WO2020084783A1 - Pressure-sensitive adhesive sheet and method of using pressure-sensitive adhesive sheet - Google Patents

Pressure-sensitive adhesive sheet and method of using pressure-sensitive adhesive sheet Download PDF

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Publication number
WO2020084783A1
WO2020084783A1 PCT/JP2018/039945 JP2018039945W WO2020084783A1 WO 2020084783 A1 WO2020084783 A1 WO 2020084783A1 JP 2018039945 W JP2018039945 W JP 2018039945W WO 2020084783 A1 WO2020084783 A1 WO 2020084783A1
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Prior art keywords
pressure
sensitive adhesive
adhesive sheet
groove
layer
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PCT/JP2018/039945
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French (fr)
Japanese (ja)
Inventor
晃司 土渕
章悟 杉浦
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リンテック株式会社
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Priority to PCT/JP2018/039945 priority Critical patent/WO2020084783A1/en
Publication of WO2020084783A1 publication Critical patent/WO2020084783A1/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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive sheet and a method of using the adhesive sheet.
  • the present inventor stuck the pressure-sensitive adhesive sheet in which grooves are formed in the pressure-sensitive adhesive layer to the adherend as in the above-mentioned conventional technique, and thereafter, in order to protect the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet and the adherend were adhered to each other.
  • a lacquer or the like was applied so as to straddle the lacquer, swelling due to air bubbles was suppressed during sticking, but swelling was confirmed in the coated state after sticking. Therefore, when the present inventor examined the factor, the gas remaining in the groove of the pressure-sensitive adhesive layer caused such swelling.
  • the groove formed in the pressure-sensitive adhesive layer is gradually crushed from the time of attachment, and in particular, in Patent Document 2, although it is not visible to the naked eye, it is only visible to the naked eye.
  • the adhesive layer still has some fine grooves, and gas remains in the grooves.
  • the coating layer is formed so as to cover the adhesive sheet in that state, the outlet of the groove is closed and the gas remaining in the groove is trapped. If the temperature rises as it is, for example, due to heating and drying of the coating layer or a change in the environment, the gas trapped in the groove expands, resulting in swelling.
  • the present invention has been made in view of such a phenomenon that has not been paid attention to in the above-mentioned conventional techniques, and a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive sheet in which swelling is suppressed not only at the time of attachment but also in a state of being coated with lacquer after attachment.
  • the purpose is to provide a method of using.
  • the pressure-sensitive adhesive sheet of the present invention for achieving the above object has a base material layer and a pressure-sensitive adhesive layer provided on one surface side of the base material layer, and has grooves on the surface of the pressure-sensitive adhesive layer. Are formed.
  • the groove has a triangular sectional shape in which each of the other two corners is smaller than the apex angle which is convex toward the base material layer.
  • the pressure-sensitive adhesive layer has the surface having a wetting index of 30 mN / m or more measured according to ISO8296.
  • the method for using the pressure-sensitive adhesive sheet of the present invention to achieve the above object is to stick the pressure-sensitive adhesive sheet to an adherend and apply a coating over the pressure-sensitive adhesive sheet and the adherend.
  • the occurrence of swelling is suppressed not only at the time of attachment but also in the coated state after attachment.
  • the pressure-sensitive adhesive sheet 100 of the embodiment is releasable to the base material layer 110, the pressure-sensitive adhesive layer 120 provided on the one surface 111 side of the base material layer 110, and the pressure-sensitive adhesive layer 120. It has a release liner 130 disposed.
  • the adhesive sheet 100 is, for example, a marking film attached to an exterior material of a vehicle such as a two-wheeled vehicle or a four-wheeled vehicle, a sticker for advertisement or display, but is not limited thereto.
  • the substrate layer 110 has a decoration on the other surface 112 opposite to the surface 111, for example formed by printing, including, for example, colors, letters, numbers, or patterns, or combinations thereof. A form that is plain is also included in the scope of the present invention.
  • the material forming the base material layer 110 is preferably polyvinyl chloride or polyurethane.
  • the material formed is not particularly limited. Not done.
  • the thickness of the pressure-sensitive adhesive layer 120 is not particularly limited, but is, for example, 10 ⁇ m to 50 ⁇ m.
  • Examples of materials for forming the pressure-sensitive adhesive layer 120 include acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and styrene-diene block copolymer pressure-sensitive adhesives. These adhesives may be used alone or in combination of two or more.
  • the acrylic pressure-sensitive adhesive which is a suitable example of the pressure-sensitive adhesives mentioned above, is a constituent material thereof.
  • the wettability (wetting index) can be adjusted by changing the amount of the functional group-containing monomer contained in the monomer constituting the acrylic copolymer.
  • the acrylic copolymer that constitutes the acrylic pressure-sensitive adhesive has a (meth) acrylic acid alkyl ester as a monomer main component, and a (meth) acrylic acid alkyl ester copolymerizable monomer (copolymer) if necessary. It is formed by using a polymerizable monomer).
  • the main component means 50% by mass or more (upper limit 100% by mass) in the monomer, preferably 65% by mass or more, and more preferably 85% by mass or more.
  • the alkyl group of the (meth) acrylic acid alkyl ester may be a linear, branched, or cyclic alkyl group.
  • the alkyl group is preferably an alkyl group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 18 carbon atoms.
  • (meth) acrylic acid alkyl ester examples include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate.
  • an acrylic copolymerizable monomer copolymerizable with (meth) acrylic acid alkyl ester a monomer having a functional group that reacts with a crosslinkable reactive group of a crosslinking agent described below (simply a functional group-containing monomer (Also referred to as the body).
  • the functional group-containing monomer examples include hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; (meth) Acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and other carboxyl group-containing monomers; aminoethyl (meth) acrylate, (meth) acrylylmorpholine and other amino group-containing monomers; glycidyl ( Examples thereof include epoxy group-containing monomers such as (meth) acrylate and methylglycidyl (meth) acrylate.
  • hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate
  • a hydroxyl group-containing monomer and / or a carboxyl group-containing monomer as the acrylic copolymerizable monomer copolymerizable with the (meth) acrylic acid alkyl ester, and at least a carboxyl group-containing monomer. Is more preferably used.
  • the acrylic copolymerizable monomer copolymerizable with the (meth) acrylic acid alkyl ester should be 1 to 15% by mass in the monomers constituting the acrylic copolymer in order to obtain desired wettability. Is preferred, but is not limited thereto. The smaller the content of the functional group-containing monomer in the monomers constituting the acrylic copolymer, the lower the wettability tends to be.
  • the method for producing the acrylic copolymer is not particularly limited, and it is conventionally a solution polymerization method using a polymerization initiator, an emulsion polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, a thin film polymerization method, a spray polymerization method, or the like.
  • a known method can be used.
  • a method of initiating the polymerization with the polymerization initiator a method of initiating the polymerization by irradiating radiation, electron beam, ultraviolet ray or the like can also be adopted.
  • the solution polymerization method using a polymerization initiator is preferable because the molecular weight can be easily adjusted and impurities can be reduced.
  • ethyl acetate, toluene, methyl ethyl ketone or the like is used as a solvent
  • 0.01 to 0.50 parts by mass of a polymerization initiator is preferably added to 100 parts by mass of the total amount of monomers, and the mixture is added under a nitrogen atmosphere, for example. It can be obtained by reacting at a reaction temperature of 60 to 90 ° C. for 3 to 10 hours.
  • the pressure-sensitive adhesive composition preferably contains a crosslinking agent together with the acrylic copolymer. Good adhesive performance is exhibited by containing a crosslinking agent.
  • cross-linking agent known cross-linking agents can be used. Examples include, but are not limited to, isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and metal chelate-based crosslinking agents.
  • isocyanate cross-linking agent examples include aliphatic diisocyanates such as hexamethylene diisocyanate (HDI); aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate; and diisocyanate compounds and trimethylol.
