WO2022131163A1 - 粘着シート - Google Patents

粘着シート Download PDF

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Publication number
WO2022131163A1
WO2022131163A1 PCT/JP2021/045595 JP2021045595W WO2022131163A1 WO 2022131163 A1 WO2022131163 A1 WO 2022131163A1 JP 2021045595 W JP2021045595 W JP 2021045595W WO 2022131163 A1 WO2022131163 A1 WO 2022131163A1
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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
weight
resin
adhesive layer
Prior art date
Application number
PCT/JP2021/045595
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English (en)
French (fr)
Japanese (ja)
Inventor
茂樹 渡辺
健一 山元
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.)
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202180080742.8A priority Critical patent/CN116568769A/zh
Publication of WO2022131163A1 publication Critical patent/WO2022131163A1/ja

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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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.
  • a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive; the same applies hereinafter) exhibits a soft solid state (viscous elastic body) in a temperature range near room temperature, and has a property of adhering to an adherend by pressure.
  • adhesives are widely used in various industrial fields such as home appliances, automobiles, and OA equipment, typically in the form of adhesive sheets containing an adhesive layer, for the purpose of joining parts and protecting the surface. It's being used.
  • Patent Documents 1 and 2 are mentioned as technical documents relating to the pressure-sensitive adhesive sheet.
  • Adhesive sheets are required to have various performances depending on the application.
  • an adhesive used to be attached to a surface (low surface free energy surface; hereinafter also referred to as "LSE surface") made of a material having a low surface free energy such as polyethylene (PE), polypropylene (PP), and fluororesin.
  • the agent is required to exhibit stable adhesion performance to the LSE surface.
  • some of the members constituting electronic devices such as the above-mentioned home appliances are made of PE, PP, fluororesin, etc., and an adherend having such an LSE surface (hereinafter referred to as "LSE adherend").
  • LSE adherend an adherend having such an LSE surface
  • the above-mentioned pressure-sensitive adhesive is required to have a certain level of adhesive strength or higher.
  • the adhesive strength of the pressure-sensitive adhesive tends to decrease with respect to the LSE surface.
  • the rubber-based adhesive is known to be relatively easy to adhere to the LSE surface, but it is easily deteriorated and it is difficult to maintain stable adhesive performance for a long period of time.
  • the adhesive area of the adhesive tends to be smaller due to the demand for miniaturization, weight reduction, and precision of electronic devices and the like in which the LSE adherend is used. Therefore, it is becoming more difficult to obtain sufficient adhesive reliability for the LSE surface in various products.
  • the present invention has been created in view of the above circumstances, and an object of the present invention is to provide an acrylic pressure-sensitive adhesive sheet having good holding power and improved adhesive strength to a low surface free energy surface.
  • a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer contains an acrylic polymer and a pressure-sensitive adhesive resin. Further, in the acrylic polymer, an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal is polymerized at a ratio of 15% by weight or more. Further, in the acrylic polymer, the carboxy group-containing monomer is not copolymerized, or the copolymerization ratio of the carboxy group-containing monomer is less than 10% by weight. Further, the content of the tackifier resin in the pressure-sensitive adhesive layer is 40 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the acrylic polymer.
  • the pressure-sensitive adhesive layer contains the pressure-sensitive adhesive resin TL having a softening point of 110 ° C. or lower as the pressure-sensitive adhesive resin.
  • the tackifier resin TL occupies 60% by weight or more of the total amount of the tackifier resin contained in the pressure-sensitive adhesive layer.
  • the adhesive sheet configured as described above can exhibit an improved adhesive force with respect to a low surface free energy surface (LSE surface) while having a good holding force.
  • LSE surface low surface free energy surface
  • the pressure-sensitive adhesive layer contains a rosin-based pressure-sensitive adhesive resin as the pressure-sensitive adhesive resin.
  • the rosin-based tackifier resin By using the rosin-based tackifier resin, the adhesive strength to the LSE surface is preferably improved.
  • the pressure-sensitive adhesive layer is free of terpene phenolic resin or contains the terpenephenolic resin in a proportion of less than 5 parts by weight relative to 100 parts by weight of the acrylic polymer.
  • the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer comprises an epoxy-based cross-linking agent.
  • an epoxy-based cross-linking agent as the cross-linking agent for the acrylic-based pressure-sensitive adhesive, a predetermined amount of the tack-imparting resin containing the above-mentioned tack-imparting resin TL , which exhibits a low softening point, is contained to obtain adhesive strength to the LSE surface. It can preferably have a good holding force.
  • the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer comprises an isocyanate-based cross-linking agent and an epoxy-based cross-linking agent.
  • an isocyanate-based cross-linking agent and an epoxy-based cross-linking agent in combination as the cross-linking agent more excellent performance can be suitably realized.
  • the pressure-sensitive adhesive sheet is configured as a base-less double-sided pressure-sensitive adhesive sheet composed of only the pressure-sensitive adhesive layer.
  • the base material-less double-sided adhesive sheet can be made thinner because it does not have a base material, and can contribute to miniaturization and space saving of products to which the double-sided pressure-sensitive adhesive sheet is applied. Further, according to the base material-less pressure-sensitive adhesive sheet, the action of the pressure-sensitive adhesive such as adhesive strength can be maximized.
  • the base material-less pressure-sensitive adhesive sheet is strongly demanded for miniaturization and weight reduction, and is suitable for applications of portable electronic devices in which a thin pressure-sensitive adhesive sheet is desirable.
  • the pressure-sensitive adhesive sheet is configured as a pressure-sensitive adhesive sheet having a base material and the pressure-sensitive adhesive layer provided on at least one surface of the base material.
  • a pressure-sensitive adhesive sheet provided with a base material such as a resin film base material is excellent in handleability and processability, and thus can be used by being processed into various shapes in various applications.
  • the adhesive sheet disclosed herein has a good holding force and an improved adhesive force to the LSE surface, so that the adhesive sheet has an LSE surface as an adherend surface and is required to have long-term adhesive reliability.
  • the adhesive sheet disclosed herein is suitable for fixing a member in an electronic device including a home electric appliance, an OA device, a portable electronic device such as a smartphone, and the like.
  • Some of the members constituting the electronic device have an LSE surface made of a material such as PE, PP, or fluororesin, and by applying the adhesive sheet disclosed here, the LSE adherend can be treated. It is possible to realize adhesive fixing with excellent adhesive reliability. From the above, according to this specification, an electronic device using any of the pressure-sensitive adhesive sheets disclosed herein, in other words, an electronic device including the pressure-sensitive adhesive sheet is provided.
  • the term "adhesive” as used herein refers to a material that exhibits a soft solid state (viscoelastic body) in a temperature range near room temperature and has the property of easily adhering to an adherend by pressure. ..
  • the pressure-sensitive adhesive here is generally defined as "C. A. Dahlquist,” Adhesion: Fundamental and Practice “, McLaren & Sons, (1966) P. 143", and generally has a complex tensile modulus E * (1 Hz). It can be a material having a property of satisfying ⁇ 107 dyne / cm 2 (typically, a material having the above-mentioned property at 25 ° C.).
  • the pressure-sensitive adhesive sheet disclosed herein is configured to include a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet is, for example, a base material-less double-sided pressure-sensitive adhesive sheet comprising a first pressure-sensitive adhesive surface formed of one surface of the pressure-sensitive adhesive layer and a second pressure-sensitive adhesive surface formed of the other surface of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet disclosed herein may be in the form of a pressure-sensitive adhesive sheet with a base material in which the pressure-sensitive adhesive layer is laminated on one side or both sides of a supporting base material.
  • the supporting base material may be simply referred to as a “base material”.
  • the concept of the pressure-sensitive adhesive sheet here may include what is called an pressure-sensitive adhesive tape, a pressure-sensitive adhesive label, a pressure-sensitive adhesive film, or the like.
  • the pressure-sensitive adhesive sheet disclosed herein may be in the form of a roll or in the form of a single leaf. Alternatively, the pressure-sensitive adhesive sheet may be further processed into various shapes.
  • the structure of the adhesive sheet according to the embodiment is schematically shown in FIG.
  • the pressure-sensitive adhesive sheet 1 is configured as a base-less double-sided pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer 21.
  • the pressure-sensitive adhesive sheet 1 has a first pressure-sensitive adhesive surface 21A composed of one surface (first surface) of the pressure-sensitive adhesive layer 21 and a second pressure-sensitive adhesive surface composed of the other surface (second surface) of the pressure-sensitive adhesive layer 21.
  • 21B and 21B are attached to different parts of the adherend and used.
  • the locations where the adhesive surfaces 21A and 21B are attached may be the respective locations of different members, or may be different locations within a single member. As shown in FIG.
  • the adhesive sheet 1 before use (that is, before being attached to the adherend) has the first adhesive surface 21A and the second adhesive surface 21B peeled off at least on the side facing the adhesive layer 21.
  • It can be a component of the pressure-sensitive adhesive sheet 100 with a release liner in a form protected by the release liners 31, 32 that are surfaces.
  • the peeling liners 31 and 32 for example, those configured by providing a peeling layer with a peeling treatment agent on one side of a sheet-shaped base material (liner base material) so that one side becomes a peeling surface are preferably used. obtain.
  • the peeling liner 32 is omitted, and a peeling liner 31 having both sides as peeling surfaces is used, and the adhesive sheet 1 is overlapped with the peeling liner 31 and wound in a spiral shape so that the second adhesive surface 21B becomes the peeling liner 31.
  • An adhesive sheet with a release liner in a protected form may be configured by abutting against the back surface of the surface.
  • the structure of the adhesive sheet according to the other embodiment is schematically shown in FIG.
  • the pressure-sensitive adhesive sheet 2 is a base material including a sheet-shaped support base material (for example, a resin film) 10 having a first surface 10A and a second surface 10B, and an adhesive layer 21 provided on the first surface 10A side thereof. It is configured as a single-sided adhesive sheet with an attachment.
  • the pressure-sensitive adhesive layer 21 is provided fixedly on the first surface 10A side of the support base material 10, that is, without the intention of separating the pressure-sensitive adhesive layer 21 from the support base material 10. As shown in FIG.
  • the pressure-sensitive adhesive sheet 2 before use is protected by a release liner 31 in which the surface (adhesive surface) 21A of the pressure-sensitive adhesive layer 21 is at least a peel-off surface on the side facing the pressure-sensitive adhesive layer 21.
  • a release liner 31 in which the surface (adhesive surface) 21A of the pressure-sensitive adhesive layer 21 is at least a peel-off surface on the side facing the pressure-sensitive adhesive layer 21.
  • the release liner 31 is omitted, the support base material 10 having the second surface 10B as the release surface is used, and the adhesive sheet 2 is wound so that the adhesive surface 21A becomes the second surface (back surface) of the support base material 10.
  • It may be in a form (roll form) in which it is in contact with 10B and protected.
  • the structure of the adhesive sheet according to still another embodiment is schematically shown in FIG.
  • the pressure-sensitive adhesive sheet 3 includes a sheet-shaped support base material (for example, a resin film) 10 having a first surface 10A and a second surface 10B, and a first pressure-sensitive adhesive layer 21 fixedly provided on the first surface 10A side thereof. It is configured as a double-sided pressure-sensitive adhesive sheet with a base material, which comprises a second pressure-sensitive adhesive layer 22 fixedly provided on the second side surface 10B side.
