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WO2023119752A1 - Feuille adhésive - Google Patents

Feuille adhésive Download PDF

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Publication number
WO2023119752A1
WO2023119752A1 PCT/JP2022/034509 JP2022034509W WO2023119752A1 WO 2023119752 A1 WO2023119752 A1 WO 2023119752A1 JP 2022034509 W JP2022034509 W JP 2022034509W WO 2023119752 A1 WO2023119752 A1 WO 2023119752A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
adhesive sheet
mass
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/034509
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English (en)
Japanese (ja)
Inventor
陽平 林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
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Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2022113444A external-priority patent/JP2023092434A/ja
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of WO2023119752A1 publication Critical patent/WO2023119752A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/18—Layered products comprising a layer of natural or synthetic rubber comprising butyl or halobutyl rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/10—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
    • 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
    • C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • C09J125/10—Copolymers of styrene with conjugated dienes
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive sheet. More specifically, the present invention relates to a pressure-sensitive adhesive sheet that is used, for example, for applying a moisture-permeable waterproof sheet to an object to be applied.
  • Patent Literature 1 describes a pressure-sensitive adhesive sheet including a first pressure-sensitive adhesive layer attached to a construction target and a second pressure-sensitive adhesive layer attached to a waterproof/moisture-permeable sheet.
  • the first adhesive layer contains a first rubber component containing 40 to 93% by mass of butyl rubber and 7 to 60% by mass of polyisobutylene
  • the first pressure-sensitive adhesive layer contains the first softener having a kinematic viscosity of 100 to 9000 mm 2 /s at 40° C. in a blending ratio of 82 to 128 parts by mass with respect to 100 parts by mass of the first rubber component. It is stated that It is also described that by configuring the pressure-sensitive adhesive sheet as described above, excellent adhesion can be achieved in a wide temperature range (-10°C to 60°C) when the moisture-permeable waterproof sheet is applied to the application site. .
  • adhesive sheets are required to exhibit excellent adhesiveness over a wide temperature range, but it is difficult to say that this requirement is fully satisfied.
  • an object of the present invention is to provide a pressure-sensitive adhesive sheet that can exhibit more sufficient adhesiveness in a wide temperature range from low to high temperatures.
  • the pressure-sensitive adhesive sheet according to the present invention is a substrate; A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer laminated on at least one surface of the substrate, The pressure-sensitive adhesive layer contains butyl rubber as an organic component,
  • the ratio of the storage modulus value G 2 ' at ⁇ 10° C. to the storage modulus value G 1 ' at 60° C. (G 2 '/G 1 ') is less than 12;
  • the value G 2 ' of the storage modulus at -10°C is 0.7 MPa or less,
  • the adhesive strength at -10°C is 2.0 N/25 mm or more.
  • FIG. 2 is a cross-sectional view showing a configuration in which a filler layer is arranged in the pressure-sensitive adhesive sheet according to one embodiment of the present invention.
  • Sectional drawing which shows the structure of the adhesive sheet which concerns on other embodiment of this invention.
  • the pressure-sensitive adhesive sheet according to the present invention is a pressure-sensitive adhesive sheet having a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material.
  • the adhesive layer contains butyl rubber (isobutylene-isoprene rubber (IIR)) as an organic component.
  • IIR isobutylene-isoprene rubber
  • the pressure-sensitive adhesive layer has a ratio of the storage elastic modulus value G 2 ' at -10°C to the storage elastic modulus value G 1 ' at 60°C (G 2 '/G 1 '). is less than 12.
  • the pressure-sensitive adhesive layer has a storage modulus value G 2 ' at -10°C of 0.7 MPa or less. Furthermore, in the adhesive sheet according to the present invention, the adhesive layer has an adhesive strength of 2.0 N/25 mm or more at -10°C.
  • the storage elastic modulus value G 2 ' of the adhesive layer at -10 ° C. is 0.7 MPa or less, and the storage elastic modulus value G 1 ' at 60 ° C. at -10 ° C.
  • the ratio (G 2 '/G 1 ') of the value G 2 ' of the storage elastic modulus is less than 12. Therefore, in the pressure-sensitive adhesive sheet according to the present invention, the pressure-sensitive adhesive layer has an appropriate elastic modulus in a wide temperature range from low temperature (-10°C) to high temperature (60°C). It is possible to exhibit good conformability to the substrate (object to be constructed such as a moisture-permeable waterproof sheet or the inner wall of a house) in a wide temperature range from low temperature to high temperature.
  • the pressure-sensitive adhesive layer has a high pressure-sensitive adhesive strength of 2 N/25 mm or more even at a low temperature (-10°C) at which the pressure-sensitive adhesiveness may decrease significantly. Therefore, in the pressure-sensitive adhesive sheet according to the present invention, the pressure-sensitive adhesive layer can exhibit sufficient adhesiveness in a wide temperature range from low to high. Thereby, the pressure-sensitive adhesive sheet according to the present invention can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • the butyl rubber may maintain a molecular weight of 20% or more after being heated at 100°C for 7 weeks.
  • the maintenance rate of the molecular weight of the butyl rubber after being heated at 100°C for 7 weeks is 20% or more
  • the peak top value of the peak of the molecular weight (range of 250,000 or more and 800,000 or less) attributed to the butyl rubber is defined as MP0
  • M P1 the value calculated by dividing M P1 by M P0 and multiplying by 100 (M P1 / M P0 ⁇ 100 calculated value ) is 20 or more.
  • the molecular weight attributed to the butyl rubber means the weight average molecular weight.
  • the molecular weight (mass average molecular weight) attributed to the butyl rubber by GPC can be determined as a standard polystyrene conversion value. More specifically, using HLC-8420GPC manufactured by TOSOH, it can be determined by measuring the sample obtained as follows under the following conditions. [Method of acquiring specimen] (1) Samples collected from the adhesive layer containing the butyl rubber (sample collected from the adhesive layer before heating at 100 ° C. and sample collected from the adhesive layer after heating at 100 ° C. for 7 weeks ) was prepared in a 1.0 g/L THF solution and allowed to stand overnight.
  • the butyl rubber is obtained by addition polymerization of isobutylene, which is one raw material monomer, and isoprene, which is another raw material monomer.
  • the deterioration of the butyl rubber is caused by the scission of the main chain due to an oxidation reaction or the like at the ⁇ -position carbon portion adjacent to the carbon-carbon double bond, and the butyl rubber becomes low-molecular or the molecular weight of the butyl rubber becomes less than 250,000. or), at the ⁇ -position carbon portion adjacent to the carbon-carbon double bond, the main chains are bonded to each other by an oxidation reaction or the like to polymerize (the molecular weight of the butyl rubber exceeds 800,000). occur.
  • the pressure-sensitive adhesive layer contains polymerized butyl rubber
  • the pressure-sensitive adhesive layer becomes hard
  • the pressure-sensitive adhesive layer contains low-molecular-weight butyl rubber
  • the pressure-sensitive adhesive layer becomes soft. Become.
  • the pressure-sensitive adhesive layer becomes hard or soft in this way, it becomes difficult for the pressure-sensitive adhesive layer to exhibit sufficient adhesiveness to an application target (for example, an inner wall of a house).
  • heating the adhesive sheet at 100 ° C. for 7 weeks means that the deterioration of butyl rubber occurring in the adhesive layer over a long period of time is considered to progress in a short time by exposing the adhesive sheet to severe conditions. This corresponds to the "deterioration test". Therefore, after heating at 100° C. for 7 weeks, the higher the molecular weight retention rate of the butyl rubber in the adhesive layer, that is, the lower the ratio of the deteriorated butyl rubber in the adhesive layer, the higher the The adhesive layer exhibits sufficient adhesiveness over a long period of time with respect to the object to be applied.
  • the pressure-sensitive adhesive layer has excellent long-term durability, and by extension, the pressure-sensitive adhesive sheet provided with the pressure-sensitive adhesive layer also has excellent long-term durability.
  • the adhesive layer when the molecular weight retention rate of the butyl rubber after being heated at 100° C. for 7 weeks is a relatively high value of 20% or more, , the adhesive layer exhibits sufficient adhesiveness to the object to be applied over a long period of time.
  • the adhesive sheet provided with the adhesive layer as described above can be applied to the object to be applied to several tens of times after application.
  • the pressure-sensitive adhesive sheet according to the present invention has the pressure-sensitive adhesive layer as described above, the pressure-sensitive adhesive sheet has excellent long-term durability.
  • the maintenance rate of the molecular weight of the butyl rubber after being heated at 100° C. for 7 weeks is also referred to as the maintenance rate of the molecular weight of the butyl rubber after the accelerated deterioration test.
  • the retention rate of the molecular weight of the butyl rubber after the accelerated deterioration test is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, and 80% or more. More preferably, it is particularly preferably 90% or more.
  • a single-sided pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is laminated on one side of a substrate will be described as an example of a pressure-sensitive adhesive sheet according to an embodiment of the present invention.
  • a pressure-sensitive adhesive sheet 10 As shown in FIG. 1A, a pressure-sensitive adhesive sheet 10 according to one embodiment of the present invention has a base material 1 and a pressure-sensitive adhesive layer 2 laminated on one side of the base material 1 .
  • the pressure-sensitive adhesive layer 2 is attached to the moisture-permeable waterproof sheet.
  • the adhesive layer 2 contains butyl rubber as an organic component.
