and operability. A physical foaming method is preferable from the viewpoint of contamination and the like. Specifically, a foaming method in which a low-boiling compound such as hydrocarbon or a foaming agent such as thermal expansion microspheres is contained in the film-forming material, and bubbles are formed from the foaming agent, a gas such as air mechanically And the like, a solvent removal foaming method using removal of a solvent such as water, a foaming method using a supercritical fluid, and the like. In addition, for example, a method of forming a foam film by injecting an inert gas (for example, oxygen dioxide) into a polymer for forming a foam film under pressure and reducing the pressure can be preferably employed. According to this method, the average cell diameter can be easily limited to a predetermined value or less, and the foam film can be easily reduced in density.
　上記のような発泡方法を採用することにより、発泡体フィルムは作製される。発泡体フィルムの形成は、特に制限されず、例えば、機械的に空気等の気体を混入させる発泡方法を採用する場合には、その後、気泡を含む樹脂組成物（例えばエマルション型樹脂組成物）を基材または剥離紙等の上に塗付し、乾燥させることにより発泡体フィルムを得ることができる。乾燥は、気泡安定性等の観点から、５０℃以上１２５℃未満の予備乾燥工程と、１２５℃～２００℃の本乾燥工程を含むことが好ましい。あるいは、カレンダや押出機、コンベアベルトキャスティング等を用いて連続的にフィルム状の発泡体を形成してもよく、発泡体形成材料の混練物をバッチ方式で発泡成形する方法を採用してもよい。発泡体フィルムの形成にあたっては、表層部分をスライス加工により除去し、所望の厚さ、発泡特性となるよう調整してもよい。 By adopting the foaming method as described above, a foam film is produced. The formation of the foam film is not particularly limited. For example, when a foaming method in which a gas such as air is mechanically mixed is employed, a resin composition containing bubbles (for example, an emulsion type resin composition) is then used. A foam film can be obtained by applying on a substrate or release paper and drying. The drying preferably includes a preliminary drying step of 50 ° C. or more and lower than 125 ° C. and a main drying step of 125 ° C. to 200 ° C. from the viewpoint of bubble stability and the like. Alternatively, a film-like foam may be continuously formed using a calendar, an extruder, a conveyor belt casting, or the like, and a method of foam-molding a kneaded product of the foam-forming material may be employed. . In forming the foam film, the surface layer portion may be removed by slicing and adjusted to have a desired thickness and foam characteristics.
　上記発泡体フィルムに含まれ得る熱可塑性ポリマー（例えばポリオレフィン系ポリマー）には、常温ではゴムとしての性質を示し、高温では熱可塑性を示す熱可塑性エラストマーが含まれ得る。柔軟性や追従性の観点から、例えば、エチレン－プロピレン共重合体、エチレン－プロピレン－ジエン共重合体、エチレン－酢酸ビニル共重合体、ポリブテン、ポリイソブチレン、塩素化ポリエチレン等のオレフィン系エラストマー；スチレン－ブタジエン－スチレン共重合体等のスチレン系エラストマー；熱可塑性ポリエステル系エラストマー；熱可塑性ポリウレタン系エラストマー；熱可塑性アクリル系エラストマー；等の熱可塑性エラストマーのうち１種または２種以上を用いることができ、そのなかでも、ガラス転移温度が室温以下（例えば２０℃以下）である熱可塑性エラストマーが好ましく用いられる。上記発泡体フィルムにおける熱可塑性エラストマーの含有割合は、発泡体フィルム中の熱可塑性ポリマーの凡そ１０～９０重量％（例えば２０～８０重量％）程度とすることが好ましい。 The thermoplastic polymer that can be included in the foam film (for example, a polyolefin-based polymer) may include a thermoplastic elastomer that exhibits properties as a rubber at room temperature and exhibits thermoplasticity at a high temperature. From the viewpoint of flexibility and followability, for example, olefin elastomers such as ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, polybutene, polyisobutylene, chlorinated polyethylene; styrene -Styrene elastomers such as butadiene-styrene copolymers; thermoplastic polyester elastomers; thermoplastic polyurethane elastomers; thermoplastic acrylic elastomers; Among them, a thermoplastic elastomer having a glass transition temperature of room temperature or lower (for example, 20 ° C. or lower) is preferably used. The content ratio of the thermoplastic elastomer in the foam film is preferably about 10 to 90% by weight (for example, 20 to 80% by weight) of the thermoplastic polymer in the foam film.
　気泡形成ガスの混入性や気泡の安定性の観点から、発泡体フィルム形成材料（例えばエマルション型アクリル系樹脂組成物）には、起泡剤として、例えば、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤等の各種界面活性剤を用いることができる。炭化水素系やフッ素系の界面活性剤を用いてもよい。なかでも、気泡径の微細化や気泡安定性の観点から、アニオン系界面活性剤が好ましく、ステアリン酸アンモニウム等の脂肪酸アンモニウム（典型的には高級脂肪酸アンモニウム）系界面活性剤がより好ましい。上記界面活性剤は１種単独でまたは２種以上を組み合わせて用いることができる。上記界面活性剤の含有量は、発泡体フィルムのベースポリマー１００重量部に対して、０．１～１０重量部（例えば０．５～８重量部）程度とすることが好ましい。なお、本明細書における起泡剤には、起泡作用を示す剤だけでなく、気泡径を微細化する気泡径調整剤や、整泡剤等の気泡安定剤が含まれるものとする。 From the viewpoint of mixing of bubble forming gas and stability of bubbles, foam film forming materials (for example, emulsion type acrylic resin compositions) have foaming agents such as anionic surfactants and cationic surfactants. Various surfactants such as an agent, a nonionic surfactant, and an amphoteric surfactant can be used. Hydrocarbon or fluorine surfactants may be used. Of these, anionic surfactants are preferred from the viewpoint of finer bubble diameter and bubble stability, and fatty acid ammonium (typically higher fatty acid ammonium) surfactants such as ammonium stearate are more preferred. The said surfactant can be used individually by 1 type or in combination of 2 or more types. The surfactant content is preferably about 0.1 to 10 parts by weight (eg 0.5 to 8 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film. In addition, the foaming agent in this specification includes not only an agent exhibiting a foaming action but also a bubble stabilizer such as a bubble diameter adjusting agent for reducing the bubble diameter and a foam stabilizer.
　発泡体フィルム形成材料が水性分散液（例えばアクリルエマルション）の場合には、上記起泡剤としてシリコーン系化合物を使用することが好ましい。これにより、圧縮後の厚さ回復性（回復の程度や速度）が向上する傾向がある。シリコーン系化合物としては、シロキサン結合が２０００以下のシリコーン系化合物が好ましい。シリコーン系化合物として、例えば、シリコーンオイル、変性シリコーンオイル、シリコーンレジン等が挙げられる。なかでも、ジメチルシリコーンオイル、メチルフェニルシリコーンオイルが好ましい。シリコーン系化合物として、シリコーン変性ポリマー（例えば、シリコーン変性アクリル系ポリマー、シリコーン変性ウレタン系ポリマー等）を用いてもよい。これらは１種を単独でまたは２種以上を組み合わせて用いることができる。シリコーン系化合物の含有量は、発泡体フィルムのベースポリマー１００重量部に対して、０．０１～５重量部（例えば０．０５～４重量部、典型的には０．１～３重量部）程度とすることが好ましい。 When the foam film-forming material is an aqueous dispersion (for example, an acrylic emulsion), it is preferable to use a silicone compound as the foaming agent. Thereby, there exists a tendency for the thickness recoverability (the extent and speed of recovery) after compression to improve. As the silicone compound, a silicone compound having a siloxane bond of 2000 or less is preferable. Examples of the silicone compound include silicone oil, modified silicone oil, and silicone resin. Of these, dimethyl silicone oil and methylphenyl silicone oil are preferable. As the silicone compound, a silicone-modified polymer (for example, silicone-modified acrylic polymer, silicone-modified urethane polymer, etc.) may be used. These can be used alone or in combination of two or more. The content of the silicone compound is 0.01 to 5 parts by weight (eg 0.05 to 4 parts by weight, typically 0.1 to 3 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film. It is preferable to set the degree.
　また、気泡安定性、成膜性向上の観点から、発泡体フィルム形成材料（例えばエマルション型アクリル系樹脂組成物）は、増粘剤を含んでもよい。増粘剤としては、特に制限されず、例えばアクリル酸系増粘剤、ウレタン系増粘剤、ポリビニルアルコール系増粘剤等が挙げられる。なかでも、ポリアクリル酸系増粘剤、ウレタン系増粘剤が好ましい。増粘剤の含有量は、発泡体フィルムのベースポリマー１００重量部に対して、０．１～１０重量部（例えば０．１～５重量部）程度とすることが好ましい。 Further, from the viewpoint of improving bubble stability and film formability, the foam film-forming material (for example, an emulsion type acrylic resin composition) may contain a thickener. The thickener is not particularly limited, and examples thereof include an acrylic acid thickener, a urethane thickener, and a polyvinyl alcohol thickener. Of these, polyacrylic acid thickeners and urethane thickeners are preferred. The content of the thickener is preferably about 0.1 to 10 parts by weight (for example, 0.1 to 5 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film.
　上記フィルム状基材として発泡体含有基材を用いる場合には、発泡体フィルムは、例えば、金属水酸化物（例えば水酸化マグネシウム）等の気泡核剤を含むことが好ましい。これによって、発泡体フィルム中の平均気泡径の調整が容易となり、所望の衝撃吸収性や柔軟性等が得られやすくなる傾向がある。気泡核剤は、金属酸化物、複合酸化物、金属炭酸塩、金属硫酸塩等であってもよい。気泡核剤の含有量は、発泡体フィルムのベースポリマー１００重量部に対して、０．５～１２５重量部（例えば１～１２０重量部）程度とすることが好ましい。 When a foam-containing substrate is used as the film-like substrate, the foam film preferably contains a cell nucleating agent such as a metal hydroxide (for example, magnesium hydroxide). Thereby, adjustment of the average cell diameter in the foam film is facilitated, and desired impact absorbability and flexibility tend to be easily obtained. The cell nucleating agent may be a metal oxide, composite oxide, metal carbonate, metal sulfate or the like. The content of the cell nucleating agent is preferably about 0.5 to 125 parts by weight (for example, 1 to 120 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film.
　上記フィルム状基材として発泡体含有基材を用いる場合には、発泡体フィルムは、気泡形成時における発泡体からのガス成分の透過を抑制する観点から、脂肪酸アミド等のガス透過抑制剤を含むことが好ましい。脂肪酸アミドは、ビスアミド構造を有するものがより好ましい。ガス透過抑制剤は、脂肪酸金属塩であってもよい。ガス透過抑制剤の含有量は、発泡体フィルムのベースポリマー１００重量部に対して０．５～１０重量部（例えば０．７～８重量部、典型的には１～６重量部）程度とすることが好ましい。 When a foam-containing substrate is used as the film-like substrate, the foam film contains a gas permeation inhibitor such as fatty acid amide from the viewpoint of suppressing the permeation of gas components from the foam during the formation of bubbles. It is preferable. The fatty acid amide is more preferably one having a bisamide structure. The gas permeation inhibitor may be a fatty acid metal salt. The content of the gas permeation inhibitor is about 0.5 to 10 parts by weight (for example, 0.7 to 8 parts by weight, typically 1 to 6 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film. It is preferable to do.
　上記フィルム状基材（例えば発泡体フィルム）は、フィルム形成材料に所望の流動性を持たせ柔軟性等の特性を改善する目的で軟化剤を含んでもよい。また、発泡体フィルムに軟化剤を含ませることにより、フィルム延伸性や発泡倍率等の特性が好ましく調節され得る。例えば、流動パラフィン、パラフィンワックス、マイクロワックス、ポリエチレンワックス等の炭化水素系軟化剤や、ステアリン酸モノグリセリド等のエステル系軟化剤、脂肪酸系軟化剤の１種または２種以上を好ましく使用することができる。軟化剤の含有量は、フィルム状基材（例えば発泡体フィルム）のベースポリマー１００重量部に対して０．５～５０重量部（例えば０．８～４０重量部、典型的には１～３０重量部）程度とすることが好ましい。 The film-like substrate (for example, a foam film) may contain a softening agent for the purpose of imparting desired fluidity to the film-forming material and improving properties such as flexibility. Moreover, by including a softening agent in the foam film, properties such as film stretchability and expansion ratio can be preferably adjusted. For example, one or more of hydrocarbon softeners such as liquid paraffin, paraffin wax, microwax and polyethylene wax, ester softeners such as stearic acid monoglyceride, and fatty acid softeners can be preferably used. . The content of the softening agent is 0.5 to 50 parts by weight (for example, 0.8 to 40 parts by weight, typically 1 to 30 parts) with respect to 100 parts by weight of the base polymer of the film-like substrate (for example, foam film). Part by weight) is preferable.
　また、エマルション型アクリル系樹脂発泡体を使用する場合、発泡体フィルムに隣接する金属部材の腐食防止のため、任意の防錆剤を含んでいてもよい。防錆剤として、アゾール環含有化合物が好ましい。アゾール環含有化合物を用いることにより、金属腐食防止性と被着体への密着性とを高いレベルで両立することができる。なかでも、アゾール環がベンゼン環等の芳香環と縮合環を形成している化合物が好ましく、ベンゾトリアゾール系化合物、ベンゾチアゾール系化合物が特に好ましい。防錆剤の含有量は、発泡体フィルムのベースポリマー１００重量部に対して、０．２～５重量部（例えば０．３～２重量部）程度とすることが好ましい。 In the case of using an emulsion type acrylic resin foam, an arbitrary rust inhibitor may be included to prevent corrosion of the metal member adjacent to the foam film. As the rust inhibitor, an azole ring-containing compound is preferable. By using an azole ring-containing compound, it is possible to achieve both high levels of metal corrosion prevention and adhesion to an adherend. Of these, compounds in which the azole ring forms a condensed ring with an aromatic ring such as a benzene ring are preferred, and benzotriazole compounds and benzothiazole compounds are particularly preferred. The content of the rust inhibitor is preferably about 0.2 to 5 parts by weight (for example, 0.3 to 2 parts by weight) with respect to 100 parts by weight of the base polymer of the foam film.
