WO2021020581A1 - ポリオレフィン系樹脂発泡体シート及びそれを用いた粘着テープ - Google Patents

ポリオレフィン系樹脂発泡体シート及びそれを用いた粘着テープ Download PDF

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Publication number
WO2021020581A1
WO2021020581A1 PCT/JP2020/029567 JP2020029567W WO2021020581A1 WO 2021020581 A1 WO2021020581 A1 WO 2021020581A1 JP 2020029567 W JP2020029567 W JP 2020029567W WO 2021020581 A1 WO2021020581 A1 WO 2021020581A1
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Prior art keywords
foam sheet
mass
polyolefin
based resin
parts
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English (en)
French (fr)
Japanese (ja)
Inventor
石田　昌也
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority to JP2020555254A priority Critical patent/JP7474704B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/26—Porous or cellular plastics
    • 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 a polyolefin-based resin foam sheet and an adhesive tape using the same.
  • Polyolefin-based resin foams are generally excellent in flexibility, light weight, shock absorption, and heat insulating properties, and are widely used as laminates with skin materials, heat insulating materials, cushioning materials, and the like. Further, the polyolefin-based resin foam has excellent flexibility and excellent shock absorption, and is therefore used as a foam tape for fixing electronic devices (see, for example, Patent Documents 1 to 3).
  • in-vehicle displays such as center information displays (CIDs) and head-up displays (HUDs) have become larger and curved, and even higher flexibility is required for foam tapes for fixing panels of modules.
  • the module may be heated by the influence of sunlight or the like, and heat resistance to the fixing foam tape is also required at the same time.
  • impact resistance to the fixing foam tape is further required.
  • a resin having a high melting point it is conceivable to use a resin having a high melting point as a raw material.
  • a foam using a high melting point resin is generally hard due to its resin characteristics.
  • an object of the present invention is to provide a polyolefin-based resin foam sheet having excellent heat resistance, flexibility and impact resistance, and an adhesive tape using the same.
  • the present invention has been made based on the finding that the above problems can be solved by using a foam sheet having a specific heat shrinkage ratio, interlayer strength and compressive strength. That is, the present invention provides the following [1] to [10].
  • [1] When at least one of the shrinkage rate of MD and the shrinkage rate of TD when cured at a temperature of 90 ° C. for 1 hour is 5% or less, and the interlayer strength at a temperature of 23 ° C. is 0.80 MPa or more.
  • a polyolefin-based resin foam sheet having a thickness of 1.5 mm or less and a 25% compression strength of 800 kPa or less.
  • the resin (A) contains a polypropylene-based resin, an ethylene-propylene random copolymer rubber, and an olefin-based thermoplastic elastomer.
  • the total content of the polypropylene-based resin and the ethylene-propylene random copolymer rubber in the resin composition is 50 to 90 parts by mass with respect to 100 parts by mass of the resin component of the resin composition.
  • the above-mentioned [7] or [8], wherein the content of the olefin-based thermoplastic elastomer in the resin composition is 5 to 45 parts by mass with respect to 100 parts by mass of the resin component of the resin composition.
  • An adhesive tape comprising the polyolefin-based resin foam sheet according to any one of the above [1] to [9] and an adhesive layer provided on at least one surface of the polyolefin-based resin foam sheet.
  • the polyolefin-based resin foam sheet of the present invention (hereinafter, may be simply referred to as “foam sheet”) has at least one of the shrinkage rate of MD and the shrinkage rate of TD when cured at a temperature of 90 ° C. for 1 hour.
  • the shrinkage rate is 5% or less
  • the interlayer strength at a temperature of 23 ° C. is 0.80 MPa or more
  • the thickness is 1.5 mm or less
  • the 25% compression strength is 800 kPa or less.
  • shrinkage rate of MD and TD when cured at a temperature of 90 ° C. for 1 hour The shrinkage rate of at least one of the shrinkage rate of MD and the shrinkage rate of TD when the foam sheet of the present invention is cured at a temperature of 90 ° C. for 1 hour is 5% or less. If both the shrinkage rate of MD and the shrinkage rate of TD when the foam sheet is cured at a temperature of 90 ° C. for 1 hour is larger than 5%, it is sufficient for use in a high temperature environment in a vehicle. A foam sheet having excellent heat resistance may not be obtained.
