WO2017002634A1 - Ruban adhésif sensible à la pression, feuille de mise en faisceau et article - Google Patents

Ruban adhésif sensible à la pression, feuille de mise en faisceau et article Download PDF

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Publication number
WO2017002634A1
WO2017002634A1 PCT/JP2016/067921 JP2016067921W WO2017002634A1 WO 2017002634 A1 WO2017002634 A1 WO 2017002634A1 JP 2016067921 W JP2016067921 W JP 2016067921W WO 2017002634 A1 WO2017002634 A1 WO 2017002634A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
mass
adhesive layer
plasticizer
Prior art date
Application number
PCT/JP2016/067921
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English (en)
Japanese (ja)
Inventor
澄生 下岡
森野　彰規
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to CN201680019512.XA priority Critical patent/CN107429131B/zh
Priority to JP2016558818A priority patent/JP6094921B1/ja
Priority to CN202110124130.6A priority patent/CN112960274B/zh
Publication of WO2017002634A1 publication Critical patent/WO2017002634A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D63/00—Flexible elongated elements, e.g. straps, for bundling or supporting articles
    • B65D63/10—Non-metallic straps, tapes, or bands; Filamentary elements, e.g. strings, threads or wires; Joints between ends thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D63/00—Flexible elongated elements, e.g. straps, for bundling or supporting articles
    • B65D63/10—Non-metallic straps, tapes, or bands; Filamentary elements, e.g. strings, threads or wires; Joints between ends thereof
    • B65D63/1009—Adhesive tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/302—Applications of adhesives in processes or use of adhesives in the form of films or foils for bundling cables
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/24—Presence of a foam
    • C09J2400/243—Presence of a foam in the substrate
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/26—Presence of textile or fabric
    • C09J2400/263—Presence of textile or fabric in the substrate

Definitions

  • the present invention relates to an adhesive tape that can be used to fix a member containing a plasticizer.
  • binding sheet specifically, a binding sheet in which an adhesive layer made of an aqueous adhesive composition containing a rubber latex and a tackifier resin emulsion is laminated on one side of a polyvinyl chloride sheet.
  • an adhesive layer made of an aqueous adhesive composition containing a rubber latex and a tackifier resin emulsion is laminated on one side of a polyvinyl chloride sheet.
  • the polyvinyl chloride sheet usually contains a large amount of plasticizer, when the plasticizer moves to the adhesive layer over time, at the interface between the polyvinyl chloride sheet and the adhesive layer. There was a case of causing peeling.
  • a polyvinyl chloride sheet having a thickness of about 0.2 mm to 1 mm is folded in two or rolled, and the polyvinyl chloride sheet is bonded with an adhesive tape to bundle several wire harnesses.
  • the transition of the plasticizer over time from the polyvinyl chloride sheet to the adhesive tape and the repulsive force of the polyvinyl chloride sheet slowly returning to the flat sheet state work on the adhesive tape over a long period of time. There has been concern about the possibility of problems such as unraveling of the binding.
  • the problem to be solved by the present invention is that, even when used for sticking an adherend containing a plasticizer, the sticking does not occur at the interface between the adherend and the pressure-sensitive adhesive layer. It is providing the adhesive tape which can hold
  • the present inventors consider that the peeling over time may be caused by the plasticizer moving to the pressure-sensitive adhesive layer and softening the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive before the plasticizer is transferred It was examined to set the hardness of the layer higher in advance.
  • the pressure-sensitive adhesive layer still cannot effectively prevent the peeling with time.
  • a polyvinyl chloride sheet having a thickness of about 0.2 mm to 1 mm is folded in two or rolled into a tubular shape, and the polyvinyl chloride sheet is bonded with an adhesive tape to bundle several wire harnesses.
  • the plasticizer is prevented from moving into the hard pressure-sensitive adhesive layer, it is concentrated on the interface between the polyvinyl chloride sheet and the pressure-sensitive adhesive layer, and is more likely to peel off at the interface. was there.
  • the present inventors have studied to further soften the pressure-sensitive adhesive layer before the plasticizer is transferred, and unexpectedly, when the range is set to a predetermined gel fraction range. The inventors have found that the peeling with time can be more effectively prevented.
  • the present inventors are pressure-sensitive adhesive tapes used for sticking the adherend (a1) containing a plasticizer, and have a pressure-sensitive adhesive layer (b1) on one surface side of the gas-permeable substrate, The pressure-sensitive adhesive layer (b2) is provided on the other surface side, and the total basis weight of the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) is in the range of 125 g / m 2 to 175 g / m 2 .
  • the present invention relates to a pressure-sensitive adhesive tape characterized in that the total gel fraction of the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) is 2% by mass to 35% by mass.
  • the pressure-sensitive adhesive tape of the present invention does not cause peeling at the interface between the adherend and the pressure-sensitive adhesive layer even when used for sticking an adherend containing a plasticizer. Can be held over.
  • the pressure-sensitive adhesive tape of the present invention has a pressure-sensitive adhesive layer (b1) on one side of a gas-permeable substrate, a pressure-sensitive adhesive layer (b2) on the other side, and the pressure-sensitive adhesive layer (b1). ) And the pressure-sensitive adhesive layer (b2) have a total basis weight in the range of 125 g / m 2 to 175 g / m 2 and the total gel fraction of the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2). Is a pressure-sensitive adhesive tape having a content of 2 to 35% by mass, which is exclusively used for attaching an adherend (a1) containing a plasticizer.
  • the adhesive tape can be used for joining two or more adherends (a1), or for joining the adherends other than the adherend (a1) and the adherend (a1).
  • the pressure-sensitive adhesive layer (b1) and pressure-sensitive adhesive layer (b2) those having a total gel fraction in the range of 2% by mass to 35% by mass are used. Thereby, even if it is a case where the said plasticizer transfers to an adhesive layer (b1) etc., generation
  • the gel fraction is preferably 2% by mass to 25% by mass, and preferably 2% by mass to 15% by mass. Even in the case of shifting to (b1) or the like, it is more preferable for effectively preventing the occurrence of peeling over time.
  • the use of the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) having a gel fraction in the above range allows the plasticizer to pass through the gas-permeable substrate so that the gas-permeable group is used. Since the adhesive layer (b1) and the adhesive layer (b2) provided on both sides of the material are relatively uniformly dispersed, the plasticizer is unevenly distributed at the interface between the adherend (a1) and the adhesive layer. As a result, interfacial peeling between the adherend (a1) and the pressure-sensitive adhesive layer can be effectively suppressed.
  • the gel fraction was determined by immersing a pressure-sensitive adhesive tape whose mass of the pressure-sensitive adhesive layer was measured in advance for 72 hours in a mixed solvent of 70 parts by mass of toluene and 30 parts by mass of methanol adjusted to 23 ° C. Using an apparatus, after vibrating for 15 minutes at a frequency of 40 kHz in an atmosphere of 23 ° C., the mass after drying of the pressure-sensitive adhesive layer remaining in the mixed solvent and a value calculated based on the following equation are used.
  • Gel fraction (mass%) ⁇ (mass of adhesive layer remaining in mixed solvent) / (mass of adhesive layer before immersion) ⁇ ⁇ 100
  • the mass of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape before the immersion refers to a value obtained by subtracting the mass of the air-permeable substrate used for the production from the mass of the pressure-sensitive adhesive tape. Further, the mass of the remaining pressure-sensitive adhesive layer refers to a value obtained by subtracting the mass of the air-permeable substrate from the mass of the residue after drying.
  • the gel fraction calculated by using the mixed solvent and applying ultrasonic vibration does not correlate with the gel fraction with respect to the solvent of toluene alone, but the intermolecular and intramolecular hydrogen of the pressure-sensitive adhesive layer.
  • the apparent bond due to bonding or the like is divided, and the gel fraction resulting from the crosslinking reaction of a crosslinking agent or the like is indicated.