　好ましい一態様では、フィルム状基材は透明性（半透明を包含する。）を有する。このようなフィルム状基材を備える粘着シートでは、粘着シートと被着体との間に気泡等が混入すると、粘着シート越しに当該気泡等が視認されて外観性が損なわれやすい。ここに開示される技術によると、粘着シートと被着体との間における気泡等の発生が防止されるので、透明性基材を備える構成において優れた外観性が得られる。具体的には、上記フィルム状基材は８０％以上（例えば９０％以上、典型的には９５％以上）の全光線透過率を示すものであり得る。また、フィルム状基材のヘイズ値は１０％以下（例えば５％以下）であることが好ましい。 In a preferred embodiment, the film-like substrate has transparency (including translucency). In the pressure-sensitive adhesive sheet having such a film-like substrate, when bubbles or the like are mixed between the pressure-sensitive adhesive sheet and the adherend, the bubbles are visually recognized through the pressure-sensitive adhesive sheet, and the appearance is easily impaired. According to the technique disclosed herein, generation of bubbles or the like between the pressure-sensitive adhesive sheet and the adherend is prevented, so that excellent appearance can be obtained in a configuration including a transparent substrate. Specifically, the film-like substrate may exhibit a total light transmittance of 80% or more (for example, 90% or more, typically 95% or more). Moreover, it is preferable that the haze value of a film-form base material is 10% or less (for example, 5% or less).
　上記フィルム状基材（例えば樹脂フィルム）は、所望の意匠性や光学特性を付与するために、各種着色剤（例えば顔料）を含ませて黒色、白色その他の色に着色されていてもよい。黒色系着色剤としてはカーボンブラックが好ましい。また、フィルム状基材の少なくとも一方の表面（片面または両面）に印刷等により１層または２層以上の着色層（例えば黒色層や白色層）を積層する方法を採用してもよい。 The film-like substrate (for example, a resin film) may be colored black, white, or other colors by including various colorants (for example, pigments) in order to impart desired designability and optical characteristics. Carbon black is preferred as the black colorant. Moreover, you may employ | adopt the method of laminating | stacking one layer or two or more colored layers (for example, a black layer or a white layer) by printing etc. on at least one surface (one side or both surfaces) of a film-form base material.
　上記フィルム状基材（例えば樹脂フィルム基材や発泡体フィルム基材）には、必要に応じて、充填剤（無機充填剤、有機充填剤等）、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、滑剤、可塑剤等の各種添加剤がさらに配合されていてもよい。 For the film-like substrate (for example, a resin film substrate or a foam film substrate), a filler (inorganic filler, organic filler, etc.), an anti-aging agent, an antioxidant, an ultraviolet absorber, as necessary. Further, various additives such as an antistatic agent, a lubricant and a plasticizer may be further blended.
　粘着シートが片面粘着シートである場合、フィルム状基材の表面のうち、粘着剤層が設けられる面とは反対側の表面（背面）は、平滑に形成されていることが好ましい。上記の平滑表面は粘着シートの外面となり得るため、当該平滑表面を有する粘着シートを例えば装飾シートや表面保護シートとして使用する場合には、より良好な外観性（意匠性）を与え得る。好ましい一態様では、粘着特性、外観性（意匠性）の観点から、フィルム状基材の背面における算術平均表面粗さは１μｍ以下（例えば凡そ０．０５～０．７５μｍ、典型的には凡そ０．１～０．５μｍ）であり得る。なお、本明細書において算術平均表面粗さは、一般的な表面粗さ測定装置（例えば、Ｖｅｅｃｏ社製の非接触３次元表面形状測定装置、型式「Ｗｙｋｏ　ＮＴ－３３００」）を用いて測定することができる。 When the pressure-sensitive adhesive sheet is a single-sided pressure-sensitive adhesive sheet, it is preferable that the surface (back surface) opposite to the surface on which the pressure-sensitive adhesive layer is provided is formed smoothly among the surfaces of the film-like substrate. Since the smooth surface can be the outer surface of the pressure-sensitive adhesive sheet, when the pressure-sensitive adhesive sheet having the smooth surface is used as, for example, a decorative sheet or a surface protective sheet, a better appearance (design) can be provided. In a preferred embodiment, the arithmetic average surface roughness on the back surface of the film-like substrate is 1 μm or less (for example, about 0.05 to 0.75 μm, typically about 0 from the viewpoint of adhesive properties and appearance (design). .1 to 0.5 μm). In this specification, the arithmetic average surface roughness is measured using a general surface roughness measuring device (for example, a non-contact three-dimensional surface shape measuring device manufactured by Veeco, model “Wyko NT-3300”). be able to.
　また、片面粘着シートを巻回して、フィルム状基材の背面に粘着剤層の表面を当接させる場合には、該フィルム状基材の背面（粘着剤層が設けられる面とは反対側の面）に、必要に応じて、シリコーン系、長鎖アルキル系、フッ素系等の剥離処理剤による剥離処理が施されていてもよい。剥離処理を施すことにより、粘着シートをロール状に巻回した巻回体の巻き戻しを容易にする等の効果が得られる。一方、上記フィルム状基材の粘着剤層側表面には、基材と粘着剤層との密着性を高めること等を目的として、コロナ放電処理、下塗り剤の塗付等の従来公知の表面処理が施されていてもよい。 In addition, when a single-sided pressure-sensitive adhesive sheet is wound and the surface of the adhesive layer is brought into contact with the back surface of the film-like substrate, the back surface of the film-like substrate (the side opposite to the surface on which the adhesive layer is provided) The surface) may be subjected to a release treatment with a release treatment agent such as a silicone-based, long-chain alkyl-based, or fluorine-based material, if necessary. By performing the peeling treatment, effects such as easy rewinding of the wound body obtained by winding the pressure-sensitive adhesive sheet into a roll shape can be obtained. On the other hand, for the purpose of improving the adhesion between the base material and the pressure-sensitive adhesive layer, the surface of the film-like base material, which has been conventionally known, such as corona discharge treatment, primer coating, etc. May be given.
　フィルム状基材の厚さは特に限定されず、目的に応じて適宜選択できる。一般的には、上記厚さは、通常は１μｍ以上（例えば２～５００μｍ程度）とすることが適当であり、５～５００μｍ（例えば１０～２００μｍ、典型的には１５～１００μｍ）程度とすることが好ましい。フィルム状基材の厚さを制限することは、粘着シートの薄膜化、小型化、軽量化、省資源化等の点で有利である。 The thickness of the film-like substrate is not particularly limited and can be appropriately selected depending on the purpose. In general, the thickness is usually 1 μm or more (for example, about 2 to 500 μm), and 5 to 500 μm (for example, 10 to 200 μm, typically 15 to 100 μm). Is preferred. Limiting the thickness of the film-like substrate is advantageous in terms of reducing the thickness, reducing the size, reducing the weight, and saving resources of the pressure-sensitive adhesive sheet.
　フィルム状基材が発泡体フィルムを含む場合、発泡体含有基材（例えば発泡体フィルム基材）の厚さは、粘着シートの強度や柔軟性、使用目的等に応じて適宜設定することができる。衝撃吸収性等の観点からは、発泡体含有基材の厚さを３０μｍ以上とすることが適当であり、好ましくは５０μｍ以上、より好ましくは６０μｍ以上（例えば８０μｍ以上）である。粘着シートの薄膜化、小型化、軽量化、省資源化等の観点から、通常は、発泡体含有基材の厚さを１ｍｍ以下とすることが適当である。ここに開示される発泡体フィルムを使用することにより、上記厚さが３５０μｍ以下（より好ましくは２５０μｍ以下、例えば１８０μｍ以下）程度でも、優れた衝撃吸収機能を発揮することができる。なお、発泡体含有基材における発泡体フィルム（発泡体層であり得る。）の厚さも、上述の発泡体含有基材の厚さとして例示した範囲から好ましく選定され得る。 When the film-like substrate includes a foam film, the thickness of the foam-containing substrate (for example, the foam film substrate) can be appropriately set according to the strength, flexibility, purpose of use, etc. of the pressure-sensitive adhesive sheet. . From the viewpoint of impact absorption and the like, it is appropriate that the thickness of the foam-containing substrate is 30 μm or more, preferably 50 μm or more, more preferably 60 μm or more (for example, 80 μm or more). From the viewpoint of reducing the thickness of the pressure-sensitive adhesive sheet, reducing the size, reducing the weight, saving resources, and the like, it is usually appropriate to set the thickness of the foam-containing substrate to 1 mm or less. By using the foam film disclosed herein, an excellent shock absorbing function can be exhibited even when the thickness is about 350 μm or less (more preferably 250 μm or less, for example, 180 μm or less). In addition, the thickness of the foam film (which may be a foam layer) in the foam-containing substrate can also be preferably selected from the range exemplified as the thickness of the above-mentioned foam-containing substrate.
　＜粘着剤層＞
　ここに開示される粘着剤層は、典型的には、室温付近の温度域において柔らかい固体（粘弾性体）の状態を呈し、圧力により簡単に被着体に接着する性質を有する材料（粘着剤）から構成された層をいう。ここでいう粘着剤は、「C. A. Dahlquist, “Adhesion : Fundamental and Practice”, McLaren & Sons, (1966) P. 143」に定義されているとおり、一般的に、複素引張弾性率Ｅ＊（１Ｈｚ）＜１０７ｄｙｎｅ／ｃｍ２を満たす性質を有する材料（典型的には、２５℃において上記性質を有する材料）である。 <Adhesive layer>
The pressure-sensitive adhesive layer disclosed herein typically exhibits a soft solid (viscoelastic body) state in a temperature range near room temperature, and is a material (pressure-sensitive adhesive) that has a property of easily adhering to an adherend by pressure. ). The adhesive here is generally complex elastic modulus E * (1 Hz) as defined in “C. A. Dahlquist,“ Adhesion: Fundamental and Practice ”, McLaren & Sons, (1966) P. 143”. <10 < 7 > dyne / cm < 2 > material (typically a material having the above properties at 25 [deg.] C.).
　ここに開示される粘着剤層は、粘着剤の分野において公知のアクリル系ポリマー、ゴム系ポリマー、ポリエステル系ポリマー、ウレタン系ポリマー、ポリエーテル系ポリマー、シリコーン系ポリマー、ポリアミド系ポリマー、フッ素系ポリマー等の１種または２種以上をベースポリマーとして含むものであり得る。粘着特性（例えば剥離強度や耐反撥性）や分子設計等の観点から、アクリル系ポリマーを好ましく採用し得る。換言すると、粘着剤層は、アクリル系ポリマーをベースポリマーとして含むアクリル系粘着剤層であることが好ましい。なお、粘着剤の「ベースポリマー」とは、該粘着剤に含まれるポリマー成分の主成分（典型的には、５０重量％を超えて含まれる成分）をいう。 The pressure-sensitive adhesive layer disclosed herein is a known acrylic polymer, rubber polymer, polyester polymer, urethane polymer, polyether polymer, silicone polymer, polyamide polymer, fluorine polymer, etc. in the field of pressure sensitive adhesive. 1 type, or 2 types or more may be included as a base polymer. From the viewpoint of adhesive properties (for example, peel strength and repulsion resistance) and molecular design, an acrylic polymer can be preferably used. In other words, the pressure-sensitive adhesive layer is preferably an acrylic pressure-sensitive adhesive layer containing an acrylic polymer as a base polymer. The “base polymer” of the pressure-sensitive adhesive refers to the main component of the polymer component contained in the pressure-sensitive adhesive (typically a component included in an amount exceeding 50% by weight).
　上記アクリル系ポリマーとしては、例えば、アルキル（メタ）アクリレートを主モノマーとして含み、該主モノマーと共重合性を有する副モノマーをさらに含み得るモノマー原料の重合物が好ましい。ここで主モノマーとは、上記モノマー原料におけるモノマー組成の５０重量％超を占める成分をいう。 As the acrylic polymer, for example, a polymer of a monomer raw material that includes alkyl (meth) acrylate as a main monomer and may further include a submonomer copolymerizable with the main monomer is preferable. Here, the main monomer means a component occupying more than 50% by weight of the monomer composition in the monomer raw material.
　アルキル（メタ）アクリレートとしては、例えば下記式（１）で表される化合物を好ましく使用することができる。
　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２　　　　　（１）
　ここで、上記式（１）中のＲ１は水素原子またはメチル基である。また、Ｒ２は炭素原子数１～２０の鎖状アルキル基（以下、このような炭素原子数の範囲を「Ｃ１－２０」と表すことがある。）である。粘着剤の貯蔵弾性率等の観点から、Ｒ２がＣ１－１２（例えばＣ２－１０、典型的にはＣ４－８）の鎖状アルキル基であるアルキル（メタ）アクリレートが好ましい。上記Ｒ２がＣ１－２０の鎖状アルキル基であるアルキル（メタ）アクリレートは、１種を単独でまたは２種以上を組み合わせて用いることができる。好ましいアルキル（メタ）アクリレートとして、ｎ－ブチルアクリレートおよび２－エチルヘキシルアクリレートが挙げられる。 As the alkyl (meth) acrylate, for example, a compound represented by the following formula (1) can be preferably used.
CH 2 = C (R 1 ) COOR 2 (1)
Here, R 1 in the above formula (1) is a hydrogen atom or a methyl group. R 2 is a chain alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of the number of carbon atoms may be represented as “C 1-20 ”). From the viewpoint of the storage elastic modulus of the pressure-sensitive adhesive, an alkyl (meth) acrylate in which R 2 is a chain alkyl group of C 1-12 (eg, C 2-10 , typically C 4-8 ) is preferable. The alkyl (meth) acrylate in which R 2 is a C 1-20 chain alkyl group can be used singly or in combination of two or more. Preferred alkyl (meth) acrylates include n-butyl acrylate and 2-ethylhexyl acrylate.