  • butyl rubber is a copolymer of isobutene (isobutylene) and a small amount of isoprene (isobutylene-isoprene).
  • examples of butyl rubber include synthetic butyl rubber and recycled butyl rubber.
  • the adhesive layer 2 preferably contains synthetic butyl rubber as a main component.
  • the pressure-sensitive adhesive layer 2 preferably contains 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more of synthetic butyl rubber based on the total amount of butyl rubber. is more preferred, and 100% by mass is particularly preferred. That is, it is particularly preferable that all of the butyl rubber contained in the pressure-sensitive adhesive layer 2 is synthetic butyl rubber.
  • the recycled butyl rubber is obtained by recycling rubber products (for example, tires and tubes) obtained using butyl rubber as a raw material.
  • oils such as pine oil and mineral oil are used. be. Therefore, the oil used in the regeneration process remains in the reclaimed butyl rubber.
  • the adhesive layer 2 contains recycled butyl rubber as the butyl rubber
  • a moisture-permeable waterproof sheet is attached to the adhesive layer 2
  • the oil contained in the recycled butyl rubber migrates to the moisture-permeable waterproof sheet.
  • the moisture-permeable waterproof sheet is made of a fiber sheet (in particular, when it is made of a high-density polyethylene non-woven fabric), the oil transferred from the pressure-sensitive adhesive layer 2 causes the moisture-permeable waterproof sheet to becomes swollen. If the moisture-permeable waterproof sheet swells in this way, it is not preferable because the adhesion of the pressure-sensitive adhesive layer 2 to the moisture-permeable waterproof sheet cannot be sufficiently ensured.
  • the adhesive layer 2 contains 70% by mass or more of synthetic butyl rubber based on the total amount of butyl rubber, the content of the oil derived from the recycled rubber in the adhesive layer 2 can be relatively reduced, it is possible to suppress swelling of the moisture-permeable waterproof sheet even if the moisture-permeable waterproof sheet is made of a fiber sheet.
  • the weight average molecular weight of the butyl rubber is preferably 30,000 or more and 1,500,000 or less.
  • the weight average molecular weight of the butyl rubber is more preferably 200,000 or more, more preferably 300,000 or more.
  • the mass-average molecular weight of the butyl rubber is more preferably 800,000 or less, more preferably 700,000 or less.
  • the weight average molecular weight of the butyl rubber contained in the pressure-sensitive adhesive layer 2 can be obtained as a standard polystyrene conversion value from GPC (gel permeation chromatography) measurement. More specifically, the mass average molecular weight of the butyl rubber contained in the pressure-sensitive adhesive layer 2 can be measured using HLC-8420GPC manufactured by TOSOH in the same manner as described above.
  • the adhesive layer 2 may contain a rubber component other than butyl rubber as an organic component.
  • Rubber components other than butyl rubber include rubbers other than butyl rubber and thermoplastic elastomers.
  • Examples of rubbers other than butyl rubber include polyisobutylene rubber, acrylic rubber, silicone rubber, urethane rubber, vinyl alkyl ether rubber, polyvinyl alcohol rubber, polyvinylpyrrolidone rubber, polyacrylamide rubber, cellulose rubber, natural rubber, butadiene rubber, and chloroprene rubber. , styrene-butadiene rubber, acrylonitrile-butadiene rubber, isoprene rubber, ethylene-propylene rubber, and the like.
  • Examples of thermoplastic elastomers include styrene-based thermoplastic elastomers and acrylic-based thermoplastic elastomers.
  • styrene-based thermoplastic elastomer examples include styrene/ethylene/butadiene/styrene block copolymer (SEBS), styrene/isoprene/styrene block copolymer (SIS), and styrene/butadiene/styrene block copolymer (SBS). ), and styrene/ethylene/propylene/styrene block copolymer (SEPS).
  • acrylic thermoplastic elastomers examples include acrylic rubbers containing acrylic acid ester as a main component.
  • the acrylic rubbers include copolymers of acrylic acid esters and 2-chloroethylvinyl ether, acrylic acid Copolymers of esters and acrylonitrile and copolymers of acrylic acid esters and acrylic acid can be mentioned.
  • the pressure-sensitive adhesive layer 2 preferably contains the thermoplastic elastomer, and preferably contains at least one of a styrene-based thermoplastic elastomer and an acrylic-based thermoplastic elastomer.
  • the thermoplastic elastomer may be a styrene-based thermoplastic elastomer.
  • the pressure-sensitive adhesive layer 2 contains at least one of styrene-isoprene-styrene block copolymer (SIS) and styrene-isobutylene-styrene block copolymer (SIBS) among the styrene-based thermoplastic elastomers. is preferred.
  • SIS styrene-isoprene-styrene block copolymer
  • SIBS styrene-isobutylene-styrene block copolymer
  • the pressure-sensitive adhesive layer 2 may contain only a thermoplastic elastomer as rubber other than the butyl rubber. In such a case, the pressure-sensitive adhesive layer 2 contains 70% by mass or more of the butyl rubber when the sum of the content of the butyl rubber and the content of the thermoplastic elastomer is taken as 100% by mass. It may contain 30% by mass or less of a thermoplastic elastomer. In the above case, the pressure-sensitive adhesive layer 2 may contain 80% by mass or more of the butyl rubber and 20% by mass or less of the thermoplastic elastomer. Furthermore, in the above case, the pressure-sensitive adhesive layer 2 may contain the thermoplastic elastomer in an amount of 1% by mass or more, 2% by mass or more, or 3% by mass or more. .
  • the pressure-sensitive adhesive layer 2 may contain synthetic butyl rubber as the butyl rubber in an amount of 70% by mass or more, 80% by mass or more, 90% by mass or more, or 100% by mass. good too.
  • the pressure-sensitive adhesive layer 2 may contain the butyl rubber as described above, and may contain only a thermoplastic elastomer as rubber other than the butyl rubber. As the content of the butyl rubber and the content of the thermoplastic elastomer, those described above can be adopted. When the pressure-sensitive adhesive layer 2 contains the butyl rubber and the thermoplastic elastomer in the form described above, it is possible to reduce the extent to which the pressure-sensitive adhesive layer 2 stains (colors and stains) the adherend.
  • the pressure-sensitive adhesive layer 2 preferably contains 1 part by mass or more of the thermoplastic elastomer with respect to 100 parts by mass of the total amount of the butyl rubber and the thermoplastic elastomer. Further, the pressure-sensitive adhesive layer 2 preferably contains 3 parts by mass or more of the thermoplastic elastomer with respect to 100 parts by mass of the total amount of the butyl rubber and the thermoplastic elastomer, and more preferably 5 parts by mass or more. is more preferable, it is more preferable that it contains 7 parts by mass or more, and it is more preferable that it contains 9 parts by mass or more.
  • the upper limit of the mass parts of the thermoplastic elastomer to 100 mass parts of the total amount of the butyl rubber and the thermoplastic elastomer is usually 30 parts by mass.
  • the upper limit value may be 20 parts by mass. Since the pressure-sensitive adhesive layer 2 contains the thermoplastic elastomer within the above numerical range, the pressure-sensitive adhesive layer 2 can withstand a wide temperature range from low temperature (eg, -10°C) to high temperature (eg, 60°C). , more sufficient adhesiveness can be exhibited. That is, the pressure-sensitive adhesive layer 2 can exhibit more sufficient adhesion to the adherend.
  • the mass average molecular weight of the thermoplastic elastomer is preferably 20,000 or more and 1,500,000 or less.
  • the mass average molecular weight can be obtained as a standard polystyrene conversion value from GPC (gel permeation chromatography) measurement.
  • the mass-average molecular weight of the thermoplastic elastomer can be measured in the same manner as the mass-average molecular weight of the butyl rubber described above.
  • the styrene content (styrene content) in the styrene-based thermoplastic elastomer is preferably 10% by mass or more, and 15% by mass. It is more preferably 20% by mass or more, and more preferably 20% by mass or more.
  • the styrene content in the styrene-based thermoplastic elastomer is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.
  • the diblock ratio of the styrene-based thermoplastic elastomer is preferably 10% or more, and preferably 25% or more. is more preferable, and 50% or more is even more preferable. Further, the diblock ratio of the styrene-based thermoplastic elastomer is preferably 70% or less. Since the diblock ratio of the styrene-based thermoplastic elastomer is within the above numerical range, the pressure-sensitive adhesive sheet 10 can be used in a wide temperature range from a low temperature (eg, -10°C) to a high temperature (eg, 60°C). Sufficient adhesiveness can be exhibited.
  • a low temperature eg, -10°C
  • a high temperature eg, 60°C
  • the diblock ratio is obtained by measuring the molecular weight of the styrene-based thermoplastic elastomer by gel permeation chromatography (GPC), and the peak attributed to the diblock copolymer in the resulting chart, It can be calculated from the area ratio to the peak attributed to the block copolymer.
  • GPC gel permeation chromatography
  • Methods for adjusting the diblock ratio in the styrenic thermoplastic elastomer include changing the amount ratio of the polymerization initiator and the coupling agent used during polymerization (coupling agent amount/polymerization initiator amount). .
  • the pressure-sensitive adhesive layer 2 preferably contains 8% by mass or more of the rubber component, more preferably 10% by mass or more.
  • the pressure-sensitive adhesive layer 2 preferably contains the rubber component in an amount of 50% by mass or less, more preferably 45% by mass or less.