  • the pressure-sensitive adhesive tape one having a pressure-sensitive adhesive layer having a total basis weight of 125 g / m 2 to 175 g / m 2 of the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) is used.
  • the basis weight is preferably in the range of 135 g / m 2 to 155 g / m 2 , and more preferably in the range of 138 g / m 2 to 145 g / m 2 .
  • the total basis weight of the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) is the mass of the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) present per unit area (1 m 2 ) of the pressure-sensitive adhesive tape. The value calculated based on the following formula is shown.
  • the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) have a storage elastic modulus at 23 ° C. measured by a dynamic viscoelastic spectrum measured at a frequency of 1 Hz of 0.08 MPa to 0.12 MPa. It is preferable to use a material having a pressure of 0.08 MPa to 0.09 MPa, and an excellent adhesive force at the initial stage of application to the adherend (a1) can be imparted, and the plasticizer migrates. It is more preferable because it can suppress a decrease in adhesive strength over time.
  • the pressure-sensitive adhesive layer (b1) and pressure-sensitive adhesive layer (b2) have a ratio (tan ⁇ ) of loss elastic modulus to storage elastic modulus at 60 ° C. measured by a dynamic viscoelastic spectrum measured at a frequency of 1 Hz. It is preferable to use one having a value of 0.40 to 0.60, and using 0.45 to 0.50 means that the pressure-sensitive adhesive tape adhered to the adherend (a1) has a temperature of 60 ° C. When left in the environment, the plasticizer that can migrate from the adherend (a1) over time is not unevenly distributed at the adhesive interface with the adherend (a1), and has excellent adhesive force and cohesive force over a long period of time. It is more preferable when obtaining the adhesive tape to hold
  • the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) have a ratio of loss elastic modulus (tan ⁇ ) to storage elastic modulus at 100 ° C. measured by a dynamic viscoelastic spectrum measured at a frequency of 1 Hz. It is preferable to use one having a thickness of 0.55 to 0.80, and using 0.60 to 0.70 means that the pressure-sensitive adhesive tape adhered to the adherend (a1) has a temperature of 100 ° C. When left in the environment, the plasticizer that can migrate from the adherend (a1) over time is not unevenly distributed at the adhesive interface with the adherend (a1), and has excellent adhesive force and cohesive force over a long period of time. It is more preferable when obtaining the adhesive tape to hold
  • the storage elastic modulus at 23 ° C. and the tan ⁇ at 60 ° C. and 100 ° C. are measured using a viscoelasticity tester (trade name: ARES-G2 manufactured by T.A. Instruments Japan Co., Ltd.). Based on the storage elastic modulus measured at a frequency of 1 Hz under a temperature condition of 23 ° C., 60 ° C. or 100 ° C., and the storage elastic modulus and loss elastic modulus. Refers to the calculated value.
  • the pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) having a storage elastic modulus at 23 ° C. within the above range and tan ⁇ of 60 ° C. and 100 ° C. is the repulsive force of the adherend (a1).
  • the adherend (a1) caused by the migration of the plasticizer from the adherend (a1) to the pressure-sensitive adhesive layer even when left in an environment of 100 ° C. or less is unlikely to cause peeling.
  • the pressure-sensitive adhesive layer can be effectively suppressed.
  • the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) can be formed by using, for example, a pressure-sensitive adhesive.
  • a pressure-sensitive adhesive examples include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, natural rubber-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives, and acrylic pressure-sensitive adhesives can be used. preferable.
  • acrylic adhesive what contains an acrylic polymer and a crosslinking agent, tackifying resin, etc. as needed can be used, and contains an acrylic polymer, a crosslinking agent, tackifying resin, etc. It is preferable to use an acrylic pressure-sensitive adhesive to obtain a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer excellent in weather resistance and heat resistance.
  • acrylic polymer a polymer obtained by polymerizing a monomer component containing a (meth) acrylic monomer or the like can be used.
  • Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and n-hexyl ( Having an alkyl group having 1 to 14 carbon atoms such as (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.
  • (Meth) acrylate can be used, and (meth) acrylate having an alkyl group having 4 to 9 carbon atoms is preferably used, and n-butyl acrylate or 2-ethylhexyl acrylate can be used alone or in combination. further Masui.
  • the adherend (a1) After adhering to the surface of the adherend (a1) from the initial stage of application and exhibiting excellent adhesive force, and after the plasticizer migrates from the adherend (a1) to the pressure-sensitive adhesive layer over time, the adherend (a1 ) And n-butyl having 4 carbon atoms, which is less affected by the steric hindrance of the alkyl group, in order to obtain a pressure-sensitive adhesive tape in which the plasticizer is not unevenly distributed at the adhesive interface and maintains excellent adhesive strength and cohesive strength over a long period of time. Most preferably, 60% by mass or more of acrylate is used.
  • the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is 80% by mass to 98.5% by mass with respect to the total amount of monomer components used for producing the acrylic polymer. It is preferable to use in the range, and it is more preferable to use in the range of 90% by mass to 98.5% by mass.
  • the (meth) acrylic monomer it is preferable to use a highly polar monomer such as a highly polar vinyl monomer in addition to those described above.
  • a (meth) acrylic monomer having a carboxyl group, a nitrogen-containing vinyl monomer having an amino group or an amide group, or the like can be used alone or in combination.
  • the adherend (a1) is, for example, high-polarity polyvinyl chloride
  • a plasticizer that easily penetrates between the molecules of the polyvinyl chloride is used in order to more effectively plasticize the polyvinyl chloride.
  • the plasticizer include those having an aromatic ring and an ester group in the molecule.
  • a plasticizer having a structure that is easily polarized between the aromatic ring and an ester group or the like easily enters between the molecules of the polyvinyl chloride.
  • the carboxyl group has an extremely high polarity like the polyvinyl chloride. It becomes easy for the agent to penetrate into the molecule of the acrylic polymer contained in the pressure-sensitive adhesive layer, and as a result, the pressure-sensitive adhesive layer tends to be plasticized and its adhesive strength tends to be slightly reduced.
  • a pressure-sensitive adhesive layer containing an acrylic polymer using a nitrogen-containing vinyl monomer alone or in combination with a (meth) acrylic monomer having a carboxyl group is used as the highly polar vinyl monomer. Then, plasticization of the pressure-sensitive adhesive layer (b1) and the like by the plasticizer is more effectively suppressed, and as a result, excellent adhesive force can be maintained for a long time.
  • nitrogen-containing vinyl monomer examples include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, acryloylmorpholine, dimethylaminoethyl acrylate, N, N-dimethylacrylamide, and N-isopropylacrylamide.
  • the nitrogen-containing vinyl monomer is preferably 0.5% by mass to 20% by mass, and 0.8% by mass to 10% by mass with respect to the total amount of monomer components used in the production of the acrylic polymer. % Is more preferable, and 1.0% by mass to 2.5% by mass is even more preferable. 1.0% by mass to 1.9% by mass is most preferable.
  • the acrylic pressure-sensitive adhesive layer is appropriately softened, and from the initial stage of application to the surface of the adherend (a1). Familiarly, after exhibiting excellent adhesive force and the plasticizer transferred from the adherend (a1) to the pressure-sensitive adhesive layer over time, the plasticizer is not unevenly distributed on the adherend (a1) and the adhesive interface, It is possible to obtain a pressure-sensitive adhesive tape that retains excellent adhesive force and cohesive force over a long period of time.
  • the vinyl monomer having a carboxyl group is preferably used in the range of 0.2% by mass to 5% by mass with respect to the total amount of the monomer component, and 0.4% by mass to 3% by mass. It is more preferable to use within a range. Most preferably, it is used in the range of 1.5 mass% to 2.5 mass%.
  • a1 such as a polyvinyl chloride resin.