　主モノマーであるアルキル（メタ）アクリレートと共重合性を有する副モノマーは、アクリル系ポリマーに架橋点を導入したり、アクリル系ポリマーの凝集力を高めたりするために役立ち得る。副モノマーとして、例えばカルボキシ基含有モノマー、水酸基含有モノマー、酸無水物基含有モノマー、アミド基含有モノマー、アミノ基含有モノマー、窒素原子含有環を有するモノマー等の官能基含有モノマーの１種または２種以上を使用することができる。副モノマーはまた、酢酸ビニル等のビニルエステル系モノマー、スチレン等の芳香族ビニル化合物、スルホン酸基含有モノマー、リン酸基含有モノマー等であり得る。例えば、凝集力向上の観点から、上記副モノマーとしてカルボキシ基含有モノマー、水酸基含有モノマーが共重合されたアクリル系ポリマーが好ましい。カルボキシ基含有モノマーの好適例としては、アクリル酸、メタクリル酸が挙げられる。水酸基含有モノマーの好適例としては、２－ヒドロキシエチルアクリレートや４－ヒドロキシブチルアクリレートが挙げられる。 The secondary monomer copolymerizable with the main monomer, alkyl (meth) acrylate, can be useful for introducing a crosslinking point into the acrylic polymer or increasing the cohesive strength of the acrylic polymer. As a submonomer, for example, one or two functional group-containing monomers such as a carboxy group-containing monomer, a hydroxyl group-containing monomer, an acid anhydride group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, and a monomer having a nitrogen atom-containing ring The above can be used. The secondary monomer may also be a vinyl ester monomer such as vinyl acetate, an aromatic vinyl compound such as styrene, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, and the like. For example, from the viewpoint of improving cohesive strength, an acrylic polymer obtained by copolymerizing a carboxy group-containing monomer and a hydroxyl group-containing monomer as the submonomer is preferable. Preferable examples of the carboxy group-containing monomer include acrylic acid and methacrylic acid. Preferable examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate.
　上記副モノマーの量は、アクリル系ポリマーの全モノマー成分中の０．５重量％以上とすることが適当であり、好ましくは１重量％以上である。また、副モノマーの量は、全モノマー成分中の３０重量％以下が適当であり、好ましくは１０重量％以下（例えば５重量％以下）である。アクリル系ポリマーにカルボキシ基含有モノマーが共重合されている場合、粘着力と凝集力との両立の観点から、カルボキシ基含有モノマーの含有量は、アクリル系ポリマーの合成に使用する全モノマー成分中、凡そ０．１～１０重量％（例えば０．２～８重量％、典型的には０．５～５重量％）の範囲内であることが好ましい。アクリル系ポリマーに水酸基含有モノマーが共重合されている場合、粘着力と凝集力との両立の観点から、水酸基含有モノマーの含有量は、アクリル系ポリマーの合成に使用する全モノマー成分中、凡そ０．００１～１０重量％（例えば０．０１～５重量％、典型的には０．０２～２重量％）の範囲内であることが好ましい。また、上記副モノマーとして酢酸ビニル等のビニルエステル系モノマーが共重合されている場合には、上記ビニルエステル系モノマーの含有量は、アクリル系ポリマーの合成に使用する全モノマー成分中、凡そ３０重量％以下（典型的には０．０１～３０重量％、例えば０．１～１０重量％）とすることが好ましい。 The amount of the submonomer is suitably 0.5% by weight or more, preferably 1% by weight or more, based on the total monomer components of the acrylic polymer. Further, the amount of the submonomer is suitably 30% by weight or less, preferably 10% by weight or less (for example, 5% by weight or less) in the total monomer components. When the carboxy group-containing monomer is copolymerized with the acrylic polymer, the content of the carboxy group-containing monomer is, among all monomer components used for the synthesis of the acrylic polymer, from the viewpoint of coexistence of adhesive force and cohesive force. It is preferably in the range of about 0.1 to 10% by weight (eg 0.2 to 8% by weight, typically 0.5 to 5% by weight). When a hydroxyl group-containing monomer is copolymerized with an acrylic polymer, the content of the hydroxyl group-containing monomer is approximately 0 out of all monomer components used for the synthesis of the acrylic polymer from the viewpoint of achieving both cohesion and cohesion. It is preferably within the range of 0.001 to 10% by weight (eg 0.01 to 5% by weight, typically 0.02 to 2% by weight). Further, when a vinyl ester monomer such as vinyl acetate is copolymerized as the submonomer, the content of the vinyl ester monomer is about 30% in the total monomer components used for the synthesis of the acrylic polymer. % Or less (typically 0.01 to 30% by weight, for example 0.1 to 10% by weight).
　アクリル系ポリマーを得る方法は特に限定されず、溶液重合法、乳化重合法、塊状重合法、懸濁重合法等の、アクリル系ポリマーの合成手法として知られている各種の重合方法を適宜採用することができる。ＵＶ等を照射して行う活性エネルギー線照射重合を採用してもよい。例えば、適当な重合溶媒（トルエン、酢酸エチル、水等）中にモノマー混合物を溶解または分散させ、アゾ系重合開始剤や過酸化物系開始剤等の重合開始剤を用いて重合操作を行うことにより、所望のアクリル系ポリマーを得ることができる。 The method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for acrylic polymers, such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization, are appropriately employed. be able to. Active energy ray irradiation polymerization performed by irradiation with UV or the like may be employed. For example, a monomer mixture is dissolved or dispersed in a suitable polymerization solvent (toluene, ethyl acetate, water, etc.), and a polymerization operation is performed using a polymerization initiator such as an azo polymerization initiator or a peroxide initiator. Thus, a desired acrylic polymer can be obtained.
　ここに開示されるアクリル系ポリマーの重量平均分子量（Ｍｗ）は、粘着力と凝集力とをバランスよく両立する観点から、１０×１０４以上１００×１０４以下の範囲にあることが好ましい。Ｍｗが２０×１０４以上７０×１０４以下（例えば３０×１０４以上５０×１０４以下）のアクリル系ポリマーによると、より良好な結果が実現され得る。なお、この明細書においてＭｗとは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により得られた標準ポリスチレン換算の値をいう。 The weight average molecular weight (Mw) of the acrylic polymer disclosed herein is preferably in the range of 10 × 10 4 or more and 100 × 10 4 or less from the viewpoint of balancing the adhesive force and the cohesive force in a balanced manner. A better result can be achieved with an acrylic polymer having an Mw of 20 × 10 4 or more and 70 × 10 4 or less (eg, 30 × 10 4 or more and 50 × 10 4 or less). In addition, in this specification, Mw means the value of standard polystyrene conversion obtained by GPC (gel permeation chromatography).
　粘着剤組成物は、凝集力を高める観点から架橋剤を含むことが好ましい。架橋剤の種類は特に制限されず、従来公知の架橋剤の１種または２種以上を適宜選択して用いることができる。架橋剤の好適例としては、イソシアネート系架橋剤、エポキシ系架橋剤が挙げられる。架橋剤の使用量は特に制限されず、例えば、アクリル系ポリマー１００重量部に対して凡そ１０重量部以下（例えば凡そ０．００５～１０重量部、好ましくは凡そ０．０１～５重量部）の範囲から選択することができる。 The pressure-sensitive adhesive composition preferably contains a crosslinking agent from the viewpoint of increasing the cohesive force. The type of the crosslinking agent is not particularly limited, and one or more conventionally known crosslinking agents can be appropriately selected and used. Preferable examples of the crosslinking agent include isocyanate crosslinking agents and epoxy crosslinking agents. The amount of the crosslinking agent used is not particularly limited, and is, for example, about 10 parts by weight or less (for example, about 0.005 to 10 parts by weight, preferably about 0.01 to 5 parts by weight) with respect to 100 parts by weight of the acrylic polymer. You can choose from a range.
　ここに開示される粘着剤層は、粘着付与剤を含む組成であり得る。粘着付与剤としては、特に制限されないが、例えば、ロジン系粘着付与樹脂、テルペン系粘着付与樹脂、炭化水素系粘着付与樹脂、エポキシ系粘着付与樹脂、ポリアミド系粘着付与樹脂、エラストマー系粘着付与樹脂、フェノール系粘着付与樹脂、ケトン系粘着付与樹脂等の各種粘着付与樹脂を用いることができる。このような粘着付与樹脂は、１種を単独でまたは２種以上を組み合わせて使用することができる。 The pressure-sensitive adhesive layer disclosed herein may have a composition containing a tackifier. The tackifier is not particularly limited, for example, rosin tackifier resin, terpene tackifier resin, hydrocarbon tackifier resin, epoxy tackifier resin, polyamide tackifier resin, elastomer tackifier resin, Various tackifying resins such as a phenolic tackifying resin and a ketone tackifying resin can be used. Such tackifier resin can be used individually by 1 type or in combination of 2 or more types.
　粘着付与樹脂の軟化点（軟化温度）は、凡そ６０℃以上（好ましくは凡そ８０℃以上、典型的には１００℃以上）であることが好ましい。これにより、接着力のより高い粘着シートが実現され得る。粘着付与樹脂の軟化点の上限は特に制限されず、凡そ１８０℃以下（例えば凡そ１４０℃以下）とすることができる。なお、ここでいう粘着付与樹脂の軟化点は、ＪＩＳ　Ｋ５９０２：２００６およびＪＩＳ　Ｋ２２０７：２００６のいずれかに規定する軟化点試験方法（環球法）によって測定された値として定義される。 The softening point (softening temperature) of the tackifier resin is preferably about 60 ° C. or higher (preferably about 80 ° C. or higher, typically 100 ° C. or higher). Thereby, the adhesive sheet with higher adhesive force can be realized. The upper limit of the softening point of the tackifying resin is not particularly limited, and can be about 180 ° C. or lower (for example, about 140 ° C. or lower). In addition, the softening point of the tackifier resin here is defined as a value measured by a softening point test method (ring ball method) defined in any of JIS K5902: 2006 and JIS K2207: 2006.
　粘着付与剤の使用量は特に制限されず、目的とする粘着性能（接着力等）に応じて適宜設定することができる。例えば、固形分基準で、ベースポリマー（好適にはアクリル系ポリマー）１００重量部に対して、粘着付与剤を凡そ１０～１００重量部（より好ましくは２０～８０重量部、さらに好ましくは３０～６０重量部）の割合で使用することが好ましい。 The amount of the tackifier used is not particularly limited, and can be appropriately set according to the target tack performance (adhesive strength, etc.). For example, the tackifier is approximately 10 to 100 parts by weight (more preferably 20 to 80 parts by weight, more preferably 30 to 60 parts by weight) with respect to 100 parts by weight of the base polymer (preferably an acrylic polymer) based on the solid content. (Part by weight) is preferably used.
　上記粘着剤組成物は、必要に応じて、レベリング剤、架橋助剤、可塑剤、軟化剤、充填剤、帯電防止剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤等の、粘着剤組成物の分野において一般的な各種の添加剤を含有するものであり得る。このような各種添加剤については、従来公知のものを常法により使用すればよい。 The pressure-sensitive adhesive composition may be a leveling agent, a crosslinking aid, a plasticizer, a softener, a filler, an antistatic agent, an anti-aging agent, an ultraviolet absorber, an antioxidant, a light stabilizer, etc., if necessary. Various additives common in the field of pressure-sensitive adhesive compositions can be contained. About such various additives, a conventionally well-known thing should just be used by a conventional method.
　ここに開示される粘着剤層は、水系、溶剤型、ホットメルト型、活性エネルギー線硬化型等の粘着剤組成物から形成された粘着剤層であり得る。水系粘着剤組成物とは、水を主成分とする溶媒（水系溶媒）中に粘着剤（粘着剤層形成成分）を含む形態の粘着剤組成物のことをいい、典型的には、水分散型粘着剤組成物（粘着剤の少なくとも一部が水に分散した形態の組成物）等と称されるものが含まれる。また、溶剤型粘着剤組成物とは、有機溶媒中に粘着剤を含む形態の粘着剤組成物のことをいう。環境負荷低減の観点からは水系粘着剤組成物が好ましく、粘着特性等の観点からは溶剤型粘着剤組成物が好ましく用いられる。 The pressure-sensitive adhesive layer disclosed herein may be a pressure-sensitive adhesive layer formed from a water-based, solvent-type, hot-melt type, active energy ray-curable pressure-sensitive adhesive composition, or the like. The water-based pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in a form containing a pressure-sensitive adhesive (pressure-sensitive adhesive layer forming component) in a water-based solvent (water-based solvent), and is typically dispersed in water. What is called a type pressure-sensitive adhesive composition (a composition in which at least a part of the pressure-sensitive adhesive is dispersed in water) and the like are included. Moreover, a solvent-type adhesive composition means the adhesive composition of the form which contains an adhesive in an organic solvent. A water-based pressure-sensitive adhesive composition is preferable from the viewpoint of reducing environmental burden, and a solvent-type pressure-sensitive adhesive composition is preferably used from the viewpoint of adhesive properties and the like.
　ここに開示される粘着剤層は、従来公知の方法によって形成することができる。例えば、基材に粘着剤組成物を直接付与（典型的には塗付）して乾燥させることにより粘着剤層を形成する方法（直接法）を好ましく採用することができる。また、剥離性を有する表面（剥離面）に粘着剤組成物を付与して乾燥させることにより該表面上に粘着剤層を形成し、その粘着剤層を基材に転写する方法（転写法）を採用してもよい。上記剥離面としては、剥離ライナーの表面や、剥離処理された基材背面等を利用し得る。 The pressure-sensitive adhesive layer disclosed herein can be formed by a conventionally known method. For example, a method (direct method) of forming a pressure-sensitive adhesive layer by directly applying (typically applying) the pressure-sensitive adhesive composition to a substrate and drying it can be preferably employed. Also, a method for forming a pressure-sensitive adhesive layer on the surface by applying a pressure-sensitive adhesive composition to a surface having a peelable property (peeling surface) and drying it, and transferring the pressure-sensitive adhesive layer to a substrate (transfer method) May be adopted. As the release surface, the surface of the release liner, the back surface of the substrate after the release treatment, or the like can be used.