  • the surface (first adhesive surface) 21A of the first adhesive layer 21 and the surface (second adhesive surface) 22A of the second adhesive layer 22 are peeling liners 31.
  • 32 may be a component of the adhesive sheet 300 with a release liner in a form protected by 32.
  • the peeling liner 32 is omitted, and a peeling liner 31 having both sides as peeling surfaces is used, and the adhesive sheet 3 is overlapped with the peeling liner 31 and wound in a spiral shape so that the second adhesive surface 22A becomes the peeling liner 31.
  • An adhesive sheet with a release liner in a protected form may be configured by abutting against the back surface of the surface.
  • the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be the pressure-sensitive adhesive layer described below.
  • the other pressure-sensitive adhesive layer (for example, the second pressure-sensitive adhesive layer) may be the pressure-sensitive adhesive layer disclosed herein, and the pressure-sensitive adhesive layer disclosed herein (specifically, one of the above-mentioned adhesive layers) may be used. It may be a pressure-sensitive adhesive layer having a composition different from that of the agent layer (for example, the first pressure-sensitive adhesive layer).
  • the other such pressure-sensitive adhesive layer may be formed from, for example, a known or conventional pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet disclosed herein contains an acrylic polymer.
  • the pressure-sensitive adhesive layer is typically a pressure-sensitive adhesive layer using an acrylic polymer as a base polymer (a main component of the polymer component, that is, a component occupying 50% by weight or more).
  • a pressure-sensitive adhesive layer is also referred to as an acrylic pressure-sensitive adhesive layer.
  • the base polymer refers to the main component of a rubber-like polymer (a polymer that exhibits rubber elasticity in a temperature range near room temperature) contained in the pressure-sensitive adhesive layer.
  • the “main component” refers to a component contained in an amount of more than 50% by weight, unless otherwise specified.
  • the following description regarding the pressure-sensitive adhesive and the components that may be contained in the pressure-sensitive adhesive layer is also applicable to the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive (layer) unless otherwise specified.
  • the “acrylic polymer” refers to a polymer containing a monomer unit derived from a monomer having at least one (meth) acryloyl group in one molecule as a monomer unit constituting the polymer. ..
  • a monomer having at least one (meth) acryloyl group in one molecule is also referred to as an “acrylic monomer”. Therefore, the acrylic polymer in this specification is defined as a polymer containing a monomer unit derived from an acrylic monomer.
  • “(meth) acryloyl” means acryloyl and methacryloyl comprehensively.
  • “(meth) acrylate” means acrylate and methacrylate
  • “(meth) acrylic” means acrylic and methacrylic, respectively.
  • ком ⁇ онент As the acrylic polymer used in the technique disclosed herein, a polymer of a monomer raw material containing an alkyl (meth) acrylate as a main monomer and further containing a submonomer having copolymerizability with the main monomer is preferable.
  • the main monomer means a component that occupies more than 50% by weight of the monomer composition in the above-mentioned 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.
  • such a range of the number of carbon atoms may be expressed as "C 1-20 ".
  • the main monomer may be an alkyl (meth) acrylate in which R 2 is a chain alkyl group of C 1-14 (for example, C 2-10 or C 4-8 ). Appropriate.
  • the main monomer is an alkyl acrylate in which R 1 is a hydrogen atom and R 2 is a chain alkyl group of C 4-8 (hereinafter, also simply referred to as C 4-8 alkyl acrylate). Is preferable.
  • alkyl (meth) acrylate in which R 2 is a C 1-20 chain alkyl group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl.
  • alkyl (meth) acrylates can be used alone or in combination of two or more.
  • Preferred alkyl (meth) acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
  • an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal is polymerized at a ratio of 15% by weight or more.
  • the adhesive force with respect to the LSE surface is improved.
  • Alkyl (meth) acrylates having an alkyl group having 6 or more carbon atoms at the ester terminal typically have an alkyl group having 6 or more carbon atoms and 20 or less carbon atoms at the ester terminal. It is a (meth) acrylate (ie, C 6-20 alkyl (meth) acrylate).
  • the number of carbon atoms of the alkyl group of the C 6-20 alkyl (meth) acrylate is preferably 7 or more, and more preferably 8 or more, from the viewpoint of adhesion to the LSE surface.
  • the upper limit of the number of carbon atoms of the alkyl group of the C 6-20 alkyl (meth) acrylate may be, for example, 14 or less, or 12 or less, from the viewpoint of compatibility with the tackifier resin and viscoelastic properties. It may be 10 or less, or 9 or less.
  • the alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal, which is used as a monomer unit of the acrylic polymer in a proportion of 15% by weight or more is preferably C6-14 alkyl (C 6-14 alkyl).
  • the polymerization ratio of the alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal in the acrylic polymer may be 20% by weight or more from the viewpoint of adhesion to the LSE surface, and is preferably 30.
  • weight% or more more preferably 40% by weight or more, still more preferably 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more. (For example, 92% by weight or more) may be used.
  • the upper limit of the polymerization ratio of the alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal is, for example, 99.9% by weight or less, and 99% by weight or less is appropriate from the viewpoint of holding power and the like. Yes, preferably 97% by weight or less, for example, 75% by weight or less, or less than 50% by weight.
  • the proportion of alkyl (meth) acrylate in all the monomer components used in the synthesis of the acrylic polymer is preferably 70% by weight or more, more preferably 85% by weight or more, and further preferably 90% by weight or more.
  • the upper limit of the ratio of the alkyl (meth) acrylate is not particularly limited, but it is usually appropriate to be 99.5% by weight or less (for example, 99% by weight or less), and the action of an accessory monomer such as a carboxy group-containing monomer is preferable. From the viewpoint of expression in the above, it is preferably about 98% by weight or less (for example, 97% by weight or less).
  • Acrylic polymers in the techniques disclosed herein may be copolymerized with submonomers.
  • a carboxy group-containing monomer, a hydroxyl group (OH group) -containing monomer, an acid anhydride group-containing monomer, and an amide group are contained as auxiliary monomers that can introduce a functional group that can serve as a cross-linking base point into an acrylic polymer or contribute to the improvement of adhesive strength.
  • Monomers ((meth) acrylamide, N, N-dimethyl (meth) acrylamide, etc.), amino group-containing monomers (aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, etc.), epoxy group-containing monomers, Examples include a cyano group-containing monomer, a keto group-containing monomer, a monomer having a nitrogen atom-containing ring (N-vinyl-2-pyrrolidone, N- (meth) acryloylmorpholine, etc.), an alkoxysilyl group-containing monomer, an imide group-containing monomer, and the like. Be done. As the submonomer, one type may be used alone or two or more types may be used in combination.
  • the content of the functional group-containing monomer in the monomer component is not particularly limited.
  • the content of the functional group-containing monomer in the monomer component can be, for example, 0.1% by weight or more, and 0.5% by weight or more. Is appropriate, and may be 1% by weight or more.
  • the content of the functional group-containing monomer in the monomer component is 40% by weight or less, and 20% by weight or less. Is preferable, and it may be 10% by weight or less (for example, 5% by weight or less).
  • the carboxy group-containing monomer is not substantially copolymerized, or the copolymerization ratio of the carboxy group-containing monomer is less than 10% by weight.
  • the fact that the carboxy group-containing monomer is not substantially copolymerized means that the carboxy group-containing monomer is not intentionally polymerized, or that the carboxy group-containing monomer is substantially copolymerized. It means that the copolymerization ratio of the carboxy group-containing monomer is less than 0.1% by weight (for example, less than 0.03% by weight, and further less than 0.01% by weight).
  • a carboxy group-containing monomer is used as the submonomer.
  • the carboxy group-containing monomer can exhibit an improvement in cohesiveness based on its polarity.
  • a cross-linking agent such as an isocyanate-based or epoxy-based cross-linking agent
  • the carboxy group serves as a cross-linking point of the acrylic polymer.
  • carboxy group-containing monomer examples include acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, and fumaric acid. Examples thereof include acid, crotonic acid, and isocrotonic acid. Among them, AA and MAA are mentioned as preferable carboxy group-containing monomers. AA is particularly preferred.
  • the carboxy group-containing monomer may be used alone or in combination of two or more.
  • the content thereof is about 0.1% by weight or more of all the monomer components, preferably about 0.5% by weight. % Or more, more preferably about 1.0% by weight or more, still more preferably about 2.0% by weight or more (for example, more than 2.0% by weight), and particularly preferably 3.0% by weight or more (for example, 3.0% by weight). It may be 4.0% by weight or more (for example, 4.5% by weight or more).
  • the content of the carboxy group-containing monomer increases, the cohesive force of the pressure-sensitive adhesive layer generally tends to improve.
  • the amount of the carboxy group-containing monomer is preferably 8% by weight or less of all the monomer components, preferably about 7% by weight or less, more preferably about 6% by weight or less, for example, about 3% by weight. It may be as follows. By setting the amount of the carboxy group-containing monomer used in the above range, a pressure-sensitive adhesive layer exhibiting good adhesion to the LSE adherend can be suitably realized.
  • the copolymerization component specifically, the functional group-containing monomer
  • 10% by weight or more of the functional group-containing monomer used may be the carboxy group-containing monomer.
  • the ratio of the carboxy group-containing monomer to the total functional group-containing monomer is preferably 30% by weight or more, preferably 50% by weight or more.
  • the upper limit of the ratio of the carboxy group-containing monomer to the entire functional group-containing monomer is 100% by weight, and may be, for example, 95% by weight or less.
  • an acrylic polymer in which a hydroxyl group-containing monomer is copolymerized as the submonomer can be mentioned.
  • the hydroxyl group-containing monomer may be copolymerized with the carboxy group-containing monomer.
  • examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
  • Hydroxyalkyl (meth) acrylates such as acrylates; polypropylene glycol mono (meth) acrylates; N-hydroxyethyl (meth) acrylamides and the like.
  • the hydroxyl group-containing monomer may be used alone or in combination of two or more.
  • the content thereof is usually preferably about 0.001% by weight or more of all the monomer components, and preferably about 0.01% by weight or more (typically). Generally, it is about 0.02% by weight or more).
  • the content of the hydroxyl group-containing monomer is preferably about 10% by weight or less, preferably about 5% by weight or less, and more preferably about 2% by weight or less in the total monomer components.
  • the technique disclosed herein can be carried out by using a pressure-sensitive adhesive containing an acrylic polymer in which the hydroxyl group-containing monomer is not copolymerized.
  • the monomer component constituting the acrylic polymer may contain a copolymerization component other than the above-mentioned submonomer for the purpose of improving the cohesive force and the like.
  • copolymerization components include vinyl ester-based monomers such as vinyl acetate; aromatic vinyl compounds such as styrene; cycloalkyl (meth) such as cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, and isobornyl (meth) acrylate.
  • aryl (meth) acrylate eg, phenyl (meth) acrylate
  • aryloxyalkyl (meth) acrylate eg, phenoxyethyl (meth) acrylate
  • arylalkyl (meth) acrylate eg, benzyl (meth) acrylate
  • Group-containing monomers; vinyl ether-based monomers such as methyl vinyl ether and ethyl vinyl ether; and the like can be mentioned.
  • the above-mentioned other copolymerization components may be used alone or in combination of two or more.