  • aliphatic diisocyanates such as hexamethylene diisocyanate (HDI); aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate
  • alicyclic diisocyanates such as isophorone diisocyanate
  • diisocyanate compounds and trimethylol examples include adducts with polyol compounds such as propane, biuret bodies of diisocyanate compounds, and isocyanate derivatives such as isocyanur
  • examples of the epoxy-based cross-linking agent include N, N, N ', N'-tetraglycidyl-m-xylenediamine and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane.
  • metal chelate-based cross-linking agent examples include acetylacetonate complexes of metals such as aluminum, titanium, nickel, chromium, iron, zinc, cobalt, manganese and zirconium.
  • the adhesive layer 120 may contain other components such as a tackifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a softener, a silane coupling agent, and a filler, if necessary. .
  • the release liner 130 has a protrusion 131 protruding toward the adhesive layer 120.
  • the protrusion 131 has a triangular cross-sectional shape and is provided in plural.
  • the release liner 130 is not particularly limited in what kind of material is formed, and may be formed of a resin film such as polyethylene terephthalate, or a paper coated with a resin such as polyethylene. It may be formed.
  • the protrusion 131 is formed by, for example, embossing such a resin film or paper.
  • a release agent such as silicone may be applied to the side of the release liner 130 that is in contact with the pressure-sensitive adhesive layer 120 to improve the releasability of the pressure-sensitive adhesive layer 120.
  • the release liner 130 is peeled off, and the adhesive sheet 100 is used.
  • a groove 122 is formed on the surface 121 of the pressure-sensitive adhesive layer 120 from which the release liner 130 has been peeled off, and the pressure-sensitive adhesive sheet 100 is attached to the adherend 140 on the surface 121.
  • the groove 122 has a triangular cross-sectional shape corresponding to the shape of the protrusion 131 in the release liner 130, and in the triangle, two other corners than the apex angle ⁇ 1 that is convex toward the base material layer 110 side.
  • Each of ⁇ 2 and ⁇ 3 is small ( ⁇ 1> ⁇ 2, ⁇ 1> ⁇ 3).
  • the angle ⁇ 2 and the angle ⁇ 3 are equal, but a form in which they are different is also included in the scope of the present invention.
  • a plurality of grooves 122 are formed.
  • the adherend 140 is, for example, a tank for a two-wheeled vehicle, but is not limited to this, and may be another exterior material for a two-wheeled vehicle such as a cowl or an exterior material for a vehicle other than a two-wheeled vehicle such as a four-wheeled vehicle. Good.
  • the surface 121 is configured to have good wettability with respect to the adherend 140, and specifically, the wetting index of the surface 121 measured according to ISO8296 is 30 mN / m or more. The larger the wetting index, the better the wettability.
  • the upper limit of the wetting index is not particularly limited, but is 73 mN / m, for example.
  • the groove 122 extends in the surface direction and reaches the exit of the edge of the adhesive sheet 100.
  • the groove 122 is formed linearly in the surface direction, but it is not limited to this and may be curved.
  • the grooves 122 are formed in a lattice shape so as to intersect with each other, the form in which they are formed is not particularly limited, and for example, the grooves 122 may be formed in parallel with each other without intersecting each other. .
  • the coating agent 150 applied in this embodiment is a lacquer paint, but the present invention is not limited thereto.
  • the pressure-sensitive adhesive layer 120 When the pressure-sensitive adhesive sheet 100 is attached to the adherend 140, the pressure-sensitive adhesive layer 120 has a groove 122, but when the pressure-sensitive adhesive layer 120 contacts the adherend 140, the pressure-sensitive adhesive layer 120 is adhered due to wettability. Since it fits into the body 140, the width of the groove 122 gradually decreases from the time of attachment.
  • the groove 122 disappears before the coating layer 151 covering the adhesive sheet 100 is formed.
  • the flexibility of the pressure-sensitive adhesive layer 120 is represented by, for example, the storage elastic modulus. The higher the storage elastic modulus is, the harder the pressure-sensitive adhesive layer 120 is to be deformed, and the smaller the storage elastic modulus is, the softer the pressure-sensitive adhesive layer 120 is. Easy to deform.
  • the storage elastic modulus is measured using, for example, MCR manufactured by Anton-Paar. Specifically, the temperature was changed in the range of -50 ° C to 150 ° C while applying a cyclic circumferential force at a frequency of 1 Hz to a disc-shaped adhesive test piece having a diameter of 8 mm and a thickness of 1 mm. The temperature dependence of the storage elastic modulus is determined by using the measured value at 23 ° C. as the storage elastic modulus.
  • the storage elastic modulus of the pressure-sensitive adhesive layer 120 thus measured is preferably 1.0 ⁇ 10 4 Pa or more and 1.0 ⁇ 10 6 Pa or less, more preferably 2.0 ⁇ 10 4 Pa or more and 3.0 ⁇ . It is 10 5 Pa or less.
  • the coating layer 151 is formed by coating the coating agent 150 so as to cover the entire pressure-sensitive adhesive sheet 100, and then dried.
  • the coating layer 151 is a transparent resin layer, and the adhesive sheet 100 is clearly visible even when it is covered with the coating layer 151.
  • the coating layer 151 prevents the pressure-sensitive adhesive sheet 100 from being damaged or soiled. Further, since the coating layer 151 is formed across the end portion of the adhesive sheet 100 and the adherend 140, the adhesive sheet 100 is difficult to peel off.
  • the coating layer 151 when the coating layer 151 is formed with the groove 122A, the outlet is blocked in the groove 122A while the gas remains, and The gas remaining in 122A is trapped.
  • the temperature of the coating layer 151 rises as it is due to heating and drying of the coating layer 151 or a change in environment, the gas trapped in the groove 122A expands and the coating layer 151 is pressed from the inside.
  • a bulge 151A may occur.
  • the appearance becomes poor, which is not preferable.
  • the groove 122 disappears before the coating layer 151 is formed, such a phenomenon is unlikely to occur.
  • each of the other two angles ⁇ 2 and ⁇ 3 is smaller than the apex angle ⁇ 1, and when the adhesive layer 120 contacts the adherend 140, the edge of the groove 122 is small.
  • 123 is close to the adherend 140, and the surface of the pressure-sensitive adhesive layer 120 has a wetting index of 30 mN / m or more and is easily wet. Therefore, the pressure-sensitive adhesive layer 120 quickly adapts to the adherend 140 from the edge 123, and the disappearance of the groove 122 is effectively promoted.
  • the apex angle ⁇ 1 is formed in the central portion, so that it is relatively easy to secure a gap communicating to the end portion.
  • the central portion is easily crushed, so that the groove is interrupted and it is difficult to expect a function such as the apex angle ⁇ 1 of the present embodiment.
  • the groove 122 since the groove 122 has a triangular cross-sectional shape and the apex angle ⁇ 1 is formed, a gap is relatively easily secured in the central portion of the groove 122.
  • the storage elastic modulus of the pressure-sensitive adhesive layer 120 is set to 1.0 ⁇ 10 4 Pa or more and 1.0 ⁇ 10 6 Pa or less at 23 ° C. and 1 Hz, the pressure-sensitive adhesive layer 120 does not become too hard and is moderate. Since it has a high degree of flexibility and is easily deformed to fit the adherend 140, it is difficult to prevent the disappearance of the groove 122 due to wettability.
  • Example> The present inventor actually manufactured the pressure-sensitive adhesive sheets of Examples 1 to 9 having a configuration similar to that of the pressure-sensitive adhesive sheet 100 of the above embodiment.
  • the base material layer was formed of polyvinyl chloride to a thickness of 50 ⁇ m
  • the pressure-sensitive adhesive layer was formed of an acrylic pressure-sensitive adhesive to a thickness of 25 ⁇ m.
  • the pressure-sensitive adhesive sheets of Examples 1 to 9 have a size of 100 mm ⁇ 50 mm.
  • the adhesive sheets of Examples 1 to 9 differ in the wetting index and the storage elastic modulus (23 ° C., 1 Hz) of the adhesive layer, but the other configurations are common.