  • the carboxyl group is highly polar as described above, if it is present in a large amount in the pressure-sensitive adhesive layer (b1) or the like, a pressure-sensitive adhesive layer that is easily plasticized by the plasticizer derived from the adherend (a1) is formed. There is a case. Therefore, use of the vinyl monomer having a carboxyl group within the above-described range suppresses the penetration of the plasticizer into the pressure-sensitive adhesive layer (b1) and the like, and the adhesive force due to the influence of the plasticizer. It is preferable for obtaining a pressure-sensitive adhesive tape that is less deteriorated and retains excellent adhesive strength and cohesive strength over a long period of time.
  • highly polar vinyl monomer examples include, in addition to those described above, monomers having a sulfonic acid group such as vinyl acetate, ethylene oxide-modified succinic acid acrylate, 2-acrylamido-2-methylpropanesulfonic acid, 2-methoxy
  • monomers having a sulfonic acid group such as vinyl acetate, ethylene oxide-modified succinic acid acrylate, 2-acrylamido-2-methylpropanesulfonic acid, 2-methoxy
  • highly polar vinyl monomers such as terminal alkoxy-modified (meth) acrylates such as ethyl (meth) acrylate and 2-phenoxyethyl (meth) acrylate can be used.
  • the other highly polar vinyl monomer is preferably used in the range of 0.2% by mass to 5% by mass with respect to the total amount of the monomer components, and in the range of 0.4% by mass to 3% by mass. More preferably it is used. Most preferably, it is used in the range of 2.0 mass% to 3.0 mass%.
  • the amount of the other highly polar vinyl monomer used is in the above range, the adhesion to the surface of the highly polar adherend (a1) such as polyvinyl chloride resin is increased from the initial stage of application, and the carboxyl group Since the plasticizer does not have the same polarity as that of the vinyl monomer having an adhesive, it is difficult for the plasticizer to enter between the molecules of the acrylic polymer, and the plasticizer moves from the adherend (a1) to the adhesive layer over time. However, it is possible to obtain a pressure-sensitive adhesive tape that retains excellent adhesive strength and cohesive strength over a long period of time.
  • the highly polar adherend (a1) such as polyvinyl chloride resin
  • the monomer that can be used for the production of the acrylic polymer those having a functional group capable of reacting with a crosslinking agent described later can be used.
  • a (meth) acrylic monomer having a hydroxyl group is used. be able to.
  • Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth). Acrylate or the like can be used.
  • the (meth) acrylic monomer having a hydroxyl group is preferably used in a range of 0.05% by mass to 2.0% by mass with respect to the total amount of the monomer component, and preferably 0.1% by mass to 0%. More preferably, it is used in the range of 0.5% by mass, and 0.1% by mass to 0.2% by mass has the gel fraction of the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) in the range described above. It is easy to adjust, and as a result, it adapts to the surface of the adherend (a1) from the initial stage of application, exhibits an excellent adhesive force, and the plasticizer moves from the adherend (a1) to the adhesive layer over time.
  • the cross-linked structure between the acrylic polymers does not inhibit the fluidity of the plasticizer and can suppress the uneven distribution of the plasticizer at the adhesive interface with the adherend (a1). An adhesive tape that retains force can be obtained.
  • the acrylic polymer can be produced by polymerizing the monomer component by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method, and is produced by a solution polymerization method. It is preferable to improve the production efficiency of the pressure-sensitive adhesive tape and reduce the production cost.
  • acrylic polymer those having a weight average molecular weight in the range of 300,000 to 1,500,000 are preferably used, and those having a weight average molecular weight in the range of 500,000 to 1,000,000 are preferably used.
  • the weight average molecular weight can be measured by gel permeation chromatograph (GPC). More specifically, as a GPC measurement device, “SC8020” manufactured by Tosoh Corporation can be used to measure and obtain the following GPC measurement conditions based on polystyrene conversion values. (GPC measurement conditions) Sample concentration: 0.5% by mass (tetrahydrofuran solution) Sample injection volume: 100 ⁇ L ⁇ Eluent: Tetrahydrofuran (THF) ⁇ Flow rate: 1.0 mL / min Column temperature (measurement temperature): 40 ° C ⁇ Column: “TSKgel GMHHR-H” manufactured by Tosoh Corporation ⁇ Detector: Differential refraction
  • the pressure-sensitive adhesive that can be used for forming the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2)
  • a material containing a crosslinking agent in addition to the acrylic polymer.
  • the adhesive strength to the surface of the adherend (a1) is excellent from the initial stage of application, and after the plasticizer is transferred from the adherend (a1) to the pressure-sensitive adhesive layer over time, it is long.
  • a pressure-sensitive adhesive tape that retains excellent adhesive force and cohesive force over a period of time can be obtained.
  • crosslinking agent examples include isocyanate crosslinking agents, epoxy crosslinking agents, chelate crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, and the like, depending on the type of crosslinking functional group that the acrylic polymer has. Can be selected and used.
  • the content of the crosslinking agent is preferably 0.3 to 1.8 parts by mass, more preferably 0.6 to 1.3 parts by mass, with respect to 100 parts by mass of the acrylic polymer. Most preferred is 6 to 0.9 parts by weight.
  • the content of the crosslinking agent can be appropriately selected and used so that the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) having the gel fraction can be formed.
  • the pressure-sensitive adhesive may be one containing a tackifying resin in order to further improve the adhesive strength of the pressure-sensitive adhesive tape.
  • rosin resin As the tackifying resin, rosin resin, terpene resin, aliphatic (C5) or aromatic (C9) petroleum resin, styrene resin, phenol resin, xylene resin, methacrylic resin, etc. are used. can do.
  • tackifier resin it is preferable to use a rosin resin, and it is preferable to use a polymerized rosin resin.
  • the tackifying resin is preferably used in an amount of 5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the acrylic polymer, at the initial stage of application to the adherend (a1). It is more preferable because excellent adhesive strength can be imparted and a decrease in the adhesive strength over time due to the migration of the plasticizer can be suppressed.
  • Examples of the embodiment of the pressure-sensitive adhesive tape of the present invention include pressure-sensitive adhesive tapes each having the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) on both sides of a gas-permeable substrate (core).
  • the pressure-sensitive adhesive tape of the present invention includes, for example, a step of forming the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) by coating the pressure-sensitive adhesive on the surface of a release liner and drying, for example. Can be manufactured through a step of transferring to the both sides of the air-permeable substrate.
  • the gas permeable substrate As the gas permeable substrate, it is possible to use a material in which the plasticizer is transferred from the adherend (a1) to the pressure-sensitive adhesive layer, and then the plasticizer can pass through the gas permeable substrate (core). It is preferable for effectively suppressing interfacial peeling between the adherend (a1) and the pressure-sensitive adhesive layer in contact therewith.
  • a test piece is formed by laminating 10 air permeable base materials, and the Gurley type air permeability measured in accordance with JISP 8117 of the test piece is 0.35 sec / 100 ml or less. It is preferable to use those in the range of 0.05 seconds / 100 ml to 0.3 seconds / 100 ml, more preferably in the range of 0.1 seconds / 100 ml to 0.2 seconds / 100 ml. Is used, the plasticizer is relatively uniformly dispersed in the entire pressure-sensitive adhesive layer formed on both surfaces of the gas-permeable substrate. As a result, the adherend (a1) and the pressure-sensitive adhesive layer in contact with the adherend (a1) Can be effectively suppressed.
  • the Gurley-type air permeability is an air permeability measured in accordance with JIS P8117 using 10 air-permeable base materials laminated and 10-layer base material as a test piece. Measurement is performed when 10 core substrates are stacked and set in 23 ° C. and 50% RH, and an inner tube with an inner diameter of 28.6 mm and a weight of 567 g is dropped and 100 ml of air is measured. Measure the transit time.