  • the term "rubber component" is a general concept that includes butyl rubber, rubbers other than butyl rubber, and thermoplastic elastomers.
  • the pressure-sensitive adhesive layer 2 may contain a softening agent, a tackifier, an anti-aging agent, etc. as organic components other than the rubber component.
  • the pressure-sensitive adhesive layer 2 preferably contains an anti-aging agent among the organic components other than the above various rubber components.
  • the adhesive layer 2 preferably contains a tackifier among the organic components other than the various rubber components described above.
  • the softening agent examples include paraffins, waxes, naphthenes, aromas, asphalts, drying oils (eg, linseed oil), animal and vegetable oils, petroleum oils (eg, process oils), polybutene , polyisobutylene, ethylene/ ⁇ -olefin co-oligomer, low-molecular-weight polyethylene glycol, phthalates, phosphates, stearic acid or its esters, and alkylsulfonates.
  • the said softening agent may be used individually and may be used in combination of 2 or more type.
  • the pressure-sensitive adhesive layer 2 preferably contains at least one of polyisobutylene and ethylene/ ⁇ -olefin co-oligomer.
  • the kinematic viscosity of the softener at 40° C. is preferably 700 mm 2 /s or more, more preferably 900 mm 2 /s or more. Also, the kinematic viscosity of the softener at 40° C. is preferably 100000 mm 2 /s or less, more preferably 50000 mm 2 /s or less.
  • the kinematic viscosity is measured according to JIS K 2283 (2000). Specifically, the kinematic viscosity is measured with a glass capillary viscometer. When using a plurality of softeners having different kinematic viscosities, the kinematic viscosity is determined as the kinematic viscosity of a mixture of the plurality of softeners.
  • the adhesive layer 2 preferably contains 30 parts by mass or more, more preferably 50 parts by mass or more, and 120 parts by mass or more of the softener with respect to 100 parts by mass of the rubber component. More preferably 130 parts by mass or more, more preferably 170 parts by mass or more.
  • the pressure-sensitive adhesive layer 2 preferably contains 500 parts by mass or less, more preferably 400 parts by mass or less, and 300 parts by mass or less of the softener with respect to 100 parts by mass of the rubber component. More preferably, it contains 260 parts by mass or less.
  • tackifiers include rosin-based resins, terpene-based resins, styrene-based resins, petroleum-based resins, phenol-based resins, and hydrogenated resins obtained by hydrogenating these resins. These tackifiers may be used alone or in combination of two or more.
  • rosin-based resins examples include rosin resins, rosin ester resins, and rosin phenol resins.
  • the terpene-based resin may be any compound having a structural unit derived from isoprene, and examples thereof include terpene resins, aromatic modified terpene resins, and terpene phenol-based resins.
  • Styrenic resins include, for example, resins obtained by copolymerizing styrenic monomers such as ⁇ -methylstyrene or ⁇ -methylstyrene with aliphatic monomers.
  • Petroleum-based resins include, for example, C5-based hydrocarbon resins obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, and 1,3-pentadiene produced by thermal decomposition of petroleum naphtha; thermal decomposition of petroleum naphtha and C9-based hydrocarbon resins obtained by copolymerizing C9 fractions such as indene and vinyltoluene produced in .
  • phenolic resins include alkylphenolic resins, xylylene formaldehyde resins, resols, and novolacs.
  • the pressure-sensitive adhesive layer 2 preferably contains a petroleum-based resin, and more preferably contains a C5-based hydrocarbon resin as the petroleum-based resin.
  • the pressure-sensitive adhesive layer 2 preferably contains 5 parts by mass or more of the tackifier, more preferably 10 parts by mass or more, relative to 100 parts by mass of the rubber component.
  • the pressure-sensitive adhesive layer 2 preferably contains 200 parts by mass or less of the tackifier, more preferably 150 parts by mass or less, and 70 parts by mass, relative to 100 parts by mass of the rubber component. More preferably, it contains 40 parts by mass or less, and more preferably 30 parts by mass or less.
  • the ratio of the content of the butyl rubber to the content of the tackifier is preferably 2.2 or more. It is more preferably 0 or more, and even more preferably 5.0 or more.
  • the ratio of the content of the butyl rubber to the content of the tackifier is preferably 15.0 or less, more preferably 10.0 or less, and 8.0 or less. is more preferable.
  • anti-aging agents examples include phenol-based anti-aging agents, amine-based anti-aging agents, phosphorus-based anti-aging agents, and sulfur-based anti-aging agents.
  • Examples of the phenol-based anti-aging agent include bisphenol-based anti-aging agents and hindered phenol-based anti-aging agents.
  • Examples of the bisphenol-based antioxidants include 2,2'-methylenebis(4-methyl-6-tert-butylphenol) represented by the following formula (1), 4,4 '-thiobis(3-methyl-6-tert-butylphenol) and the like.
  • Commercially available products of the bisphenol-based antioxidant represented by the following formula (1) include "Nocrac NS-6" (trade name) manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., and the like.
  • Commercially available products of the bisphenol-based antioxidant represented by the following formula (2) include "Nocrac 300" (trade name) manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., and the like.
  • hindered phenol anti-aging agent examples include, for example, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane represented by the following formula (3), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4, represented by (4), 8,10-tetraoxaspiro[5.5]undecane and the like.
  • hindered phenol anti-aging agent represented by the following formula (3)
  • Commercial products of the hindered phenol anti-aging agent represented by the following formula (3) include ADEKA's trade name "ADEKA STAB AO-60", SONGWON's trade name “SONGNOX (registered trademark) 1010", and BASF. trade name "Irganox (registered trademark) 1000" manufactured by the company.
  • Commercially available hindered phenol anti-aging agents represented by the following formula (4) include "SUMILIZER GA-80" (trade name) manufactured by Sumitomo Chemical Co., Ltd., "ADEKA STAB AO-80” (trade name) manufactured by ADEKA, and the like. is mentioned.
  • the phenol-based antioxidant preferably has a mass average molecular weight of 350 or more, more preferably 500 or more, more preferably 600 or more, more preferably 700 or more, and 800 or more. , more preferably 900 or more, and more preferably 1000 or more.
  • mass average molecular weight of the phenolic antiaging agent is within the above numerical range, volatilization of the phenolic antiaging agent from the pressure-sensitive adhesive layer 2 can be suppressed.
  • deterioration of the butyl rubber contained in the pressure-sensitive adhesive layer 2 due to an oxidation reaction or the like polymerization or low-molecularization of the butyl rubber
  • the amine anti-aging agent is preferably an aromatic secondary amine anti-aging agent.
  • the aromatic secondary amine anti-aging agent is a secondary amine in which an aromatic pipe is bound to a nitrogen atom.
  • the aromatic secondary amine antioxidant preferably has a softening point of 50°C or higher, more preferably 80°C or higher.
  • the aromatic secondary amine anti-aging agent preferably has a mass average molecular weight of 300 or more, more preferably 350 or more.
  • aromatic secondary amine-based antioxidant examples include, for example, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine represented by the following formula (5); ), and 4,4'-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine represented by the following formula (7).
  • aromatic secondary amine anti-aging agent represented by the following formula (5) examples include "Nocrac 6C" (trade name) manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., and the like.
  • aromatic secondary amine anti-aging agents represented by the following formula (6) include "Nocrac White” (trade name) manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., and the like. Further, commercial products of the aromatic secondary amine anti-aging agent represented by the following formula (7) include "Nocrac CD” (trade name) manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., and the like.
  • Amine anti-aging agents generally have the property of being highly colored with respect to rubber components such as the butyl rubber.
  • the aromatic secondary amine anti-aging agent represented by the above formula (5) has the property of being highly colored with respect to rubber components such as the butyl rubber.
  • the aromatic secondary amine anti-aging agent represented by the above formula (6) and the aromatic secondary amine anti-aging agent represented by the above formula (7) are the butyl rubber and the like. It has the property of being low in colorability (staining resistance) to the rubber component. That is, the aromatic secondary amine anti-aging agents represented by the above formulas (6) and (7) are amine anti-aging agents characterized by being non-staining. Therefore, from the viewpoint of suppressing contamination due to coloring of the rubber component, it is preferable to use an aromatic secondary amine antioxidant represented by the above formula (6) or (7) as the amine antioxidant. .
  • Examples of the phosphorus anti-aging agent include tris(2,4-di-tert-butylphenyl)phosphite represented by the following formula (8).
  • Commercially available phosphorus-based antioxidants represented by the following formula (8) include BASF's trade name "Irgafos (registered trademark) 168" and SONGWON's trade name "SONGNOX (registered trademark) 168". mentioned.
  • sulfur-based anti-aging agent examples include 2-mercaptobenzimidazole represented by the following formula (9).
  • Commercial products of the sulfur-based anti-aging agent represented by the following formula (9) include "Sumilizer (registered trademark) MB” manufactured by Sumika Chemtex Co., Ltd., and the like.
  • the phenol-based anti-aging agent and the amine-based anti-aging agent are called primary anti-aging agents, and the phosphorus-based anti-aging agent and the sulfur-based anti-aging agent are They are called secondary antioxidants.
  • the primary anti-aging agent is caused by radicals generated from the butyl rubber, in other words, a reaction in which radicals are generated from the butyl rubber becomes an initiation reaction, and oxidation of the butyl rubber progresses. (hereinafter referred to as auto-oxidation reaction), it is an anti-aging agent that preferentially reacts with the radical to stabilize the radical, and the secondary anti-aging agent decomposes the hydroperoxide generated in the auto-oxidation reaction.