　粘着剤組成物の塗付は、例えば、グラビアロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、ダイコーター、バーコーター、ナイフコーター、スプレーコーター等の、公知ないし慣用のコーターを用いて行うことができる。あるいは、含浸やカーテンコート法等により粘着剤組成物を塗付してもよい。
　架橋反応の促進、製造効率向上等の観点から、粘着剤組成物の乾燥は加熱下で行うことが好ましい。乾燥温度は、例えば４０～１５０℃程度とすることができ、通常は６０～１３０℃程度とすることが好ましい。粘着剤組成物を乾燥させた後、さらに、粘着剤層内における成分移行の調整、架橋反応の進行、基材や粘着剤層内に存在し得る歪の緩和等を目的としてエージングを行ってもよい。 The pressure-sensitive adhesive composition is applied using a known or conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, die coater, bar coater, knife coater, spray coater, etc. be able to. Alternatively, the pressure-sensitive adhesive composition may be applied by impregnation or curtain coating.
From the viewpoint of promoting the crosslinking reaction and improving the production efficiency, the pressure-sensitive adhesive composition is preferably dried under heating. The drying temperature can be, for example, about 40 to 150 ° C., and is usually preferably about 60 to 130 ° C. After drying the pressure-sensitive adhesive composition, it may be further aged for the purpose of adjusting component migration in the pressure-sensitive adhesive layer, progress of the crosslinking reaction, relaxation of strain that may exist in the base material or pressure-sensitive adhesive layer, etc. Good.
　ここに開示される粘着剤層の厚さは特に限定されず、目的に応じて適宜選択することができる。通常は、乾燥効率等の生産性や接着特性等の観点から、０．５～２００μｍ程度とすることが適当であり、２～２００μｍ（例えば５～１００μｍ、典型的には１０～５０μｍ）程度とすることが好ましい。粘着剤層の厚さを制限することは、粘着シートの薄膜化、小型化、軽量化、省資源化等の点で有利である。ここに開示される技術が、基材の両面に粘着剤層を備える両面粘着シートの形態で実施される場合、各粘着剤層の厚さは同じであってもよく、異なっていてもよい。 The thickness of the pressure-sensitive adhesive layer disclosed herein is not particularly limited and can be appropriately selected depending on the purpose. Usually, from the viewpoint of productivity such as drying efficiency and adhesive properties, it is appropriate to be about 0.5 to 200 μm, and about 2 to 200 μm (for example, 5 to 100 μm, typically 10 to 50 μm). It is preferable to do. Limiting the thickness of the pressure-sensitive adhesive layer is advantageous in terms of reducing the thickness of the pressure-sensitive adhesive sheet, reducing the size, reducing the weight, and saving resources. When the technique disclosed here is implemented in the form of a double-sided pressure-sensitive adhesive sheet having pressure-sensitive adhesive layers on both sides of the substrate, the thickness of each pressure-sensitive adhesive layer may be the same or different.
　＜コート層＞
　粘着剤層表面を部分的に覆うコート層は、空気抜け性を付与し得るものであればよく、その限りにおいて特に制限はない。コート層材料の好適例としては樹脂材料が挙げられる。外観性の観点から、透明または半透明の樹脂材料から形成されたコート層が好ましい。 <Coat layer>
The coat layer that partially covers the surface of the pressure-sensitive adhesive layer is not particularly limited as long as it can impart air bleedability. A preferred example of the coating layer material is a resin material. From the viewpoint of appearance, a coat layer formed from a transparent or translucent resin material is preferable.
　コート層を構成し得る樹脂材料としては、例えば、ポリウレタン系樹脂、フェノール系樹脂、エポキシ系樹脂、ポリアミド系樹脂、尿素メラミン系樹脂、シリコーン系樹脂、ポリシラザン系樹脂、フッ素系樹脂、フェノキシ樹脂、メタクリル系樹脂、アクリル系樹脂、アクリル－ウレタン系樹脂、アクリル－スチレン系樹脂、ポリアリレート樹脂、ポリエステル系樹脂、ポリオレフィン系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル、塩化ビニル－酢酸ビニル共重合体、ポリ酢酸ビニル、ポリ塩化ビニリデン、ポリカーボネート、セルロース類、ポリアセタール等が挙げられる。これらの樹脂は、熱硬化型樹脂、紫外線硬化型樹脂、電子線硬化型樹脂、二液混合型樹脂等の各種タイプの樹脂から選択される１種または２種以上の樹脂であり得る。 Examples of the resin material that can constitute the coating layer include polyurethane resins, phenol resins, epoxy resins, polyamide resins, urea melamine resins, silicone resins, polysilazane resins, fluorine resins, phenoxy resins, methacrylic resins. Resin, acrylic resin, acrylic-urethane resin, acrylic-styrene resin, polyarylate resin, polyester resin, polyolefin resin, polystyrene resin, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyacetic acid Examples thereof include vinyl, polyvinylidene chloride, polycarbonate, celluloses, polyacetal and the like. These resins may be one type or two or more types of resins selected from various types of resins such as thermosetting resins, ultraviolet curable resins, electron beam curable resins, and two-component mixed resins.
　ここに開示されるコート層は、充填剤、老化防止剤、酸化防止剤、紫外線吸収剤、架橋剤、滑剤、着色剤（顔料、染料等）、帯電防止剤、流動性調整剤（チクソトロピー剤、増粘剤等）、造膜助剤等の各種添加剤を、必要に応じて含んでよい。 The coating layer disclosed herein includes a filler, an antioxidant, an antioxidant, an ultraviolet absorber, a crosslinking agent, a lubricant, a colorant (pigment, dye, etc.), an antistatic agent, a fluidity modifier (thixotropic agent, Various additives such as thickeners and film-forming aids may be included as necessary.
　コート層は、非粘着性または弱粘着性であることが好ましい。これにより、良好な空気抜け性が好ましく実現される。ここで、コート層が非粘着性または弱粘着性であるとは、コート層の１８０度剥離強度が３Ｎ／２５ｍｍ未満（典型的には１Ｎ／２５ｍｍ未満、接着力が低すぎて測定不可能な場合を包含する。）であることをいう。コート層の１８０度剥離強度は、具体的には下記の方法で測定される。すなわち、粘着剤層表面の全面にコート層を配置した粘着シートを幅２５ｍｍ、長さ１００ｍｍのサイズにカットした測定サンプルにつき、２３℃、５０％ＲＨの環境下にて、上記測定サンプルのコート層表面をステンレス鋼板（ＳＵＳ３０４ＢＡ板）の表面に、２ｋｇのローラを１往復させて圧着し（接着しない場合には、この時点で非粘着性とみなされる。）、これを同環境下に３０分間放置した後、万能引張圧縮試験機を使用して、ＪＩＳ　Ｚ　０２３７：２０００に準じて、引張速度３００ｍｍ／分、剥離角度１８０度の条件で、剥離強度（Ｎ／２５ｍｍ）を測定する。 The coat layer is preferably non-adhesive or weakly adhesive. Thereby, good air escape properties are preferably realized. Here, that the coating layer is non-tacky or weakly tacky means that the 180 ° peel strength of the coating layer is less than 3 N / 25 mm (typically less than 1 N / 25 mm, and the adhesive force is too low to be measured. Including the case.) Specifically, the 180 degree peel strength of the coat layer is measured by the following method. That is, for a measurement sample obtained by cutting a pressure-sensitive adhesive sheet having a coating layer on the entire surface of the pressure-sensitive adhesive layer into a size of 25 mm in width and 100 mm in length, the coating layer of the measurement sample is used at 23 ° C. and 50% RH The surface is pressed against the surface of a stainless steel plate (SUS304BA plate) by reciprocating a 2 kg roller (if it does not adhere, it is considered non-adhesive at this point), and this is left in the same environment for 30 minutes. Then, using a universal tensile compression tester, peel strength (N / 25 mm) is measured according to JIS Z 0237: 2000 under conditions of a tensile speed of 300 mm / min and a peel angle of 180 degrees.
　粘着剤層表面にコート層を配置する方法は特に限定されない。例えば、次のような方法が採用され得る。具体的には、コート層形成用組成物を、必要に応じて適当な溶媒に溶解または分散する等して調製する。次いで、公知または慣用の各種の印刷処理方法のうち適当な方法を採用して、当該組成物を剥離性支持体（「コート層転写用フィルム」ともいう。典型的には剥離ライナー）の剥離性表面に付与して硬化させる。そして、コート層が形成された剥離性支持体表面を粘着剤層表面に当接させてコート層を粘着剤層表面に転写する。このようにして、粘着剤層表面にコート層を部分的に配置することができる。例えば、オフセット印刷、シルクスクリーン印刷、凸版印刷、フレキソ印刷、グラビア印刷、インクジェット印刷等の方法を採用することにより、格子状パターン等の所望のコート層パターンを好ましく形成することができる。空気抜け性の観点から、グラビア印刷がより好ましい。あるいは、粘着剤層表面に直接コート層形成用組成物を付与して、例えば紫外線硬化等の手法により硬化させることにより、粘着剤層表面にコート層を部分的に配置してもよい。 The method for arranging the coat layer on the surface of the pressure-sensitive adhesive layer is not particularly limited. For example, the following method can be adopted. Specifically, the composition for forming a coat layer is prepared by dissolving or dispersing in a suitable solvent as necessary. Next, by adopting an appropriate method among various known or commonly used printing methods, the composition is also referred to as a peelable support (also referred to as “coat layer transfer film”, typically a release liner). Apply to the surface and cure. And the peelable support body surface in which the coating layer was formed is contact | abutted to the adhesive layer surface, and a coating layer is transcribe | transferred to the adhesive layer surface. In this way, the coat layer can be partially disposed on the pressure-sensitive adhesive layer surface. For example, a desired coat layer pattern such as a grid pattern can be preferably formed by employing a method such as offset printing, silk screen printing, letterpress printing, flexographic printing, gravure printing, or ink jet printing. From the viewpoint of air escape, gravure printing is more preferable. Alternatively, the coating layer may be partially disposed on the surface of the pressure-sensitive adhesive layer by applying the composition for forming a coating layer directly to the surface of the pressure-sensitive adhesive layer and curing it by a technique such as ultraviolet curing.
　コート層の厚さは、所望の空気抜け性が得られるよう設計すればよく特に限定されないが、空気抜け性と外観性とを両立する観点から、粘着剤層の厚さの半分以下（例えば１／３以下、典型的には１／５以下）とすることが好ましい。具体的には、コート層の厚さは、空気抜け性の観点から、０．１μｍ以上（例えば０．５μｍ以上、典型的には１μｍ以上）とすることが好ましい。また、外観性の観点から、コート層の厚さは１０μｍ以下とすることが好ましく、５μｍ以下（例えば３μｍ以下、典型的には２μｍ以下）とすることがより好ましい。なお、コート層の厚さは、粘着シートの断面を透過型電子顕微鏡（ＴＥＭ）で観察することにより把握することができる。 The thickness of the coat layer is not particularly limited as long as it is designed so as to obtain a desired air escape property. However, from the viewpoint of achieving both air escape properties and appearance properties, the thickness of the pressure-sensitive adhesive layer is not more than half (for example, 1 / 3 or less, typically 1/5 or less). Specifically, the thickness of the coat layer is preferably 0.1 μm or more (for example, 0.5 μm or more, typically 1 μm or more) from the viewpoint of air bleeding. From the viewpoint of appearance, the thickness of the coat layer is preferably 10 μm or less, more preferably 5 μm or less (eg, 3 μm or less, typically 2 μm or less). In addition, the thickness of a coating layer can be grasped | ascertained by observing the cross section of an adhesive sheet with a transmission electron microscope (TEM).
　ここに開示される技術は、上述の粘着シートの粘着性表面を保護する剥離ライナーを備える剥離ライナー付き粘着シートの形態で好ましく実施される。剥離ライナーとしては、慣用の剥離紙等を使用することができ、特に限定されない。例えば、ＰＥＴ等の樹脂フィルムや紙等のライナー基材の表面に剥離処理層を有する剥離ライナーや、フッ素系ポリマー（ポリテトラフルオロエチレン等）やポリオレフィン系樹脂（ＰＥ、ＰＰ等）の低接着性材料からなる剥離ライナー等を用いることができる。上記剥離処理層は、例えば、シリコーン系、長鎖アルキル系、フッ素系、硫化モリブデン等の剥離処理剤により上記ライナー基材を表面処理して形成されたものであり得る。 The technique disclosed herein is preferably implemented in the form of a pressure-sensitive adhesive sheet with a release liner provided with a release liner that protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet. A conventional release paper or the like can be used as the release liner, and is not particularly limited. For example, a low-adhesiveness of a release liner having a release treatment layer on the surface of a liner substrate such as a resin film such as PET or paper, or a fluorine-based polymer (polytetrafluoroethylene, etc.) or a polyolefin resin (PE, PP, etc.) A release liner made of a material can be used. The release treatment layer may be formed, for example, by surface-treating the liner base material with a release treatment agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.