  • the air-permeable substrate As the air-permeable substrate, a substrate having a thickness of 10 ⁇ m to 50 ⁇ m, preferably 20 ⁇ m to 45 ⁇ m is used.
  • the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) have been impregnated into the pores of the gas-permeable base material and have migrated from the adherend (a1) by using the gas-permeable base material having the thickness. Since the plasticizer is allowed to pass through, it is possible to suppress the uneven distribution of the plasticizer in the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2), and to obtain a pressure-sensitive adhesive tape that maintains excellent adhesive force and cohesive force over a long period of time. be able to.
  • the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) are impregnated into the pores of the gas-permeable substrate by using the gas-permeable substrate having the thickness, and the tensile strength of the gas-permeable substrate is increased.
  • an adhesive tape excellent in handling workability in the cutting process and the sticking process can be obtained.
  • the gas permeable substrate it is preferable to use a nonwoven fabric substrate or a porous film substrate as the gas permeable substrate because it is easy to ensure the air permeability in the above range.
  • the gas permeable substrate include a nonwoven fabric substrate, a woven fabric substrate, and a fiber woven fabric (mesh substrate) composed of monofilament yarn. It is preferable to use a non-woven fabric base material that easily obtains the rate and a mesh base material that easily obtains a high Gurley air permeability.
  • a known and conventional nonwoven fabric used as a nonwoven fabric for adhesive tape can be used.
  • Typical examples include hemp such as Manila hemp, cellulosic fibers such as rayon, regenerated cellulose, and wood pulp, chemical fibers such as acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, and mixtures thereof.
  • hemp such as Manila hemp
  • cellulosic fibers such as rayon, regenerated cellulose, and wood pulp
  • chemical fibers such as acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, and mixtures thereof.
  • the nonwoven fabric manufacturing process it is preferable to add a known and usual reinforcing agent in the nonwoven fabric manufacturing process.
  • a known and usual reinforcing agent an internal additive reinforcing agent or an external additive reinforcing agent may be used alone or in combination.
  • an internal reinforcement polyacrylamide resin, urea-formaldehyde resin, melamine-formaldehyde resin, epoxy-polyamide resin, etc. can be used.
  • a polyamidoamine / epichlorohydrin resin which is an epoxy-polyamide resin, is preferable because it significantly increases the interlayer strength of the nonwoven fabric.
  • the amount of the internal reinforcing agent added is preferably 0.2 to 1% by mass, more preferably 0.3 to 0.5% by mass, based on the nonwoven fabric.
  • a thermoplastic resin such as starch; viscose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide or the like can be used.
  • the above-mentioned internal additive reinforcement agent it is preferable to use the above-mentioned internal additive reinforcement agent.
  • the basis weight of the nonwoven fabric substrate is preferably 5 to 15 g / m 2 , and more preferably 7 to 12 g / m 2 .
  • the density of the nonwoven fabric substrate is preferably 0.15 to 0.35 g / m 3 , more preferably 0.2 to 0.3 g / m 3 .
  • the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) are impregnated into the pores of the nonwoven fabric base and have migrated from the adherend (a1) when the basis weight range of the nonwoven fabric base is within the range.
  • the plasticizer Since the plasticizer is allowed to pass through, it is possible to suppress the uneven distribution of the plasticizer in the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2), and to obtain a pressure-sensitive adhesive tape that maintains excellent adhesive force and cohesive force over a long period of time. Can do. Furthermore, by using the nonwoven fabric substrate having the basis weight, the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) impregnate the pore portions of the substrate, and the tensile strength of the nonwoven fabric substrate is improved. The handling workability in the cutting step and the pasting step can be improved.
  • the paper making method of the nonwoven fabric substrate is not particularly limited, but can be obtained by a known wet method, using a circular net paper machine, a short net paper machine, a long net paper machine, an inclined short net paper machine, etc. Various papermaking methods are used.
  • a mesh base material in which a known monofilament fiber such as polyester resin, amide resin, polyarylate resin or the like is woven in a screen shape can be used. Among them, it is preferable to use a polyester resin having a high tensile elastic modulus and high tensile strength as a monofilament.
  • a mesh substrate having a thickness of 10 to 50 ⁇ m in which 80 to 300 monofilament yarns having a fiber diameter of 5 to 25 ⁇ m are alternately woven in MD and TD per inch is used.
  • it is a mesh substrate having a thickness of 10 to 50 ⁇ m in which 100 to 200 monofilament yarns having a fiber diameter of 5 to 25 ⁇ m are alternately woven in MD and TD per inch.
  • the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) are impregnated into the pores of the base material, and the plastic that has migrated from the adherend (a1) Since the agent is allowed to pass through, it is possible to suppress the uneven distribution of the plasticizer in the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2), and to obtain a pressure-sensitive adhesive tape that maintains excellent adhesive force and cohesive force over a long period of time. it can.
  • the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) are impregnated into the pores of the base material, and the tensile strength of the mesh base material is improved.
  • the handling workability in the cutting step and the pasting step can be improved.
  • a release liner may be laminated on the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2).
  • the release liner include papers such as kraft paper, glassine paper, and high-quality paper, polyethylene, polypropylene (orientated polypropylene (OPP), cast polypropylene (CPP)), resin films such as polyethylene terephthalate, and the papers.
  • Laminated paper laminated with a resin film, paper that has been sealed with clay, polyvinyl alcohol, or the like on the paper, or the like that has one or both sides peeled off with a silicone resin or the like can be used. .
  • adherend (a1) for example, one containing a plasticizer and polyvinyl chloride, or a plasticizer and rubber can be used.
  • plasticizer examples include aliphatic esters such as di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, phosphate esters such as trioctyl phosphate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate.
  • aliphatic esters such as di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate
  • phosphate esters such as trioctyl phosphate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate.
  • trimellitic acid esters such as dibasic acid esters and trimellitic acid tri-2-ethylhexyl
  • epoxy plasticizers such as butyl epoxy stearate. Two or more kinds of the plasticizer
  • the pressure-sensitive adhesive tape of the present invention is preferably used for an adherend containing a phthalate ester as the plasticizer, and is preferably used for an adherend containing diisononyl phthalate. Since the plasticization of the sheet can be efficiently performed, the polyvinyl chloride sheet can be plasticized with a small amount of addition, and the decrease in the adhesive force due to the plasticizer can be effectively prevented, which is more preferable.
  • the plasticizer content preferably includes a plasticizer in the range of 15% by mass to 30% by mass with respect to the mass of the adherend (a1), and the mass of the adherend (a1) More preferably, it contains a plasticizer in the range of 20 to 26% by mass.
  • the adherend (a1) having a plasticizer content within the above range has sufficient flexibility to bundle the wire harness even in a low temperature environment of about 5 ° C. or less, and adheres from the adherend.
  • the amount of plasticizer transferred to the tape is also preferable because it is more effectively suppressed.
  • an inorganic filler such as calcium carbonate, talc, calcined clay, kaolin, aluminum hydroxide, titanium oxide or the like is provided in order to impart moderate impact resistance according to the application.
  • the amount of the inorganic additive to be used is preferably 10% by mass to 60% by mass with respect to the mass of polyvinyl chloride or rubber, and 20% by mass to 40% by mass is excellent in impact resistance and wire. A sufficient level of flexibility to bundle the harness can be achieved. Carbon black or the like can be used as the organic pigment. When the amount of the organic pigment used is in the range of 2% by mass to 10% by mass with respect to the mass of polyvinyl chloride or rubber, good impact resistance and flexibility can be maintained.
  • the thickness of the adherend (a1) containing the plasticizer is preferably 0.2 mm to 1 mm, and the thickness of 0.3 mm to 0.5 mm is flexible enough to bundle the wire harness. It is more preferable because the adherend (a1) is not easily stretched when the wire harness is bent, and the binding of the wire harness is difficult to loosen.