  • the secondary anti-aging agent is also called a peroxide-decomposing anti-aging agent because it has the property of decomposing hydroperoxide as described above.
  • the autoxidation reaction is one aspect of the oxidation reaction of the butyl rubber.
  • Another aspect of the oxidation reaction of the butyl rubber is a direct oxidation reaction in which the pressure-sensitive adhesive layer 2 contains an oxidizing agent so that the oxidation of the butyl rubber proceeds.
  • the anti-aging agent may be a composite anti-aging agent having both the properties of the primary anti-aging agent and the properties of the secondary anti-aging agent.
  • the composite anti-aging agent include those in which sulfur is contained in the structure of a compound having a phenol structure, that is, a sulfur-containing phenol anti-aging agent.
  • the sulfur-containing phenolic anti-aging agent include, for example, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5- triazin-2-ylamino)phenol and the like.
  • Commercially available sulfur-containing phenol antioxidants represented by the following formula (10) include BASF's trade name "Irganox (registered trademark) 565".
  • the pressure-sensitive adhesive layer 2 preferably contains 2 parts by mass or more, more preferably 3 parts by mass or more, and 4 parts by mass or more of the antioxidant with respect to 100 parts by mass of the rubber component. more preferably 5 parts by mass or more.
  • the pressure-sensitive adhesive layer 2 preferably contains 15 parts by mass or less, more preferably 12 parts by mass or less, of the antioxidant with respect to 100 parts by mass of the rubber component, and 10 parts by mass. It is more preferable to contain the following, and it is more preferable to contain 8 parts by mass or less.
  • the content of the anti-aging agent is within the above range, it is possible to suppress the bleeding phenomenon due to the anti-aging agent in the pressure-sensitive adhesive layer 2, and to suppress the deterioration of the butyl rubber due to the oxidation reaction. . Moreover, setting the upper limit of the anti-aging agent as described above is advantageous in terms of cost.
  • the pressure-sensitive adhesive layer 2 contains at least one selected from the group consisting of the phenol-based anti-aging agent, the amine-based anti-aging agent, the phosphorus-based anti-aging agent, and the sulfur-based anti-aging agent. is preferred.
  • the pressure-sensitive adhesive layer 2 preferably contains the phenol-based anti-aging agent. That is, the pressure-sensitive adhesive layer 2 preferably contains the phenol-based anti-aging agent as the primary anti-aging agent.
  • the pressure-sensitive adhesive layer 2 comprises at least one selected from the first group consisting of the phenol-based antioxidant and the amine-based antioxidant, and the second antioxidant consisting of the phosphorus-based antioxidant and the sulfur-based antioxidant. and at least one selected from the group. That is, the pressure-sensitive adhesive layer 2 preferably contains both the primary anti-aging agent and the secondary anti-aging agent. Moreover, it is preferable that the pressure-sensitive adhesive layer 2 contains the phenol-based anti-aging agent as the primary anti-aging agent and the phosphorus-based anti-aging agent as the secondary anti-aging agent.
  • the pressure-sensitive adhesive layer 2 contains the amine-based antioxidant in addition to the phenol-based antioxidant as the primary anti-aging agent, and the phosphorus-based anti-aging agent as the secondary anti-aging agent. is more preferable.
  • the pressure-sensitive adhesive layer 2 contains at least one of the primary anti-aging agent and the secondary anti-aging agent, so that the molecular weight of the butyl rubber after being heated at 100 ° C. for 7 weeks is It can be sufficiently maintained at 20% by mass or more. As a result, the adhesive layer 2 becomes excellent in long-term durability, and by extension the adhesive sheet 10 also becomes excellent in long-term durability.
  • the phenol-based anti-aging agent is the phosphorus-based anti-aging agent. It is preferably contained in a larger amount than the anti-aging agent.
  • the ratio of CF to CP is preferably 1.1 or more, more preferably 1.5 or more, and more preferably 1.8 or more.
  • the phenol antioxidant is contained in a larger amount than the amine antioxidant. preferably.
  • the ratio of C F to C A is preferably 1.1 or more. More preferably 5 or more, more preferably 2.0 or more, more preferably 2.5 or more, more preferably 3.0 or more, more preferably 3.5 or more more preferred.
  • the autoxidation reaction extracts hydrogen from the main chain of the butyl rubber to obtain radicals derived from the butyl rubber (hereinafter also referred to as first radicals) generated by the abstraction of hydrogen, and hydrogen
  • An initiation reaction to obtain a radical see (a) in FIG. 2)
  • a chain-growth reaction to generate a plurality of radicals different from the first radical and to obtain a plurality of products while regenerating the first radical.
  • a termination reaction (see (c) in FIG. 2).
  • (a) initiation reaction, (b) chain-propagation reaction, and (c) termination reaction will be described.
  • H represents the hydrogen that is abstracted by the initiation reaction
  • R represents the portion that forms the first radical by abstraction of the hydrogen H.
  • the butyl rubber contained in the pressure-sensitive adhesive layer 2 has carbon-carbon double bonds derived from isoprene in its main chain.
  • the hydrogen (H ) is the most likely to be pulled out. Therefore, when the pressure-sensitive adhesive layer 2 containing the butyl rubber receives external energy such as heat or light, the bond between carbon (C) at the ⁇ -position and hydrogen (H) is excited to a high energy state. As a result, the hydrogen (H) bonded to the ⁇ -position carbon (C) is extracted from the ⁇ -position carbon (C).
  • the first radical R. generated by the initiation reaction can easily react with oxygen ( O.sub.2 ) in the air.
  • a peroxy radical (ROO*) different from R* is generated (see formula (2) in FIG. 2).
  • the peroxy radical (ROO) abstracts hydrogen (H) from the ⁇ -position carbon (C) different from the previous ⁇ -position carbon (C), thereby producing hydroperoxide (ROOH) as a product.
  • the first radical R. is generated (see formula (3) in FIG. 2). That is, the first radical R ⁇ is regenerated and hydroperoxide (ROOH) is obtained as a product.
  • the hydroperoxide (ROOH) is a peroxide, and the bond between RO and OH is easily broken. Therefore, in the hydroperoxide (ROOH), the bond between RO and OH is then broken to generate a radical RO and a hydroxyl radical (.OH), which are different from the first radical R. (see equation (4) in FIG. 2).
  • the radical RO generated by the formula (4) abstracts hydrogen (H) from the ⁇ -position carbon (C) different from the ⁇ -position carbon (C) above, thereby producing An alcohol (ROH) is obtained and the first radical R* is generated (see formula (5) in FIG. 2).
  • the hydroxy radical (.OH) generated by the formula (4) also produces the product
  • water (H 2 O) is obtained
  • the first radical R ⁇ is generated (see formula (6) in FIG. 2). That is, the first radical R ⁇ is regenerated, and alcohol (ROH) and water (H 2 O) are obtained as products.
  • the radicals RO generated by the formula (4) undergo a main chain scission reaction at the R portion, resulting in a compound R 2 having an aldehyde group (CHO). CHO is obtained and a radical R 1. different from the first radical R. is generated (see formula (7) in FIG. 2).
  • the butyl rubber Due to the occurrence of the reaction of formula (7), the butyl rubber is made to have a low molecular weight.
  • the pressure-sensitive adhesive layer 2 containing such degraded butyl rubber softens and deteriorates.
  • ⁇ (c) termination reaction As described above, while the chain-propagation reaction proceeds, various radicals generated by the chain-propagation reaction also react with each other. Then, when all the generated radicals disappear, the chain/propagation reaction stops (termination reaction).
  • the termination reaction for example, a reaction in which a first radical R and a hydrogen radical H are reacted to obtain RH as a product (see formula (8) in FIG. 2), is obtained as a product RR (see formula (9) in FIG. 2), and a reaction in which radicals RO react with each other to obtain ROOR as a product (see formula (10) in FIG. 2 See ).
  • the butyl rubber is polymerized when the termination reaction produces a product such as RR or ROOR.
  • the pressure-sensitive adhesive layer 2 containing the polymerized butyl rubber is cured and deteriorated.
  • the butyl rubber contained in the pressure-sensitive adhesive layer 2 deteriorates due to the radical reaction.
  • the various radicals generated as described above in the pressure-sensitive adhesive layer 2 are preferentially reacted with the primary anti-aging agent to obtain the above Radical species can be stabilized.
  • the progress of the auto-oxidation reaction in the pressure-sensitive adhesive layer 2 can be suppressed.
  • the pressure-sensitive adhesive layer 2 contains the secondary antioxidant, the hydroperoxide (ROOH) generated in the pressure-sensitive adhesive layer 2 as described above can be decomposed. Also in this way, the progress of the auto-oxidation reaction in the pressure-sensitive adhesive layer 2 can be suppressed.
  • ROOH hydroperoxide
  • the pressure-sensitive adhesive layer 2 may contain a diene rubber such as a styrene-isoprene-styrene block copolymer (SIS) in addition to the butyl rubber as the rubber component.
  • SIS styrene-isoprene-styrene block copolymer
  • a diene rubber such as SIS has a larger number of carbon-carbon double bonds than the butyl rubber. It also has many ⁇ -position carbons. Therefore, in the diene rubber, hydrogen (H) is more easily extracted from the ⁇ -position carbon (C) as shown by the formula (1) in FIG. 2 than in the butyl rubber.