  • the amount of the other copolymerization component may be appropriately selected depending on the purpose and application, and is not particularly limited, but is appropriately set to 0.05% by weight or more from the viewpoint of appropriately exerting the effect of use. , 0.5% by weight or more may be used. Further, from the viewpoint of facilitating the balance of the adhesive performance, it is appropriate that the content of the other copolymerizing component in the monomer component is 20% by weight or less, and the adhesive property based on the main monomer is preferably exhibited. Therefore, it is preferably 10% by weight or less, more preferably 8% by weight or less, still more preferably less than 5% by weight, for example, less than 3% by weight, or less than 1% by weight.
  • the technique disclosed herein may also be preferably carried out in an embodiment in which the monomer component is substantially free of other copolymerization components.
  • the fact that the monomer component does not substantially contain other copolymerization components means that the other copolymerization components are not used at least intentionally, and the other copolymerization components are, for example, 0.01% by weight or less. To some extent, unintentional inclusion is acceptable.
  • Acrylic polymers are polyfunctional with at least two polymerizable functional groups (typically radically polymerizable functional groups) having unsaturated double bonds such as (meth) acryloyl groups and vinyl groups as other monomer components. It may contain a monomer. By using a polyfunctional monomer as the monomer component, the cohesive force of the pressure-sensitive adhesive layer can be enhanced.
  • the polyfunctional monomer can be used as a cross-linking agent.
  • the polyfunctional monomer is not particularly limited, and is, for example, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate. And so on.
  • the polyfunctional monomer may be used alone or in combination of two or more.
  • the amount of the polyfunctional monomer used is not particularly limited, and can be appropriately set so that the purpose of use of the polyfunctional monomer is achieved.
  • the amount of the polyfunctional monomer used can be about 3% by weight or less of the above-mentioned monomer component, preferably about 2% by weight or less, and more preferably about 1% by weight or less (for example, about 0.5% by weight or less).
  • the lower limit of the amount used may be larger than 0% by weight and is not particularly limited.
  • the amount of the polyfunctional monomer to be used in an amount of about 0.001% by weight or more (for example, about 0.01% by weight or more) of the monomer component the effect of using the polyfunctional monomer can be appropriately exhibited.
  • the copolymerization composition of the acrylic polymer is designed so that the Tg of the polymer is about ⁇ 15 ° C. or lower (typically, about ⁇ 70 ° C. or higher and ⁇ 15 ° C. or lower).
  • the Tg of the acrylic polymer means the Tg obtained by the Fox formula based on the composition of the monomer component used for the synthesis of the polymer.
  • the Fox formula is a relational formula between the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer.
  • Tg is the glass transition temperature (unit: K) of the copolymer
  • Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio based on the weight)
  • Tgi is the monomer i. Represents the glass transition temperature (unit: K) of the homopolymer.
  • the glass transition temperature of the homopolymer used for calculating Tg the value described in the publicly known material shall be used.
  • the monomers listed below the following values are used as the glass transition temperature of the homopolymer of the monomer.
  • the Tg of the acrylic polymer is about ⁇ 25 ° C. or lower, preferably about ⁇ 35 ° C. or lower, and more preferably about ⁇ 35 ° C. or lower. It may be ⁇ 45 ° C. or lower, more preferably ⁇ 55 ° C. or lower, particularly preferably ⁇ 60 ° C. or lower, and ⁇ 62 ° C. or lower (for example, ⁇ 64 ° C. or lower).
  • the low Tg of the acrylic polymer is also advantageous in terms of impact resistance. Further, from the viewpoint of the cohesive force of the pressure-sensitive adhesive layer, it is advantageous that the Tg of the acrylic polymer is about ⁇ 70 ° C.
  • the Tg of the acrylic polymer can be adjusted by appropriately changing the monomer composition (that is, the type and amount ratio of the monomers used in the synthesis of the polymer).
  • the method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for the acrylic polymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method. Can be adopted as appropriate.
  • a solution polymerization method can be preferably adopted.
  • a monomer supply method for solution polymerization a batch charging method, a continuous supply (drop) method, a split supply (drop) method, or the like in which all the monomer raw materials are supplied at once can be appropriately adopted.
  • the polymerization temperature can be appropriately selected depending on the type of the monomer and solvent used, the type of the polymerization initiator, etc., and is, for example, about 20 ° C to 170 ° C (typically about 40 ° C to 140 ° C). Can be done.
  • the solvent (polymerization solvent) used for solution polymerization can be appropriately selected from conventionally known organic solvents.
  • aromatic compounds such as toluene (typically aromatic hydrocarbons); acetates such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; 1,2-dichloroethane and the like.
  • Alkanes halogenated lower alcohols such as isopropyl alcohol (for example, monohydric alcohols having 1 to 4 carbon atoms); ethers such as tert-butylmethyl ether; ketones such as methyl ethyl ketone; etc. Any one kind of solvent or two or more kinds of mixed solvents can be used.
  • the initiator used for the polymerization can be appropriately selected from the conventionally known polymerization initiators according to the type of the polymerization method.
  • one or more azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) may be preferably used.
  • Other examples of polymerization initiators include persulfates such as potassium persulfate; peroxide-based initiators such as benzoyl peroxide (BPO) and hydrogen peroxide; substituted ethane-based initiators such as phenyl-substituted ethane; aromatics. Group carbonyl compounds; and the like.
  • polymerization initiator is a redox-based initiator in which a peroxide and a reducing agent are combined.
  • a polymerization initiator can be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be a normal amount, for example, about 0.005 to 1 part by weight (typically about 0.01 to 1 part by weight) with respect to 100 parts by weight of all the monomer components. It can be selected from the range of degree).
  • the pressure-sensitive adhesive layer disclosed herein includes a pressure-sensitive adhesive resin.
  • the adhesive-imparting resin is not particularly limited, and for example, a rosin-based adhesive-imparting resin, a terpene-based adhesive-imparting resin, a hydrocarbon-based adhesive-imparting resin, an epoxy-based adhesive-imparting resin, a polyamide-based adhesive-imparting resin, and an elastomer-based adhesive-imparting resin,
  • Various tackifying resins such as phenol-based tackifier resins and ketone-based tackifier resins can be used. Such a tackifier resin may be used alone or in combination of two or more.
  • rosin-based tackifier resin examples include unmodified rosins (raw rosins) such as gum rosin, wood rosin, and tall oil rosin; modified rosins obtained by modifying these unmodified rosins by hydrogenation, disproportionation, polymerization, etc. ( Hydrogenated rosins, disproportionated rosins, polymerized rosins, other chemically modified rosins, etc. The same shall apply hereinafter); Other various rosin derivatives; etc. may be mentioned.
  • unmodified rosins such as gum rosin, wood rosin, and tall oil rosin
  • modified rosins obtained by modifying these unmodified rosins by hydrogenation, disproportionation, polymerization, etc.
  • Other various rosin derivatives; etc. may be mentioned
  • rosin derivatives examples include rosins obtained by esterifying unmodified rosin with alcohols (that is, esterified rosin) and esterifying modified rosin with alcohols (that is, esterified rosin).
  • Esters Unmodified rosins and unsaturated fatty acid-modified rosins obtained by modifying modified rosins with unsaturated fatty acids; unsaturated fatty acid-modified rosin esters modified from rosin esters with unsaturated fatty acids; unmodified rosins, modified rosins, unsaturated Rosin alcohols obtained by reducing the carboxy group in fatty acid-modified rosins or unsaturated fatty acid-modified rosin esters; metal salts of rosins (particularly rosin esters) such as unmodified rosin, modified rosin, and various rosin derivatives; rosins Examples thereof include a rosin phenol resin obtained by adding phenol to (unmodified rosin, modified
  • rosin esters include esters of unmodified rosin or modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.), such as methyl ester, triethylene glycol ester, and glycerin ester. , Pentaerythritol ester and the like.
  • terpene-based tackifier resins examples include terpene resins such as ⁇ -pinene polymers, ⁇ -pinene polymers, and dipentene polymers; these terpene resins are modified (phenolic modification, aromatic modification, hydrogenation modification, hydrocarbons). Modified terpene resin (modified, etc.); etc.
  • An example of the modified terpene resin is a terpene phenol resin.
  • the terpene phenolic resin refers to a polymer containing a terpene residue and a phenol residue, and is a copolymer of terpene and a phenol compound (terpene-phenol copolymer resin) and a homopolymer or copolymer of terpene. Is a concept that includes both phenol-modified products (phenol-modified terpene resin). Specific examples of terpenes constituting such a terpene phenol resin include monoterpenes such as ⁇ -pinene, ⁇ -pinene, and limonene (including d-form, l-form, and d / l-form (dipentene)). Can be mentioned.
  • the hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin. It is also called hydrogenated terpene phenolic resin.
  • hydrocarbon-based tackifier resins examples include aliphatic (C5 series) petroleum resins, aromatic (C9 series) petroleum resins, and aliphatic / aromatic copolymerized (C5 / C9 series) petroleum resins.
  • Hydrogenated substances for example, aliphatic petroleum resins obtained by hydrogenating aromatic petroleum resins
  • various modified products thereof for example, maleic anhydride modified products
  • kumaron resins for example, kumaron inden resins And the like
  • various hydrocarbon-based resins can be mentioned.
  • a rosin-based tackifier resin as the tackifier resin.
  • the adhesive strength to the LSE surface can be preferably improved.
  • rosin ester is preferable.
  • the ratio of the rosin-based tackifier resin to the entire tackifier resin contained in the pressure-sensitive adhesive layer can be, for example, about 50% by weight or more, about 70% by weight or more, or about 80% by weight or more. ..
  • the technique disclosed herein is preferably in the embodiment in which substantially all of the tackifier resin (for example, about 97% by weight or more, 99% by weight or more, and 100% by weight) is a rosin-based tackifier resin. Can be carried out.
  • the content ratio of the tackifier resin (non-rosin-based tackifier resin) other than the rosin-based tackifier resin in the pressure-sensitive adhesive layer is, for example, 100 parts by weight of the acrylic polymer. On the other hand, it is appropriate that the amount is 40 parts by weight or less. As a result, the effect of including the rosin ester is preferably exhibited.
  • the amount of the non-rosin-based tackifier resin used is preferably about 20 parts by weight or less (for example, less than 20 parts by weight), more preferably about 10 parts by weight or less, still more preferably about 5 parts by weight, based on 100 parts by weight of the acrylic polymer. It is not less than a part by weight, and may be about 1 part by weight or less.
  • the amount of the non-rosin-based tackifier resin used may be, for example, about 1 part by weight or more, about 5 parts by weight or more, or 15 parts by weight or more with respect to 100 parts by weight of the acrylic polymer.
  • the pressure-sensitive adhesive layer contains less than 5 parts by weight of the terpene phenol resin as the tackifier resin with respect to 100 parts by weight of the acrylic polymer.
  • the content of the terpene phenol resin is less than 5 parts by weight with respect to 100 parts by weight of the acrylic polymer means that the pressure-sensitive adhesive layer does not contain the terpene phenol resin and that the terpene phenol resin is an acrylic polymer. It is used in the sense of including both containing less than 5 parts by weight with respect to 100 parts by weight.