  • the surface of the adherend (a1) containing the plasticizer may have an embossed pattern or the like as necessary. The said embossed pattern can be provided in the surface by letting a to-be-adhered body (a1) pass between the metal nip rolls heated at 80 degreeC or more.
  • the adherend (a1) containing the plasticizer is formed into a sheet shape by any film forming method such as T-die extrusion molding, calendar molding, inflation molding, etc., in a state where the resin compound is melted at a high temperature. can do.
  • the pressure-sensitive adhesive tape of the present invention obtained by the above method can be used for bonding and fixing a sheet for bundling two or more wire harnesses used in, for example, vehicles.
  • the sheet is continuously bonded to one end of a long adherend (a1) slit in a roll having a width of 50 mm, in the flow direction, and bonded to a wire harness. It becomes a sheet.
  • the sheet can be left for several days under wet heat conditions of 60 ° C. and 80% RH, for example, in order to evaluate the peeling resistance due to the migration of the plasticizer during storage in stock.
  • the wet heat condition it is preferable to leave the substrate at a temperature equal to or lower than the softening temperature of the adherend (a1). Specifically, it is preferably left for 3 to 10 days at a temperature of 40 ° C. to 70 ° C. and a humidity of 70% to 90% RH.
  • the adherend (a1) is less likely to be thermally deformed, and abrupt transition of the plasticizer can be suppressed, and the plasticizer can enter the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2). Easy to disperse uniformly.
  • the sheet to which the adherend (a1) and the pressure-sensitive adhesive tape are stuck is attached to one end of the same sheet surface to which the pressure-sensitive adhesive tape is not stuck, while wrapping two or more wire harnesses in the center. Two or more wire harnesses can be bundled by combining them or by sticking them to one end of the back surface in a roll shape.
  • the plasticizer for example, diisononyl phthalate is used as the plasticizer, and the pressure-sensitive adhesive layer (b1) and the pressure-sensitive adhesive layer (b2) are formed.
  • the value measured by the following methods (1) to (3) is taken as an example when an acrylic pressure-sensitive adhesive is used as the pressure-sensitive adhesive.
  • a pressure-sensitive adhesive layer is formed by applying and drying a pressure-sensitive adhesive in which 10 parts by mass of a plasticizer is uniformly added to 100 parts by mass of the solid content of the acrylic pressure-sensitive adhesive and drying it. Then, the adhesive tape (C1) is prepared by transferring it onto both surfaces of the nonwoven fabric substrate.
  • an acrylic pressure-sensitive adhesive without adding a plasticizer is applied to the surface of the release liner and dried to form a pressure-sensitive adhesive layer, which is then transferred to both sides of the nonwoven fabric base material, thereby giving a pressure-sensitive adhesive tape (C0).
  • the infrared absorption spectrum of the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive tape (C1) is measured by the ATR method to obtain an infrared absorption spectrum (D1).
  • the infrared absorption spectrum of the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive tape (C0) is measured by the ATR method to obtain an infrared absorption spectrum (D0).
  • the infrared absorption spectrum (E1) of the plasticizer is extracted by subtracting the infrared absorption spectrum (D0) from the infrared absorption spectrum (D1) (difference spectrum).
  • the height (F1) of the absorption peak at 1285 cm ⁇ 1 derived from the plasticizer is measured.
  • the infrared absorption spectrum of the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive tape (C1) is measured by the ATR method to obtain an infrared absorption spectrum (D1).
  • the height (G1) of the absorption peak at 1160 cm ⁇ 1 derived from the acrylic polymer is measured from the infrared absorption spectrum (D1).
  • 4 types of pressure-sensitive adhesives are prepared by preparing each pressure-sensitive acrylic pressure-sensitive adhesive, applying each pressure-sensitive adhesive to the surface of the release liner and drying to form a pressure-sensitive adhesive layer, and transferring it to both sides of the nonwoven fabric substrate. Create a tape.
  • the infrared absorption spectrum of the adhesive layer surface of the four types of adhesive tapes is measured by the ATR method. From the four types of infrared absorption spectra, the height of the absorption peak at 1285 cm ⁇ 1 derived from the plasticizer and the height of the absorption peak at 1160 cm ⁇ 1 derived from the acrylic polymer are measured.
  • the vertical axis represents the plasticizer addition amount [parts by mass] added to 100 parts by mass of the solid content of the acrylic pressure-sensitive adhesive
  • the horizontal axis represents the height of the absorption peak at 1160 cm ⁇ 1 derived from the acrylic polymer ( G1) is the ratio (F1 / G1) of the absorption peak height (F1) of 1285 cm ⁇ 1 derived from the plasticizer, and the added amount of the plasticizer contained in the four types of adhesive tape and the ratio (F1 / G1).
  • a value corresponding to G1) is plotted to create a calibration curve.
  • the infrared absorption spectrum is measured using a Fourier transform infrared spectrophotometer (JASCO Corporation FT / IR-4100).
  • the adhesive tape (C2) is obtained by allowing it to stand for 9 days in wet heat conditions such as 80 ° C. and 80% RH.
  • the release liner is removed from the surface of the pressure-sensitive adhesive layer (b2) of the pressure-sensitive adhesive tape (C2), and the infrared absorption spectrum (D2) of the surface of the pressure-sensitive adhesive layer (b2) is measured by the ATR method. based on the external absorption spectrum (D2), the ratio of the height of the absorption peak of 1285 -1 derived from the plasticizer (F2) and the height of the absorption peak of 1160 cm -1 derived from the acrylic polymer (G2) (F2 / G2) is obtained.
  • F2 / G2 is applied to the horizontal axis of the calibration curve, and the content (H2) [part by mass] of the plasticizer contained in the adhesive layer (b2) of the adhesive tape (C2) is calculated.
  • the content of the plasticizer indicates the migration amount [parts by mass] of the plasticizer that has migrated from the polyvinyl chloride sheet when the pressure-sensitive adhesive layer (b2) excluding the plasticizer is 100 parts by mass. .
  • the pressure-sensitive adhesive layer (b1) in contact with the adherend (a1) is peeled off, and the plasticizer content (J2) [parts by mass] contained in the surface of the pressure-sensitive adhesive layer (b1) Calculate in the same way.
  • the uniform dispersibility of the plasticizer is based on the difference between the plasticizer content (H2) obtained by the method and the plasticizer content (J2). If the difference between the content (H2) and the content (J2) is in the range of ⁇ 2 parts by mass, it can be evaluated as an adhesive tape excellent in uniform dispersibility of the plasticizer. it can.
  • the amount of plasticizer transferred from the adherend (a1) to the pressure-sensitive adhesive layer (b1) and pressure-sensitive adhesive layer (b2) constituting the pressure-sensitive adhesive tape is preferably 0 to 35 parts by weight, and 0 parts by weight. More preferred is 20 parts by mass. If the amount of migration of the plasticizer is within 35 parts by mass, the plasticizer can be dispersed relatively uniformly in the pressure-sensitive adhesive layer (A), so that the plasticizer is bonded to the adherend (a1) and the pressure-sensitive adhesive layer ( Adhesion with A) is not inhibited and good peeling resistance can be maintained.
  • T-peel adhesive strength An adhesive tape from which the release liner was removed from the adhesive layer (b1) was affixed to the adherend (a1-1) and cut into 15 mm width and 100 mm length to obtain test pieces. The test piece was left for 9 days under wet heat conditions such as 60 ° C. and 80% RH. Further, the adherend (a1-2) to which the adhesive tape was not attached was cut into a width of 15 mm and a length of 100 mm, and left under the same conditions as the test piece.
  • test piece and the adherend (a1-2) are taken out in an atmosphere of 23 ° C. and 50% RH, and the release liner is peeled off from the pressure-sensitive adhesive layer (b2) of the test piece.