  • the present inventor also manufactured the pressure-sensitive adhesive sheets of Comparative Examples 1 to 3 in which the cross-sectional shape of the groove formed in the pressure-sensitive adhesive layer was different from that of the example.
  • the pressure-sensitive adhesive sheets of Comparative Examples 1 to 3 have the same configurations as those of Examples 1 to 9 except for the cross-sectional shape of the grooves formed in the pressure-sensitive adhesive layer.
  • the groove 122A formed in the pressure-sensitive adhesive layer has a triangular cross-sectional shape in which the other two angles ⁇ 2 and ⁇ 3 are larger than the apex angle ⁇ 1 ( ⁇ 1 ⁇ 2, ⁇ 1 ⁇ 3), which is different from the cross-sectional shape of the groove of the embodiment as shown in FIG.
  • the adhesive sheet 100A of the comparative example has the same configuration as that of the example except for the cross-sectional shape of the groove 122A.
  • the present inventor adhered the pressure-sensitive adhesive sheets of Examples 1 to 9 and Comparative Examples 1 to 3 to acrylic coated plates, sprayed them with a lacquer paint, and left them in an environment of 170 ° C. for 30 minutes to obtain a pressure-sensitive adhesive sheet. It was confirmed whether or not a bulge was generated at the edge of the.
  • Table 1 below shows the difference in the constitution of the pressure-sensitive adhesive sheets of Examples 1 to 9 and Comparative Examples 1 to 3 and the swelling test results thereof. Comparing the respective configurations of Comparative Example 1 and Example 5, Comparative Example 2 and Example 7, and Comparative Example 3 and Example 9, they differ only in the cross-sectional shape of the groove and the wetting index And other configurations such as storage elastic modulus are the same.
  • FIG. 5 of the above-described embodiment schematically shows a state in which the groove 122 is completely eliminated as an example, but the disappearance of the groove is effectively promoted so as to prevent swelling after coating.
  • it is not necessarily limited to the form in which all the grooves are completely eliminated.
  • the pressure-sensitive adhesive sheet 100 of the above embodiment has the base layer 110, the pressure-sensitive adhesive layer 120, and the release liner 130, but a pressure-sensitive adhesive sheet provided with layers other than these is also included in the scope of the present invention.

Abstract

[Problem] To provide: a pressure-sensitive adhesive sheet for which swelling is suppressed not only at the time of affixing but also in a coated state after affixing; and a method for using the pressure-sensitive adhesive sheet. [Solution] A pressure-sensitive adhesive sheet 100 includes: a base layer 110; and a pressure-sensitive adhesive layer 120 provided on one side 111 of the base layer. Grooves 122 are formed on a surface 121 of the pressure-sensitive adhesive layer. The grooves each have a triangular cross-sectional shape in which each of two angles α2, α3 is smaller than an apex angle α1 protruding toward the base material layer. The pressure-sensitive adhesive layer includes the surface 121 having a wetting index measured according to ISO 8296 of 30 mN/m or more.

Description

粘着シートおよび粘着シートの使用方法Adhesive sheet and usage of adhesive sheet
　本発明は、粘着シートおよび粘着シートの使用方法に関する。 The present invention relates to an adhesive sheet and a method of using the adhesive sheet.
　従来、被着体への粘着シートの貼り付けの際に、それらの間に気泡が入り込んで膨れが生じないよう、例えば特許文献１および特許文献２に記載の粘着シートでは、被着体に接する粘着剤層に溝が形成されており、その溝に沿って気泡が排出されることによって、膨れが抑制される。 Conventionally, when the pressure-sensitive adhesive sheet is attached to an adherend, bubbles do not enter between them and swell, so that the pressure-sensitive adhesive sheets disclosed in Patent Document 1 and Patent Document 2 are in contact with the adherend. Grooves are formed in the pressure-sensitive adhesive layer, and bubbles are discharged along the grooves to suppress swelling.
特許第４４５９１４８号公報Japanese Patent No. 4459148 特許第５０７４２２９号公報Japanese Patent No. 5074229
　しかしながら、本発明者が、上記従来技術のように粘着剤層に溝の形成された粘着シートを被着体に貼り付け、さらにその後、粘着シートを保護するために、粘着シートと被着体とにまたがるようにラッカー等をコーティングしたところ、貼り付け時においては、気泡による膨れは抑制されたものの、貼り付け後のコーティングされた状態においては、膨れの発生が確認された。そこで、本発明者がその要因について検討すると、粘着剤層の溝に残存する気体が、そのような膨れを生じさせていた。 However, the present inventor stuck the pressure-sensitive adhesive sheet in which grooves are formed in the pressure-sensitive adhesive layer to the adherend as in the above-mentioned conventional technique, and thereafter, in order to protect the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet and the adherend were adhered to each other. When a lacquer or the like was applied so as to straddle the lacquer, swelling due to air bubbles was suppressed during sticking, but swelling was confirmed in the coated state after sticking. Therefore, when the present inventor examined the factor, the gas remaining in the groove of the pressure-sensitive adhesive layer caused such swelling.
　上記従来技術において、粘着剤層に形成された溝は、貼り付け時点から徐々に潰れていき、特に上記特許文献２にあっては、肉眼では分らない程度になるが、肉眼で分らないだけで粘着剤層にはいくつかの微細な溝が依然としてあり、その溝に気体が残存している。その状態で粘着シートを覆うようにコーティング層が形成されると、溝の出口が塞がれ、溝に残存する気体が閉じ込められる。そのまま例えばコーティング層の加熱乾燥や環境変化にともなって温度上昇すると、溝に閉じ込められている気体が膨張し、その結果、膨れが生じてしまう。 In the above-mentioned conventional technique, the groove formed in the pressure-sensitive adhesive layer is gradually crushed from the time of attachment, and in particular, in Patent Document 2, although it is not visible to the naked eye, it is only visible to the naked eye. The adhesive layer still has some fine grooves, and gas remains in the grooves. When the coating layer is formed so as to cover the adhesive sheet in that state, the outlet of the groove is closed and the gas remaining in the groove is trapped. If the temperature rises as it is, for example, due to heating and drying of the coating layer or a change in the environment, the gas trapped in the groove expands, resulting in swelling.
　本発明は、そのような上記従来技術で着目されていない事象に鑑みてなされ、貼り付け時だけでなく、貼り付け後にラッカー等がコーティングされた状態においても膨れが抑制される粘着シートおよび粘着シートの使用方法を提供することを目的とする。 The present invention has been made in view of such a phenomenon that has not been paid attention to in the above-mentioned conventional techniques, and a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive sheet in which swelling is suppressed not only at the time of attachment but also in a state of being coated with lacquer after attachment. The purpose is to provide a method of using.
　上記目的を達成するための本発明の粘着シートは、基材層と、当該基材層の一方の面の側に設けられた粘着剤層と、を有し、前記粘着剤層の表面に溝が形成されている。前記溝は、前記基材層の側に凸となった頂角よりも他の２角のそれぞれが小さい三角形の断面形状を有する。前記粘着剤層は、ＩＳＯ８２９６に準拠して測定される濡れ指数が３０ｍＮ／ｍ以上である前記表面を有する。 The pressure-sensitive adhesive sheet of the present invention for achieving the above object has a base material layer and a pressure-sensitive adhesive layer provided on one surface side of the base material layer, and has grooves on the surface of the pressure-sensitive adhesive layer. Are formed. The groove has a triangular sectional shape in which each of the other two corners is smaller than the apex angle which is convex toward the base material layer. The pressure-sensitive adhesive layer has the surface having a wetting index of 30 mN / m or more measured according to ISO8296.
　上記目的を達成するための本発明の粘着シートの使用方法は、前記粘着シートを被着体に貼り付け、前記粘着シートおよび前記被着体にまたがってコーティングを施す。 The method for using the pressure-sensitive adhesive sheet of the present invention to achieve the above object is to stick the pressure-sensitive adhesive sheet to an adherend and apply a coating over the pressure-sensitive adhesive sheet and the adherend.