  • the content of the terpene phenol resin in the pressure-sensitive adhesive layer is preferably less than 3 parts by weight with respect to 100 parts by weight of the acrylic polymer, and is in the range of 1 part by weight or less (for example, 0 to 0.1 parts by weight). Is more preferable.
  • the tackifier resin contains a tackifier resin TL having a softening point of 110 ° C. or lower.
  • the softening point of the tackifier resin TL is preferably less than 110 ° C. from the viewpoint of adhesion to the LSE surface, preferably about 105 ° C. or lower, more preferably about 100 ° C. or lower, still more preferably about 100 ° C. It is 95 ° C. or lower (for example, less than 95 ° C.), particularly preferably about 90 ° C. or lower (for example, about 85 ° C. or lower).
  • the lower limit of the softening point of the tackifier resin TL is not particularly limited.
  • the softening point of the tackifier resin TL may be, for example, about 50 ° C. or higher, about 60 ° C. or higher, or about 65 ° C. or higher, from the viewpoint of exerting an appropriate cohesive force. It may be about 70 ° C. or higher.
  • the tackifier resin TL As the tackifier resin TL , one of the tackifier resins exemplified above, which is appropriately selected from those having a softening point of 110 ° C. or lower, may be used alone or in combination of two or more. In some embodiments, the tackifier resin TL preferably comprises a rosin-based tackifier resin.
  • the tackifier resin TL may contain one kind of rosin-based tackifier resin alone, or may contain two or more kinds of rosin-based tackifier resins in combination.
  • examples of the rosin-based tackifier resin that can be preferably adopted as the tackifier resin TL include rosin esters such as unmodified rosin ester and modified rosin ester.
  • Preferred examples of the modified rosin ester include hydrogenated rosin ester.
  • an ester of unmodified rosin or modified rosin for example, hydrogenated rosin
  • rosin esters such as methyl ester and glycerin ester
  • the tack-imparting resin TL contains a hydrogenated rosin ester. Further, the tackifier resin TL may contain a non-hydrogenated rosin ester.
  • the non-hydrogenated rosin ester is a concept that comprehensively refers to the above-mentioned rosin esters other than the hydrogenated rosin ester. Examples of non-hydrogenated rosin esters include unmodified rosin esters, disproportionated rosin esters and polymerized rosin esters.
  • the tackifier resin TL may contain a combination of a hydrogenated rosin ester and a non-hydrogenated rosin ester as rosin esters, or may contain only one kind or two or more kinds of hydrogenated rosin esters. It may contain only seeds or two or more non-hydrogenated rosin esters.
  • the pressure-sensitive adhesive layer according to some preferred embodiments contains only one or more hydrogenated rosin esters as the rosin esters contained in the tackifier resin TL .
  • the tackifier resin TL may contain another tackifier resin in addition to the rosin-based tackifier resin.
  • the other tackifier resin one of the tackifier resins exemplified above, which is appropriately selected from those having a softening point of 110 ° C. or lower, may be used alone or in combination of two or more.
  • the proportion of the rosin-based tackifier resin in the total tackifier resin TL can be, for example, approximately 50% by weight or more, may be approximately 65% by weight or more, and may be approximately 75% by weight or more. May be good.
  • the technique disclosed herein is an embodiment in which substantially all of the tackifier resin TL (for example, about 97% by weight or more, 99% by weight or more, and 100% by weight) is a rosin-based tackifier resin. Can be preferably carried out in.
  • tackifier resin TL for example, a tackifier resin having a softening point of less than 50 ° C., more preferably about 40 ° C. or lower (typically, a tackifier resin such as a rosin-based, terpene-based, or hydrocarbon-based resin, for example. Hydrocarbon rosin methyl ester, etc.) may or may not be contained.
  • the tackifier resin exhibiting such a low softening point can be a liquid tackifier resin that exhibits a liquid state at 30 ° C.
  • the liquid tackifier resin may be used alone or in combination of two or more.
  • the content of the liquid tackifier resin may be about 30% by weight or less of the entire tackifier resin TL from the viewpoint of cohesive force and the like, and should be about 10% by weight or less (for example, 0 to 10% by weight). Is appropriate, and may be approximately 2% by weight or less (0.5 to 2% by weight) or less than 1% by weight.
  • the content of the tackifier resin TL (the total amount when two or more kinds of tackifier resins TL are included) is 80 parts by weight or less with respect to 100 parts by weight of the acrylic polymer.
  • the amount of the tackifier resin TL used in the above range is preferably about 70 parts by weight or less, more preferably about 60 parts by weight or less, still more preferably about 55 parts by weight, based on 100 parts by weight of the acrylic polymer from the viewpoint of holding power and the like. It is not less than a part, and may be about 45 parts by weight or less.
  • the amount of the tackifier resin TL used is, for example, about 24 parts by weight or more, preferably about 30 parts by weight or more (for example, more than 30 parts by weight), more preferably about about 30 parts by weight, based on 100 parts by weight of the acrylic polymer. It may be 35 parts by weight or more, more preferably about 38 parts by weight or more, and may be about 45 parts by weight or more (for example, 60 parts by weight or more).
  • the pressure-sensitive adhesive layer comprises a combination of a tack -imparting resin TL and a tack-imparting resin TH having a softening point greater than 110 ° C. (typically greater than 110 ° C. and 200 ° C. or lower).
  • a softening point greater than 110 ° C. (typically greater than 110 ° C. and 200 ° C. or lower).
  • the tackifier resin TH preferably contains one or more selected from rosin-based tackifier resins. It is more preferable that both the tackifier resin TL and the tackifier resin TH contain a rosin-based tackifier resin.
  • the softening point of the tackifier resin TH is preferably about 115 ° C. or higher, more preferably about 120 ° C. or higher, may be about 130 ° C. or higher, or may be about 140 ° C. or higher. ..
  • the upper limit of the softening point of the tackifier resin TH is not particularly limited, and the softening point is about 200 ° C. or lower (more preferably about 160 ° C. or lower, still more preferably 145 ° C. or lower, for example, from the viewpoint of adhesion to the adherend.
  • a tackifier resin having a temperature of about 130 ° C. or lower) can be preferably used.
  • the softening point of the tackifier resin referred to here is defined as a value measured based on the softening point test method (ring ball method) specified in JIS K5902 and JIS K2207. Specifically, the sample is melted as quickly as possible at the lowest possible temperature, and the ring placed on a flat metal plate is carefully filled to prevent bubbles. After cooling, use a slightly heated knife to cut off the raised part from the plane including the upper end of the ring. Next, a support (ring stand) is placed in a glass container (heating bath) having a diameter of 85 mm or more and a height of 127 mm or more, and glycerin is poured until the depth becomes 90 mm or more.
  • a glass container heating bath
  • the steel ball (diameter 9.5 mm, weight 3.5 g) and the ring filled with the sample are immersed in glycerin so as not to contact each other, and the temperature of the glycerin is kept at 20 ° C plus or minus 5 ° C for 15 minutes. ..
  • a steel ball is placed in the center of the surface of the sample in the ring and placed in place on the support.
  • the distance from the upper end of the ring to the glycerin surface is kept at 50 mm, a thermometer is placed, the position of the center of the mercury bulb of the thermometer is set to the same height as the center of the ring, and the container is heated.
  • the flame of the Bunsen burner used for heating should be in the middle between the center and the edge of the bottom of the container to equalize the heating.
  • the rate at which the bath temperature rises after reaching 40 ° C. after the start of heating must be 5.0 plus or minus 0.5 ° C. per minute.
  • the temperature at which the sample gradually softens and flows down from the ring and finally comes into contact with the bottom plate is read, and this is used as the softening point. Two or more softening points are measured at the same time, and the average value is adopted.
  • the tackifier resin TL accounts for 60% by weight or more of the total amount of the tackifier resin contained in the pressure-sensitive adhesive layer. Thereby, it is possible to improve the adhesive force to the LSE surface while having a good holding force.
  • the tackifier resin comprises a tackifier resin TL and a tackifier resin TH .
  • the ratio of the tackifier resin TL to the total amount of the tackifier resin contained in the pressure-sensitive adhesive layer is preferably 70% by weight or more from the viewpoint of more effectively exerting the effect of using the tackifier resin TL . It may be 75% by weight or more, or 78% by weight or more.
  • the ratio of the tackifier resin TL to the total amount of the tackifier resin TH is preferably 95% by weight or less, more preferably 90% by weight, from the viewpoint of better expressing the effect of using the tackifier resin TH. Hereinafter, it is more preferably 85% by weight or less, and may be 80% by weight or less.
  • the tackifier resin contained in the pressure-sensitive adhesive layer consists substantially only of the tackifier resin TL . In such an embodiment, the ratio of the tackifier resin TL to the total amount of the tackifier resin contained in the pressure-sensitive adhesive layer is in the range of 99 to 100% by weight.
  • the tackifier resin may include a tackifier resin having a hydroxyl value of less than 70 mgKOH / g.
  • a tackifier resin having a hydroxyl value of less than 60 mgKOH / g (more preferably less than 50 mgKOH / g, still more preferably less than 45 mgKOH / g) is preferable.
  • the tackifier resin having a hydroxyl value of less than 70 mgKOH / g may be referred to as "low hydroxyl value resin".
  • a pressure-sensitive adhesive layer having excellent adhesion to an LSE adherend can be preferably realized.
  • the lower limit of the hydroxyl value of the low hydroxyl value resin is 0 mgKOH / g or more, may be about 10 mgKOH / g or more, or may be about 15 mgKOH / g or more.
  • the low hydroxyl value resin one type can be used alone or two or more types can be used in combination.
  • the low hydroxyl value resin one of the tackifier resins exemplified above, which is appropriately selected from those having a hydroxyl value of less than 70 mgKOH / g, can be used alone or in combination of two or more.
  • the low hydroxyl value resin preferably comprises a rosin-based tackifier resin.
  • the low hydroxyl value resin may contain one kind of rosin-based tackifier resin alone, or may contain two or more kinds of rosin-based tackifier resins in combination.
  • the low hydroxyl value resin may be the above-mentioned pressure-sensitive adhesive resin TL or the pressure-sensitive adhesive resin TH, and both the pressure-sensitive adhesive resin TL and the pressure-sensitive adhesive resin TH are low hydroxyl value resins. It may be.
  • the low hydroxyl value resin preferably accounts for 60% by weight or more of the total amount of the tackifier resin contained in the pressure-sensitive adhesive layer. As a result, it is possible to improve the adhesive force with respect to the LSE surface.
  • the proportion of the low hydroxyl value resin in the total amount of the tackifier resin contained in the pressure-sensitive adhesive layer is preferably 70% by weight from the viewpoint of more effectively exerting the effect of using the low hydroxyl value resin. As mentioned above, it may be 75% by weight or more, or 78% by weight or more.
  • the tackifier resin contained in the pressure-sensitive adhesive layer comprises substantially only a low hydroxyl value resin. In such an embodiment, the ratio of the low hydroxyl value resin to the total amount of the tackifier resin contained in the pressure-sensitive adhesive layer is in the range of 99 to 100% by weight.
  • the pressure-sensitive adhesive layer disclosed herein has a hydroxyl value of 70 mgKOH / g or more as a pressure-sensitive adhesive resin (hereinafter, also referred to as “high hydroxyl value resin”) containing 100 weight of an acrylic polymer. It is preferably less than 5 parts by weight with respect to the part. By limiting the amount of the high hydroxyl value resin used in this way, it is easy to obtain the effect of improving the adhesive force on the LSE surface.