  • At least one of the shrinkage rate of MD and the shrinkage rate of TD when the foam sheet of the present invention is cured at a temperature of 90 ° C. for 1 hour is preferably 4.5. % Or less, more preferably 4.0% or less, still more preferably 3.5% or less.
  • the lower limit of the range of the shrinkage rate of at least one of the shrinkage rate of MD and the shrinkage rate of TD when the foam sheet of the present invention is cured at a temperature of 90 ° C. for 1 hour is not particularly limited, but is, for example, 0.1%. is there. It is more preferable that both the shrinkage rate of MD and the shrinkage rate of TD when the foam sheet of the present invention is cured at a temperature of 90 ° C. for 1 hour are within the above range.
  • the dimensional changes of MD and TD of the foam sheet at 90 ° C. are measured, the heat shrinkage rate (%) of MD and TD is calculated, and the value is used as the value of the foam sheet of the present invention.
  • the shrinkage rate of MD and the shrinkage rate of TD when cured at a temperature of 90 ° C. for 1 hour is the shrinkage rate of MD and the shrinkage rate of TD when cured at a temperature of 90 ° C. for 1 hour.
  • MD means Machine Direction, which is a direction that coincides with the extrusion direction of the sheet and the like.
  • TD means Transverse Direction, which is orthogonal to the MD and parallel to the surface of the sheet.
  • the shrinkage rate of MD and the shrinkage rate of TD when the foam sheet is cured at a temperature of 90 ° C. for 1 hour can be adjusted by adjusting the type and content of the resin constituting the foam sheet.
  • the interlayer strength of the foam sheet of the present invention at a temperature of 23 ° C. is 0.80 MPa or more. If the interlayer strength of the foam sheet at a temperature of 23 ° C. is less than 0.80 MPa, a foam sheet having sufficient impact resistance against high vibration caused by the module being used in a vehicle cannot be obtained. In some cases. From the viewpoint of impact resistance of the foam sheet, the interlayer strength of the foam sheet of the present invention at a temperature of 23 ° C. is preferably 0.90 MPa or more, more preferably 1.50 MPa or more. The upper limit of the range of interlayer strength of the foam sheet of the present invention at a temperature of 23 ° C.
  • the interlayer strength of the foam sheet at a temperature of 23 ° C. can be measured by the method described in Examples described later. The measuring method is to pull the foam sheet in the thickness direction and measure the maximum load when the sheet is broken (peeled). Since the fracture that occurs in the interlayer strength measurement of the foam sheet of the present invention occurs inside the foam sheet, the interlayer strength mainly reflects the tensile strength in the thickness direction of the foam sheet. The interlayer strength of the foam sheet at a temperature of 23 ° C. can be adjusted by adjusting the type and content of the resin constituting the foam sheet.
  • the interlayer strength of the foam sheet of the present invention at a temperature of 90 ° C. is preferably 0.40 MPa or more.
  • the interlayer strength of the foam sheet at a temperature of 90 ° C. is 0.40 MPa or more, sufficient impact resistance is provided against the high vibration received by the module being used in the vehicle even in a high temperature environment inside the vehicle.
  • a foam sheet having is obtained.
  • the interlayer strength of the foam sheet of the present invention at a temperature of 90 ° C. is more preferably 0.50 MPa or more, still more preferably 0. It is 60 MPa or more, and particularly preferably 0.70 MPa or more.
  • the upper limit of the range of interlayer strength of the foam sheet of the present invention at a temperature of 90 ° C. is not particularly limited, but is, for example, 3.00 MPa.
  • the interlayer strength of the foam sheet at a temperature of 90 ° C. can be measured by the method described in Examples described later.
  • the interlayer strength of the foam sheet at a temperature of 90 ° C. can be adjusted by adjusting the type and content of the resin constituting the foam sheet.