　上記構成を有する発明によれば、粘着シートが被着体に貼り付けられた際、それらの間に入り込んだ気泡は粘着剤層の溝を通じて排出される。また、粘着剤層の溝の形状と濡れ易さとの相乗効果によって、溝の消失が一層促されるため、溝に残存する気体が無くなり易い。従って、上記構成を有する発明によれば、貼り付け時だけでなく、貼り付け後のコーティングされた状態においても膨れの発生が抑制される。 According to the invention having the above configuration, when the pressure-sensitive adhesive sheet is attached to the adherend, the bubbles trapped between them are discharged through the groove of the pressure-sensitive adhesive layer. Further, the synergistic effect of the shape of the groove of the pressure-sensitive adhesive layer and the ease of wetting further promotes the disappearance of the groove, so that the gas remaining in the groove tends to disappear. Therefore, according to the invention having the above configuration, the occurrence of swelling is suppressed not only at the time of attachment but also in the coated state after attachment.
実施形態の粘着シートを示す図である。It is a figure which shows the adhesive sheet of embodiment. 実施形態の粘着シートの被着体への貼り付けを示す図である。It is a figure which shows sticking to the to-be-adhered body of the adhesive sheet of embodiment. 実施形態の粘着シートと被着体との間に入った気泡の排出を示す図である。It is a figure which shows discharge | emission of the air bubble which entered between the adhesive sheet and adherend of embodiment. 実施形態の粘着シートおよび被着体に施されるコーティングを示す図である。It is a figure which shows the adhesive sheet of embodiment, and the coating applied to an adherend. コーティングされた実施形態の粘着シートおよび被着体を示す図である。It is a figure which shows the adhesive sheet and adherend of embodiment which were coated. コーティングされた比較例の粘着シートを示す図である。It is a figure which shows the coated adhesive sheet of a comparative example. コーティングされた比較例の粘着シートにおける膨れの発生を示す図である。It is a figure which shows generation | occurrence | production of the swelling in the coated adhesive sheet of the comparative example. 被着体に貼り付けられた実施形態の粘着シートの要部を拡大して示す図である。It is a figure which expands and shows the principal part of the adhesive sheet of embodiment stuck on an adherend. 比較例の粘着シートにおいて粘着剤層に形成された溝を拡大して示す図である。It is a figure which expands and shows the groove | channel formed in the adhesive layer in the adhesive sheet of a comparative example.
　以下、添付した図面を参照しながら、本発明の実施形態を説明する。なお、図面の寸法比率は、説明の都合上誇張されており、実際の比率とは異なる。 Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. It should be noted that the dimensional ratios in the drawings are exaggerated for convenience of explanation, and are different from the actual ratios.
　図１に示すように、実施形態の粘着シート１００は、基材層１１０、基材層１１０の一方の面１１１の側に設けられた粘着剤層１２０、および、粘着剤層１２０に剥離自在に配置された剥離ライナー１３０を有する。 As shown in FIG. 1, the pressure-sensitive adhesive sheet 100 of the embodiment is releasable to the base material layer 110, the pressure-sensitive adhesive layer 120 provided on the one surface 111 side of the base material layer 110, and the pressure-sensitive adhesive layer 120. It has a release liner 130 disposed.
　粘着シート１００は、例えば、二輪車または四輪車等の車輌の外装材に貼り付けられるマーキングフィルム、広告もしくは表示用のステッカー類であるが、それらに限定されない。 The adhesive sheet 100 is, for example, a marking film attached to an exterior material of a vehicle such as a two-wheeled vehicle or a four-wheeled vehicle, a sticker for advertisement or display, but is not limited thereto.
　基材層１１０は、面１１１と反対の他方の面１１２に、例えば、色、文字、数字、もしくは模様、またはそれらの組み合わせ等を含む、例えば印刷によって形成された装飾を有するが、面１１２が無地である形態も本発明の範囲に含まれる。基材層１１０を形成する材料は、好ましくは、ポリ塩化ビニル、ポリウレタンである。 The substrate layer 110 has a decoration on the other surface 112 opposite to the surface 111, for example formed by printing, including, for example, colors, letters, numbers, or patterns, or combinations thereof. A form that is plain is also included in the scope of the present invention. The material forming the base material layer 110 is preferably polyvinyl chloride or polyurethane.
　粘着剤層１２０は、濡れ性（固体表面に対し液体が濡れ広がるように付着する性質）を有し所望の粘着力が発揮されるよう構成できれば、どのような材料によって形成されるかは特に限定されない。粘着剤層１２０の厚みは、特に限定されないが、例えば１０μｍ～５０μｍである。 If the pressure-sensitive adhesive layer 120 has a wettability (property that a liquid adheres to a solid surface so that the liquid wets and spreads) and a desired pressure-sensitive adhesive force is exerted, the material formed is not particularly limited. Not done. The thickness of the pressure-sensitive adhesive layer 120 is not particularly limited, but is, for example, 10 μm to 50 μm.
　粘着剤層１２０の形成材料として、例えば、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、スチレン－ジエンブロック共重合体粘着剤等が挙げられる。それらの粘着剤は、１種単独で用いても２種以上併用してもよい。 Examples of materials for forming the pressure-sensitive adhesive layer 120 include acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and styrene-diene block copolymer pressure-sensitive adhesives. These adhesives may be used alone or in combination of two or more.
　粘着剤層１２０の濡れ性をどのようにして調整するかは特に限定されないが、例えば、上で挙げた粘着剤のうち好適な一例であるアクリル系粘着剤にあっては、その構成材であるアクリル系共重合体を構成する単量体に含まれる官能基含有単量体の量を変えることによって、濡れ性（濡れ指数）を調整できる。 How to adjust the wettability of the pressure-sensitive adhesive layer 120 is not particularly limited. For example, the acrylic pressure-sensitive adhesive, which is a suitable example of the pressure-sensitive adhesives mentioned above, is a constituent material thereof. The wettability (wetting index) can be adjusted by changing the amount of the functional group-containing monomer contained in the monomer constituting the acrylic copolymer.
　アクリル系粘着剤を構成するアクリル系共重合体は、（メタ）アクリル酸アルキルエステルを単量体主成分とし、必要に応じて（メタ）アクリル酸アルキルエステルに共重合可能な単量体（共重合性単量体）を用いることにより形成される。ここで、主成分とは、単量体中５０質量％以上（上限１００質量％）であることを指し、好ましくは６５質量％以上、より好ましくは８５質量％以上である。 The acrylic copolymer that constitutes the acrylic pressure-sensitive adhesive has a (meth) acrylic acid alkyl ester as a monomer main component, and a (meth) acrylic acid alkyl ester copolymerizable monomer (copolymer) if necessary. It is formed by using a polymerizable monomer). Here, the main component means 50% by mass or more (upper limit 100% by mass) in the monomer, preferably 65% by mass or more, and more preferably 85% by mass or more.
　（メタ）アクリル酸アルキルエステルのアルキル基は、直鎖、分岐鎖、または環状のアルキル基のいずれであってもよい。アルキル基は炭素数１～２４のアルキル基であることが好ましく、炭素数１～１８のアルキル基であることがより好ましい。 The alkyl group of the (meth) acrylic acid alkyl ester may be a linear, branched, or cyclic alkyl group. The alkyl group is preferably an alkyl group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 18 carbon atoms.
　（メタ）アクリル酸アルキルエステルの具体例としては、以下に制限されないが、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－ヘプチル（メタ）アクリレート、イソ－オクチル（メタ）アクリレート、ｔｅｒｔ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、４－ｎ－ブチルシクロヘキシル（メタ）アクリレート等が挙げられる。これらの（メタ）アクリル酸アルキルエステルは１種単独で用いてもよいし、２種以上併用してもよい。 Specific examples of the (meth) acrylic acid alkyl ester include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, iso-octyl (meth) acrylate, tert-octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate DOO, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate and the like. These (meth) acrylic acid alkyl esters may be used alone or in combination of two or more.