  • the content of the high hydroxyl value resin is less than 5 parts by weight with respect to 100 parts by weight of the acrylic polymer means that the pressure-sensitive adhesive layer does not contain the high hydroxyl value resin and that the high hydroxyl value resin is used.
  • the content of the high hydroxyl value resin in the pressure-sensitive adhesive layer is preferably less than 3 parts by weight with respect to 100 parts by weight of the acrylic polymer, and is in the range of 1 part by weight or less (for example, 0 to 0.1 parts by weight). It is more preferable to have.
  • the value of the hydroxyl value the value measured by the potentiometric titration method specified in JIS K0070: 1992 can be adopted.
  • the specific measurement method is as shown below.
  • [Measurement method of hydroxyl value] 1.
  • Reagent (1) As the acetylation reagent, about 12.5 g (about 11.8 mL) of acetic anhydride is taken, pyridine is added thereto to make the total volume 50 mL, and the reagent is sufficiently stirred. Alternatively, take about 25 g (about 23.5 mL) of acetic anhydride, add pyridine to this to make the total volume 100 mL, and use the one that has been sufficiently stirred.
  • Hydroxy group value [(BC) x f x 28.05] / S + D here
  • B Amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test
  • C Amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for the sample
  • f Factor of 0.5 mol / L potassium hydroxide ethanol solution
  • S Sample weight (g)
  • D Acid value
  • 28.05 1/2 of the molecular weight of potassium hydroxide 56.11, Is.
  • the content of the tackifier resin (the total amount when two or more kinds of tackifier resins are included) is within the range of 40 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the acrylic polymer.
  • the amount of the tackifier resin used is within the above range, the adhesive strength with respect to the LSE surface can be improved. Further, by setting the amount of the tackifier resin used to 100 parts by weight of the acrylic polymer to 80 parts by weight or less, it is easy to maintain a good holding force.
  • the amount of the tackifier resin used may be, for example, more than 40 parts by weight, may be about 42 parts by weight or more, and may be about 45 parts by weight or more with respect to 100 parts by weight of the acrylic polymer. It may be about 48 parts by weight or more, and may be about 50 parts by weight or more (for example, 60 parts by weight or more). Further, the amount of the tackifier resin used is preferably about 70 parts by weight or less, more preferably about 65 parts by weight or less, still more preferably about 60 parts by weight, based on 100 parts by weight of the acrylic polymer from the viewpoint of holding power and the like. It is less than a part, and may be about 55 parts by weight or less.
  • the total content of the acrylic polymer and the tackifier resin in the pressure-sensitive adhesive layer is appropriately set and limited to a specific range so that the effects of the techniques disclosed herein can be exerted. It's not something.
  • the total amount (total amount) of the acrylic polymer and the tackifier resin contained in the pressure-sensitive adhesive layer is more than 50% by weight from the viewpoint of preferably exerting the effect of the technique disclosed herein. Is suitable, preferably about 70% by weight or more, more preferably about 90% by weight or more, still more preferably 95% by weight or more (for example, 95% by weight or more and 100% by weight or less or less than 100% by weight), and 97% by weight. It may be% or more.
  • the pressure-sensitive adhesive composition used to form the pressure-sensitive adhesive layer may contain a cross-linking agent, if necessary.
  • the type of the cross-linking agent is not particularly limited, and for example, an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, a melamine-based cross-linking agent, a peroxide-based cross-linking agent, a urea-based cross-linking agent, and a metal.
  • Examples thereof include an alkoxide-based cross-linking agent, a metal chelate-based cross-linking agent, a metal salt-based cross-linking agent, a carbodiimide-based cross-linking agent, a hydrazine-based cross-linking agent, an amine-based cross-linking agent, and a silane coupling agent.
  • the cross-linking agent may be used alone or in combination of two or more.
  • isocyanate-based cross-linking agents isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and melamine-based cross-linking agents are preferable, isocyanate-based cross-linking agents and epoxy-based cross-linking agents are more preferable, and epoxy-based cross-linking agents are particularly preferable. ..
  • the cross-linking agent it is possible to obtain the cohesive force of the pressure-sensitive adhesive layer and improve the adhesive force to the LSE surface.
  • the pressure-sensitive adhesive layer in the technique disclosed herein is obtained by using the above-mentioned cross-linking agent in a form after the cross-linking reaction, a form before the cross-linking reaction, a form partially cross-linked, an intermediate or a composite form thereof, or the like. May contain.
  • the cross-linking agent is typically contained in the pressure-sensitive adhesive layer exclusively in the form after the cross-linking reaction.
  • epoxy-based cross-linking agent a compound having two or more epoxy groups in one molecule can be used without particular limitation.
  • An epoxy-based cross-linking agent having 3 to 5 epoxy groups in one molecule is preferable.
  • the epoxy-based cross-linking agent may be used alone or in combination of two or more.
  • epoxy-based cross-linking agent examples include, for example, N, N, N', N'-tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl).
  • Commercially available epoxy-based cross-linking agents include the product name "TETRAD-C” and product name "TETRAD-X” manufactured by Mitsubishi Gas Chemical Company, the product name “Epicron CR-5L” manufactured by DIC, and Nagase ChemteX.
  • the product name "Denacol EX-512", the product name "TEPIC-G” manufactured by Nissan Chemical Industries, Ltd., and the like can be mentioned.
  • the amount of epoxy cross-linking agent used is not particularly limited.
  • the amount of the epoxy-based cross-linking agent used may be, for example, more than 0 parts by weight and about 1 part by weight or less (typically about 0.001 to 1 part by weight) with respect to 100 parts by weight of the acrylic polymer. can. From the viewpoint of preferably exerting the effect of improving the cohesive force, it is appropriate that the amount of the epoxy-based cross-linking agent used is about 0.005 part by weight or more with respect to 100 parts by weight of the acrylic polymer, and is about 0.01. By weight or more is preferable, and about 0.02 parts by weight or more is more preferable.
  • the amount of the epoxy-based cross-linking agent used is about 0.5 parts by weight or less with respect to 100 parts by weight of the acrylic polymer, which is about 0.2. It is preferably not less than parts by weight, more preferably about 0.1 parts by weight or less, and may be 0.07 parts by weight or less, or 0.04 parts by weight or less. Impact resistance tends to be improved by reducing the amount of the epoxy-based cross-linking agent used.
  • the cross-linking agent is a combination of an epoxy-based cross-linking agent and at least one cross-linking agent having a different type of cross-linking functional group from the epoxy-based cross-linking agent.
  • a cross-linking agent other than an epoxy-based cross-linking agent that is, a cross-linking agent having a different type of cross-linking reactive group from the epoxy-based cross-linking agent; hereinafter also referred to as "non-epoxy-based cross-linking agent").
  • non-epoxy cross-linking agent that can be used in combination with the epoxy-based cross-linking agent is not particularly limited, and can be appropriately selected and used from the above-mentioned cross-linking agents.
  • the non-epoxy cross-linking agent may be used alone or in combination of two or more.
  • an isocyanate-based cross-linking agent can be adopted as the non-epoxy-based cross-linking agent.
  • an epoxy-based cross-linking agent and an isocyanate-based cross-linking agent in combination, more excellent adhesive properties can be realized.
  • polyfunctional isocyanate meaning a compound having an average of two or more isocyanate groups per molecule, including those having an isocyanurate structure
  • the isocyanate-based cross-linking agent may be used alone or in combination of two or more.
  • polyfunctional isocyanates examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and the like.
  • aliphatic polyisocyanes include 1,2-ethylene diisocyanate; 1,2-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 1,4-tetramethylene diisocyanate and other tetramethylene diisocyanates; 1,2.
  • -Hexamethylene diisocyanate such as hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate;
  • Examples thereof include 2-methyl-1,5-pentanediisocyanate, 3-methyl-1,5-pentanediisocyanate, and lysine diisocyanate.
  • alicyclic polyisocyanates include isophorone diisocyanates; 1,2-cyclohexyldiisocyanates, 1,3-cyclohexyldiisocyanates, 1,4-cyclohexyldiisocyanates and other cyclohexyldiisocyanates; 1,2-cyclopentyldiisocyanates, 1,3.
  • -Cyclopentyl diisocyanate such as cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like.
  • aromatic polyisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate.
  • polyfunctional isocyanate As a preferable polyfunctional isocyanate, a polyfunctional isocyanate having an average of 3 or more isocyanate groups per molecule is exemplified.
  • trifunctional or higher functional isocyanates are bifunctional or trifunctional or higher functional isocyanate multimers (typically dimers or trimers), derivatives (eg, polyhydric alcohols and two or more molecules of polyfunctional isocyanates). It can be an addition reaction product), a polymer, or the like.
  • diphenylmethane diisocyanate dimer or trimer diphenylmethane diisocyanate dimer or trimer, hexamethylene diisocyanate isocyanurate (isocyanurate structure trimer adduct), reaction product of trimethylolpropane and tolylene diisocyanate, trimethylolpropane and hexa.
  • polyfunctional isocyanates such as reaction products with methylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, and polyester polyisocyanate.
  • the amount of the isocyanate-based cross-linking agent used is not particularly limited.
  • the amount may be approximately 0.1 part by weight or more with respect to 100 parts by weight of the acrylic polymer.
  • the amount of the isocyanate-based cross-linking agent used per 100 parts by weight of the acrylic polymer can be, for example, 0.5 parts by weight or more, and 1.0 weight by weight. More than a portion is suitable, preferably 1.5 parts by weight or more.
  • the amount of the isocyanate-based cross-linking agent used is preferably 10 parts by weight or less with respect to 100 parts by weight of the acrylic type, preferably less than 5 parts by weight, more preferably less than 4.0 parts by weight, and further. It is preferably less than 3.0 parts by weight (for example, 2.5 parts by weight or less).
  • the technique disclosed herein is preferably carried out in a mode in which an epoxy-based cross-linking agent and an isocyanate-based cross-linking agent are used in combination.
  • the relationship between the content of the epoxy-based cross-linking agent and the content of the isocyanate-based cross-linking agent is not particularly limited.
  • the content of the epoxy-based cross-linking agent can be, for example, approximately 1/10 or less of the content of the isocyanate-based cross-linking agent. From the viewpoint of more preferably achieving both adhesion to the adherend and the substrate and cohesive force, it is appropriate that the content of the epoxy-based cross-linking agent is about 1/30 or less of the content of the isocyanate-based cross-linking agent.
  • the content of the epoxy-based cross-linking agent is usually about 1/1000 of the content of the isocyanate-based cross-linking agent.
  • the total amount of the cross-linking agent used is not particularly limited, and is, for example, approximately 0.005 parts by weight or more (for example, 0.01 parts by weight or more, typically 0.1 parts by weight or more) with respect to 100 parts by weight of the acrylic polymer. It can be selected from a range of about 10 parts by weight or less (for example, about 8 parts by weight or less, preferably about 5 parts by weight or less).
  • the pressure-sensitive adhesive composition includes a leveling agent, a cross-linking aid, a plasticizer, a softening agent, a filler, a colorant (pigment, dye, etc.), an antioxidant, and an antiaging agent, if necessary.