  • the adherend (a1-2) was affixed, the 2 kg roller was reciprocated once, and left in the same atmosphere for 30 minutes to adhere them.
  • adherend (a1-2) One end of the adherend (a1-2) is fixed to the lower chuck of the tensile device portion of the Tensilon tensile tester, and the adherend (a1-1) is attached to the upper chuck of the tensile device portion of the Tensilon tensile tester.
  • the adhesive strength (T-peel adhesive strength) was measured by fixing and pulling the upper chuck at a speed of 3 mm / min.
  • the range of the adhesive force is preferably 1.5 N / 15 mm or more, and more preferably 2.0 N / 15 mm or more.
  • the pressure-sensitive adhesive layer cohesively breaks when measuring the adhesive force.
  • Example 1 Preparation of acrylic pressure-sensitive adhesive composition (S) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 93.4 parts by mass of butyl acrylate, 3 parts by mass of vinyl acetate, acrylic 2.5 parts by weight of acid, 1 part by weight of N-vinyl-2-pyrrolidolin, 0.1 part by weight of 2-hydroxyethyl acrylate, and 0.2 part by weight of 2,2′-azobisisobutylnitrile as a polymerization initiator The resultant was dissolved in 100 parts by mass of ethyl acetate and polymerized at 80 ° C.
  • an acrylic polymer solution having a weight average molecular weight of 700,000.
  • solid content 15 parts by mass of rosin ester resin A-100 (Arakawa Chemical Industries, Ltd.) as a tackifier resin, and polymerized rosin ester resin D-135 (Arakawa Chemical Industries) 15 parts by mass) was added and diluted with toluene to obtain an acrylic pressure-sensitive adhesive composition (S) having a nonvolatile content of 40% by mass.
  • two pressure-sensitive adhesive layers were prepared, which were laminated on both sides of a 43 ⁇ m-thick nonwoven fabric A (Nippon Paper Papillia, No. 1215) and heated to 100 ° C. (manufactured by Tester Sangyo Co., Ltd.) SA-1010, a small tabletop test laminator) was applied at a rate of 1 m / min while applying a pressure of 0.4 MPa, and then cured for 48 hours in a dryer at 40 ° C., so that it was provided on both sides of the nonwoven fabric.
  • a 43 ⁇ m-thick nonwoven fabric A Natural Paper Papillia, No. 1215
  • SA-1010 a small tabletop test laminator
  • a double-sided pressure-sensitive adhesive tape having a total basis weight of the pressure-sensitive adhesive layer of 138 g / m 2 , a gel fraction of the pressure-sensitive adhesive layer of 10% by mass and a thickness of 145 ⁇ m was prepared.
  • the Gurley air permeability of 1215 was 0.2 seconds / 100 ml.
  • Example 2 (2-1) Double-sided adhesive tape S-2 Except having changed the usage-amount of the isocyanate type crosslinking agent (The Tosoh Corporation make, Coronate L-45E, solid content 45 mass%) from 0.52 mass part to 0.39 mass part, it carried out similarly to Example 1. A double-sided adhesive tape S-2 was obtained. The gel fraction of the pressure-sensitive adhesive layer was 2% by mass. The content of the crosslinking agent (solid content) with respect to 100 parts by mass of the acrylic polymer (solid content) was 0.57 parts by mass.
  • the isocyanate type crosslinking agent The Tosoh Corporation make, Coronate L-45E, solid content 45 mass
  • Example 3 (Example 3) (3-1) Double-sided adhesive tape S-3 Except having changed the usage-amount of the isocyanate type crosslinking agent (the Tosoh Corporation make, Coronate L-45E, solid content 45 mass%) from 0.52 mass part to 0.71 mass part, it carried out similarly to Example 1. A double-sided adhesive tape S-3 was obtained. The gel fraction of the pressure-sensitive adhesive layer was 30% by mass. The content of the crosslinking agent (solid content) with respect to 100 parts by mass of the acrylic polymer (solid content) was 1.04 parts by mass.
  • the isocyanate type crosslinking agent the Tosoh Corporation make, Coronate L-45E, solid content 45 mass
  • Example 4 (4-1) Preparation of acrylic pressure-sensitive adhesive composition (T) In a container, 75 g of deionized water and Aqualon KH-1025 as a surfactant [Daiichi Kogyo Seiyaku Co., Ltd .; active ingredient 25 mass%] 20 mass Part and 37.5 parts by mass of Latemul PD-104 [manufactured by Kao Corporation; active ingredient 20% by mass] as a surfactant were uniformly dissolved.
  • n-butyl acrylate 227.5 parts by mass of n-butyl acrylate, 227.5 parts by mass of 2-ethylhexyl acrylate, 25 parts by mass of methyl methacrylate, 6 parts by mass of N-vinyl-2-pyrrolidone, 4 parts by mass of acrylic acid, 10 parts by mass of methacrylic acid And 0.2 part by mass of lauryl mercaptan as a chain transfer agent was added and emulsified to obtain an emulsion (1) 632.7 parts by mass.
  • the reaction vessel was stirred for 1 hour while maintaining the temperature at 60 ° C., and then the contents were cooled and adjusted with ammonia water [active ingredient 10% by mass] so that the pH was 7.2. This was filtered through a 200-mesh wire mesh to obtain an acrylic polymer emulsion (1).
  • the obtained acrylic polymer emulsion (1) had a solid content concentration of 50 mass%, an average particle size of 333 nm, and a weight average molecular weight of 800,000.
  • Epocros WS-700 [manufactured by Nippon Shokubai Co., Ltd., water-soluble type, non-volatile content 25% by mass, oxazoline group content 4.5 mmol / g (solid) to 1000 parts by mass of the acrylic polymer emulsion (1) ] 25 parts by mass, superester E-865NT [Arakawa Chemical Industries, Ltd., softening point, solid content 50% by mass] 200 parts by weight, leveling emulsion type rosin ester type tackifying resin as tackifying resin 2.5 parts by mass of Surfinol PSA-336 [manufactured by Air Products Japan Co., Ltd.] as an agent and 2.5 parts by mass of Surfinol DF-110D [manufactured by Air Products Japan Co., Ltd.] as an antifoaming agent are added did.
  • the acrylic pressure-sensitive adhesive composition (T) was obtained by curing for 30 days in a 23 ° C. environment.
  • the content of the crosslinking agent (solid content) with respect to 100 parts by mass of the acrylic polymer (solid content) was 1.28 parts by mass.
  • Double-sided adhesive tape T-1 The total basis weight of the pressure-sensitive adhesive layer provided on both sides of the nonwoven fabric was 130 g, as in Example 1, except that the release liner was coated with a roll coater so that the basis weight after drying was 65 g / m 2. A double-sided adhesive tape T-1 having a thickness of / m 2 and a thickness of 140 ⁇ m was obtained. The gel fraction of the pressure-sensitive adhesive layer was 28% by mass.
  • a basis weight of 130 g / m 2 and a thickness of 140 ⁇ m are the same as in Example 4 except that the acrylic pressure-sensitive adhesive composition (U) is used instead of the acrylic pressure-sensitive adhesive composition (T).
  • a double-sided adhesive tape U-1 was obtained.
  • the gel fraction of the pressure-sensitive adhesive layer was 26% by mass.
  • the content of the crosslinking agent (solid content) with respect to 100 parts by mass of the acrylic polymer (solid content) was 1.28 parts by mass.
  • Example 6 Same as Example 1 except that a 50 ⁇ m thick mesh base material B in which polyester monofilament yarns with a fiber diameter of 25 ⁇ m are alternately woven into MD and TD so as to be 132 per inch is used as the base material. Thus, a double-sided pressure-sensitive adhesive tape S-5 was obtained.
  • the mesh substrate had a Gurley air permeability of 0.1 sec / 100 ml.