  • derived radicals hereinafter also referred to as 1' radicals
  • ROOH hydroperoxide
  • the pressure-sensitive adhesive layer 2 contains the diene rubber in addition to the butadiene rubber, the pressure-sensitive adhesive layer 2 contains at least one of the primary anti-aging agent and the secondary anti-aging agent. Thus, deterioration of the butyl rubber in the pressure-sensitive adhesive layer 2 can be suppressed.
  • the adhesive layer 2 may contain an inorganic component.
  • the adhesive layer 2 may contain an inorganic filler and an inorganic colorant as inorganic components.
  • the adhesive layer 2 preferably contains an inorganic filler as an inorganic component.
  • the inorganic filler examples include calcium carbonate (eg, heavy calcium carbonate, light calcium carbonate, etc.), talc, titanium oxide, silica, and magnesium oxide. Among these, it is preferable to use calcium carbonate.
  • the content of the inorganic filler in the adhesive layer 2 is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more.
  • the content of the inorganic filler in the pressure-sensitive adhesive layer 2 is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • Carbon is preferably used as the inorganic colorant, and carbon black is more preferably used.
  • the pressure-sensitive adhesive layer 2 preferably contains 500 parts by mass or less, more preferably 450 parts by mass or less, and 400 parts by mass or less of the inorganic component with respect to 100 parts by mass of the rubber component. More preferably. In addition, the pressure-sensitive adhesive layer 2 preferably contains 50 parts by mass or more of the inorganic component, more preferably 150 parts by mass or more, and 270 parts by mass or more, relative to 100 parts by mass of the rubber component. It is more preferable to include
  • the ratio of the mass value WO of the organic component to the mass value WI of the inorganic component is preferably 0.5 or more and 1.3 or less.
  • the adhesive sheet 10 can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • W O /W I is more preferably 0.7 or more, even more preferably 0.8 or more. Further, W O /W I is more preferably 1.2 or less, and even more preferably 1.0 or less.
  • the ratio of the butyl rubber content to the inorganic component content is preferably 0.15 or more, and preferably 0.20 or more. It is more preferable to have Moreover, in the adhesive layer 2, the ratio of the content of the butyl rubber to the content of the inorganic component is preferably 0.45 or less, more preferably 0.30 or less.
  • the oxidation start temperature of the pressure-sensitive adhesive layer 2 measured using a chemiluminescence analyzer is preferably 200°C or higher. Further, the oxidation initiation temperature of the adhesive layer 2 is more preferably 220° C. or higher, more preferably 240° C. or higher, more preferably 250° C. or higher, and more preferably 260° C. or higher. preferable. In addition, the upper limit of the oxidation start temperature of the adhesive layer 2 is usually 300°C. When the oxidation initiation temperature of the pressure-sensitive adhesive layer 2 is within the above numerical range, the pressure-sensitive adhesive layer 2 is less susceptible to deterioration due to oxidation. Thereby, the adhesive sheet 10 becomes excellent in long-term durability.
  • the oxidation start temperature of the pressure-sensitive adhesive layer 2 using a chemiluminescence analyzer is measured under the following conditions using, for example, a chemiluminescence analyzer with the trade name "CLA-FS4" manufactured by Tohoku Denshi Sangyo Co., Ltd. After obtaining a graph in which the horizontal axis is the temperature and the vertical axis is the light emission luminance, the graph can be obtained by analyzing the graph as follows.
  • the pressure-sensitive adhesive layer 2 has a ratio (G 2 '/G 1 ' ) of the storage modulus value G 2 ' at ⁇ 10° C. to the storage modulus value G 1 ' at 60° C. of less than 12. be. Further, in the pressure-sensitive adhesive sheet according to the present invention, the pressure-sensitive adhesive layer has a storage elastic modulus value G 2 ' at -10°C of 0.7 MPa or less.
  • G 1 ' and G 2 ' satisfy the above relationship, the pressure-sensitive adhesive layer 2 has an appropriate elastic modulus in a wide temperature range from low temperature (eg, ⁇ 10° C.) to high temperature (eg, 60° C.). will have. Therefore, such a pressure-sensitive adhesive layer 2 can exhibit good conformability to adherends (objects to be applied such as moisture-permeable waterproof sheets and inner walls of houses) in a wide temperature range from low to high temperatures. become.
  • G 2 '/G 1 ' is preferably 11 or less.
  • G 2 ′/G 1 ′ is preferably 3 or more, more preferably 5 or more.
  • G 2 ′ is preferably 0.6 MPa or less, more preferably 0.5 MPa or less.
  • G 2 ′ is preferably 0.1 MPa or more, more preferably 0.2 MPa or more.
  • G 1 ′ is preferably 0.03 MPa or more and 0.06 MPa or less.
  • the storage modulus value G 1 ' at 60°C and the storage modulus value G 2 ' at -10°C were measured using a dynamic viscoelasticity measuring device "ARES" manufactured by Rheometric Co., Ltd. It can be obtained by performing dynamic viscoelasticity measurement under the following conditions. As a measurement sample, a part of the adhesive obtained from the adhesive layer 2 is pressed to a thickness of 2 mm at a temperature of 80° C. for 1 minute.
  • Apparatus ARES (Advanced Rheometric Expansion System) manufactured by Rheometric Scientific ⁇ Frequency: 1Hz ⁇ Temperature: -30 to 120°C ⁇ Temperature increase rate: 5°C/min ⁇ Deformation mode: twist ⁇ Shape: parallel plate (7.9mm ⁇ )
  • G 1 ′ is the value at 60° C. in the above measurement
  • G 2 ′ is the value at ⁇ 10° C. in the above measurement.
  • the adhesive layer 2 has an adhesive strength of 2.0 N/25 mm or more at -10°C.
  • the adhesive layer 2 preferably has an adhesive strength of 3.0 N/25 mm or more at -10°C, more preferably 5.0 N/25 mm or more.
  • the upper limit of the adhesive strength of the adhesive layer 2 at ⁇ 10° C. is usually 20.0 N/25 mm.
  • the adhesive layer 2 preferably has an adhesive strength at 23° C. of 9.0 N/25 mm or more, more preferably 11.0 N/25 mm or more. Thereby, the pressure-sensitive adhesive layer 2 can exhibit sufficient adhesiveness even at normal temperature such as 23°C.
  • the upper limit of the adhesive strength of the adhesive layer 2 at 23° C. is usually 30.0 N/25 mm.
  • the adhesive layer 2 preferably has an adhesive strength at 60° C. of 4.0 N/25 mm or more, more preferably 6.0 N/25 mm or more. Thereby, the pressure-sensitive adhesive layer 2 can exhibit sufficient adhesiveness even at a high temperature of 60°C.
  • the upper limit of the adhesive strength of the adhesive layer 2 at 60° C. is usually 20.0 N/25 mm.
  • the adhesive strength of the adhesive layer 2 at each evaluation temperature can be measured according to the following procedure.
  • a test piece having a width of 25 mm is cut out from the adhesive sheet 10 .
  • the test piece and the adherend moisture-permeable waterproof sheet (Lamitect Hi (product number RI-100-50), manufactured by Seiren Co., Ltd.) at each evaluation temperature (-10 ° C., 23 ° C., and 60 ° C.) Incubate for 1 hour.
  • the pressure-sensitive adhesive layer 2 of the test piece is attached to one surface of the moisture-permeable waterproof sheet in an atmosphere of each evaluation temperature, and a roller with a mass of 2 kg is applied. By reciprocating once, the test piece is crimped to the moisture-permeable waterproof sheet.
  • the adhesive strength of the pressure-sensitive adhesive layer 2 to the moisture-permeable waterproof sheet is measured under conditions of a peeling angle of 180° and a peeling speed of 300 mm/min. The above measurement is performed for three samples at each evaluation temperature, and the adhesive strength of the adhesive layer 2 at each evaluation temperature is determined by arithmetically averaging the measured values of the three samples.
  • the substrate 1, the first adhesive layer 2a laminated on one surface of the substrate 1, and the second adhesive layer 2b laminated on the other surface of the substrate 1 In the case of measuring the adhesive strength of the adhesive sheet 10 ' (double-sided adhesive sheet) having the For the agent layer, measure adhesion according to the procedure above. For example, in the pressure-sensitive adhesive sheet 10' shown in FIG. After attaching a backing material to the first adhesive layer 2a, the adhesive force is measured.
  • the backing material thin printed paper with a width of 30 mm, or polyethylene terephthalate film (hereinafter referred to as PET film) with a thickness of 25 ⁇ 2.5 ⁇ m specified in JIS C 2318, or equivalent or higher quality A PET film etc. are mentioned.
  • the thin printing paper means printing paper having a basis weight of 40 g/m 2 or less, and includes, for example, India paper used for dictionaries and type/copy paper.
  • a PET film as the backing material
  • thin printing paper is preferably used as the backing material.
  • the thickness of the adhesive layer 2 is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more. Moreover, the thickness of the adhesive layer 2 is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less.