  • a leveling agent e.g., a plasticizer, a softening agent, a filler, a colorant (pigment, dye, etc.), an antioxidant, and an antiaging agent, if necessary.
  • UV absorbers, antioxidants, light stabilizers and the like which may contain various additives commonly used in the field of pressure-sensitive adhesives.
  • the pressure-sensitive adhesive composition may optionally contain a polymer other than the acrylic polymer (rubber-based polymer, etc.) as long as the effect of the invention is not impaired.
  • conventionally known additives can be used by a conventional method and do not particularly characterize the present invention, and therefore detailed description thereof will be omitted.
  • the pressure-sensitive adhesive layer (layer composed of a pressure-sensitive adhesive) disclosed herein is formed of a water-based pressure-sensitive adhesive composition, a solvent-type pressure-sensitive adhesive composition, a hot-melt type pressure-sensitive adhesive composition, and an active energy ray-curable pressure-sensitive adhesive composition. It can be an adhesive layer.
  • the water-based pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in which a pressure-sensitive adhesive (sticking agent layer-forming component) is contained in a solvent containing water as a main component (water-based solvent), and is typically water-dispersed.
  • a type pressure-sensitive adhesive composition (a composition in which at least a part of the pressure-sensitive adhesive is dispersed in water) or the like is included.
  • the solvent-type pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in which the pressure-sensitive adhesive is contained in an organic solvent.
  • the organic solvent contained in the solvent-type pressure-sensitive adhesive composition one kind or two or more kinds exemplified as the organic solvent (toluene, ethyl acetate, etc.) that can be used in the above-mentioned solution polymerization can be used without particular limitation.
  • the technique disclosed herein can be preferably carried out in an embodiment including a pressure-sensitive adhesive layer formed from a solvent-type pressure-sensitive adhesive composition from the viewpoint of pressure-sensitive adhesive properties and the like.
  • the pressure-sensitive adhesive layer disclosed here can be formed by a conventionally known method.
  • a method of forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive composition to a peelable surface (peeling surface) or a non-peeling surface and drying it can be adopted.
  • a method (direct method) of directly applying (typically applying) a pressure-sensitive adhesive composition to the base material and drying it to form a pressure-sensitive adhesive layer is adopted. be able to.
  • a method (transfer method) in which a pressure-sensitive adhesive composition is applied to a peelable surface (peeling surface) and dried to form a pressure-sensitive adhesive layer on the surface, and the pressure-sensitive adhesive layer is transferred to a substrate May be adopted. From the viewpoint of productivity, the transfer method is preferable.
  • the peeling surface the surface of the peeling liner, the back surface of the base material that has been peeled off, or the like can be used.
  • the pressure-sensitive adhesive layer disclosed herein is typically formed continuously, but is not limited to such a form, and may have a regular or random pattern such as a dot shape or a striped shape. It may be a formed pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive composition can be applied using a conventionally known coater such as a gravure roll coater, a die coater, or a bar coater. Alternatively, the pressure-sensitive adhesive composition may be applied by impregnation, a curtain coating method, or the like. From the viewpoint of promoting the crosslinking reaction and improving the production efficiency, it is preferable to dry the pressure-sensitive adhesive composition under heating.
  • the drying temperature can be, for example, about 40 to 150 ° C., and is usually preferably about 60 to 130 ° C.
  • aging may be further performed for the purpose of adjusting the component transfer in the pressure-sensitive adhesive layer, advancing the cross-linking reaction, alleviating the strain that may exist in the pressure-sensitive adhesive layer, and the like.
  • the thickness of the adhesive layer is not particularly limited. From the viewpoint of avoiding excessive thickening of the pressure-sensitive adhesive sheet, the thickness of the pressure-sensitive adhesive layer is usually preferably about 100 ⁇ m or less, preferably about 70 ⁇ m or less, more preferably about 60 ⁇ m or less, still more preferably about 50 ⁇ m or less. Is.
  • the thickness of the pressure-sensitive adhesive layer can be about 35 ⁇ m or less, and may be, for example, about 30 ⁇ m or less.
  • the thickness-limited pressure-sensitive adhesive layer can well meet the demand for thinner and lighter weight. In general, as the thickness of the pressure-sensitive adhesive layer becomes smaller, the adhesiveness to the adherend tends to decrease.
  • the structure has a pressure-sensitive adhesive layer having a limited thickness. , It is possible to improve the adhesive force to the LSE surface.
  • the lower limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, and from the viewpoint of adhesion to the adherend, it is advantageous to set it to about 3 ⁇ m or more, preferably about 10 ⁇ m or more, and more preferably about 12 ⁇ m or more (for example). More than 12 ⁇ m), more preferably about 15 ⁇ m or more, and may be, for example, about 18 ⁇ m or more.
  • the pressure-sensitive adhesive sheet disclosed herein may be a pressure-sensitive adhesive sheet having pressure-sensitive adhesive layers having the above-mentioned thickness on both sides of a base material.
  • the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer have the same thickness. They may be of different thicknesses.
  • the base material that supports (linees) the pressure-sensitive adhesive layer includes a resin film, paper, cloth, and rubber. Sheets, foam sheets, metal foils, composites thereof and the like can be used.
  • resin films include polyethylene (PE), polypropylene (PP), ethylene / propylene copolymer and other polyolefin films; polyethylene terephthalates (PET) and other polyester films; vinyl chloride resin films; vinyl acetate resin films; polyimides. Resin film; polyamide resin film; fluororesin film; cellophane and the like.
  • Examples of paper include Japanese paper, kraft paper, glassin paper, high-quality paper, synthetic paper, top-coated paper and the like.
  • Examples of the cloth include woven cloths and non-woven fabrics made by spinning various fibrous substances alone or by blending them.
  • Examples of the fibrous material include cotton, sufu, Manila hemp, pulp, rayon, acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, polyolefin fiber and the like.
  • Examples of the rubber sheet include a natural rubber sheet, a butyl rubber sheet and the like.
  • Examples of the foam sheet include a foamed polyolefin sheet, a foamed polyurethane sheet, a foamed polychloroprene rubber sheet, and the like.
  • Examples of the metal foil include aluminum foil, copper foil and the like.
  • the base material that supports the pressure-sensitive adhesive layer is also referred to as a base material layer in the pressure-sensitive adhesive sheet.
  • a base film containing a resin film can be preferably used as the base material constituting the pressure-sensitive adhesive sheet with a base material.
  • the base film is typically an independently shape-maintainable (independent) member.
  • the substrate in the techniques disclosed herein may be substantially composed of such a base film.
  • the substrate may include an auxiliary layer in addition to the base film. Examples of the auxiliary layer include a colored layer, a reflective layer, an undercoat layer, an antistatic layer, and the like provided on the surface of the base film.
  • the resin film is a film containing a resin material as a main component (for example, a component contained in the resin film in an amount of more than 50% by weight).
  • resin films include polyethylene (PE), polypropylene (PP), ethylene / propylene copolymer and other polyolefin resin films; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like.
  • the resin film may be a rubber-based film such as a natural rubber film or a butyl rubber film. Among them, a polyester film is preferable from the viewpoint of handleability and processability, and a PET film is particularly preferable.
  • the "resin film” is typically a non-porous sheet, and is a concept that is distinguished from so-called non-woven fabrics and woven fabrics (in other words, a concept excluding non-woven fabrics and woven fabrics).
  • the resin film may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.
  • such resin films can be non-foaming.
  • the non-foaming resin film refers to a resin film that has not been intentionally treated to form a foam.
  • the non-effervescent resin film can be a resin film having a foaming ratio of less than 1.1 times (for example, less than 1.05 times, typically less than 1.01 times).
  • the base material may contain a filler (inorganic filler, organic filler, etc.), a colorant, a dispersant (surfactant, etc.), an antistatic agent, an antioxidant, an ultraviolet ray, if necessary.
  • a filler inorganic filler, organic filler, etc.
  • a colorant for example, a colorant, a dispersant (surfactant, etc.)
  • an antistatic agent for example, an antioxidant, an ultraviolet ray, if necessary.
  • Various additives such as absorbents, antistatic agents, lubricants, and plasticizers may be blended.
  • the blending ratio of the various additives is about less than 30% by weight (for example, less than 20% by weight, typically less than 10% by weight).
  • the base material (for example, a resin film) may have a single-layer structure or may have a multi-layer structure of two layers, three layers or more. From the viewpoint of shape stability, the base material preferably has a single-layer structure. In the case of a multi-layer structure, it is preferable that at least one layer (preferably all layers) is a layer having a continuous structure of the above resin (for example, a polyester resin).
  • the method for producing the base material (typically, the resin film) may be appropriately adopted by a conventionally known method, and is not particularly limited. For example, conventionally known general film molding methods such as extrusion molding, inflation molding, T-die casting molding, and calender roll molding can be appropriately adopted.
  • the surface of the base material may be subjected to conventionally known surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of an undercoat agent.
  • a surface treatment may be a treatment for improving the adhesion between the base material and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer on the base material.
  • the back surface of the base material may be peeled off, if necessary.
  • a general silicone-based, long-chain alkyl-based, fluorine-based or other peeling treatment agent is formed into a thin film of typically 0.01 ⁇ m to 1 ⁇ m (for example, 0.01 ⁇ m to 0.1 ⁇ m). It can be a process of giving. By performing such a peeling treatment, it is possible to obtain an effect such as facilitating the rewinding of the wound body in which the adhesive sheet is wound in a roll shape.
  • the thickness of the base material is not particularly limited in the pressure-sensitive adhesive sheet containing the base material. From the viewpoint of avoiding the pressure-sensitive adhesive sheet from becoming excessively thick, the thickness of the base material can be, for example, about 200 ⁇ m or less, preferably about 150 ⁇ m or less, and more preferably about 100 ⁇ m or less. Depending on the purpose and mode of use of the pressure-sensitive adhesive sheet, the thickness of the base material may be about 70 ⁇ m or less, about 50 ⁇ m or less, or about 30 ⁇ m or less (for example, about 25 ⁇ m or less). In some embodiments, the thickness of the substrate may be about 20 ⁇ m or less, about 15 ⁇ m or less, or about 10 ⁇ m or less (eg, about 5 ⁇ m or less).
  • the thickness of the pressure-sensitive adhesive layer can be further increased even if the total thickness of the pressure-sensitive adhesive sheets is the same. It can be advantageous from the viewpoint of improving the adhesion to the adherend and the base material.
  • the lower limit of the thickness of the base material is not particularly limited. From the viewpoint of handleability (handleability) and processability of the pressure-sensitive adhesive sheet, the thickness of the base material is usually about 0.5 ⁇ m or more (for example, 1 ⁇ m or more), preferably about 2 ⁇ m or more, for example, about 6 ⁇ m or more. In some embodiments, the thickness of the substrate can be approximately 15 ⁇ m or greater, and may be approximately 25 ⁇ m or greater.
  • a release liner can be used in the formation of an adhesive layer, the production of an adhesive sheet, the storage of an adhesive sheet before use, distribution, shape processing, and the like.
  • the release liner is not particularly limited, and for example, a release liner having a release treatment layer on the surface of a liner base material such as a resin film or paper, a release liner made of a fluoropolymer (polytetrafluoroethylene or the like), or the like is used. be able to.
  • the peeling treatment layer may be formed by surface-treating the liner base material with a peeling treatment agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.