  • the thickness of the foam sheet of the present invention is 1.5 mm or less. If the thickness of the foam sheet is larger than 1.5 mm, the foam sheet may be too thick for use in an in-vehicle electronic device having a curved surface. From such a viewpoint, the thickness of the foam sheet is more preferably 1.0 mm or less, further preferably 0.5 mm or less, and even more preferably 0.3 mm or less.
  • the lower limit of the thickness range of the foam sheet of the present invention is not particularly limited, but is, for example, 0.03 mm. Further, from the viewpoint of obtaining a foam sheet in which both the front surface and the back surface are smooth surfaces, the foam sheet of the present invention slices a thick foam sheet in a direction perpendicular to the thickness direction. It is preferable that the foam sheet is not obtained.
  • the 25% compressive strength of the foam sheet of the present invention is 800 kPa or less. If the 25% compression strength of the foam sheet is larger than 800 kPa, the flexibility of the foam sheet becomes insufficient, and the curved surface followability may be significantly lowered. Further, the 25% compressive strength of the foam sheet of the present invention is preferably 30 kPa or more. When the 25% compression strength of the foam sheet is 30 kPa or more, it is possible to obtain a foam sheet having sufficient mechanical strength for use in electronic devices or in-vehicle electronic devices.
  • the 25% compressive strength of the foam sheet of the present invention is preferably 30 to 800 kPa, more preferably 40 to 750 kPa, and further preferably 50 to 700 kPa. It is particularly preferably 60 to 650 kPa.
  • the 25% compressive strength of the foam sheet can be measured according to JIS K 7181. Further, the 25% compressive strength of the foam sheet can be adjusted by adjusting the type and content of the resin constituting the foam sheet, the degree of cross-linking of the foam sheet, and the like.
  • the average cell diameter of at least one of the average cell diameter of MD and the average cell diameter of TD in the foam sheet of the present invention is preferably 250 ⁇ m or less.
  • the average cell diameter of at least one of the average cell diameter of MD and the average cell diameter of TD is 250 ⁇ m or less, the mechanical strength of the foam sheet is improved and the impact resistance of the foam sheet is further improved.
  • the average cell diameter of at least one of the average cell diameter of MD and the average cell diameter of TD is more preferably 230 ⁇ m or less, still more preferably 200 ⁇ m or less. Is.
  • the lower limit of the range of the average cell diameter of at least one of the average cell diameter of MD and the average cell diameter of TD in the foam sheet of the present invention is not particularly limited, but is, for example, 120 ⁇ m. It is more preferable that the average cell diameter of both the MD average cell diameter and the TD average cell diameter in the foam sheet of the present invention is within the above range. Further, the average cell diameter of MD and TD can be adjusted by adjusting the degree of cross-linking of the foam sheet.
  • the degree of cross-linking of the foam sheet of the present invention is preferably 30 to 70% by mass.
  • the degree of cross-linking of the foam sheet is 30 to 70% by mass, it becomes easy to adjust the average pore diameters of MD and TD of the pores of the foam sheet to a desired range. In addition, it becomes easy to increase the interlayer strength.
  • the degree of cross-linking of the foam sheet is more preferably 40 to 70% by mass, further preferably 45 to 65% by mass, and particularly preferably 50 to 60% by mass.
  • the degree of cross-linking can be measured according to the method described in Examples described later.
  • the degree of cross-linking of the foam sheet can be adjusted by adjusting the type and content of the cross-linking aid, the irradiation dose of ionizing radiation, and the like.
  • the apparent density of the foam sheet of the present invention is preferably 0.06 to 0.7 g / cm 3 .
  • the apparent density of the foam sheet is 0.06 to 0.7 g / cm 3 , the heat resistance of the foam sheet can be improved, and the flexibility and impact resistance can be improved in a well-balanced manner.
  • the apparent density of the foam sheet is more preferably 0.07 to 0.6 g / cm 3 , still more preferably 0.07 to 0.5 g / cm 3 , and particularly preferably 0. .1 to 0.5 g / cm 3 .