　また、（メタ）アクリル酸アルキルエステルに共重合可能なアクリル共重合性単量体として、後述の架橋剤が有する架橋性反応基と反応する官能基を有する単量体（単に官能基含有単量体とも称する）を用いることが好ましい。官能基含有単量体としては、具体的には、２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートなどのヒドロキシアルキル（メタ）アクリレートなどの水酸基含有単量体；（メタ）アクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸などのカルボキシル基含有単量体；アミノエチル（メタ）アクリレート、（メタ）アクリルイルモルホリンなどのアミノ基含有単量体；グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレートなどのエポキシ基含有単量体などを挙げることができる。中でも、（メタ）アクリル酸アルキルエステルに共重合可能なアクリル共重合性単量体として、水酸基含有単量体および／またはカルボキシル基含有単量体を用いることが好ましく、少なくともカルボキシル基含有単量体を用いることがより好ましい。 In addition, as an acrylic copolymerizable monomer copolymerizable with (meth) acrylic acid alkyl ester, a monomer having a functional group that reacts with a crosslinkable reactive group of a crosslinking agent described below (simply a functional group-containing monomer (Also referred to as the body). Specific examples of the functional group-containing monomer include hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; (meth) Acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and other carboxyl group-containing monomers; aminoethyl (meth) acrylate, (meth) acrylylmorpholine and other amino group-containing monomers; glycidyl ( Examples thereof include epoxy group-containing monomers such as (meth) acrylate and methylglycidyl (meth) acrylate. Among them, it is preferable to use a hydroxyl group-containing monomer and / or a carboxyl group-containing monomer as the acrylic copolymerizable monomer copolymerizable with the (meth) acrylic acid alkyl ester, and at least a carboxyl group-containing monomer. Is more preferably used.
　（メタ）アクリル酸アルキルエステルに共重合可能なアクリル共重合性単量体は、所望の濡れ性を得るため、アクリル系共重合体を構成する単量体中、１～１５質量％であることが好ましいが、これに限定されない。なお、アクリル系共重合体を構成する単量体中の官能基含有単量体の含有量が少なければ少ないほど濡れ性は低下する傾向にある。 The acrylic copolymerizable monomer copolymerizable with the (meth) acrylic acid alkyl ester should be 1 to 15% by mass in the monomers constituting the acrylic copolymer in order to obtain desired wettability. Is preferred, but is not limited thereto. The smaller the content of the functional group-containing monomer in the monomers constituting the acrylic copolymer, the lower the wettability tends to be.
　アクリル系共重合体の製造方法は、特に制限されず、重合開始剤を使用する溶液重合法、乳化重合法、懸濁重合法、逆相懸濁重合法、薄膜重合法、噴霧重合法など従来公知の方法を用いることができる。また、重合開始剤により重合を開始させる方法の他に、放射線、電子線、紫外線等を照射して重合を開始させる方法を採用することもできる。中でも重合開始剤を使用する溶液重合法が、分子量の調節が容易であり、また不純物も少なくできるために好ましい。例えば、溶剤として酢酸エチル、トルエン、メチルエチルケトンなどを用い、モノマーの合計量１００質量部に対して、重合開始剤を好ましくは０．０１～０．５０質量部を添加し、窒素雰囲気下で、例えば反応温度６０～９０℃で、３～１０時間反応させることで得られる。 The method for producing the acrylic copolymer is not particularly limited, and it is conventionally a solution polymerization method using a polymerization initiator, an emulsion polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, a thin film polymerization method, a spray polymerization method, or the like. A known method can be used. In addition to the method of initiating the polymerization with the polymerization initiator, a method of initiating the polymerization by irradiating radiation, electron beam, ultraviolet ray or the like can also be adopted. Among them, the solution polymerization method using a polymerization initiator is preferable because the molecular weight can be easily adjusted and impurities can be reduced. For example, ethyl acetate, toluene, methyl ethyl ketone or the like is used as a solvent, 0.01 to 0.50 parts by mass of a polymerization initiator is preferably added to 100 parts by mass of the total amount of monomers, and the mixture is added under a nitrogen atmosphere, for example. It can be obtained by reacting at a reaction temperature of 60 to 90 ° C. for 3 to 10 hours.
　粘着剤組成物は、アクリル系共重合体とともに架橋剤を含むことが好ましい。架橋剤を含有することで良好な粘着性能が発揮される。 The pressure-sensitive adhesive composition preferably contains a crosslinking agent together with the acrylic copolymer. Good adhesive performance is exhibited by containing a crosslinking agent.
　架橋剤としては、公知の架橋剤が使用できる。例えば、以下に制限されないが、イソシアネート系架橋剤、エポキシ系架橋剤、金属キレート系架橋剤などが挙げられる。 As the cross-linking agent, known cross-linking agents can be used. Examples include, but are not limited to, isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and metal chelate-based crosslinking agents.
　イソシアネート系架橋剤としては、ヘキサメチレンジイソシアネート（ＨＤＩ）などの脂肪族ジイソシアネート；トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネートなどの芳香族ジイソシアネート；イソホロンジイソシアネートなどの脂環式ジイソシアネート；ならびにジイソシアネート化合物とトリメチロールプロパン等のポリオール化合物とのアダクト体、ジイソシアネート化合物のビウレット体やイソシアヌレート体などのイソシアネート誘導体が挙げられる。 Examples of the isocyanate cross-linking agent include aliphatic diisocyanates such as hexamethylene diisocyanate (HDI); aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate; and diisocyanate compounds and trimethylol. Examples thereof include adducts with polyol compounds such as propane, biuret bodies of diisocyanate compounds, and isocyanate derivatives such as isocyanurate bodies.
　また、エポキシ系架橋剤としては、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミンや１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロへキサン等が挙げられる。 Further, examples of the epoxy-based cross-linking agent include N, N, N ', N'-tetraglycidyl-m-xylenediamine and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane.
　金属キレート系架橋剤としては、アルミニウム、チタン、ニッケル、クロム、鉄、亜鉛、コバルト、マンガン、ジルコニウム等の金属のアセチルアセトネート錯体等が挙げられる。 Examples of the metal chelate-based cross-linking agent include acetylacetonate complexes of metals such as aluminum, titanium, nickel, chromium, iron, zinc, cobalt, manganese and zirconium.
　粘着剤層１２０には、必要に応じて、粘着付与剤、酸化防止剤、紫外線吸収剤、光安定剤、軟化剤、シランカップリング剤、充填剤等のその他の成分が含まれていてもよい。 The adhesive layer 120 may contain other components such as a tackifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a softener, a silane coupling agent, and a filler, if necessary. .
　剥離ライナー１３０は、粘着剤層１２０の側に突出した突部１３１を有する。突部１３１は、三角形の断面形状を有し、複数設けられている。突部１３１を形成できれば、剥離ライナー１３０はどのような材料から形成されるか特に限定されず、例えばポリエチレンテレフタレート等の樹脂フィルムから形成されてもよいし、ポリエチレン等の樹脂によって被覆された紙から形成されてもよい。そのような樹脂フィルムまたは紙が例えばエンボス加工されることによって、突部１３１は形成される。 The release liner 130 has a protrusion 131 protruding toward the adhesive layer 120. The protrusion 131 has a triangular cross-sectional shape and is provided in plural. As long as the protrusion 131 can be formed, the release liner 130 is not particularly limited in what kind of material is formed, and may be formed of a resin film such as polyethylene terephthalate, or a paper coated with a resin such as polyethylene. It may be formed. The protrusion 131 is formed by, for example, embossing such a resin film or paper.
　剥離ライナー１３０において粘着剤層１２０と接する側には、粘着剤層１２０に対する剥離性向上のため、シリコーン等の剥離剤が塗布されていてもよい。剥離ライナー１３０を剥がして、粘着シート１００は使用される。 A release agent such as silicone may be applied to the side of the release liner 130 that is in contact with the pressure-sensitive adhesive layer 120 to improve the releasability of the pressure-sensitive adhesive layer 120. The release liner 130 is peeled off, and the adhesive sheet 100 is used.