  • the total thickness of the pressure-sensitive adhesive sheet disclosed herein is not particularly limited.
  • the total thickness of the pressure-sensitive adhesive sheet can be, for example, about 300 ⁇ m or less, and from the viewpoint of thinning, about 200 ⁇ m or less is appropriate, and it may be about 150 ⁇ m or less (for example, about 100 ⁇ m or less).
  • the thickness of the pressure-sensitive adhesive sheet can be about 50 ⁇ m or less, for example, about 35 ⁇ m or less, or less than 30 ⁇ m.
  • the lower limit of the thickness of the pressure-sensitive adhesive sheet is not particularly limited, but for example, it is suitable to be about 3 ⁇ m or more, preferably about 10 ⁇ m or more, more preferably about 15 ⁇ m or more, and may be about 50 ⁇ m or more. It may be 100 ⁇ m or more.
  • An adhesive sheet having a thickness of a predetermined value or more tends to have good adhesion to an adherend and impact resistance, and also tends to be excellent in handleability.
  • the thickness of the pressure-sensitive adhesive layer is the total thickness of the pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet disclosed herein preferably has a 180-degree peel strength (adhesive strength against PP) of about 12 N / 20 mm or more with respect to polypropylene.
  • a 180-degree peel strength adheresive strength against PP
  • the adhesive strength against PP is more preferably about 12.5 N / 20 mm or more, further preferably about 13.5 N / 20 mm or more, and particularly preferably 14.5 / 20 mm or more (for example, about 15.0 N / 20 mm or more). ..
  • the upper limit of the adhesive force against PP is not particularly limited, but from the viewpoint of compatibility with other adhesive properties such as holding force, it is usually, for example, about 30 N / 20 mm or less, and may be 25 N / 20 mm or less.
  • the adhesive force against PP is measured using PP as an adherend under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 degrees in a measurement environment of 23 ° C. and 50% RH. More specifically, it is measured by the method described in Examples described later.
  • the pressure-sensitive adhesive sheet disclosed here preferably has a 180-degree peel strength (adhesive strength against PE) of about 6 N / 20 mm or more with respect to polyethylene.
  • a 180-degree peel strength adheresive strength against PE
  • the adhesive strength against PE is more preferably about 7.0 N / 20 mm or more, still more preferably about 8.0 N / 20 mm or more, and particularly preferably 9.0 / 20 mm or more (for example, about 10.0 N / 20 mm or more, further. 12N / 20mm or more).
  • the upper limit of the adhesive force against PE is not particularly limited, but from the viewpoint of compatibility with other adhesive properties such as holding force, it is usually, for example, about 30 N / 20 mm or less, and may be 20 N / 20 mm or less.
  • the adhesive force against PE is measured using PE as an adherend under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 degrees in a measurement environment of 23 ° C. and 50% RH. More specifically, it is measured by the method described in Examples described later.
  • the adhesive sheet disclosed here may exhibit an adhesive strength of a predetermined value or more with respect to PP and PE.
  • the pressure-sensitive adhesive sheet exhibiting the adhesive strength against PP and the adhesive strength against PE can stably have sufficient adhesive reliability with respect to the surface of the adherend (LSE surface) composed of various LSE materials. Wide range of use and useful.
  • the pressure-sensitive adhesive sheet disclosed here preferably has a 180-degree peel strength (adhesive strength against SUS) with respect to a stainless steel sheet of about 12 N / 20 mm or more.
  • a 180-degree peel strength adheresive strength against SUS
  • Such an adhesive sheet exhibiting adhesive strength against SUS can exhibit high adhesive reliability to various adherends other than the LSE adherend (for example, an adherend such as a metal member).
  • the adhesive strength against SUS is more preferably about 13.0 N / 20 mm or more, further preferably about 14.0 N / 20 mm or more, and particularly preferably 15.0 N / 20 mm or more.
  • the upper limit of the adhesive force against SUS is not particularly limited, but from the viewpoint of compatibility with other adhesive properties such as holding force, it is usually, for example, about 50 N / 20 mm or less, and may be 30 N / 20 mm or less.
  • the adhesive force against SUS is measured using a SUS plate as an adherend under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 degrees in a measurement environment of 23 ° C. and 50% RH. More specifically, it is measured by the method described in Examples described later.
  • the pressure-sensitive adhesive sheet disclosed herein may have a deviation distance of 1.0 mm or less from the adherend one hour after the start of the holding force test in the holding force test carried out by the method described in Examples described later. ..
  • Such an adhesive sheet has a high cohesive force and a good holding force.
  • the deviation distance in the holding force test is preferably 0.5 mm or less, more preferably 0.3 mm or less, further preferably 0.2 mm or less, and particularly preferably 0.1 mm or less (0 to 0.1 mm). ..
  • the pressure-sensitive adhesive sheet disclosed herein has good holding power and exhibits improved adhesiveness to the LSE surface, and is therefore suitable for adhesive fixing of members having an LSE surface or the like.
  • the material constituting such an LSE surface include polyolefin resins such as polyethylene (PE) and polypropylene (PP), which are generally known as materials having low surface free energy, and fluoropolymers (polytetrafluoroethylene and the like).
  • PE polyethylene
  • PP polypropylene
  • fluoropolymers polytetrafluoroethylene and the like.
  • examples thereof include polystyrene, polyoxymethylene and polyvinyl acetate.
  • the pressure-sensitive adhesive sheet disclosed herein is preferably used for adhesive fixing of an adherend having a surface made of a material containing polyolefin such as PE and PP and a fluoropolymer.
  • the pressure-sensitive adhesive sheet disclosed herein is used in the form of a double-sided pressure-sensitive adhesive sheet, the surface of at least one (for example, both) adherends to which each adhesive surface of the pressure-sensitive adhesive sheet is attached is made of the above-mentioned material. It is preferably configured.
  • the pressure-sensitive adhesive sheet disclosed herein may have sufficient adhesive strength not only for LSE materials but also for various materials. Therefore, for example, a metal member or a polyester resin member such as PET has the above-mentioned LSE surface. It can also be preferably used for attaching a member (LSE adherend) having.
  • the suitable application target of the adhesive sheet disclosed here is suitable for fixing members in electronic devices such as home appliances, OA devices, and portable electronic devices. Since a material having a low surface free energy such as PE, PP, or fluororesin can be used as a member constituting the electronic device, the adhesive sheet disclosed here is applied and the adhesive reliability with respect to the LSE surface is applied. It is meaningful to realize excellent adhesive fixing.
  • Examples of the above-mentioned electronic devices include various home appliances, personal computers (desktop type, notebook type, tablet type, etc.) and the like.
  • Non-limiting examples of the above-mentioned portable electronic devices include mobile phones, smartphones, tablet computers, laptop computers, various wearable devices (for example, wristwear type worn on the wrist like a wristwatch, clips, straps, etc.).
  • Modular type to be attached to a part of eyewear type including glasses type (monocular type and binocular type, including head mount type), clothes type to be attached to shirts, socks, hats, etc. in the form of accessories, earphones (Earwear type, etc. attached to the ear), digital camera, digital video camera, audio equipment (portable music player, IC recorder, etc.), computer (computer, etc.), portable game equipment, electronic dictionary, electronic notebook, electronic book, in-vehicle Includes information devices, mobile radios, mobile TVs, mobile printers, mobile scanners, mobile modems, etc.
  • "portable” means that it is not enough to be portable, but to have a level of portability that an individual (standard adult) can carry relatively easily. It shall mean.
  • the matters disclosed herein include: [1] It is an electronic device and An adhesive sheet is joined to the members constituting the electronic device.
  • the adhesive sheet has an adhesive layer and has an adhesive layer.
  • the pressure-sensitive adhesive layer contains an acrylic polymer and a pressure-sensitive adhesive resin, and contains.
  • the acrylic polymer is polymerized with an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal at a ratio of 15% by weight or more.
  • the carboxy group-containing monomer is not copolymerized, or the copolymerization ratio of the carboxy group-containing monomer is less than 10% by weight.
  • the content of the tackifier resin in the pressure-sensitive adhesive layer is 40 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the acrylic polymer.
  • the pressure-sensitive adhesive layer contains the pressure-sensitive adhesive resin TL having a softening point of 110 ° C. or lower as the pressure-sensitive adhesive resin.
  • the tackifier resin TL is an electronic device that accounts for 60% by weight or more of the total amount of the tackifier resin contained in the pressure-sensitive adhesive layer. [2] The electronic device according to the above [1], wherein the surface of the member is made of a polyolefin resin or a fluororesin. [3] The electronic device according to the above [1] or [2], wherein the electronic device is a home electric appliance.
  • the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer contains an isocyanate-based cross-linking agent and an epoxy-based cross-linking agent.
  • the pressure-sensitive adhesive sheet is a base-less double-sided pressure-sensitive adhesive sheet composed of only the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet has a base material and the pressure-sensitive adhesive layer provided on at least one surface of the base material.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer contains an acrylic polymer and a pressure-sensitive adhesive resin, and contains.
  • the acrylic polymer is polymerized with an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal at a ratio of 15% by weight or more.
  • the carboxy group-containing monomer is not copolymerized, or the copolymerization ratio of the carboxy group-containing monomer is less than 10% by weight.
  • the content of the tackifier resin in the pressure-sensitive adhesive layer is 40 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the acrylic polymer.
  • the pressure-sensitive adhesive layer contains the pressure-sensitive adhesive resin TL having a softening point of 110 ° C. or lower as the pressure-sensitive adhesive resin.
  • the pressure-sensitive adhesive resin TL is a pressure-sensitive adhesive sheet that occupies 60% by weight or more of the total amount of the pressure-sensitive adhesive resin contained in the pressure-sensitive adhesive layer.
  • the adhesive sheet according to any one of the above [11] to [17] which is used for fixing members in electronic devices.
  • ⁇ Evaluation method> [Adhesive strength against SUS] Under a measurement environment of 23 ° C. and 50% RH, a PET film with a thickness of 50 ⁇ m is attached to one of the adhesive surfaces of the adhesive sheet (double-sided adhesive sheet), lined, and cut into a size of 20 mm in width and 100 mm in length. Make a measurement sample. In an environment of 23 ° C. and 50% RH, the other adhesive surface of the measurement sample is pressure-bonded to the surface of a stainless steel plate (SUS304BA plate) washed with ethyl acetate by reciprocating 2.5 kg of rollers.
  • SUS304BA plate stainless steel plate
  • the peel strength (against SUS) under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 degrees according to JIS Z 0237: 2000.
  • Adhesive strength [N / 20 mm] is measured.
  • the peel strength (against PP) under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 degrees according to JIS Z 0237: 2000. Adhesive strength) [N / 20 mm] is measured.
  • the PP plate for example, the product name "Koube Polysheet PP-N-AN" (thickness 2 mm) manufactured by Showa Denko Materials Co., Ltd. is used.
  • a PET film with a thickness of 50 ⁇ m is attached to one of the adhesive surfaces of the adhesive sheet (double-sided adhesive sheet), lined, and cut into a size of 20 mm in width and 100 mm in length.
  • the other adhesive surface of the measurement sample is pressure-bonded to the surface of a polyethylene plate (PE plate) washed with ethanol by reciprocating 2.5 times with a 2 kg roller.