　好ましい一態様では、上記剥離ライナー（剥離フィルム）の剥離性表面（粘着シートの粘着性表面に接する側の面）は、平滑に形成されている。このような剥離ライナーの剥離性表面にコート層を部分的に形成し、該コート層が部分的に形成された剥離ライナー表面に粘着剤層の表面を当接させてコート層を粘着剤層表面に転写する場合に（その場合、剥離ライナーはコート層転写用フィルム（剥離フィルム）ともなる。）、良好なコート層転写性を実現し得る。また剥離ライナーの平滑表面が粘着剤層表面に転写されることにより、粘着特性も向上する傾向がある。また、上記のような剥離ライナーの剥離性表面にコート層を部分的に形成し、該コート層が形成された剥離性表面上に、該コート層を覆うように粘着剤層をさらに形成することによっても、上記と同様の効果が得られる。この場合、形成された粘着剤層はフィルム状基材の表面に転写される。上記のような理由から、上記剥離ライナーの剥離性表面における算術平均表面粗さは１μｍ以下（例えば凡そ０．０５～０．７５μｍ、典型的には凡そ０．１～０．５μｍ）であることが好ましい。 In a preferred embodiment, the peelable surface (the surface on the side in contact with the adhesive surface of the pressure-sensitive adhesive sheet) of the release liner (release film) is formed smoothly. A coat layer is partially formed on the peelable surface of such a release liner, and the surface of the pressure-sensitive adhesive layer is brought into contact with the surface of the release liner on which the coat layer is partially formed so that the coat layer is the surface of the pressure-sensitive adhesive layer. (In that case, the release liner also serves as a coat layer transfer film (release film)), it is possible to achieve good coat layer transferability. Moreover, there exists a tendency for an adhesive characteristic to improve because the smooth surface of a release liner is transcribe | transferred to the adhesive layer surface. Further, a coat layer is partially formed on the peelable surface of the release liner as described above, and an adhesive layer is further formed on the peelable surface on which the coat layer is formed so as to cover the coat layer. The same effect as described above can be obtained. In this case, the formed pressure-sensitive adhesive layer is transferred to the surface of the film-like substrate. For the reasons described above, the arithmetic average surface roughness of the release surface of the release liner is 1 μm or less (eg, about 0.05 to 0.75 μm, typically about 0.1 to 0.5 μm). Is preferred.
　また、ここに開示される粘着シートの作製に用いられる剥離ライナーは、図５に示すように、剥離性表面１２０Ａを有する剥離性支持体１２０を備えるコート層付きの剥離ライナー１１０であり得る。剥離性支持体１２０は、ライナー基材の少なくとも一方の表面に剥離処理層を有するものであってもよく、低接着性材料からなる支持体であってもよい。この剥離性支持体１２０の剥離性表面１２０Ａ上に、粘着シートに転写可能なコート層３０が設けられる。つまり、コート層３０は、粘着剤の粘着力等によって分離可能な状態で剥離性表面１２０Ａ上に配置されている。このような、転写可能なコート層３０を表面に有する剥離ライナー１１０を用いることにより、ここに開示される粘着シートが好ましく作製される。剥離性支持体の剥離性表面上に設けられるコート層の構成（形状、配置状態、配置関係、サイズ、パターン等）は、上述した粘着シートの粘着剤層表面を部分的に覆うコート層の構成と基本的に同じであり、したがって、上記剥離性表面上におけるコート層配置部およびコート層非配置部の構成や相対的関係（コート層非配置部の面積割合を包含する。）も、上記粘着剤層表面におけるコート層配置部およびコート層非配置部の構成や相対的関係（コート層非配置部の面積割合を包含する。）と基本的に同じであるので、説明は省略する。 Also, the release liner used for the production of the pressure-sensitive adhesive sheet disclosed herein may be a release liner 110 with a coat layer including a peelable support 120 having a peelable surface 120A as shown in FIG. The peelable support 120 may have a release treatment layer on at least one surface of the liner substrate, or may be a support made of a low adhesive material. On the peelable surface 120A of the peelable support 120, a coat layer 30 that can be transferred to an adhesive sheet is provided. That is, the coat layer 30 is disposed on the peelable surface 120A in a state where it can be separated by the adhesive force of the pressure-sensitive adhesive. By using such a release liner 110 having a transferable coat layer 30 on the surface, the pressure-sensitive adhesive sheet disclosed herein is preferably produced. The configuration of the coat layer (shape, arrangement state, arrangement relationship, size, pattern, etc.) provided on the peelable surface of the peelable support is the configuration of the coat layer that partially covers the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet described above. Therefore, the structure and relative relationship (including the area ratio of the coat layer non-arranged part) of the coat layer disposition part and the coat layer non-arrangement part on the peelable surface are also included in the adhesive. Since it is basically the same as the configuration and relative relationship (including the area ratio of the coat layer non-arranged part) of the coat layer arrangement part and the coat layer non-arrangement part on the surface of the agent layer, description thereof is omitted.
剥離ライナーの厚さ（総厚さ）は特に限定されないが、剥離作業性や取扱い性、強度等の観点から、１０～５００μｍ（例えば１５～１００μｍ）程度とすることが好ましい。 The thickness (total thickness) of the release liner is not particularly limited, but is preferably about 10 to 500 μm (for example, 15 to 100 μm) from the viewpoints of release workability, handleability, strength, and the like.
　ここに開示される粘着シートは、上述のように、被着体への貼り付け時において、被着体との間における気泡等の発生を効率よく防止することができる。したがって、手作業による貼り付け（手貼り）や、自動貼り機等を用いての貼り付け（自動貼り）のいずれの貼り付け方法においても、貼り付け性が向上する。例えば、手貼りで貼り付ける場合には、個人の技量への依存度を低減し得るので、貼り付け効率や貼り付け品質の向上、安定化等の利点が得られる。また、自動貼りで貼り付ける場合には、気泡の混入等の貼り付け不良の低減や、貼り直し作業の低減が実現され得る。したがって、手貼り、自動貼りいずれの場合も、貼り付け効率や品質の向上、品質の安定化等を実現することが可能となり、これによって粘着シートを使用して構築される物品の生産性や品質も向上する。ここに開示される技術は、より均一な貼り付けを実現し得ることから、自動貼り機を用いて貼り付けられる態様の粘着シートとして、特に好適である。 As described above, the pressure-sensitive adhesive sheet disclosed herein can efficiently prevent generation of bubbles and the like between the adherend and the adherend. Therefore, in any pasting method of manual pasting (hand pasting) or pasting (automatic pasting) using an automatic pasting machine or the like, the pasting property is improved. For example, in the case of pasting by hand, the dependence on the individual skill can be reduced, so that advantages such as improvement and stabilization of pasting efficiency and pasting quality can be obtained. In addition, when pasting by automatic pasting, it is possible to realize a reduction in pasting failure such as mixing of bubbles and a reduction in pasting work. Therefore, in both cases of manual pasting and automatic pasting, it becomes possible to improve the pasting efficiency and quality, stabilize the quality, etc., and thereby the productivity and quality of articles constructed using adhesive sheets Will also improve. Since the technique disclosed here can implement | achieve more uniform affixing, it is especially suitable as an adhesive sheet of the aspect affixed using an automatic sticking machine.
　また、粘着シートと被着体との間には、貼り付け時だけでなく、貼り付け後、時間が経過するにつれて気泡等が発生する場合がある。典型的には、粘着シートを貼り付けた後に、比較的高温（例えば３５℃以上）環境下で保管、使用等された場合に、上述の気泡等が粘着シートと被着体との間に発生し、外観性の低下を引き起こし得る。例えば、夏場の工場内や屋外、電子機器内部等は、上記のような高温状態となりやすい。ここに開示される技術によると、上記のような高温環境に曝される用途に用いられても、気泡等の発生を防止することができる。 In addition, bubbles may be generated between the pressure-sensitive adhesive sheet and the adherend not only at the time of pasting but also as time passes after pasting. Typically, when the adhesive sheet is attached and then stored and used in a relatively high temperature (eg, 35 ° C. or higher) environment, the above-mentioned bubbles and the like are generated between the adhesive sheet and the adherend. However, the appearance may be deteriorated. For example, the inside of a factory in summer, the outdoors, the inside of an electronic device, and the like are likely to be in a high temperature state as described above. According to the technology disclosed herein, generation of bubbles and the like can be prevented even when used in applications exposed to the high temperature environment as described above.
　ここに開示される粘着シートは、上述したような特徴を活かして、各種物品の表面に貼り付ける用途に好ましく利用され得る。好ましい一態様では、各種の装飾シートや表面保護シート、フレキソ印刷等の印刷板の固定シート、遮光シート等として利用され得る。例えば、車両の外装や住宅建材等に貼り付けられる装飾シート（典型的には塗装代替シート）として好適である。また、テレビ等の電子機器の内部において、例えばシャーシ外面の平滑性を向上する目的や、各種部材表面のネジ穴等の不均一部分を覆う目的で使用される被覆シートとしても好適である。このような被覆シートを用いることで、被着体外面における外観ムラの低減や寸法精度の均一化が実現され得る。また、外観性が重視されるバッテリーパックの外装シートとしても好ましく使用され得る。 The pressure-sensitive adhesive sheet disclosed herein can be preferably used for applications to be applied to the surface of various articles by taking advantage of the characteristics described above. In a preferred embodiment, it can be used as various decorative sheets, surface protective sheets, fixing sheets for printing plates such as flexographic printing, light shielding sheets, and the like. For example, it is suitable as a decorative sheet (typically a paint substitute sheet) that is affixed to the exterior of a vehicle, a housing building material, or the like. In addition, it is also suitable as a covering sheet used for the purpose of improving the smoothness of the outer surface of the chassis and for covering non-uniform portions such as screw holes on the surfaces of various members inside an electronic device such as a television. By using such a covering sheet, it is possible to reduce the appearance unevenness on the outer surface of the adherend and make the dimensional accuracy uniform. Moreover, it can be preferably used as an exterior sheet of a battery pack in which appearance is important.
　また、ここに開示される粘着シートは、薄厚に構成した場合であっても、貼り付け後の外観品質の低下を防ぎつつ、良好な粘着特性を維持することが可能である。したがって、薄厚化や軽量化が求められており、かつ省資源化が望ましい用途（例えば携帯電子機器用途）に好ましく適用され得る。具体的には、携帯電子機器（例えば、携帯電話、スマートフォン、タブレット型パソコン、ノートパソコン等）の表面保護シート、上記携帯電子機器の液晶表示装置における接合固定用途、上記携帯電子機器の表示部を保護する保護パネル（レンズ）固定用途、携帯電話のキーモジュール部材固定用途等に好ましく適用され得る。上記携帯電子機器に用いられる場合、粘着シートは、目的等に応じて、枠状（額縁状）、帯状（ストリップ状）等の形状を有するものであり得る。なお、本明細書において「携帯」とは、単に携帯することが可能であるだけでは十分ではなく、個人（標準的な成人）が相対的に容易に持ち運び可能なレベルの携帯性を有することを意味するものとする。 In addition, even if the pressure-sensitive adhesive sheet disclosed herein is configured to be thin, it is possible to maintain good pressure-sensitive adhesive properties while preventing deterioration of the appearance quality after pasting. Therefore, it can be preferably applied to applications (for example, portable electronic devices) where reduction in thickness and weight is required and resource saving is desired. Specifically, a surface protective sheet for a portable electronic device (for example, a mobile phone, a smartphone, a tablet computer, a notebook computer, etc.), a bonding and fixing application in a liquid crystal display device of the portable electronic device, a display unit of the portable electronic device It can be preferably applied to a protection panel (lens) fixing application to be protected, a key module member fixing application of a cellular phone, and the like. When used in the portable electronic device, the pressure-sensitive adhesive sheet may have a frame shape (frame shape), a band shape (strip shape), or the like depending on the purpose or the like. In this specification, “portable” means that it is not sufficient to be able to carry it alone, but to have a portability that allows an individual (standard adult) to carry it relatively easily. Shall mean.
　この明細書により開示される事項には以下のものが含まれる。
（１）　フィルム状基材と、該フィルム状基材の少なくとも一方の表面に設けられた粘着剤層と、を備える粘着シートであって、
　前記粘着剤層表面を部分的に覆うコート層を備え、これによって、該粘着剤層表面はコート層配置部とコート層非配置部とを有しており、
　前記粘着剤層表面における前記コート層非配置部の面積割合は７０％以上であり、
　前記コート層配置部は、前記粘着剤層表面を上方から見たときに、該粘着剤層の一端から他端に向かって線状に延びる部分を有しており、
　前記線状に延びる部分の幅は０．１～２ｍｍの範囲内である、粘着シート。
（２）　前記粘着剤層表面には、前記線状に延びる部分が複数配置されており、
　前記複数の線状に延びる部分のうち一群を構成する複数の線状に延びる部分は、その幅方向にて間隔をおいて配置されており、これによって、前記コート層配置部はストライプ状パターンを有する、上記（１）に記載の粘着シート。
（３）　前記コート層配置部は、第１ストライプ状パターン部と、該第１ストライプ状パターン部と交差するように配置された第２ストライプ状パターン部とを含み、これによって、前記コート層配置部は格子状パターンを有する、上記（２）に記載の粘着シート。
（４）　前記コート層配置部において、一のストライプ状パターンを構成する複数の線状に延びる部分の間隔は１．０～１０ｍｍの範囲内である、上記（２）または（３）に記載の粘着シート。
（５）　前記コート層が部分的に配置された粘着性表面は、１３Ｎ／２５ｍｍ以上の２４時間経過後１８０度剥離強度を示す、上記（１）～（４）のいずれかに記載の粘着シート。 The matters disclosed by this specification include the following.
(1) A pressure-sensitive adhesive sheet comprising a film-like substrate and a pressure-sensitive adhesive layer provided on at least one surface of the film-like substrate,
A coating layer partially covering the pressure-sensitive adhesive layer surface, whereby the pressure-sensitive adhesive layer surface has a coating layer disposition portion and a coating layer non-disposition portion;
The area ratio of the coating layer non-arranged portion on the pressure-sensitive adhesive layer surface is 70% or more,
The coat layer arrangement portion has a portion extending linearly from one end of the pressure-sensitive adhesive layer to the other when the pressure-sensitive adhesive layer surface is viewed from above,
The pressure-sensitive adhesive sheet has a width of the linearly extending portion within a range of 0.1 to 2 mm.