  • the flexural modulus of the foam sheet of the present invention is preferably 150 kPa or less.
  • the flexural modulus of the foam sheet of the present invention is 150 kPa or less, the curved surface followability of the foam sheet is further improved.
  • the flexural modulus of the foam sheet is more preferably 100 kPa or less, still more preferably 50 kPa or less.
  • the lower limit of the flexural modulus of the foam sheet is not particularly limited, but is, for example, 5 kPa or more.
  • the flexural modulus can be measured by the method described in Examples described later.
  • the foam sheet of the present invention is a resin composition containing a resin (A) having a constituent unit derived from propylene (hereinafter, may be simply referred to as "resin (A)") (hereinafter, "resin composition (C)"". It is preferable that the plastic is foamed. Further, it is more preferable that the foam sheet of the present invention is obtained by cross-linking and foaming the resin composition (C). Further, it is more preferable that the resin composition (C) further contains a polyethylene-based resin (B) (hereinafter, may be simply referred to as "resin (B)") in addition to the resin (A).
  • a polyethylene-based resin (B) hereinafter, may be simply referred to as "resin (B)
  • the content of the resin (A) in the resin composition (C) is preferably 55 to 99 parts by mass with respect to 100 parts by mass of the resin component of the resin composition (C).
  • the content of the resin (A) in the resin composition (C) is more preferably 75 to 97 parts by mass with respect to 100 parts by mass of the resin component of the resin composition (C).
  • the resin (A) preferably contains a polypropylene-based resin, an ethylene-propylene random copolymer rubber, and an olefin-based thermoplastic elastomer.
  • the resin composition (C) containing such a resin (A) By using the resin composition (C) containing such a resin (A), the heat shrinkage of the foam sheet at a temperature of 90 ° C. is lowered, and the interlayer strength at a temperature of 23 ° C. is increased to 25%. It becomes easy to adjust the compression strength within a predetermined range.
  • the total content of the polypropylene-based resin, the ethylene-propylene random copolymer rubber, and the olefin-based thermoplastic elastomer in the resin (A) is preferably 80 to 100% by mass, more preferably 90. It is -100% by mass, more preferably 95-100% by mass.
  • the polypropylene-based resin is not particularly limited, and examples thereof include a copolymer of propylene and another olefin.
  • the copolymer of propylene and other olefins may be a block copolymer, a random copolymer, or a random block copolymer, but it may be a random copolymer of propylene (random polypropylene). preferable.
  • random polypropylene By using random polypropylene, the heat resistance of the foam sheet is further improved.
  • other olefins copolymerized with propylene include, for example, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-.
  • examples thereof include ⁇ -olefins such as octene, 1-nonene and 1-decene, and among these, ethylene is particularly preferable. That is, as the propylene random copolymer (random polypropylene), an ethylene-propylene random copolymer is more preferable.
  • the content of the polypropylene-based resin in the resin composition (C) is preferably 30 to 70 parts by mass with respect to 100 parts by mass of the resin component of the resin composition (C).
  • the content of the polypropylene-based resin in the resin composition (C) is more preferably 35 to 65 parts by mass with respect to 100 parts by mass of the resin component of the resin composition (C), and further preferably. Is 40 to 60 parts by mass, and more preferably 40 to 50 parts by mass.
  • Ethylene-propylene random copolymer rubber When the resin (A) contains an ethylene-propylene random copolymer rubber, the interlayer strength of the foam sheet at a temperature of 23 ° C. is increased, and the 25% compression strength can be easily adjusted within a predetermined range.
  • Ethylene-propylene random copolymerized rubber is an amorphous or low-crystalline rubber-like substance in which ethylene and propylene are copolymerized substantially randomly.
  • the ethylene-propylene random copolymer rubber may have other monomer units in addition to the ethylene unit and the propylene unit.
  • Examples of the monomer forming another monomer unit include carbons such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene.