  • the peel strength (against PE) under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 degrees according to JIS Z 0237: 2000. Adhesive strength) [N / 20 mm] is measured.
  • the PE plate for example, the product name "Koube Polysheet EL-N-AN" (thickness 2 mm) manufactured by Showa Denko Materials Co., Ltd. is used.
  • the universal tensile compression tester Minebea's "tensile compression tester, TG-1kN" or its equivalent is used.
  • the peel strength measurement is performed on the single-sided adhesive sheet, it is not necessary to line the PET film.
  • the base material thickness is thin (for example, when the base material thickness is 25 ⁇ m or less), the PET film may be lined.
  • the adhesive strength against PP is 12N / 20mm or more and the adhesive strength against PE is 6N / 20mm or more, it is determined that the adhesive strength is high with respect to the LSE surface.
  • a PET film having a thickness of 50 ⁇ m is attached to one of the adhesive surfaces of the adhesive sheet (double-sided adhesive sheet), lined, and cut to a width of 10 mm to prepare a measurement sample. ..
  • the other adhesive surface of the measurement sample is pressure-bonded to a bakelite plate (phenol resin plate) as an adherend by reciprocating a 2 kg roller once with a sticking area of 10 mm in width and 20 mm in length. After the sample attached to the adherend in this way was left in the same environment for 30 minutes, the adherend was hung so that the length direction of the sample was the vertical direction, and 500 g of the sample was placed on the free end of the sample.
  • the obtained pressure-sensitive adhesive composition was applied to the peeling surface of a polyester release film (trade name "Diafoil MRF", manufactured by Mitsubishi Polyester Co., Ltd.) having a thickness of 38 ⁇ m, dried at 120 ° C. for 2 minutes, and had a thickness of 20 ⁇ m.
  • a pressure-sensitive adhesive layer was formed.
  • a peeling surface of a polyester peeling film (trade name "Diafoil MRF", manufactured by Mitsubishi Polyester Co., Ltd.) having a thickness of 25 ⁇ m was attached to this pressure-sensitive adhesive layer, and then aged at 50 ° C. for 24 hours. In this way, a base material-less double-sided pressure-sensitive adhesive sheet having a thickness of 20 ⁇ m was obtained in which both sides were protected by the above two polyester release films.
  • Example 2 to 3 The amount of the epoxy-based cross-linking agent used was changed to 0.03 part (Example 2) or 0.05 part (Example 3) with respect to 100 parts of the acrylic polymer.
  • the pressure-sensitive adhesive composition according to each example was prepared in the same manner as in Example 1, and the base-less double-sided pressure-sensitive adhesive sheet according to each example was prepared using the pressure-sensitive adhesive composition.
  • Example 4 As the tackifying resin, 30 parts of the tackifying resin B1 is applied to 100 parts of the acrylic polymer, the tackifying resin B2 (polymerized rosin ester manufactured by Arakawa Chemical Industry Co., Ltd., trade name "Pencel D-125", softening points 120 to 130). ° C.) was used in 10 parts. Other than that, the pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 2, and the base-less double-sided pressure-sensitive adhesive sheet according to this example was prepared using the pressure-sensitive adhesive composition.
  • Example 5 The amount of the tackifier resin B1 used for 100 parts of the acrylic polymer was changed to 50 parts.
  • the pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 2, and the base-less double-sided pressure-sensitive adhesive sheet according to this example was prepared using the pressure-sensitive adhesive composition.
  • Example 6 As the tackifier resin, 40 parts of the tackifier resin B1 and 10 parts of the tackifier resin B2 were used for 100 parts of the acrylic polymer. Other than that, the pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 4, and the base-less double-sided pressure-sensitive adhesive sheet according to this example was prepared using the pressure-sensitive adhesive composition.
  • Example 7 The amount of the tackifier resin B1 used for 100 parts of the acrylic polymer was changed to 75 parts.
  • the pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 2, and the base-less double-sided pressure-sensitive adhesive sheet according to this example was prepared using the pressure-sensitive adhesive composition.
  • Example 8> A solution of the acrylic polymer A2 was obtained in the same manner as in Example 1 except that the monomer composition was changed to 25 parts of 2EHA, 70 parts of n-butyl acrylate (BA) and 5 parts of AA.
  • a substrate-less double-sided pressure-sensitive adhesive sheet according to this example was produced in the same manner as in Example 1 except that the obtained pressure-sensitive adhesive composition was used.
  • Example 9 A solution of the acrylic polymer A3 was obtained in the same manner as in Example 1 except that the monomer composition was changed to 42 parts of 2EHA, 43 parts of BA and 5 parts of AA.
  • a pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 8 except that the obtained acrylic polymer A3 was used, and the base-less double-sided pressure-sensitive adhesive sheet according to this example was used using the pressure-sensitive adhesive composition.
  • Example 9 A solution of the acrylic polymer A3 was obtained in the same manner as in Example 1 except that the monomer composition was changed to 42 parts of 2EHA, 43 parts of BA and 5 parts of AA.
  • a pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 8 except that the obtained acrylic polymer A3 was used, and the base-less double-sided pressure-sensitive adhesive sheet according to this example was used using the pressure-sensitive adhesive composition. was produced.
  • Example 10 As the tackifier resin, 40 parts of the tackifier resin B3 (product name "Super Ester A-100", rosin ester manufactured by Arakawa Chemical Industry Co., Ltd., softening point 95 to 105 ° C.) was used for 100 parts of the acrylic polymer. Other than that, the pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 2, and the base-less double-sided pressure-sensitive adhesive sheet according to this example was prepared using the pressure-sensitive adhesive composition.
  • the tackifier resin B3 product name "Super Ester A-100", rosin ester manufactured by Arakawa Chemical Industry Co., Ltd., softening point 95 to 105 ° C.
  • the pressure-sensitive adhesive composition according to each example was prepared in the same manner as in Example 2 except that the type and amount of the pressure-sensitive adhesive resin were changed as shown in Table 2, and the pressure-sensitive adhesive composition was used in each example.
  • a substrate-less double-sided pressure-sensitive adhesive sheet was produced.
  • the tackifier resin B4 has a product name "Super Ester A-125" (rosin ester manufactured by Arakawa Chemical Industry Co., Ltd., softening point 120 to 130 ° C.).
  • the adhesives according to Examples 1 to 10 have an adhesive force against PP of 12 N / 20 mm or more, an adhesive force against PE of 6 N / 20 mm or more, and a deviation distance of 1 in the holding force test. It was 0.0 mm or less, showed high adhesive strength to the LSE surface, and had good holding power.
  • Comparative Examples 1 and 2 in which the amount of the tackifier resin used is less than 40 parts by weight with respect to 100 parts of the acrylic polymer are Examples 1 in which the amount of the tackifier resin used is 40 parts, 50 parts, and 75 parts.
  • the adhesive strength against PP tended to be lower, and the adhesive strength against PE also tended to be lower.
  • Comparative Examples 5 to 7 in which the use ratio of the tackifier resin TL having a softening point of 110 ° C. or lower is less than 60% are the same as in Examples 4 and 6 in which the use ratio of the tackifier resin TL is 60% or more.
  • the result was that the adhesive strength against PP was low. It is considered that high adhesion to various LSE surfaces (particularly PP) can be obtained by using a sufficient amount of the tackifier resin TL showing a low softening point.
  • Comparative Examples 10 and 11 using an acrylic polymer in which the usage ratio of the alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal is less than 15%, as compared with Examples 8 and 9. ,
  • the adhesive strength tended to decrease for all adherends. From the results of Examples 8 and 9 and Comparative Examples 10 and 11, the polymerization ratio of the alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal was set to 15% or more to obtain a tackifier resin. It is considered that the compatibility was improved, the effect of containing the tackifier resin was effectively exhibited, and the adhesive strength was improved.
  • the alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms at the ester terminal is polymerized at a ratio of 15% by weight or more, and the carboxy group-containing monomer is not copolymerized, or the carboxy is used.
  • An acrylic polymer having a copolymerization ratio of less than 10% by weight of the group-containing monomer is used, and a tackifier resin is used at a ratio of 40 to 80 parts with respect to 100 parts of the acrylic polymer to impart a tackiness having a softening point of 110 ° C. or lower.
  • the pressure-sensitive adhesive sheet containing the resin TL and the content ratio thereof is 60% by weight or more of the total amount of the pressure-sensitive adhesive resin, the adhesive strength to the low surface free energy surface can be improved while having a good holding power. I understand.
  • 1,2,3 Adhesive sheet 10 Supporting base material 10A First side 10B Second side (back side) 21 Adhesive layer (first adhesive layer) 21A Adhesive surface (first adhesive surface) 21B Second adhesive surface 22 Adhesive layer (second adhesive layer) 22A Adhesive surface (second adhesive surface) 31,32 Peeling liner 100,200,300 Adhesive sheet with peeling liner

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Citations (9)

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Publication number Priority date Publication date Assignee Title
US20110275748A1 (en) * 2010-05-04 2011-11-10 Griffith William B Method for adhering roofing membranes
WO2015037378A1 (ja) * 2013-09-10 2015-03-19 積水化学工業株式会社 電子機器用粘着シート
JP2015165023A (ja) * 2014-02-28 2015-09-17 日東電工株式会社 粘着剤組成物および粘着シート
JP2017214595A (ja) * 2017-08-30 2017-12-07 株式会社クラレ 粘接着剤組成物
JP2017538810A (ja) * 2014-11-18 2017-12-28 テーザ・ソシエタス・ヨーロピア 感圧接着剤の巻き出し力の制御のための変性層状シリケート及び接着テープのバリア特性の改善法
JP2018177902A (ja) * 2017-04-07 2018-11-15 綜研化学株式会社 粘着剤組成物および粘着シート
JP2020019928A (ja) * 2019-04-17 2020-02-06 東洋インキＳｃホールディングス株式会社 粘着剤および粘着シート
JP2020097649A (ja) * 2018-12-17 2020-06-25 Dic株式会社 自動車用組電線固定用粘着テープ
JP2021161138A (ja) * 2020-03-30 2021-10-11 リンテック株式会社 粘着シート、及び粘着シートの製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110275748A1 (en) * 2010-05-04 2011-11-10 Griffith William B Method for adhering roofing membranes
WO2015037378A1 (ja) * 2013-09-10 2015-03-19 積水化学工業株式会社 電子機器用粘着シート
JP2015165023A (ja) * 2014-02-28 2015-09-17 日東電工株式会社 粘着剤組成物および粘着シート
JP2017538810A (ja) * 2014-11-18 2017-12-28 テーザ・ソシエタス・ヨーロピア 感圧接着剤の巻き出し力の制御のための変性層状シリケート及び接着テープのバリア特性の改善法
JP2018177902A (ja) * 2017-04-07 2018-11-15 綜研化学株式会社 粘着剤組成物および粘着シート
JP2017214595A (ja) * 2017-08-30 2017-12-07 株式会社クラレ 粘接着剤組成物
JP2020097649A (ja) * 2018-12-17 2020-06-25 Dic株式会社 自動車用組電線固定用粘着テープ
JP2020019928A (ja) * 2019-04-17 2020-02-06 東洋インキＳｃホールディングス株式会社 粘着剤および粘着シート
JP2021161138A (ja) * 2020-03-30 2021-10-11 リンテック株式会社 粘着シート、及び粘着シートの製造方法

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