(2) A plurality of linearly extending portions are disposed on the pressure-sensitive adhesive layer surface,
Among the plurality of linearly extending portions, the plurality of linearly extending portions constituting a group are arranged at intervals in the width direction, whereby the coat layer arranging portion has a stripe pattern. The pressure-sensitive adhesive sheet according to (1) above.
(3) The coat layer arrangement portion includes a first stripe pattern portion and a second stripe pattern portion arranged to intersect the first stripe pattern portion, whereby the coat layer arrangement is performed. The adhesive sheet according to (2), wherein the part has a lattice pattern.
(4) In the coat layer arrangement portion, the interval between a plurality of linearly extending portions constituting one stripe pattern is in the range of 1.0 to 10 mm, according to (2) or (3) above Adhesive sheet.
(5) The pressure-sensitive adhesive sheet according to any one of the above (1) to (4), wherein the adhesive surface on which the coating layer is partially disposed exhibits a 180-degree peel strength after 24 hours of 13 N / 25 mm or more. .
（６）　前記粘着剤層は、該粘着剤層に含まれるポリマー成分の５０重量％を超える割合でアクリル系ポリマーを含み、
　前記アクリル系ポリマーは、モノマー成分として、式（１）：
　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２　　　　　（１）
（上記式（１）中のＲ１は水素原子またはメチル基である。また、Ｒ２は炭素原子数１～２０の鎖状アルキル基である。）；で表されるアルキル（メタ）アクリレートを５０重量％を超える割合で含む、上記（１）～（５）のいずれかに記載の粘着シート。
（７）　前記アルキル（メタ）アクリレートは、ｎ－ブチルアクリレートおよび／または２－エチルヘキシルアクリレートである、上記（６）に記載の粘着シート。
（８）　前記アクリル系ポリマーは、副モノマーとしてカルボキシ基含有モノマーおよび／または水酸基含有モノマーが共重合されたアクリル系ポリマーである、上記（６）または（７）のいずれかに記載の粘着シート。
（９）　前記アクリル系ポリマーは、アクリル酸、メタクリル酸、２－ヒドロキシエチルアクリレートおよび４－ヒドロキシブチルアクリレートからなる群から選択される少なくとも１種の副モノマーが共重合されたアクリル系ポリマーである、上記（６）～（８）のいずれかに記載の粘着シート。
（１０）　前記アクリル系ポリマーには、カルボキシ基含有モノマーが共重合されており、前記カルボキシ基含有モノマーの共重合割合は、前記アクリル系ポリマーの合成に使用する全モノマー成分中、０．１～１０重量％である、上記（６）～（９）のいずれかに記載の粘着シート。
（１１）　前記アクリル系ポリマーには水酸基含有モノマーが共重合されており、
　前記水酸基含有モノマーの共重合割合は、前記アクリル系ポリマーの合成に使用する全モノマー成分中、０．００１～１０重量％である、上記（６）～（１０）のいずれかに記載の粘着シート。
（１２）　前記粘着剤層は、イソシアネート系架橋剤および／またはエポキシ系架橋剤を含む、上記（６）～（１１）のいずれかに記載の粘着シート。
（１３）　前記粘着剤層は、軟化点が１００℃～１４０℃である粘着付与樹脂を、前記アクリル系ポリマー１００重量部に対して３０～６０重量部の割合で含み、
　前記粘着付与樹脂は、ロジン系粘着付与樹脂、テルペン系粘着付与樹脂および炭化水素系粘着付与樹脂からなる群から選択される少なくとも１種である、上記（６）～（１２）のいずれかに記載の粘着シート。 (6) The pressure-sensitive adhesive layer contains an acrylic polymer in a proportion exceeding 50% by weight of the polymer component contained in the pressure-sensitive adhesive layer,
The acrylic polymer has a formula (1):
CH 2 = C (R 1 ) COOR 2 (1)
(In the above formula (1), R 1 is a hydrogen atom or a methyl group. R 2 is a chain alkyl group having 1 to 20 carbon atoms.) The pressure-sensitive adhesive sheet according to any one of the above (1) to (5), which is contained in a proportion exceeding 50% by weight.
(7) The pressure-sensitive adhesive sheet according to (6), wherein the alkyl (meth) acrylate is n-butyl acrylate and / or 2-ethylhexyl acrylate.
(8) The pressure-sensitive adhesive sheet according to any one of (6) and (7), wherein the acrylic polymer is an acrylic polymer obtained by copolymerizing a carboxy group-containing monomer and / or a hydroxyl group-containing monomer as a submonomer.
(9) The acrylic polymer is an acrylic polymer obtained by copolymerizing at least one submonomer selected from the group consisting of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. The pressure-sensitive adhesive sheet according to any one of (6) to (8) above.
(10) The acrylic polymer is copolymerized with a carboxy group-containing monomer, and a copolymerization ratio of the carboxy group-containing monomer is 0.1 to about 0.1 to about all monomer components used in the synthesis of the acrylic polymer. The pressure-sensitive adhesive sheet according to any one of (6) to (9), wherein the pressure-sensitive adhesive sheet is 10% by weight.
(11) The acrylic polymer is copolymerized with a hydroxyl group-containing monomer,
The pressure-sensitive adhesive sheet according to any one of the above (6) to (10), wherein the copolymerization ratio of the hydroxyl group-containing monomer is 0.001 to 10% by weight in the total monomer components used in the synthesis of the acrylic polymer. .
(12) The pressure-sensitive adhesive sheet according to any one of (6) to (11), wherein the pressure-sensitive adhesive layer contains an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent.
(13) The pressure-sensitive adhesive layer contains a tackifying resin having a softening point of 100 ° C. to 140 ° C. in a ratio of 30 to 60 parts by weight with respect to 100 parts by weight of the acrylic polymer,
The tackifier resin is at least one selected from the group consisting of a rosin tackifier resin, a terpene tackifier resin, and a hydrocarbon tackifier resin, according to any one of the above (6) to (12). Adhesive sheet.
（１４）　前記コート層は透明樹脂からなる、上記（１）～（１３）のいずれかに記載の粘着シート。
（１５）　前記コート層は、ポリウレタン系樹脂、フェノール系樹脂、エポキシ系樹脂、ポリアミド系樹脂、尿素メラミン系樹脂、シリコーン系樹脂、ポリシラザン系樹脂、フッ素系樹脂、フェノキシ樹脂、メタクリル系樹脂、アクリル系樹脂、アクリル－ウレタン系樹脂、アクリル－スチレン系樹脂、ポリアリレート樹脂、ポリエステル系樹脂、ポリオレフィン系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル、塩化ビニル－酢酸ビニル共重合体、ポリ酢酸ビニル、ポリ塩化ビニリデン、ポリカーボネート、セルロース類およびポリアセタールからなる群から選択される少なくとも１種の樹脂を含む、上記（１）～（１４）のいずれかに記載の粘着シート。
（１６）　前記コート層はポリウレタン系樹脂である、上記（１）～（１５）のいずれかに記載の粘着シート。
（１７）　前記コート層は、二液混合硬化型のポリウレタン系樹脂である、上記（１）～（１６）のいずれかに記載の粘着シート。
（１８）　前記フィルム状基材は、ポリオレフィン系樹脂フィルム、ポリエステル系樹脂フィルム、塩化ビニル系樹脂フィルム、酢酸ビニル系樹脂フィルム、ポリイミド系樹脂フィルム、ポリアミド系樹脂フィルム、フッ素系樹脂フィルムまたはセロハンフィルムである、上記（１）～（１７）のいずれかに記載の粘着シート。
（１９）　前記フィルム状基材はポリエステルフィルムである、上記（１）～（１８）のいずれかに記載の粘着シート。
（２０）　前記フィルム状基材はポリエチレンテレフタレートフィルムである、上記（１）～（１９）のいずれかに記載の粘着シート。
（２１）　前記フィルム状基材は８０％以上の全光線透過率を示す、上記（１）～（２０）のいずれかに記載の粘着シート。
（２２）　前記フィルム状基材は発泡体フィルムである、上記（１）～（１７）のいずれかに記載の粘着シート。
（２３）　前記発泡体フィルムの平均気泡径は１０～２００μｍであり、密度は０．０１～０．７ｇ／ｃｍ３である、上記（２２）に記載の粘着シート。
（２４）　前記発泡体フィルムは、アクリル系樹脂発泡体またはポリオレフィン系樹脂発泡体である、上記（２２）または（２３）に記載の粘着シート。 (14) The pressure-sensitive adhesive sheet according to any one of (1) to (13), wherein the coat layer is made of a transparent resin.
(15) The coating layer is made of polyurethane resin, phenol resin, epoxy resin, polyamide resin, urea melamine resin, silicone resin, polysilazane resin, fluorine resin, phenoxy resin, methacrylic resin, acrylic resin. Resin, acrylic-urethane resin, acrylic-styrene resin, polyarylate resin, polyester resin, polyolefin resin, polystyrene resin, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride The pressure-sensitive adhesive sheet according to any one of (1) to (14) above, comprising at least one resin selected from the group consisting of polycarbonate, celluloses and polyacetal.
(16) The pressure-sensitive adhesive sheet according to any one of (1) to (15), wherein the coat layer is a polyurethane resin.
(17) The pressure-sensitive adhesive sheet according to any one of (1) to (16), wherein the coat layer is a two-component mixed curing type polyurethane resin.
(18) The film-like substrate is a polyolefin resin film, a polyester resin film, a vinyl chloride resin film, a vinyl acetate resin film, a polyimide resin film, a polyamide resin film, a fluorine resin film, or a cellophane film. The pressure-sensitive adhesive sheet according to any one of the above (1) to (17).
(19) The pressure-sensitive adhesive sheet according to any one of (1) to (18), wherein the film-like substrate is a polyester film.
(20) The pressure-sensitive adhesive sheet according to any one of (1) to (19), wherein the film-like substrate is a polyethylene terephthalate film.
(21) The pressure-sensitive adhesive sheet according to any one of (1) to (20), wherein the film-like substrate exhibits a total light transmittance of 80% or more.
(22) The pressure-sensitive adhesive sheet according to any one of (1) to (17), wherein the film-like substrate is a foam film.
(23) The pressure-sensitive adhesive sheet according to (22), wherein the foam film has an average cell diameter of 10 to 200 μm and a density of 0.01 to 0.7 g / cm 3 .
(24) The pressure-sensitive adhesive sheet according to (22) or (23), wherein the foam film is an acrylic resin foam or a polyolefin resin foam.
（２５）　上記（１）～（２４）のいずれかに記載の粘着シートと、該粘着シートの粘着面を保護する剥離ライナーと、を備えており、
　前記剥離ライナーの表面のうち前記粘着面側の表面は、平滑に形成されている、剥離ライナー付き粘着シート。
（２６）　少なくとも一方の表面が剥離性表面である剥離性支持体を備える粘着シート用剥離ライナーであって、
　前記剥離性支持体の剥離性表面上には、粘着シートに転写可能なコート層が設けられており、これによって、該剥離性表面はコート層配置部とコート層非配置部とを有しており、
　前記剥離性表面における前記コート層非配置部の面積割合は７０％以上であり、
　前記コート層は、前記剥離性表面の一端から他端に向かって線状に延びる部分を有しており、
　前記線状に延びる部分の幅は０．１～２ｍｍの範囲内である、剥離ライナー。 (25) The pressure-sensitive adhesive sheet according to any one of (1) to (24) above, and a release liner that protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet,
The pressure-sensitive adhesive sheet with a release liner, wherein the surface on the pressure-sensitive adhesive side of the surface of the release liner is formed smoothly.
(26) A release liner for a pressure-sensitive adhesive sheet comprising a peelable support, wherein at least one surface is a peelable surface,
On the peelable surface of the peelable support, a coat layer that can be transferred to the pressure-sensitive adhesive sheet is provided, whereby the peelable surface has a coat layer placement portion and a coat layer non-placement portion. And
The area ratio of the coat layer non-arranged portion on the peelable surface is 70% or more,
The coat layer has a portion extending linearly from one end to the other end of the peelable surface,
A release liner in which the width of the linearly extending portion is in the range of 0.1 to 2 mm.
　以下、本発明に関するいくつかの実施例を説明するが、本発明を実施例に示すものに限定することを意図したものではない。なお、以下の説明において「部」および「％」は、特に断りがない限り重量基準である。 Hereinafter, some examples related to the present invention will be described, but the present invention is not intended to be limited to the examples shown in the examples. In the following description, “parts” and “%” are based on weight unless otherwise specified.
　≪実験１≫
　＜例１Ａ＞
　（粘着剤組成物の調製）
　攪拌機、温度計、窒素ガス導入管、還流冷却器、滴下ロートを備えた反応容器に、ｎ－ブチルアクリレート７０部と、２－エチルヘキシルアクリレート３０部と、アクリル酸３部と、４－ヒドロキシブチルアクリレート０．０５部と、重合開始剤としてアゾビスイソブチロニトリル０．０８部と、重合溶媒としてのトルエンとを仕込み、６０℃で６時間溶液重合してアクリル系ポリマーのトルエン溶液（粘度２８Ｐａ・ｓ、固形分４０％）を得た。得られたアクリル系ポリマーのＭｗは約４４万であった。
　上記トルエン溶液に含まれるアクリル系ポリマー１００部に対し、粘着付与樹脂としての重合ロジンペンタエリスリトールエステル（荒川化学工業社製、商品名「ペンセルＤ－１２５」、軟化点１２５℃）３０部を加えた後、イソシアネート系架橋剤（日本ポリウレタン工業社製、商品名「コロネートＬ」）３部を添加、混合して、アクリル系粘着剤組成物を調製した。 ≪Experiment 1≫
<Example 1A>
(Preparation of adhesive composition)
In a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser, and dropping funnel, 70 parts of n-butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, and 4-hydroxybutyl acrylate 0.05 part, 0.08 part of azobisisobutyronitrile as a polymerization initiator, and toluene as a polymerization solvent were charged, and solution polymerization was performed at 60 ° C. for 6 hours to obtain a toluene solution of an acrylic polymer (viscosity 28 Pa · s, 40% solids). Mw of the obtained acrylic polymer was about 440,000.