  • the base material 1 is preferably made of any sheet selected from the group consisting of a fiber sheet, a rubber sheet, a plastic sheet, a metal sheet, and a foam sheet. Since the substrate 1 is composed of any sheet selected from the above group, it becomes easier to form the pressure-sensitive adhesive layer 2 on the substrate 1 with a relatively uniform thickness. Moreover, the pressure-sensitive adhesive layer 2 can be preferably held on the base material 1 . Furthermore, among the sheets included in the above group, plastic sheets and metal sheets generally have high tensile strength. can improve sexuality. In addition, among the sheets included in the above group, fiber sheets, rubber sheets, and foam sheets generally have high flexibility. can be sufficiently followed even by an adherend having Among these, the base material 1 is preferably made of a fiber sheet.
  • fibers constituting the fiber sheet include synthetic resin fibers, metal fibers, and natural fibers. Among these, synthetic resin fibers are preferred.
  • the synthetic resin fibers include fibers made of thermoplastic resins and thermosetting resins.
  • the synthetic resin fibers are preferably fibers made of a thermoplastic resin.
  • thermoplastic resin examples include polyolefin resins such as polyethylene (PE) and polypropylene (PP); polyester resins such as polyethylene terephthalate (PET); polyamide resins such as polyamide 6 and polyamide 6,6; is mentioned. These thermoplastic resins may be used singly or in combination of two or more. Among these, the thermoplastic resin is preferably a polyester-based resin or a polyolefin-based resin, and more preferably polyethylene terephthalate or polypropylene.
  • the fiber sheet is preferably a nonwoven fabric sheet or a woven fabric sheet.
  • the fiber sheet is preferably composed of a nonwoven fabric sheet or a woven fabric sheet.
  • the nonwoven fabric sheet may be manufactured by various known manufacturing methods.
  • Various known production methods include, for example, a dry method, a wet method, a spunbond method, a thermal bond method, a chemical bond method, a stitch bond method, a needle punch method, a melt blow method, a spunlace method, and a steam jet method.
  • a commercial thing can be used as a nonwoven fabric sheet.
  • the basis weight of the nonwoven fabric sheet is preferably 25 g/m 2 or more, more preferably 30 g/m 2 or more, and even more preferably 40 g/m 2 or more.
  • the basis weight of the nonwoven fabric sheet is preferably 80 g/m 2 or less, more preferably 70 g/m 2 or less.
  • the woven sheet can be made using various known looms.
  • the woven sheet may be woven in any weave. Examples of the weaving method of the woven fabric sheet include plain weave, twill weave, and satin weave. A commercially available product can be used as the woven fabric sheet.
  • the thickness of the substrate 1 is preferably 60 ⁇ m or more, more preferably 80 ⁇ m or more. Also, the thickness of the substrate 1 is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less.
  • the pressure-sensitive adhesive layer 2 is obtained by mixing the above-described organic component and inorganic component in the above-described amounts, kneading the resulting pressure-sensitive adhesive composition, and molding (gluing) the resulting pressure-sensitive adhesive composition into a sheet on the substrate 1. be able to.
  • a kneader for example, a kneader, a Banbury mixer, a batch type kneader such as a mixing roll, a continuous kneader such as a twin-screw kneader, or the like is used.
  • a forming apparatus such as a press (heat press) is used.
  • a filler layer 3 may be provided between the substrate 1 and the pressure-sensitive adhesive layer 2 as shown in FIG. 1B.
  • the filler layer 3 is a barrier layer for preventing the components contained in the pressure-sensitive adhesive layer 2 from penetrating into the substrate 1 .
  • thermoplastic resin is preferably used as the material (filling material) forming the filling layer 3 .
  • thermoplastic resins include ethylene-vinyl acetate copolymers, polyolefin resins such as polyethylene and polypropylene; and polyester resins such as polyethylene terephthalate. These thermoplastic resins may be used singly or in combination of two or more. Among these, the thermoplastic resin is preferably a polyolefin resin, more preferably polyethylene.
  • the filling layer 3 can be laminated on the base material 1 by, for example, thermally melting a filling material and applying the melted material to one surface of the base material 1 .
  • the coating method of the melt includes doctor blade method, calender roll coating, screen coating, gravure coating and the like. Further, the filling layer 3 can be laminated on the base material 1 by transferring it to the base material 1 via an adhesive.
  • the thickness of the filling layer 3 is preferably 12 ⁇ m or more, more preferably 15 ⁇ m or more.
  • the thickness of the filling layer 3 is preferably 35 ⁇ m or less, more preferably 25 ⁇ m or less.
  • the single-sided pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer 2 is laminated on one side of the substrate 1 has been described above as the pressure-sensitive adhesive sheet 10 according to one embodiment of the present invention with reference to FIGS. 1A and 1B.
  • the pressure-sensitive adhesive sheet may be a double-sided pressure-sensitive adhesive sheet in which pressure-sensitive adhesive layers are laminated on both sides of a substrate, as shown in FIG. That is, as shown in FIG. 3, a pressure-sensitive adhesive sheet 10' according to another embodiment of the present invention includes a substrate 1, a first pressure-sensitive adhesive layer 2a laminated on one surface of the substrate 1, and a substrate and a second pressure-sensitive adhesive layer 2b laminated on the other side of the first adhesive layer.
  • one pressure-sensitive adhesive layer (for example, the first pressure-sensitive adhesive layer 2a) is attached to the moisture-permeable waterproof sheet in the same manner as described for the single-sided pressure-sensitive adhesive sheet. Therefore, for example, when the first pressure-sensitive adhesive layer 2a is a pressure-sensitive adhesive layer to be attached to a moisture-permeable waterproof sheet, the first pressure-sensitive adhesive layer 2a is the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 10 according to one embodiment of the present invention. Configured in the same manner as Layer 2. On the other hand, the other pressure-sensitive adhesive layer (for example, the second pressure-sensitive adhesive layer 2b) is attached to a construction target such as an inner wall of a house.
  • a construction target such as an inner wall of a house.
  • the second pressure-sensitive adhesive layer 2b is a pressure-sensitive adhesive layer that is attached to a construction target such as an inner wall of a house
  • the second pressure-sensitive adhesive layer 2b is configured in the same manner as the first pressure-sensitive adhesive layer 2a. , or may be configured differently.
  • the second pressure-sensitive adhesive layer 2b has a different structure from the first pressure-sensitive adhesive layer 2a, from the viewpoint of sufficiently adhering the second pressure-sensitive adhesive layer 2b to the object to be applied, the second pressure-sensitive adhesive layer 2b is, for example, Japan 100 parts by mass of a rubber component containing 40 to 93% by mass of butyl rubber and 7 to 60% by mass of polyisobutylene, as described in JP-A-2013-189523 and JP-A-2015-54888, and 82 to 128 parts by mass of a softener having a kinematic viscosity of 100 to 9000 mm 2 /s, and a butyl rubber base, such as described in Japanese Patent Application Laid-Open No. 2003-213231.
  • a cross-linking agent for cross-linking the butyl rubber and (a) a rubbery polymer, as described in Japanese Patent Application Laid-Open No. 2003-41233, ( b) a tackifier; and (c) a pressure-sensitive adhesive composition comprising a cross-linking agent containing at least one selected from thilium vulcanizing agents, quinoid vulcanizing agents, quinonedioxime vulcanizing agents, and maleimide vulcanizing agents. It is preferable to use a material.
  • a suitable one is adopted according to the object to be applied.
  • the first pressure-sensitive adhesive layer 2a and the second pressure-sensitive adhesive layer 2b are the same as described in the pressure-sensitive adhesive sheet 10 according to one embodiment of the present invention.
  • Each pressure-sensitive adhesive composition (composition for the first pressure-sensitive adhesive layer and composition for the second pressure-sensitive adhesive layer) obtained by kneading with a batch type kneader or a continuous kneader is kneaded using a molding device such as an extruder. can be obtained by forming sheets on both sides of the base material 1 respectively.
  • the adhesive sheet according to this embodiment is used for attaching a moisture-permeable waterproof sheet to construction objects such as building materials used for construction and civil engineering work.
  • Moisture-permeable and waterproof properties are required for construction objects, for example, building materials for housing (peripheral parts around windows, girth parts, roofing materials, walls, etc.), members for construction and civil engineering work ( penetration portion, joint portion, etc.). That is, the pressure-sensitive adhesive sheet according to the present invention is used as a waterproof tape for houses.
  • Moisture-permeable waterproof sheets are made of resin sheets with multiple fine holes formed through the thickness direction, non-woven fabrics with gaps between fibers, etc. Moisture passes through the fine holes and gaps, but rainwater is blocked. It is a sheet that is The moisture-permeable waterproof sheet is not particularly limited as long as it has the above functions. and the like. The moisture-permeable waterproof sheet is usually formed larger than the pressure-sensitive adhesive sheet.
  • the adhesive sheets 10, 10' are laminated on at least one side of the substrate and the substrate. and a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer contains butyl rubber as an organic component, and further, the molecular weight retention rate of the butyl rubber after being heated at 100 ° C. for 7 weeks is 20%. or more. That is, when focusing only on the problem of excellent long-term durability, the pressure-sensitive adhesive sheets 10 and 10' have a storage elastic modulus value G 2 at ⁇ 10° C.
  • a substrate A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer laminated on at least one surface of the substrate, The pressure-sensitive adhesive layer contains butyl rubber as an organic component,
  • the ratio of the storage modulus value G 2 ' at ⁇ 10° C. to the storage modulus value G 1 ' at 60° C. (G 2 '/G 1 ') is less than 12;
  • the value G 2 ' of the storage modulus at -10°C is 0.7 MPa or less,
  • An adhesive sheet having an adhesive strength of 2.0 N/25 mm or more at -10°C.