　図２に示すように、剥離ライナー１３０の剥がされた粘着剤層１２０の表面１２１には、溝１２２が形成されており、粘着シート１００は、表面１２１で被着体１４０に貼り付けられる。 As shown in FIG. 2, a groove 122 is formed on the surface 121 of the pressure-sensitive adhesive layer 120 from which the release liner 130 has been peeled off, and the pressure-sensitive adhesive sheet 100 is attached to the adherend 140 on the surface 121.
　溝１２２は、剥離ライナー１３０における突部１３１の形状に対応して三角形の断面形状を有し、その三角形では、基材層１１０の側に凸となった頂角α１よりも、他の２角α２、α３のそれぞれが小さい（α１＞α２、α１＞α３）。本実施形態において、角α２と角α３とは等しいが、それらが異なる形態も本発明の範囲に含まれる。溝１２２は複数形成されている。 The groove 122 has a triangular cross-sectional shape corresponding to the shape of the protrusion 131 in the release liner 130, and in the triangle, two other corners than the apex angle α1 that is convex toward the base material layer 110 side. Each of α2 and α3 is small (α1> α2, α1> α3). In the present embodiment, the angle α2 and the angle α3 are equal, but a form in which they are different is also included in the scope of the present invention. A plurality of grooves 122 are formed.
　被着体１４０は、例えば二輪車のタンクであるが、これに限定されず、例えば、カウル等の二輪車の他の外装材、もしくは二輪車以外の例えば四輪車等の車輛の外装材であってもよい。 The adherend 140 is, for example, a tank for a two-wheeled vehicle, but is not limited to this, and may be another exterior material for a two-wheeled vehicle such as a cowl or an exterior material for a vehicle other than a two-wheeled vehicle such as a four-wheeled vehicle. Good.
　被着体１４０に対し良好な濡れ性を有するよう表面１２１は構成されており、具体的に、ＩＳＯ８２９６に準拠して測定される表面１２１の濡れ指数が、３０ｍＮ／ｍ以上である。濡れ指数が大きいほど、濡れ性が良好である。濡れ指数の上限値は、特に限定されないが、例えば７３ｍＮ／ｍである。 The surface 121 is configured to have good wettability with respect to the adherend 140, and specifically, the wetting index of the surface 121 measured according to ISO8296 is 30 mN / m or more. The larger the wetting index, the better the wettability. The upper limit of the wetting index is not particularly limited, but is 73 mN / m, for example.
　図３に示すように、被着体１４０への粘着シート１００の貼り付けの際、それらの間に気泡Ｂが入り込むことがあるが、本実施形態では、溝１２２を通じて気泡Ｂは排出される。溝１２２は、面方向に伸びて、粘着シート１００の縁の出口に達している。本実施形態において、溝１２２は面方向に直線状に形成されているが、これに限定されず、曲がっていてもよい。また、溝１２２は互いに交差して格子状に形成されているが、どのような形態に形成されるかは特に限定されず、例えば溝１２２同士が交差せず互いに平行に形成されていてもよい。 As shown in FIG. 3, when the adhesive sheet 100 is attached to the adherend 140, the bubbles B may enter between them, but in the present embodiment, the bubbles B are discharged through the groove 122. The groove 122 extends in the surface direction and reaches the exit of the edge of the adhesive sheet 100. In the present embodiment, the groove 122 is formed linearly in the surface direction, but it is not limited to this and may be curved. Further, although the grooves 122 are formed in a lattice shape so as to intersect with each other, the form in which they are formed is not particularly limited, and for example, the grooves 122 may be formed in parallel with each other without intersecting each other. .
　図４に示すように、被着体１４０への粘着シート１００の貼り付け後、粘着シート１００および被着体１４０にまたがってコーティングが施される。本実施形態で塗布されるコーティング剤１５０は、ラッカー塗料であるが、本発明はこれに限定されない。 As shown in FIG. 4, after the adhesive sheet 100 is attached to the adherend 140, the adhesive sheet 100 and the adherend 140 are coated over the adhesive sheet 100. The coating agent 150 applied in this embodiment is a lacquer paint, but the present invention is not limited thereto.
　粘着シート１００が被着体１４０に貼り付けられた際、粘着剤層１２０には溝１２２があるが、粘着剤層１２０が被着体１４０に接すると、粘着剤層１２０は濡れ性によって被着体１４０に馴染んでいくため、貼り付け時点から溝１２２の幅は徐々に縮小していく。 When the pressure-sensitive adhesive sheet 100 is attached to the adherend 140, the pressure-sensitive adhesive layer 120 has a groove 122, but when the pressure-sensitive adhesive layer 120 contacts the adherend 140, the pressure-sensitive adhesive layer 120 is adhered due to wettability. Since it fits into the body 140, the width of the groove 122 gradually decreases from the time of attachment.
　そして、図５に示すように、粘着シート１００を覆うコーティング層１５１が形成されるまでの間に、溝１２２は消失する。 Then, as shown in FIG. 5, the groove 122 disappears before the coating layer 151 covering the adhesive sheet 100 is formed.
　その際、粘着剤層１２０が柔軟で変形し易ければ、溝１２２の消失が妨げられ難いため、好ましい。粘着剤層１２０の柔軟さは、例えば、貯蔵弾性率によって表され、貯蔵弾性率が大きいほど粘着剤層１２０は硬く変形し難く、反対に、貯蔵弾性率が小さいほど粘着剤層１２０は柔軟で変形し易い。 At that time, if the pressure-sensitive adhesive layer 120 is flexible and easily deformed, disappearance of the groove 122 is not easily prevented, which is preferable. The flexibility of the pressure-sensitive adhesive layer 120 is represented by, for example, the storage elastic modulus. The higher the storage elastic modulus is, the harder the pressure-sensitive adhesive layer 120 is to be deformed, and the smaller the storage elastic modulus is, the softer the pressure-sensitive adhesive layer 120 is. Easy to deform.
　貯蔵弾性率は、例えばＡｎｔｏｎ－Ｐａａｒ社製ＭＣＲを用いて測定される。具体的に、直径８ｍｍ厚さ１ｍｍの円板状をした粘着剤の試験片に、１Ｈｚの周波数で周期的な周方向の力を加えつつ、－５０℃から１５０℃の範囲で温度を変化させて貯蔵弾性率の温度依存性を求め、２３℃における測定値をもって貯蔵弾性率とする。 The storage elastic modulus is measured using, for example, MCR manufactured by Anton-Paar. Specifically, the temperature was changed in the range of -50 ° C to 150 ° C while applying a cyclic circumferential force at a frequency of 1 Hz to a disc-shaped adhesive test piece having a diameter of 8 mm and a thickness of 1 mm. The temperature dependence of the storage elastic modulus is determined by using the measured value at 23 ° C. as the storage elastic modulus.
　こうして測定される粘着剤層１２０の貯蔵弾性率は、好ましくは、１．０×１０４Ｐａ以上１．０×１０６Ｐａ以下、より好ましくは、２．０×１０４Ｐａ以上３．０×１０５Ｐａ以下である。 The storage elastic modulus of the pressure-sensitive adhesive layer 120 thus measured is preferably 1.0 × 10 4 Pa or more and 1.0 × 10 6 Pa or less, more preferably 2.0 × 10 4 Pa or more and 3.0 ×. It is 10 5 Pa or less.
　コーティング層１５１は、コーティング剤１５０の塗布によって、粘着シート１００全体を覆うように形成され、その後、乾燥される。コーティング層１５１は、透明な樹脂層であり、粘着シート１００はコーティング層１５１に被覆された状態でもはっきりと視認可能である。コーティング層１５１は、粘着シート１００が傷ついたり汚れたりするのを防止する。また、粘着シート１００の端部と被着体１４０にまたがってコーティング層１５１が形成されていることによって、粘着シート１００が剥がれ難い。 The coating layer 151 is formed by coating the coating agent 150 so as to cover the entire pressure-sensitive adhesive sheet 100, and then dried. The coating layer 151 is a transparent resin layer, and the adhesive sheet 100 is clearly visible even when it is covered with the coating layer 151. The coating layer 151 prevents the pressure-sensitive adhesive sheet 100 from being damaged or soiled. Further, since the coating layer 151 is formed across the end portion of the adhesive sheet 100 and the adherend 140, the adhesive sheet 100 is difficult to peel off.