To 100 parts of the acrylic polymer contained in the toluene solution, 30 parts of polymerized rosin pentaerythritol ester (made by Arakawa Chemical Industries, trade name “Pencel D-125”, softening point 125 ° C.) as a tackifier resin was added. Thereafter, 3 parts of an isocyanate-based crosslinking agent (trade name “Coronate L”, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added and mixed to prepare an acrylic pressure-sensitive adhesive composition.
　（コート層の形成）
　厚さ７５μｍの剥離フィルム（フジコー社製、商品名「ＦＭＮ－７５ＷＤ（Ｃ１－ＣＡ１）」）の剥離性表面にコート層形成材料（ウレタン系：２液混合硬化型インク）をグラビア印刷により付与し、格子状パターンを有するコート層（塗付厚１．５μｍ、透明）を形成した。 (Formation of coat layer)
A coat layer forming material (urethane-based: two-component mixed curable ink) was applied to the peelable surface of a 75 μm-thick release film (trade name “FMN-75WD (C1-CA1)” manufactured by Fujiko) by gravure printing Then, a coat layer (coating thickness 1.5 μm, transparent) having a lattice pattern was formed.
　（粘着シートの作製）
　厚さ７５μｍのＰＥＴフィルム基材（商品名「ルミラー」、東レ社製）を用意し、このＰＥＴ基材のコロナ放電処理面に、上記粘着剤組成物を乾燥後の厚さが１５μｍとなるように塗付し、１００℃で３分間乾燥させて、ＰＥＴフィルム基材の片面に粘着剤層を形成した。
　上記粘着剤層の表面に、上記で得たコート層形成剥離フィルムのコート層形成面を当接させて、粘着剤層表面にコート層を転写した。剥離フィルムは、そのまま粘着剤層表面の保護に用いた。このようにして本例に係る粘着シートを作製した。この粘着シートの粘着剤層表面には、図１に示すコート層からなる格子状パターンが形成されており、コート層配置部の長尺部の幅（線幅）は２ｍｍ、間隔は８ｍｍであった。 (Preparation of adhesive sheet)
A 75 μm thick PET film substrate (trade name “Lumirror”, manufactured by Toray Industries, Inc.) is prepared, and the pressure-sensitive adhesive composition is dried on the corona discharge treated surface of the PET substrate so that the thickness after drying is 15 μm. And dried at 100 ° C. for 3 minutes to form an adhesive layer on one side of the PET film substrate.
The surface of the pressure-sensitive adhesive layer was brought into contact with the surface of the release layer-coated release film obtained above to transfer the coat layer to the surface of the pressure-sensitive adhesive layer. The release film was used for protecting the pressure-sensitive adhesive layer surface as it was. Thus, the adhesive sheet which concerns on this example was produced. On the surface of the pressure-sensitive adhesive layer of this pressure-sensitive adhesive sheet, a lattice pattern comprising the coating layer shown in FIG. 1 is formed. The width (line width) of the long portion of the coating layer arrangement portion is 2 mm, and the interval is 8 mm. It was.
　＜例１Ｂ＞
　コート層配置部の長尺部の間隔を１３ｍｍに変更した他は例１Ａと同様にして本例に係る粘着シートを作製した。 <Example 1B>
A pressure-sensitive adhesive sheet according to this example was produced in the same manner as in Example 1A, except that the interval between the long portions of the coat layer arrangement portion was changed to 13 mm.
　＜例１Ｃ＞
　コート層を形成しなかった他は例１Ａと同様にして本例に係る粘着シートを作製した。 <Example 1C>
A pressure-sensitive adhesive sheet according to this example was prepared in the same manner as Example 1A except that the coat layer was not formed.
　［１８０度剥離強度］
　各例に係る粘着シートにつき、対ＳＵＳ１８０度剥離強度（接着力）を評価した。具体的には、粘着シートを幅２５ｍｍ、長さ１００ｍｍのサイズにカットした測定サンプルにつき、２３℃、５０％ＲＨの環境下にて、上記測定サンプルの粘着性表面をステンレス鋼板（ＳＵＳ３０４ＢＡ板）の表面に、２ｋｇのローラを１往復させて圧着した。これを同環境下に３０分間、２４時間または７２時間放置した後、万能引張圧縮試験機を使用して、ＪＩＳ　Ｚ　０２３７：２０００に準じて、引張速度３００ｍｍ／分、剥離角度１８０度の条件で、剥離強度（Ｎ／２５ｍｍ）を測定した。測定は、各例および各条件（圧着後経過時間）につき３回ずつ行い、その平均値を採用した。また、コート層非配置部の面積割合が１００％の例１Ｃにおける１８０度剥離強度値を１００％として、例１Ａ，１Ｂにおける１８０度剥離強度値を相対値（％）で示し、コート層非配置部の面積の減少にともなう接着力の低下の度合を評価した。結果を、コート層非配置部の面積割合（％）とともに表１に示す。 [180 degree peel strength]
About the adhesive sheet which concerns on each example, SUS180 degree peel strength (adhesive force) was evaluated. Specifically, for a measurement sample obtained by cutting the pressure-sensitive adhesive sheet into a size of 25 mm in width and 100 mm in length, the adhesive surface of the measurement sample is made of a stainless steel plate (SUS304BA plate) in an environment of 23 ° C. and 50% RH. A 2 kg roller was reciprocated once on the surface and pressed. After leaving this in the same environment for 30 minutes, 24 hours or 72 hours, using a universal tensile compression tester in accordance with JIS Z 0237: 2000 under conditions of a tensile speed of 300 mm / minute and a peeling angle of 180 degrees. The peel strength (N / 25 mm) was measured. The measurement was performed three times for each example and each condition (elapsed time after pressure bonding), and the average value was adopted. Further, assuming that the 180 degree peel strength value in Example 1C where the area ratio of the coat layer non-arranged portion is 100% is 100%, the 180 degree peel strength values in Examples 1A and 1B are shown as relative values (%). The degree of decrease in adhesive strength accompanying the decrease in area of the part was evaluated. The results are shown in Table 1 together with the area ratio (%) of the coating layer non-arranged part.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示されるように、コート層の面積が大きくなり粘着剤層の露出面積が減少すると、それに比例するように、被着体に貼り合わせて３０分経過した後の初期接着力は低下した。一方、被着体に貼り合わせて２４時間または７２時間経過した後の経時接着力については、コート層非配置部の面積割合が６４％である例１Ａでは、経時的な接着力上昇が起こらず、初期接着力のような比例関係が崩れ、コート層非配置部の面積割合が７５％である例１Ｂや、１００％である例１Ｃにおける結果から予想される値よりも有意に低い値を示した。この結果から、コート層を粘着剤層表面に部分的に配置した構成において、高い経時接着力を得るためには、コート層非配置部の面積割合は７０％以上必要であることがわかる。 As shown in Table 1, when the area of the coating layer increases and the exposed area of the pressure-sensitive adhesive layer decreases, the initial adhesive strength after 30 minutes after bonding to the adherend decreases in proportion thereto. . On the other hand, regarding the time-dependent adhesive force after 24 hours or 72 hours have been pasted to the adherend, in Example 1A in which the area ratio of the coating layer non-arranged portion is 64%, the adhesive force does not increase with time. In addition, the proportional relationship such as the initial adhesive strength is broken, and the area ratio of the coating layer non-arranged portion is 75%, and the value is significantly lower than the value expected from the result in Example 1C of 100%. It was. From this result, it can be seen that, in the configuration in which the coat layer is partially disposed on the surface of the pressure-sensitive adhesive layer, in order to obtain a high adhesive strength with time, the area ratio of the coat layer non-arranged portion needs to be 70% or more.
　≪実験２≫
　＜例２Ａ～例２Ｊ＞
　コート層配置部の長尺部の幅（ｍｍ）および間隔（ｍｍ）を表２に示す値に設定し、例１Ａと同様の方法で各例に係る粘着シートを作製した。各例について測定した２４時間経過後１８０度剥離強度（Ｎ／２５ｍｍ）を表２に示す。その測定方法は上述のとおりである。なお、例２Ａ、例２Ｉ、例２Ｊはそれぞれ、例１Ｂ、例１Ａ、例１Ｃと同じ構成を有する。 ≪Experiment 2≫
<Example 2A to Example 2J>
The width (mm) and interval (mm) of the long part of the coat layer arrangement part were set to the values shown in Table 2, and pressure-sensitive adhesive sheets according to each example were produced in the same manner as in Example 1A. Table 2 shows the 180-degree peel strength (N / 25 mm) after 24 hours measured for each example. The measuring method is as described above. Note that Example 2A, Example 2I, and Example 2J have the same configurations as Example 1B, Example 1A, and Example 1C, respectively.
　［空気抜け性］
　各例に係る粘着シートにつき、透明被着体の平滑表面に貼り付けた際の空気抜け性を目視で観察し、下記の４段階で評価した。結果を表２に示す。
　　Ａ：優れた空気抜け性を示し、粘着シートと被着体との間に気泡は残存しなかった。
　　Ｂ：粘着シートと被着体との間の気泡は比較的速い速度で抜け、気泡は残存しなかった。
　　Ｃ：粘着シートと被着体との間の気泡は比較的ゆっくりと抜け、気泡は残存しなかった。
　　Ｄ：粘着シートと被着体との間に気泡が残存した。 [Air venting]
About the adhesive sheet which concerns on each example, the air release property at the time of affixing on the smooth surface of a transparent adherend was observed visually, and the following four steps evaluated. The results are shown in Table 2.
A: Excellent air escape property was exhibited, and no air bubbles remained between the pressure-sensitive adhesive sheet and the adherend.
B: Bubbles between the pressure-sensitive adhesive sheet and the adherend were removed at a relatively high speed, and no bubbles remained.
C: Air bubbles between the adhesive sheet and the adherend were removed relatively slowly, and no air bubbles remained.
D: Air bubbles remained between the pressure-sensitive adhesive sheet and the adherend.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示されるように、粘着剤層表面におけるコート層非配置部の面積割合が７０％以上であり、コート層配置部の長尺部の幅が０．１～２ｍｍの範囲内である例２Ａ～例２Ｈに係る粘着シートは、高い経時接着力（２４時間経過後１８０度剥離強度）を示し、粘着シートと被着体との間における空気抜け性が良好であった。さらに、例２Ｃ～例２Ｈに係る粘着シートは、被着体への貼り合わせ後、被着体側および粘着シート側から見たときにコート層が視認され難く、外観性に優れていた。例２Ｃ～例２Ｇに係る粘着シートは、外観性に優れ、かつ高い経時接着力と空気抜け性とをバランスよく両立するものであった。そのなかでも、例２Ｅ、例２Ｆ、例２Ｇの外観性は特に優れていた。一方、コート層非配置部の面積割合が７０％未満であった例２Ｉでは、例２Ａ～例２Ｈと比べて低い経時接着力を示した。また、コート層を配置しなかった例２Ｊでは、粘着シートと被着体との間に気泡が残存した。 As shown in Table 2, the area ratio of the coating layer non-arranged portion on the surface of the pressure-sensitive adhesive layer is 70% or more, and the width of the long portion of the coating layer disposed portion is in the range of 0.1 to 2 mm. The pressure-sensitive adhesive sheets according to 2A to Example 2H showed high adhesive strength with time (180-degree peel strength after 24 hours), and good air bleeding between the pressure-sensitive adhesive sheet and the adherend. Furthermore, the pressure-sensitive adhesive sheets according to Examples 2C to 2H were excellent in appearance because the coating layer was hardly visible when viewed from the adherend side and the pressure-sensitive adhesive sheet side after being bonded to the adherend. The pressure-sensitive adhesive sheets according to Examples 2C to 2G were excellent in appearance and achieved both a good balance between high adhesive strength with time and air release. Among them, the appearance properties of Example 2E, Example 2F, and Example 2G were particularly excellent. On the other hand, in Example 2I in which the area ratio of the coating layer non-arranged portion was less than 70%, the adhesive strength with time was lower than in Examples 2A to 2H. In Example 2J in which no coat layer was disposed, air bubbles remained between the adhesive sheet and the adherend.
　以上、本発明の具体例を詳細に説明したが、これらは例示にすぎず、特許請求の範囲を限定するものではない。特許請求の範囲に記載の技術には、以上に例示した具体例を様々に変形、変更したものが含まれる。 Specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.