  • the adhesive sheet can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • the adhesive sheet can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature, and also has excellent long-term durability.
  • the adhesive sheet can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • the pressure-sensitive adhesive layer is less susceptible to deterioration due to oxidation. This makes the pressure-sensitive adhesive sheet more excellent in long-term durability.
  • the pressure-sensitive adhesive layer further contains an inorganic component, Any one of the above (1) to (4), wherein the ratio of the mass value W O of the organic component to the mass value W I of the inorganic component (W O /W I ) is 0.5 or more and 1.3 or less. 1.
  • the adhesive sheet can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • the adhesive sheet can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • thermoplastic elastomer is at least one of a styrene thermoplastic elastomer and an acrylic thermoplastic elastomer.
  • the adhesive sheet can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • thermoplastic elastomer is a styrene-based thermoplastic elastomer.
  • the adhesive sheet can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • the adhesive sheet can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • the adhesive sheet can exhibit more sufficient adhesiveness in a wide temperature range from low temperature to high temperature.
  • the inclusion of the inorganic filler facilitates ensuring the thickness of the pressure-sensitive adhesive sheet.
  • the adhesive sheet can exhibit more sufficient adhesive strength in a wide temperature range from low to high temperatures.
  • the pressure-sensitive adhesive layer is more resistant to deterioration due to oxidation. This makes the pressure-sensitive adhesive sheet more excellent in long-term durability.
  • the anti-aging agent contains at least one selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus anti-aging agent, and a sulfur-based anti-aging agent. adhesive sheet.
  • the pressure-sensitive adhesive layer is much less susceptible to deterioration due to oxidation. As a result, the pressure-sensitive adhesive sheet becomes more excellent in long-term durability.
  • the anti-aging agent is selected from at least one selected from the first group consisting of phenol-based anti-aging agents and amine-based anti-aging agents, and the second group consisting of phosphorus-based anti-aging agents and sulfur-based anti-aging agents.
  • the pressure-sensitive adhesive layer is much less susceptible to deterioration due to oxidation. As a result, the pressure-sensitive adhesive sheet becomes more excellent in long-term durability.
  • the substrate is made of any sheet selected from the group consisting of a fiber sheet, a rubber sheet, a plastic sheet, a metal sheet, and a foam sheet. adhesive sheet.
  • the pressure-sensitive adhesive layer can be favorably retained.
  • plastic sheets and metal sheets generally have high tensile strength. can be improved.
  • fiber sheets, rubber sheets, and foam sheets generally have high flexibility. can be sufficiently followed even by an adherend having
  • Such a configuration makes it easier to form the pressure-sensitive adhesive layer with a relatively uniform thickness. Moreover, the pressure-sensitive adhesive layer can be held more favorably.
  • a substrate having a pressure-sensitive adhesive layer laminated on at least one surface of the substrate,
  • the pressure-sensitive adhesive layer contains butyl rubber as an organic component,
  • a pressure-sensitive adhesive sheet wherein the butyl rubber maintains a molecular weight of 20% or more after being heated at 100°C for 7 weeks.
  • the adhesive strength of the adhesive layer at -10 ° C. is 2.0 N / 25 mm or more
  • the ratio (G 2 '/G 1 ') of the storage modulus value G 2 ' of the pressure-sensitive adhesive layer at -10°C to the value G 1 ' of the storage modulus of the pressure-sensitive adhesive layer at 60°C is less than 12; ,
  • the pressure-sensitive adhesive layer further contains an inorganic component,
  • the ratio of the mass value W O of the organic component to the mass value W I of the inorganic component (W O /W I ) is 0.5 or more and 1.3 or less of the above (1′) to (4′)
  • the pressure-sensitive adhesive sheet according to any one of the above.
  • thermoplastic elastomer is a styrene-based thermoplastic elastomer.
  • the anti-aging agent contains at least one selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus anti-aging agent, and a sulfur-based anti-aging agent. adhesive sheet.
  • the anti-aging agent is selected from at least one selected from the first group consisting of phenol-based anti-aging agents and amine-based anti-aging agents, and the second group consisting of phosphorus-based anti-aging agents and sulfur-based anti-aging agents.
  • the adhesive tape which concerns on this invention is not limited to the said embodiment.
  • the pressure-sensitive adhesive tape according to the present invention is not limited by the effects described above. Various modifications can be made to the adhesive tape according to the present invention without departing from the gist of the present invention.
  • Rubber component (a) butyl rubber (IIR) ⁇ JSR BUTYL 268 (manufactured by JSR, mass average molecular weight 500,000) ⁇ Recycled butyl rubber: Recycled butyl S (manufactured by Kangomu Kogyo Co., Ltd., mass average molecular weight 200,000)
  • PIB Polyisobutylene
  • Oppanol N100 (manufactured by BASF Japan, mass average molecular weight 1,300,000)
  • SIS Thermoplastic elastomer/styrene/isoprene/styrene copolymer
  • SIS1 styrene content 24% by mass, diblock ratio 67%
  • SIS2 styrene content 16% by mass
  • diblock ratio 56% SIS3 styrene content 14% by mass
  • diblock ratio 26% SIS4 styrene
  • Polyisobutylene 3 HV-15 (manufactured by Nippon Petrochemical Co., Ltd., number average molecular weight 630, kinematic viscosity at 40° C. 655 mm 2 /s)
  • Ethylene- ⁇ -olefin co-oligomer Lucant LX-400 manufactured by Mitsui Chemicals, mass average molecular weight 12000, dynamic viscosity at 40° C.
  • a rubber component (butyl rubber, polyisobutylene rubber, and thermoplastic elastomer), a tackifier, a softening agent, an inorganic filler, a coloring agent, and an antiaging agent are blended at the blending ratio (parts by mass) shown in Table 1 below. Then, while heating, adhesive compositions according to Examples 1 to 10 and Comparative Examples 1 to 3 were obtained.
  • the pressure-sensitive adhesive composition according to each example was applied to one side of a substrate (polyethylene terephthalate nonwoven fabric (thickness: 100 ⁇ m)). Specifically, one side of the base material was coated with a calendar roll (8-inch roll, 4 rolls) while being heated to 80° C. so as to have a thickness of 0.2 mm. Thus, a pressure-sensitive adhesive sheet according to each example was obtained.
  • the storage elastic modulus G 1 ' at 60°C and the storage elastic modulus G 2 ' at -10°C were measured for the PSA sheet according to each example.
  • the storage moduli G 1 ′ and G 2 ′ were measured by the method described in the embodiment section above.
  • the results of measuring the storage elastic moduli G 1 ′ and G 2 ′ are shown in Table 2 below.
  • Table 2 below also shows the ratio of the value of the storage modulus G 2 ′ to the value of the storage modulus G 1 ′ (G 2 ′/G 1 ′ ).
  • Adhesive force The pressure-sensitive adhesive sheet according to each example was measured for pressure-sensitive adhesive strength at -10°C, 23°C, and 60°C. Adhesion was measured by the method described in the embodiment section above. Table 2 below shows the measurement results of adhesive strength at each temperature.
  • Adhesion stability test In accordance with JIS A 6112: 2019 (Double-sided adhesive waterproof tape for housing), "5.8 Adhesion stability test 10", the adhesive sheet according to each example was subjected to an adhesion stability test, and adhesion at 60 ° C. Stability was evaluated. Adhesion stability was evaluated according to the following criteria. ⁇ Good: Water leakage is confirmed. ⁇ Poor: No water leakage is confirmed. The results of the adhesion stability test are shown in Table 2 below.
  • the pressure-sensitive adhesive sheet according to each example is fixed to a support in an atmosphere of room temperature (23 ⁇ 2° C.). As the adhesive sheet according to each example, a sheet with a width of 50 mm is used.
  • the fixing of the pressure-sensitive adhesive sheet according to each example to the support is carried out in such a manner that the substrate is brought into contact with the support. That is, the pressure-sensitive adhesive sheet according to each example is fixed to the support with the pressure-sensitive adhesive layer exposed.
  • a 50-mm-wide cotton cloth Kanahwa No. 3 is crimped onto the pressure-sensitive adhesive layer. The cotton cloth is pressed onto the pressure-sensitive adhesive layer by placing the cotton cloth on the pressure-sensitive adhesive layer and then reciprocating a 2-kg pressure roller once.
  • the cotton cloth is separated from the pressure-sensitive adhesive layer one minute after the cotton cloth is pressure-bonded onto the pressure-sensitive adhesive layer.
  • the cotton cloth is peeled off from the pressure-sensitive adhesive layer under conditions of a peeling angle of 90° and a tensile speed of 100 mm/min.
  • a multi-angle spectrophotometer MA68II, manufactured by X-rite
  • the whiteness L * 1 is measured in the same manner as the whiteness L * 0 .
  • the adhesive sheets according to Examples 1 to 10 exhibited excellent adhesiveness in a wide range from low temperature (-10°C) to high temperature (60°C).
  • the pressure-sensitive adhesive sheets according to Comparative Examples 1 to 3 were inferior in adhesiveness at at least one of low temperature and high temperature.
  • the adhesive sheets according to Examples 1 to 10 are all excellent in adhesion stability at 60°C. From this, it was found that the pressure-sensitive adhesive sheets according to Examples 1 to 10 can exhibit excellent holdability to the adherend at 60°C.