　図６に示す比較例の粘着シート１００Ａのように、本実施形態と異なり、溝１２２Ａのある状態でコーティング層１５１が形成されると、溝１２２Ａでは気体が残存したまま出口が塞がれ、溝１２２Ａに残存する気体が閉じ込められる。そのまま例えばコーティング層１５１の加熱乾燥や環境変化にともなって温度上昇すると、溝１２２Ａに閉じ込められている気体が膨張し、コーティング層１５１が内側から押圧される。 Unlike the adhesive sheet 100A of the comparative example shown in FIG. 6, unlike the present embodiment, when the coating layer 151 is formed with the groove 122A, the outlet is blocked in the groove 122A while the gas remains, and The gas remaining in 122A is trapped. When the temperature of the coating layer 151 rises as it is due to heating and drying of the coating layer 151 or a change in environment, the gas trapped in the groove 122A expands and the coating layer 151 is pressed from the inside.
　その結果、図７に示すように、膨れ１５１Ａが生じてしまう虞がある。膨れ１５１Ａが生じると、外観不良となり、好ましくない。一方、本実施形態では、コーティング層１５１が形成されるまでの間に溝１２２は消失するため、そのようなことが生じ難い。 As a result, as shown in FIG. 7, a bulge 151A may occur. When the bulge 151A is generated, the appearance becomes poor, which is not preferable. On the other hand, in the present embodiment, since the groove 122 disappears before the coating layer 151 is formed, such a phenomenon is unlikely to occur.
　図８に示すように、本実施形態の溝１２２では、頂角α１よりも他の２角α２、α３のそれぞれが小さく、粘着剤層１２０が被着体１４０に接した際、溝１２２の縁１２３が被着体１４０に近接し、さらに、粘着剤層１２０の表面が３０ｍＮ／ｍ以上の濡れ指数を有し濡れ易い。そのため、縁１２３の部分から粘着剤層１２０が被着体１４０に速く馴染んでいき、溝１２２の消失が効果的に促される。 As shown in FIG. 8, in the groove 122 of the present embodiment, each of the other two angles α2 and α3 is smaller than the apex angle α1, and when the adhesive layer 120 contacts the adherend 140, the edge of the groove 122 is small. 123 is close to the adherend 140, and the surface of the pressure-sensitive adhesive layer 120 has a wetting index of 30 mN / m or more and is easily wet. Therefore, the pressure-sensitive adhesive layer 120 quickly adapts to the adherend 140 from the edge 123, and the disappearance of the groove 122 is effectively promoted.
　また、溝１２２は、縁１２３の部分から速やかに消失していく一方で、中央部分では頂角α１が形成されていることによって、端部まで連通する隙間が相対的に確保され易い。本実施形態と異なり、例えば断面形状が台形の溝では、中央部分が潰れ易いため、溝が途切れ、本実施形態の頂角α１のような機能は期待でき難い。しかし、本実施形態では、溝１２２が三角形の断面形状を有し、頂角α１が形成されていることによって、溝１２２の中央部分で相対的に隙間が確保され易い。 Further, while the groove 122 disappears rapidly from the edge 123 portion, the apex angle α1 is formed in the central portion, so that it is relatively easy to secure a gap communicating to the end portion. Unlike the present embodiment, for example, in the case of a groove having a trapezoidal cross-sectional shape, the central portion is easily crushed, so that the groove is interrupted and it is difficult to expect a function such as the apex angle α1 of the present embodiment. However, in this embodiment, since the groove 122 has a triangular cross-sectional shape and the apex angle α1 is formed, a gap is relatively easily secured in the central portion of the groove 122.
　このため、貼り付け時には、溝１２２の中央部分に確保される隙間を通じて、図３のような気泡Ｂの排出を可能にし、また、コーティング層１５１が形成されるまでには、縁１２３の部分からの溝１２２の効果的な消失促進によって中央部分でも隙間が消えており、溝１２２に残存する気体が無くなる。 Therefore, at the time of sticking, it is possible to discharge the bubbles B as shown in FIG. 3 through the gap secured in the central portion of the groove 122, and from the edge 123 portion until the coating layer 151 is formed. Due to the effective disappearance promotion of the groove 122, the gap disappears even in the central portion, and the gas remaining in the groove 122 disappears.
　従って、本実施形態によれば、貼り付け時においては粘着シート１００と被着体１４０との間に入り込む気泡Ｂに起因した膨れを抑制でき、さらに、貼り付け後のコーティングされた状態においては、溝１２２に残存する気体に起因した膨れを抑制できる。 Therefore, according to the present embodiment, it is possible to suppress the swelling caused by the bubbles B entering between the pressure-sensitive adhesive sheet 100 and the adherend 140 at the time of attachment, and further, in the coated state after attachment, Swelling due to the gas remaining in the groove 122 can be suppressed.
　粘着剤層１２０の貯蔵弾性率が、２３℃、１Ｈｚにおいて、１．０×１０４Ｐａ以上１．０×１０６Ｐａ以下であるようにすれば、粘着剤層１２０が、硬くなり過ぎず適度な柔軟さを有し、被着体１４０に馴染むよう変形し易いため、濡れ性による溝１２２の消失が妨げられ難い。 When the storage elastic modulus of the pressure-sensitive adhesive layer 120 is set to 1.0 × 10 4 Pa or more and 1.0 × 10 6 Pa or less at 23 ° C. and 1 Hz, the pressure-sensitive adhesive layer 120 does not become too hard and is moderate. Since it has a high degree of flexibility and is easily deformed to fit the adherend 140, it is difficult to prevent the disappearance of the groove 122 due to wettability.
　＜実施例＞
　本発明者は、上記実施形態の粘着シート１００に準じた構成を有する実施例１～９の粘着シートを実際に作製した。作製した実施例１～９の粘着シートでは、基材層がポリ塩化ビニルによって５０μｍの厚みで形成されており、粘着剤層がアクリル系粘着剤によって２５μｍの厚みで形成されている。また、実施例１～９の粘着シートは、１００ｍｍ×５０ｍｍの大きさを有する。実施例１～９の粘着シートのそれぞれでは、粘着剤層の濡れ指数および貯蔵弾性率（２３℃、１Ｈｚ）が異なるが、他の構成については共通している。 <Example>
The present inventor actually manufactured the pressure-sensitive adhesive sheets of Examples 1 to 9 having a configuration similar to that of the pressure-sensitive adhesive sheet 100 of the above embodiment. In the produced pressure-sensitive adhesive sheets of Examples 1 to 9, the base material layer was formed of polyvinyl chloride to a thickness of 50 μm, and the pressure-sensitive adhesive layer was formed of an acrylic pressure-sensitive adhesive to a thickness of 25 μm. The pressure-sensitive adhesive sheets of Examples 1 to 9 have a size of 100 mm × 50 mm. The adhesive sheets of Examples 1 to 9 differ in the wetting index and the storage elastic modulus (23 ° C., 1 Hz) of the adhesive layer, but the other configurations are common.
　また、本発明者は、粘着剤層に形成された溝の断面形状が実施例とは異なる比較例１～３の粘着シートを作製した。比較例１～３の粘着シートは、粘着剤層に形成された溝の断面形状以外については、実施例１～９のいずれかと同様の構成を有する。 The present inventor also manufactured the pressure-sensitive adhesive sheets of Comparative Examples 1 to 3 in which the cross-sectional shape of the groove formed in the pressure-sensitive adhesive layer was different from that of the example. The pressure-sensitive adhesive sheets of Comparative Examples 1 to 3 have the same configurations as those of Examples 1 to 9 except for the cross-sectional shape of the grooves formed in the pressure-sensitive adhesive layer.