　　１，２　　粘着シート
　　１Ａ　　粘着性表面
　１０　　フィルム状基材
　２０，２１，２２　　粘着剤層
　２０Ａ　　粘着剤層表面
　３０　　コート層
　４０，４１，４２　　剥離ライナー
　５０　　コート層配置部
　５１　　コート層非配置部
　６０　　コート層パターン（格子状パターン）
　７０　　第１ストライプ状パターン部
　７５Ａ，７５Ｂ，７５Ｃ　　長尺部（線状に延びる部分）
　８０　　第２ストライプ状パターン部
　８５Ａ，８５Ｂ，８５Ｃ　　長尺部（線状に延びる部分）
１１０　　コート層付き剥離ライナー
１２０　　剥離性支持体
１２０Ａ　　剥離性表面

  DESCRIPTION OF SYMBOLS 1, 2 Adhesive sheet 1A Adhesive surface 10 Film- like base material 20,21,22 Adhesive layer 20A Adhesive layer surface 30 Coat layer 40,41,42 Release liner 50 Coat layer arrangement part 51 Coat layer non-arrangement part 60 Coat Layer pattern (lattice pattern)
70 1st stripe pattern part 75A, 75B, 75C long part (part extended linearly)
80 Second stripe pattern portion 85A, 85B, 85C Long portion (portion extending linearly)
110 Release liner with coat layer 120 Peelable support 120A Peelable surface

Claims (26)

  1. 　フィルム状基材と、該フィルム状基材の少なくとも一方の表面に設けられた粘着剤層と、を備える粘着シートであって、
    　前記粘着剤層表面を部分的に覆うコート層を備え、これによって、該粘着剤層表面はコート層配置部とコート層非配置部とを有しており、
    　前記粘着剤層表面における前記コート層非配置部の面積割合は７０％以上であり、
    　前記コート層配置部は、前記粘着剤層表面を上方から見たときに、該粘着剤層の一端から他端に向かって線状に延びる部分を有しており、
    　前記線状に延びる部分の幅は０．１～２ｍｍの範囲内である、粘着シート。     A pressure-sensitive adhesive sheet comprising: a film-like base material; and a pressure-sensitive adhesive layer provided on at least one surface of the film-like base material,
    A coating layer partially covering the pressure-sensitive adhesive layer surface, whereby the pressure-sensitive adhesive layer surface has a coating layer disposition portion and a coating layer non-disposition portion;
    The area ratio of the coating layer non-arranged portion on the pressure-sensitive adhesive layer surface is 70% or more,
    The coat layer arrangement portion has a portion extending linearly from one end of the pressure-sensitive adhesive layer to the other when the pressure-sensitive adhesive layer surface is viewed from above,
    The pressure-sensitive adhesive sheet has a width of the linearly extending portion within a range of 0.1 to 2 mm.
  2. 　前記粘着剤層表面には、前記線状に延びる部分が複数配置されており、
    　前記複数の線状に延びる部分のうち一群を構成する複数の線状に延びる部分は、その幅方向にて間隔をおいて配置されており、これによって、前記コート層配置部はストライプ状パターンを有する、請求項１に記載の粘着シート。     A plurality of linearly extending portions are disposed on the pressure-sensitive adhesive layer surface,
    Among the plurality of linearly extending portions, the plurality of linearly extending portions constituting a group are arranged at intervals in the width direction, whereby the coat layer arranging portion has a stripe pattern. The pressure-sensitive adhesive sheet according to claim 1.
  3. 　前記コート層配置部は、第１ストライプ状パターン部と、該第１ストライプ状パターン部と交差するように配置された第２ストライプ状パターン部とを含み、これによって、前記コート層配置部は格子状パターンを有する、請求項２に記載の粘着シート。 The coat layer arrangement portion includes a first stripe pattern portion and a second stripe pattern portion arranged to intersect the first stripe pattern portion, whereby the coat layer arrangement portion is a lattice. The pressure-sensitive adhesive sheet according to claim 2, having a pattern.
  4. 　前記コート層配置部において、一のストライプ状パターンを構成する複数の線状に延びる部分の間隔は１．０～１０ｍｍの範囲内である、請求項２または３に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 2 or 3, wherein in the coat layer arrangement portion, a plurality of linearly extending portions constituting one stripe pattern have a distance of 1.0 to 10 mm.
  5. 　前記コート層が部分的に配置された粘着性表面は、１３Ｎ／２５ｍｍ以上の２４時間経過後１８０度剥離強度を示す、請求項１～４のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the adhesive surface on which the coat layer is partially disposed exhibits a 180-degree peel strength after 24 hours of 13 N / 25 mm or more.
  6. 　前記粘着剤層は、該粘着剤層に含まれるポリマー成分の５０重量％を超える割合でアクリル系ポリマーを含み、
    　前記アクリル系ポリマーは、モノマー成分として、式（１）：
    　ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２　　　　　（１）
    （上記式（１）中のＲ１は水素原子またはメチル基である。また、Ｒ２は炭素原子数１～２０の鎖状アルキル基である。）；で表されるアルキル（メタ）アクリレートを５０重量％を超える割合で含む、請求項１～５のいずれか一項に記載の粘着シート。     The pressure-sensitive adhesive layer contains an acrylic polymer in a proportion exceeding 50% by weight of the polymer component contained in the pressure-sensitive adhesive layer,
    The acrylic polymer has a formula (1):
    CH 2 = C (R 1 ) COOR 2 (1)
    (In the above formula (1), R 1 is a hydrogen atom or a methyl group. R 2 is a chain alkyl group having 1 to 20 carbon atoms.) The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, which is contained in a proportion exceeding 50% by weight.
  7. 　前記アルキル（メタ）アクリレートは、ｎ－ブチルアクリレートおよび／または２－エチルヘキシルアクリレートである、請求項６に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 6, wherein the alkyl (meth) acrylate is n-butyl acrylate and / or 2-ethylhexyl acrylate.
  8. 　前記アクリル系ポリマーは、副モノマーとしてカルボキシ基含有モノマーおよび／または水酸基含有モノマーが共重合されたアクリル系ポリマーである、請求項６または７のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 6 and 7, wherein the acrylic polymer is an acrylic polymer obtained by copolymerizing a carboxy group-containing monomer and / or a hydroxyl group-containing monomer as a submonomer.
  9. 　前記アクリル系ポリマーは、アクリル酸、メタクリル酸、２－ヒドロキシエチルアクリレートおよび４－ヒドロキシブチルアクリレートからなる群から選択される少なくとも１種の副モノマーが共重合されたアクリル系ポリマーである、請求項６～８のいずれか一項に記載の粘着シート。 The acrylic polymer is an acrylic polymer obtained by copolymerizing at least one submonomer selected from the group consisting of acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. The pressure-sensitive adhesive sheet according to any one of 1 to 8.
  10. 　前記アクリル系ポリマーには、カルボキシ基含有モノマーが共重合されており、前記カルボキシ基含有モノマーの共重合割合は、前記アクリル系ポリマーの合成に使用する全モノマー成分中、０．１～１０重量％である、請求項６～９のいずれか一項に記載の粘着シート。 The acrylic polymer is copolymerized with a carboxy group-containing monomer, and the copolymerization ratio of the carboxy group-containing monomer is 0.1 to 10% by weight in the total monomer components used for the synthesis of the acrylic polymer. The pressure-sensitive adhesive sheet according to any one of claims 6 to 9, wherein
  11. 　前記アクリル系ポリマーには水酸基含有モノマーが共重合されており、
    　前記水酸基含有モノマーの共重合割合は、前記アクリル系ポリマーの合成に使用する全モノマー成分中、０．００１～１０重量％である、請求項６～１０のいずれか一項に記載の粘着シート。     The acrylic polymer is copolymerized with a hydroxyl group-containing monomer,
    The pressure-sensitive adhesive sheet according to any one of claims 6 to 10, wherein a copolymerization ratio of the hydroxyl group-containing monomer is 0.001 to 10% by weight in all monomer components used in the synthesis of the acrylic polymer.
  12. 　前記粘着剤層は、イソシアネート系架橋剤および／またはエポキシ系架橋剤を含む、請求項６～１１のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 6 to 11, wherein the pressure-sensitive adhesive layer contains an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent.
  13. 　前記粘着剤層は、軟化点が１００℃～１４０℃である粘着付与樹脂を、前記アクリル系ポリマー１００重量部に対して３０～６０重量部の割合で含み、
    　前記粘着付与樹脂は、ロジン系粘着付与樹脂、テルペン系粘着付与樹脂および炭化水素系粘着付与樹脂からなる群から選択される少なくとも１種である、請求項６～１２のいずれか一項に記載の粘着シート。     The pressure-sensitive adhesive layer contains a tackifying resin having a softening point of 100 ° C. to 140 ° C. in a ratio of 30 to 60 parts by weight with respect to 100 parts by weight of the acrylic polymer,
    The tackifier resin according to any one of claims 6 to 12, wherein the tackifier resin is at least one selected from the group consisting of a rosin tackifier resin, a terpene tackifier resin, and a hydrocarbon tackifier resin. Adhesive sheet.
  14. 　前記コート層は透明樹脂からなる、請求項１～１３のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 13, wherein the coating layer is made of a transparent resin.
  15. 　前記コート層は、ポリウレタン系樹脂、フェノール系樹脂、エポキシ系樹脂、ポリアミド系樹脂、尿素メラミン系樹脂、シリコーン系樹脂、ポリシラザン系樹脂、フッ素系樹脂、フェノキシ樹脂、メタクリル系樹脂、アクリル系樹脂、アクリル－ウレタン系樹脂、アクリル－スチレン系樹脂、ポリアリレート樹脂、ポリエステル系樹脂、ポリオレフィン系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル、塩化ビニル－酢酸ビニル共重合体、ポリ酢酸ビニル、ポリ塩化ビニリデン、ポリカーボネート、セルロース類およびポリアセタールからなる群から選択される少なくとも１種の樹脂を含む、請求項１～１４のいずれか一項に記載の粘着シート。 The coating layer is made of polyurethane resin, phenol resin, epoxy resin, polyamide resin, urea melamine resin, silicone resin, polysilazane resin, fluorine resin, phenoxy resin, methacrylic resin, acrylic resin, acrylic resin. -Urethane resin, acrylic-styrene resin, polyarylate resin, polyester resin, polyolefin resin, polystyrene resin, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polycarbonate, The pressure-sensitive adhesive sheet according to any one of claims 1 to 14, comprising at least one resin selected from the group consisting of celluloses and polyacetals.
  16. 　前記コート層はポリウレタン系樹脂である、請求項１～１５のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 15, wherein the coating layer is a polyurethane resin.
  17. 　前記コート層は、二液混合硬化型のポリウレタン系樹脂である、請求項１～１６のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 16, wherein the coating layer is a two-component mixed curing type polyurethane resin.
  18. 　前記フィルム状基材は、ポリオレフィン系樹脂フィルム、ポリエステル系樹脂フィルム、塩化ビニル系樹脂フィルム、酢酸ビニル系樹脂フィルム、ポリイミド系樹脂フィルム、ポリアミド系樹脂フィルム、フッ素系樹脂フィルムまたはセロハンフィルムである、請求項１～１７のいずれか一項に記載の粘着シート。 The film-like substrate is a polyolefin resin film, a polyester resin film, a vinyl chloride resin film, a vinyl acetate resin film, a polyimide resin film, a polyamide resin film, a fluorine resin film, or a cellophane film, Item 18. The pressure-sensitive adhesive sheet according to any one of items 1 to 17.
  19. 　前記フィルム状基材はポリエステルフィルムである、請求項１～１８のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 18, wherein the film-like substrate is a polyester film.
  20. 　前記フィルム状基材はポリエチレンテレフタレートフィルムである、請求項１～１９のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 19, wherein the film-like substrate is a polyethylene terephthalate film.
  21. 　前記フィルム状基材は８０％以上の全光線透過率を示す、請求項１～２０のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 20, wherein the film-like substrate exhibits a total light transmittance of 80% or more.
  22. 　前記フィルム状基材は発泡体フィルムである、請求項１～１７のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 17, wherein the film-like substrate is a foam film.
  23. 　前記発泡体フィルムの平均気泡径は１０～２００μｍであり、密度は０．０１～０．７ｇ／ｃｍ３である、請求項２２に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 22, wherein the foam film has an average cell diameter of 10 to 200 µm and a density of 0.01 to 0.7 g / cm 3 .
  24. 　前記発泡体フィルムは、アクリル系樹脂発泡体またはポリオレフィン系樹脂発泡体である、請求項２２または２３に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 22 or 23, wherein the foam film is an acrylic resin foam or a polyolefin resin foam.
  25. 　請求項１～２４のいずれか一項に記載の粘着シートと、該粘着シートの粘着面を保護する剥離ライナーと、を備えており、
    　前記剥離ライナーの表面のうち前記粘着面側の表面は、平滑に形成されている、剥離ライナー付き粘着シート。     A pressure-sensitive adhesive sheet according to any one of claims 1 to 24, and a release liner that protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet,
    The pressure-sensitive adhesive sheet with a release liner, wherein the surface on the pressure-sensitive adhesive side of the surface of the release liner is formed smoothly.
  26. 　少なくとも一方の表面が剥離性表面である剥離性支持体を備える粘着シート用剥離ライナーであって、
    　前記剥離性支持体の剥離性表面上には、粘着シートに転写可能なコート層が設けられており、これによって、該剥離性表面はコート層配置部とコート層非配置部とを有しており、
    　前記剥離性表面における前記コート層非配置部の面積割合は７０％以上であり、
    　前記コート層は、前記剥離性表面の一端から他端に向かって線状に延びる部分を有しており、
    　前記線状に延びる部分の幅は０．１～２ｍｍの範囲内である、剥離ライナー。     A release liner for a pressure-sensitive adhesive sheet comprising a peelable support in which at least one surface is a peelable surface,
    On the peelable surface of the peelable support, a coat layer that can be transferred to the pressure-sensitive adhesive sheet is provided, whereby the peelable surface has a coat layer placement portion and a coat layer non-placement portion. And
    The area ratio of the coat layer non-arranged portion on the peelable surface is 70% or more,
    The coat layer has a portion extending linearly from one end to the other end of the peelable surface,
    A release liner in which the width of the linearly extending portion is in the range of 0.1 to 2 mm.
PCT/JP2015/083445 2014-11-28 2015-11-27 Adhesive sheet WO2016084948A1 (en)

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WO2018221336A1 (en) * 2017-05-31 2018-12-06 日東電工株式会社 Adhesive sheet
JP2018203836A (en) * 2017-05-31 2018-12-27 日東電工株式会社 Adhesive sheet
CN110691828A (en) * 2017-05-31 2020-01-14 日东电工株式会社 Adhesive sheet
US11267998B2 (en) 2017-05-31 2022-03-08 Nitto Denko Corporation Pressure-sensitive adhesive sheet
CN110691828B (en) * 2017-05-31 2022-04-26 日东电工株式会社 Adhesive sheet
JP7075727B2 (en) 2017-05-31 2022-05-26 日東電工株式会社 Adhesive sheet
CN113631376A (en) * 2019-03-26 2021-11-09 琳得科株式会社 Release sheet

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