  • the pressure-sensitive adhesive sheets according to Examples 1 to 10 were evaluated as "good” in terms of the degree of staining of the cotton cloth to be adhered, that is, the degree of staining the cotton cloth was small.
  • the recycled butyl rubber contained in the adhesive layer of the adhesive sheet according to Comparative Example 2 contains a large amount of carbon black (for example, it was obtained from a rubber product containing about 30% by mass), so it is presumed that the value of ⁇ L * was particularly high.
  • Polyisobutylene 3′ HV-15 (manufactured by Nippon Petrochemical Co., Ltd., number average molecular weight 630, kinematic viscosity at 40° C. 655 mm 2 /s) (4) Inorganic filler Heavy calcium carbonate (manufactured by Maruo Calcium Co., Ltd., sieve residue (350 mesh) 0.5% or less (according to JIS K5101)) (5) Colorant Carbon: Seast 3H (manufactured by Tokai Carbon Co., Ltd., carbon black) (6) Anti-aging agent/primary anti-aging agent Amine anti-aging agent 1': Nocrack 6C (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Amine anti-aging agent 2': Nocrack White (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) Amine anti-aging agent 3': Nocrack CD (manufactured by
  • a rubber component butyl rubber and thermoplastic elastomer
  • a tackifier e.g., a softening agent
  • an inorganic filler e.g., a coloring agent
  • an anti-aging agent e.g., a tackifier, a softening agent, an inorganic filler, a coloring agent, and an anti-aging agent
  • PSA compositions according to Examples 1' to 8' and Comparative Examples 1' to 4' were obtained.
  • a pressure-sensitive adhesive composition according to each example was obtained while heating the liquid temperature to 140° C. using a kneader.
  • the pressure-sensitive adhesive composition according to each example was applied to one side of a substrate (polyethylene terephthalate nonwoven fabric (thickness: 100 ⁇ m)). Specifically, one side of the base material was coated with a calendar roll (8-inch roll, 4 rolls) while being heated to 80° C. so as to have a thickness of 0.2 mm. Thus, a pressure-sensitive adhesive sheet according to each example was obtained.
  • the storage elastic modulus G 1 ' of the adhesive layer at 60°C and the storage elastic modulus G 2 ' of the adhesive layer at -10°C were measured.
  • the storage moduli G 1 ′ and G 2 ′ were measured by the method described in the embodiment section above.
  • the results of measuring the storage elastic moduli G 1 ′ and G 2 ′ are shown in Table 4 below.
  • Table 4 below also shows the ratio of the value of the storage modulus G 2 ′ to the value of the storage modulus G 1 ′ (G 2 ′/G 1 ′ ).
  • the oxidation start temperature of the pressure-sensitive adhesive layer was measured using a chemiluminescence analyzer.
  • the oxidation initiation temperature of the pressure-sensitive adhesive layer was measured by the method described in the embodiment section above. Table 4 below shows the results of measuring the oxidation initiation temperature of the pressure-sensitive adhesive layer.
  • Adhesive force The pressure-sensitive adhesive sheet according to each example was measured for pressure-sensitive adhesive strength at -10°C, 23°C, and 60°C. Adhesion was measured by the method described in the embodiment section above. Table 4 below shows the measurement results of adhesive strength at each temperature.
  • Adhesion stability test An adhesion stability test was conducted in accordance with JIS A 6112:2019 (Double-sided adhesive waterproof tape for housing), Section "5.8 Adhesion stability test 10", and adhesion stability at 60°C was evaluated. Adhesion stability was evaluated according to the following criteria. ⁇ Good: Water leakage is confirmed. ⁇ Poor: No water leakage is confirmed. The results are shown in Table 4 below.
  • the pressure-sensitive adhesive sheet according to each example was evaluated for discoloration of the pressure-sensitive adhesive layer according to the following procedure.
  • (1) The pressure-sensitive adhesive sheet according to each example is pressed so that the pressure-sensitive adhesive layer has a thickness of 0.2 mm.
  • (2) The exposed surface of the adhesive layer of the adhesive sheet according to each example is attached to a hard type Tyvek sheet (trade name "Tyvek Hard Type 1060B", manufactured by Asahi DuPont Flashspun Products), and the Tyvek sheet and A first laminate is obtained with the pressure-sensitive adhesive sheet.
  • Tyvek sheet trade name "Tyvek Hard Type 1060B", manufactured by Asahi DuPont Flashspun Products
  • the maintenance rate of the molecular weight of the butyl rubber after being heated at 100° C. for 7 weeks is 20% or more. From this, it can be said that the pressure-sensitive adhesive sheet according to each example is excellent in long-term durability.
  • the maintenance rate of the molecular weight of the butyl rubber after being heated at 100° C. for 7 weeks was found to be less than 15%. From this, it can be said that the pressure-sensitive adhesive sheets according to the respective comparative examples cannot sufficiently exhibit long-term durability.
  • the pressure-sensitive adhesive sheet according to each example can exhibit excellent adhesiveness in a wide range from low temperature ( ⁇ 10° C.) to high temperature (60° C.).
  • the pressure-sensitive adhesive sheet according to Comparative Example 1' does not exhibit sufficient low-temperature pressure-sensitive adhesiveness.
  • the pressure-sensitive adhesive sheets according to each example are all excellent in adhesion stability at 60°C. From this, it can be seen that the pressure-sensitive adhesive sheet according to each example can exhibit excellent holdability to the object to be adhered at 60°C.
  • the discoloration (yellowing) of the pressure-sensitive adhesive layer was evaluated as “no", whereas in the pressure-sensitive adhesive sheet according to Comparative Example 3', the discoloration (yellowing) of the pressure-sensitive adhesive layer ) is evaluated as “yes”. This is probably because the pressure-sensitive adhesive sheet according to Comparative Example 3' contains the amine-based anti-aging agent 1' whose coloring (staining property) to the rubber component is not suppressed in the pressure-sensitive adhesive layer. .
  • Base Material 2 Adhesive Layer 2a First Adhesive Layer 2b Second Adhesive Layer 3 Sealing Layer 10 Adhesive Sheet 10' Adhesive Sheet

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

Abstract

Une feuille adhésive selon la présente invention a un substrat, et une couche adhésive stratifiée sur au moins une surface du substrat, la couche adhésive contenant un caoutchouc butyle en tant que composant actif, le rapport de la valeur G2' du module élastique de stockage à – 10 °C à la valeur G1'du module élastique de stockage à 60 °C (G2'/G1') étant inférieur à 12, la valeur G2 'du module élastique de stockage à – 10 °C étant inférieure ou égale à 0,7 MPa, et la force adhésive à – 10 °C étant supérieure ou égale à 2,0 N/25 mm.
PCT/JP2022/034509 2021-12-21 2022-09-15 Feuille adhésive Ceased WO2023119752A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003517343A (ja) * 1999-03-17 2003-05-27 コロプラスト アクティーゼルスカブ 感圧接着剤組成物
WO2014084352A1 (fr) * 2012-11-30 2014-06-05 リンテック株式会社 Composition d'agent adhésif, feuille adhésive et dispositif électronique et procédé de production correspondant
WO2018199177A1 (fr) * 2017-04-28 2018-11-01 Ａｇｃ株式会社 Verre à double vitrage, son procédé de fabrication, et matériau d'étanchéité pour verres à double vitrage
JP2019508566A (ja) * 2016-04-22 2019-03-28 エルジー・ケム・リミテッド 光学用粘着剤組成物及びこの硬化物を含む光学用粘着層
JP2019157350A (ja) * 2018-03-07 2019-09-19 マクセルホールディングス株式会社 コンクリート劣化抑制粘着テープの使用方法及びそれに使用するコンクリート劣化抑制粘着テープ
WO2021041418A1 (fr) * 2019-08-26 2021-03-04 Bostik, Inc. Sous-couche de couverture utilisant une adhésif sensible à la pression et ses procédés de fabrication et d'utilisation
WO2021251021A1 (fr) * 2020-06-12 2021-12-16 日東電工株式会社 Feuille étanche à l'eau

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003517343A (ja) * 1999-03-17 2003-05-27 コロプラスト アクティーゼルスカブ 感圧接着剤組成物
WO2014084352A1 (fr) * 2012-11-30 2014-06-05 リンテック株式会社 Composition d'agent adhésif, feuille adhésive et dispositif électronique et procédé de production correspondant
JP2019508566A (ja) * 2016-04-22 2019-03-28 エルジー・ケム・リミテッド 光学用粘着剤組成物及びこの硬化物を含む光学用粘着層
WO2018199177A1 (fr) * 2017-04-28 2018-11-01 Ａｇｃ株式会社 Verre à double vitrage, son procédé de fabrication, et matériau d'étanchéité pour verres à double vitrage
JP2019157350A (ja) * 2018-03-07 2019-09-19 マクセルホールディングス株式会社 コンクリート劣化抑制粘着テープの使用方法及びそれに使用するコンクリート劣化抑制粘着テープ
WO2021041418A1 (fr) * 2019-08-26 2021-03-04 Bostik, Inc. Sous-couche de couverture utilisant une adhésif sensible à la pression et ses procédés de fabrication et d'utilisation
WO2021251021A1 (fr) * 2020-06-12 2021-12-16 日東電工株式会社 Feuille étanche à l'eau

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