　図９に示すように、比較例１～３の粘着シート１００Ａにおいて、粘着剤層に形成された溝１２２Ａは、頂角α１よりも他の２角α２、α３のそれぞれが大きい三角形の断面形状（α１＜α２、α１＜α３）を有し、図２で示したような実施例の溝の断面形状とは異なっている。溝１２２Ａの断面形状以外の構成については、比較例の粘着シート１００Ａは、実施例と同じである。 As shown in FIG. 9, in the pressure-sensitive adhesive sheets 100A of Comparative Examples 1 to 3, the groove 122A formed in the pressure-sensitive adhesive layer has a triangular cross-sectional shape in which the other two angles α2 and α3 are larger than the apex angle α1 ( α1 <α2, α1 <α3), which is different from the cross-sectional shape of the groove of the embodiment as shown in FIG. The adhesive sheet 100A of the comparative example has the same configuration as that of the example except for the cross-sectional shape of the groove 122A.
　本発明者は、実施例１～９および比較例１～３の粘着シートを、アクリル塗装板に貼り付け、それらにラッカー塗料を吹き付けた後、１７０℃の環境下で３０分間放置し、粘着シートの縁に膨れが生じるか否かを確認した。 The present inventor adhered the pressure-sensitive adhesive sheets of Examples 1 to 9 and Comparative Examples 1 to 3 to acrylic coated plates, sprayed them with a lacquer paint, and left them in an environment of 170 ° C. for 30 minutes to obtain a pressure-sensitive adhesive sheet. It was confirmed whether or not a bulge was generated at the edge of the.
　下の表１に、実施例１～９および比較例１～３の粘着シートの構成の違い、およびそれらについての膨れの試験結果をまとめて示す。比較例１と実施例５、比較例２と実施例７、および比較例３と実施例９のそれぞれについて、互いの構成を比較すると、それらは、溝の断面形状だけが異なっており、濡れ指数や貯蔵弾性率等の他の構成は同じである。 Table 1 below shows the difference in the constitution of the pressure-sensitive adhesive sheets of Examples 1 to 9 and Comparative Examples 1 to 3 and the swelling test results thereof. Comparing the respective configurations of Comparative Example 1 and Example 5, Comparative Example 2 and Example 7, and Comparative Example 3 and Example 9, they differ only in the cross-sectional shape of the groove and the wetting index And other configurations such as storage elastic modulus are the same.
　表１の「膨れ」の欄において、○は膨れが生じなかったことを表し、△は微細な膨れが生じたが外観に大きな影響を及ぼさない程度であることを表し、×は外観が損なわれる程の大きな膨れが生じたことを表す。 In the column “Blistering” in Table 1, “◯” means that no blistering occurred, “Δ” means that minute blistering occurred but the appearance was not greatly affected, and “x” impairs the appearance. This indicates that a moderate swelling has occurred.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の「膨れ」の結果を参照すると、実施例の粘着シートではいずれも膨れが抑制されたのに対し、比較例の粘着シートでは膨れによって外観が損なわれており、本願発明に基づく粘着剤層の特徴的構成によれば、貼り付け時だけでなく、貼り付け後のコーティングされた状態においても膨れが効果的に抑制されることが確認できた。 Referring to the result of "blister" in Table 1, the swelling was suppressed in each of the pressure-sensitive adhesive sheets of Examples, whereas the appearance was impaired by the swelling in the pressure-sensitive adhesive sheets of Comparative Examples. It was confirmed that, according to the characteristic structure of the layer, the swelling was effectively suppressed not only at the time of application but also in the coated state after application.
　本発明は、上述した実施形態に限定されるものではなく、特許請求の範囲内で種々改変できる。 The present invention is not limited to the above-described embodiment, but can be variously modified within the scope of the claims.
　例えば、上記実施形態の図５は、一例として溝１２２が完全に無くなった状態を模式的に示しているが、コーティング後の膨れ防止が可能なように溝の消失が効果的に促されるのであれば、必ずしも全ての溝が完全に消失する形態に限定されない。 For example, FIG. 5 of the above-described embodiment schematically shows a state in which the groove 122 is completely eliminated as an example, but the disappearance of the groove is effectively promoted so as to prevent swelling after coating. For example, it is not necessarily limited to the form in which all the grooves are completely eliminated.
　また、上記実施形態の粘着シート１００は、基材層１１０、粘着剤層１２０、および剥離ライナー１３０を有するが、それら以外の層が設けられた粘着シートも本発明の範囲に含まれる。 The pressure-sensitive adhesive sheet 100 of the above embodiment has the base layer 110, the pressure-sensitive adhesive layer 120, and the release liner 130, but a pressure-sensitive adhesive sheet provided with layers other than these is also included in the scope of the present invention.
１００　　実施形態の粘着シート、
１００Ａ　　比較例の粘着シート、
１１０　　基材層、
１１１　　基材層の一方の面、
１１２　　基材層の他方の面、
１２０　　粘着剤層、
１２１　　粘着剤層の表面、
１２２　　実施形態の溝、
１２２Ａ　　比較例の溝、
１２３　　実施形態の溝の縁、
１３０　　剥離ライナー、
１３１　　突部、
１４０　　被着体、
１５０　　コーティング剤、
１５１　　コーティング層、
１５１Ａ　　比較例においてコーティング後に生じた膨れ、
Ｂ　　気泡、
α１　　基材層の側に凸となった頂角、
α２、α３　　頂角と異なる他の２角。 100 adhesive sheet of the embodiment,
100A pressure-sensitive adhesive sheet of a comparative example,
110 base material layer,
111 One surface of the base material layer,
112 the other surface of the base material layer,
120 adhesive layer,
121 surface of adhesive layer,
122 Embodiment Groove,
122A comparative example groove,
123 edge of groove of embodiment,
130 release liner,
131 protrusions,
140 adherend,
150 coating agents,
151 coating layer,
151A swelling that occurred after coating in Comparative Example,
B bubbles,
The apex angle that is convex on the side of the α1 substrate layer,
α2, α3 Other two angles different from the apex angle.

Claims (3)

  1. 　基材層と、当該基材層の一方の面の側に設けられた粘着剤層と、を有し、前記粘着剤層の表面に溝が形成された粘着シートであって、
    　前記溝は、前記基材層の側に凸となった頂角よりも他の２角のそれぞれが小さい三角形の断面形状を有し、
    　前記粘着剤層は、ＩＳＯ８２９６に準拠して測定される濡れ指数が３０ｍＮ／ｍ以上である前記表面を有する、粘着シート。     A pressure-sensitive adhesive sheet having a base material layer and a pressure-sensitive adhesive layer provided on one surface side of the base material layer, wherein a groove is formed on the surface of the pressure-sensitive adhesive layer,
    The groove has a triangular cross-sectional shape in which each of the other two corners is smaller than the apex angle that is convex toward the base material layer,
    The pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive layer has the surface having a wetting index of 30 mN / m or more measured according to ISO8296.
  2. 　前記粘着剤層の貯蔵弾性率は、２３℃、１Ｈｚにおいて、１．０×１０４Ｐａ以上１．０×１０６Ｐａ以下である、請求項１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer has a storage elastic modulus of 1.0 × 10 4 Pa or more and 1.0 × 10 6 Pa or less at 23 ° C. and 1 Hz.
  3. 　請求項１または請求項２に記載の粘着シートを、被着体に貼り付け、前記粘着シートおよび前記被着体にまたがってコーティングを施す、粘着シートの使用方法。 A method of using a pressure-sensitive adhesive sheet, which comprises applying the pressure-sensitive adhesive sheet according to claim 1 or 2 to an adherend and applying a coating over the pressure-sensitive adhesive sheet and the adherend.
PCT/JP2018/039945 2018-10-26 2018-10-26 Pressure-sensitive adhesive sheet and method of using pressure-sensitive adhesive sheet WO2020084783A1 (en)

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WO2003025078A1 (en) * 2001-09-14 2003-03-27 Lintec Corporation Easily stuck adhesive sheet and its manufacture method
JP2017082032A (en) * 2015-10-23 2017-05-18 王子ホールディングス株式会社 Adhesive sheet

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