  • Example 7-1) Preparation of acrylic pressure-sensitive adhesive composition (V) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 93.4 parts by mass of butyl acrylate, 3 parts by mass of methyl acrylate, acrylic Acetic acid was mixed with 2.3 parts by weight of acid, 1.2 parts by weight of N-isopropylacrylamide, 0.1 part by weight of 2-hydroxyethyl acrylate, and 0.2 part by weight of 2,2′-azobisisobutylnitrile as a polymerization initiator. The resultant was dissolved in 100 parts by mass of ethyl and polymerized at 80 ° C.
  • Double-sided adhesive tape V-1 A double-sided pressure-sensitive adhesive tape V-1 was prepared in the same manner as in Example 1 except that the amount of the isocyanate-based crosslinking agent (Tosoh Corporation, Coronate L-45E, solid content 45% by mass) was changed to 1.24 parts by mass. Obtained.
  • the gel fraction of the pressure-sensitive adhesive layer was 2% by mass.
  • the content of the crosslinking agent (solid content) with respect to 100 parts by mass of the acrylic polymer (solid content) was 1.61 parts by mass.
  • Example 8-1) Preparation of acrylic pressure-sensitive adhesive composition (W) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, and a thermometer, 76.4 parts by mass of n-butyl acrylate, 2-ethylhexyl acrylate 18 .6 parts by mass, 1.2 parts by mass of acrylic acid, 3.9 parts by mass of vinyl acetate, 0.1 part by mass of 2-hydroxyethyl acrylate, 98 parts by mass of ethyl acetate, and with stirring, up to 80 ° C. while blowing nitrogen The temperature rose.
  • Double-sided adhesive tape W-1 A double-sided pressure-sensitive adhesive tape W-1 was prepared in the same manner as in Example 1 except that the amount of the isocyanate-based crosslinking agent (Tosoh Corporation, Coronate L-45E, solid content 45% by mass) was 0.90 parts by mass. Obtained. The gel fraction of the pressure-sensitive adhesive layer was 2% by mass.
  • Example 1 Except having changed the usage-amount of the isocyanate type crosslinking agent (The Tosoh Corporation make, Coronate L-45E, solid content 45 mass%) from 0.52 mass part to 1.1 mass part, it carried out similarly to Example 1, and. A double-sided adhesive tape S-6 was obtained. The gel fraction of the pressure-sensitive adhesive layer was 42% by mass. The content of the crosslinking agent (solid content) with respect to 100 parts by mass of the acrylic polymer (solid content) was 1.61 parts by mass.
  • the isocyanate type crosslinking agent The Tosoh Corporation make, Coronate L-45E, solid content 45 mass
  • Example 2 In Example 1, the total basis weight of the pressure-sensitive adhesive layers provided on both surfaces of the nonwoven fabric was 100 g / m in the same manner as in Example 1 except that the basis weight after drying on the release liner was 50 g / m 2. 2. Double-sided pressure-sensitive adhesive tape S-7 having a pressure-sensitive adhesive layer thickness of 110 ⁇ m was prepared.
  • Example 3 Except having changed the usage-amount of the isocyanate type crosslinking agent (The Tosoh Corporation make, Coronate L-45E, solid content 45 mass%) from 0.52 mass part to 1.9 mass parts, it is the same as that of Example 1.
  • a double-sided adhesive tape S-8 was obtained.
  • the gel fraction of the pressure-sensitive adhesive layer was 52% by mass.
  • the content of the crosslinking agent (solid content) with respect to 100 parts by mass of the acrylic polymer (solid content) was 2.78 parts by mass.
  • Polyvinyl chloride resin compound using 100 parts by weight of polyvinyl chloride (polymerization degree 1400), 34 parts by weight of diisononyl phthalate, 25 parts by weight of calcium carbonate, 3 parts by weight of carbon black, and 3 parts by weight of barium-zinc stabilizer. was prepared.
  • the obtained polyvinyl chloride resin compound was calendered (processing temperature 170 ° C.) to obtain a polyvinyl chloride sheet having a thickness of 0.4 mm.
  • the gel fraction was calculated based on the mass and the following formula.
  • Gel fraction (mass%) ⁇ (mass of adhesive layer remaining in mixed solvent) / (mass of adhesive layer before immersion) ⁇ ⁇ 100
  • the mass of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape before immersion refers to a value obtained by subtracting the mass of the air-permeable substrate used for the production from the mass of the double-sided pressure-sensitive adhesive tape. Further, the mass of the remaining pressure-sensitive adhesive layer refers to a value obtained by subtracting the mass of the air-permeable substrate from the mass of the residue after drying.
  • the initial adhesive force was measured according to JIS Z 0237. Specifically, it measured by the following method.
  • a double-sided pressure-sensitive adhesive tape from which one release liner was removed was affixed to an adherend (a1-1) and cut into 15 mm width and 100 mm length as test pieces.
  • the test piece was left in an atmosphere of 23 ° C. and 50% RH for 1 day. Further, the adherend (a1-2) to which the double-sided adhesive tape was not attached was cut into 15 mm width and 100 mm length and left under the same conditions as the above test pieces.
  • test piece and the adherend (a1-2) were peeled and removed from the other release liner of the test piece in an atmosphere of 23 ° C. and 50% RH. a1-2) was affixed, and the 2 kg roller was reciprocated once, and left in the same atmosphere for 30 minutes to adhere them.
  • adherend (a1-2) One end of the adherend (a1-2) is fixed to the lower chuck of the tensile device portion of the Tensilon tensile tester, and the adherend (a1-1) is attached to the upper chuck of the tensile device portion of the Tensilon tensile tester.
  • the adhesive strength (T-peel adhesive strength) was measured by fixing and pulling the upper chuck at a speed of 3 mm / min.
  • T-peel adhesive strength Method for evaluating adhesive strength after long-term storage (T-peel adhesive strength)
  • adherend (a1-2) One end of the adherend (a1-2) is fixed to the lower chuck of the tensile device portion of the Tensilon tensile tester, and the adherend (a1-1) is attached to the upper chuck of the tensile device portion of the Tensilon tensile tester.
  • the adhesive strength (T-peel adhesive strength) was measured by fixing and pulling the upper chuck at a speed of 3 mm / min.
  • Cohesive failure The adherend peeled off due to the cohesive failure of the adhesive layer.
  • Interfacial peeling In the test piece that was left before leaving wet heat, it peeled off at the interface between the polyvinyl chloride sheet and the double-sided adhesive tape.
  • an acrylic pressure-sensitive adhesive composition (S) containing no plasticizer is applied to the surface of the release liner and dried to form a pressure-sensitive adhesive layer, which is then transferred to both sides of the nonwoven fabric A.
  • a double-sided adhesive tape (C0) was prepared.
  • the infrared absorption spectrum on the surface of the pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive tape (C1) was measured by the ATR method to obtain an infrared absorption spectrum (D1).
  • the infrared absorption spectrum of the pressure-sensitive adhesive layer surface of the double-sided pressure-sensitive adhesive tape (C0) was measured by the ATR method to obtain an infrared absorption spectrum (D0).
  • the infrared absorption spectrum (E1) of the plasticizer was extracted by subtracting the infrared absorption spectrum (D0) from the infrared absorption spectrum (D1) (difference spectrum).
  • the infrared absorption spectrum of the pressure-sensitive adhesive layer surface of the double-sided pressure-sensitive adhesive tape (C1) is measured by the ATR method to obtain an infrared absorption spectrum (D1).
  • the height (G1) of the absorption peak at 1160 cm ⁇ 1 derived from the acrylic polymer was measured from the infrared absorption spectrum (D1).
  • an acrylic pressure-sensitive adhesive in which 20 parts by mass of diisononyl phthalate used as a plasticizer for a polyvinyl chloride sheet is added to 100 parts by mass of the solid content of the acrylic pressure-sensitive adhesive composition (S), and 30 parts by mass is added.
  • the acrylic pressure-sensitive adhesive and the acrylic pressure-sensitive adhesive added with 40 parts by mass were prepared, and each pressure-sensitive adhesive was applied to the surface of the release liner and dried to form a pressure-sensitive adhesive layer.
  • 4 types of double-sided pressure-sensitive adhesive tapes were prepared by transferring to both sides.
  • the release liner of either one of the four types of double-sided pressure-sensitive adhesive tape is removed, and the infrared absorption spectrum of the pressure-sensitive adhesive layer surface is measured by the ATR method. From the four types of infrared absorption spectra, the height of the absorption peak at 1285 cm ⁇ 1 derived from diisononyl phthalate and the height of the absorption peak at 1160 cm ⁇ 1 derived from the acrylic polymer were measured.
  • the vertical axis represents the amount of diisononyl phthalate added to 100 parts by mass of the acrylic copolymer [parts by mass], and the horizontal axis represents the height of the absorption peak (G1) of 1160 cm ⁇ 1 derived from the acrylic polymer.
  • the ratio (F1 / G1) of the absorption peak height (F1) of 1285 cm ⁇ 1 derived from diisononyl phthalate, and the ratio (F1 / G1) of diisononyl phthalate contained in the four types of double-sided adhesive tapes A calibration curve was created by plotting the values corresponding to G1).
  • the infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer (JASCO Corporation FT / IR-4100).
  • the acrylic pressure-sensitive adhesive composition (S) the acrylic pressure-sensitive adhesive composition (T), the acrylic pressure-sensitive adhesive composition (U), the acrylic pressure-sensitive adhesive composition (V), and the acrylic pressure-sensitive adhesive Calibration curves were prepared in the same manner as described above except that each of the compositions (W) was used.
  • the release liner is removed from the surface of the pressure-sensitive adhesive layer corresponding to the pressure-sensitive adhesive layer (b2) of the double-sided pressure-sensitive adhesive tape (C2) after being left, and the infrared absorption spectrum of the surface of the pressure-sensitive adhesive layer (b2) ( D2) was measured by the ATR method, and based on the infrared absorption spectrum (D2), the height of the absorption peak at 1285 cm ⁇ 1 derived from diisononyl phthalate (F2) and the absorption at 1160 cm ⁇ 1 derived from the acrylic polymer The ratio (F2 / G2) of peak height (G2) was determined.
  • F2 / G2 is applied to the horizontal axis of the calibration curve, and the content (H2) of the plasticizer contained in the adhesive layer corresponding to the adhesive layer (b2) of the adhesive tape (C2) [ Parts by mass] were calculated.
  • the content of the plasticizer is the amount of plasticizer transferred from the polyvinyl chloride sheet when the pressure-sensitive adhesive layer corresponding to the pressure-sensitive adhesive layer (b2) excluding the plasticizer is 100 parts by mass. [Mass] is shown.
  • the pressure-sensitive adhesive layer (b1) in contact with the polyvinyl chloride sheet is peeled off from the surface of the polyvinyl chloride sheet, and the content of the plasticizer contained in the surface of the pressure-sensitive adhesive layer (b1) (J2) [mass Part] was calculated by the same method as described above.
  • the uniform dispersibility of the plasticizer depends on the difference between the diisononyl phthalate content (H2) obtained by the above method and the diisononyl phthalate content (J2). Based on the following evaluation criteria.
  • ⁇ The difference between the content (H2) and the content (J2) is within a range of ⁇ 2 parts by mass, and the plasticizer is excellent in uniform dispersibility.
  • X The difference between the content (H2) and the content (J2) is outside the range of ⁇ 2 parts by mass, and the plasticizer is not uniformly dispersed.
  • the polyvinyl chloride sheet was folded in the middle, and the adhesive layer on the other side was attached to the end (center bending attachment).
  • the specimens obtained by the above center bending and spiral winding were left for 24 hours in an environment of 23 ° C. and 50% RH, and their peel resistance was evaluated according to the following criteria.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Insulated Conductors (AREA)
  • Package Frames And Binding Bands (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention a pour but de fournir un ruban adhésif sensible à la pression qui, même lorsqu'il est utilisé pour fixer une partie à coller contenant un plastifiant, ne subit pas de décollage à l'interface entre la partie à coller et une couche adhésive sensible à la pression, et peut maintenir la fixation sur une longue durée. La présente invention concerne un ruban adhésif sensible à la pression utilisé pour fixer une partie à coller (a1) contenant un plastifiant, le ruban adhésif sensible à la pression étant caractérisé en ce : qu'il possède une couche adhésive sensible à la pression (b1) sur un côté surface d'un substrat perméable à l'air et une couche adhésive sensible à la pression (b2) sur l'autre côté surface ; que le poids de base total de la couche adhésive sensible à la pression (b1) et de la couche adhésive sensible à la pression (b2) se trouve dans la plage de 125 à 175 g/m2 ; que la fraction de gel totale de la couche adhésive sensible à la pression (b1) et de la couche adhésive sensible à la pression (b2) est de 2 à 35 % en masse.
PCT/JP2016/067921 2015-06-29 2016-06-16 Ruban adhésif sensible à la pression, feuille de mise en faisceau et article WO2017002634A1 (fr)

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CN201680019512.XA CN107429131B (zh) 2015-06-29 2016-06-16 粘合带、电线束捆扎用片材及物品
JP2016558818A JP6094921B1 (ja) 2015-06-29 2016-06-16 粘着テープ、ハーネス結束用シート及び物品
CN202110124130.6A CN112960274B (zh) 2015-06-29 2016-06-16 电线束捆扎用片材及物品

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CN112680130A (zh) * 2019-10-18 2021-04-20 日东电工株式会社 线束用粘合带
CN113825609A (zh) * 2019-05-24 2021-12-21 Dic株式会社 粘接片、物品和物品的制造方法
US20220195252A1 (en) * 2019-04-04 2022-06-23 Avery Dennison Corporation Reinforced label assembly
WO2022172814A1 (fr) * 2021-02-12 2022-08-18 住友電装株式会社 Feuille de fusion et élément de câblage

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WO2017002634A1 (fr) * 2015-06-29 2017-01-05 Dic株式会社 Ruban adhésif sensible à la pression, feuille de mise en faisceau et article
JPWO2019066060A1 (ja) * 2017-09-28 2020-09-10 積水化学工業株式会社 粘着剤組成物、及び粘着テープ
JP6844751B2 (ja) * 2018-06-15 2021-03-17 Dic株式会社 粘着剤組成物
JP7310135B2 (ja) * 2018-12-27 2023-07-19 東洋インキＳｃホールディングス株式会社 可塑剤含有塩化ビニルフィルム用粘着シートおよびアクリル系粘着剤
JP7342507B2 (ja) * 2019-08-08 2023-09-12 Dic株式会社 粘着剤組成物及び粘着フィルム

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US20220195252A1 (en) * 2019-04-04 2022-06-23 Avery Dennison Corporation Reinforced label assembly
CN113825609A (zh) * 2019-05-24 2021-12-21 Dic株式会社 粘接片、物品和物品的制造方法
CN113825609B (zh) * 2019-05-24 2024-04-26 Dic株式会社 粘接片、物品和物品的制造方法
CN112680130A (zh) * 2019-10-18 2021-04-20 日东电工株式会社 线束用粘合带
WO2022172814A1 (fr) * 2021-02-12 2022-08-18 住友電装株式会社 Feuille de fusion et élément de câblage
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CN112960274A (zh) 2021-06-15
JP2017014529A (ja) 2017-01-19
JPWO2017002634A1 (ja) 2017-07-06
CN112960274B (zh) 2023-04-25
JP6256560B2 (ja) 2018-01-10
JP6094921B1 (ja) 2017-03-15

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