  • Conjugated diene dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-dicyclooctadiene, 7-methyl-1,6-octadien, 5-vinyl-2 of numbers 4-8 -Non-conjugated diene having 5 to 15 carbon atoms such as norbornene, vinyl ester compound such as vinyl acetate, unsaturated carboxylic acid ester such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, etc., acrylic Examples thereof include unsaturated carboxylic acids such as acid and methacrylic acid.
  • These monomers can be used alone or in combination of two or more.
  • non-conjugated diene having 5 to 15 carbon atoms is preferable, and 5-ethylidene-2-norbornene, 1,4-hexadiene, and dicyclopentadiene (DCPD) are more preferable, and 5-ethylidene is more preferable from the viewpoint of availability.
  • DCPD dicyclopentadiene
  • -2-Norbornene is more preferred.
  • the content of ethylene unit of the ethylene-propylene random copolymer rubber is usually 30 to 85% by mass, preferably 40 to 80% by mass, more preferably 45 to 75% by mass, and the content of propylene unit is usually 10.
  • the content is usually 0 to 60% by mass, preferably 15 to 50% by mass, and the content of other monomer units such as non-conjugated diene is usually 0 to 20% by mass, preferably 0 to 10% by mass.
  • ethylene-propylene random copolymer rubber ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-diene copolymer rubber (EPDM) are more preferable, and EPDM is further preferable.
  • EPDM include ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-1,4-hexadiene copolymer rubber, and ethylene-propylene-dicyclopentadiene copolymer rubber. Of these, ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber is preferable.
  • These ethylene-propylene random copolymer rubbers can be used alone or in combination of two or more.
  • the content of the ethylene-propylene random copolymer rubber in the resin composition (C) is preferably 10 to 30 parts by mass with respect to 100 parts by mass of the resin component of the resin composition (C).
  • the interlayer strength of the foam sheet at a temperature of 23 ° C. is increased, and the 25% compression strength can be easily adjusted within a predetermined range.
  • the content of the ethylene-propylene random copolymer rubber in the resin composition (C) is more preferably 15 to 25 parts by mass with respect to 100 parts by mass of the resin component of the resin composition (C). Yes, more preferably 17 to 23 parts by mass.
  • the total content of the polypropylene-based resin and the ethylene-propylene random copolymer rubber in the resin composition (C) is preferably 50 to 90 parts by mass with respect to 100 parts by mass of the resin component of the resin composition (C). ..
  • the heat shrinkage of the foam sheet at a temperature of 90 ° C. is lowered, the interlayer strength at a temperature of 23 ° C. is increased, and the 25% compression strength is within a predetermined range. It becomes easy to adjust to.
  • the total content of the polypropylene-based resin and the ethylene-propylene random copolymer rubber in the resin composition (C) is more preferably 100 parts by mass of the resin component of the resin composition (C). It is 55 to 85 parts by mass, more preferably 60 to 80 parts by mass, and particularly preferably 60 to 70 parts by mass.
  • the olefin-based thermoplastic elastomer (TPO) is generally a hard segment of a polyolefin-based resin such as a polyethylene-based resin or a polypropylene-based resin, and a soft segment of a polyolefin-based rubber such as EPR or EPDM.
  • a polyolefin-based resin such as a polyethylene-based resin or a polypropylene-based resin
  • a soft segment of a polyolefin-based rubber such as EPR or EPDM.
  • EPR polyethylene-based resin
  • EPDM polypropylene-based resin
  • any of a blend type, a dynamic cross-linking type, and a polymerization type can be used.
  • the TPO is preferably one in which fine particles of polyolefin-based rubber are dispersed in a matrix of polyolefin-based resin.
  • the TPO used in the foam sheet of the present invention has a constituent unit in which at least one of the above-mentioned polyolefin-based resin and polyolefin-based rubber is derived from propylene.
  • the resin (A) contains such TPO, the interlayer strength of the foam sheet at a temperature of 23 ° C. is increased, and the 25% compression strength can be easily adjusted within a predetermined range.
  • the polyolefin-based resin and the polyolefin-based rubber have a propylene-derived structural unit.
  • the polyolefin resin is more preferably a polypropylene resin.
  • TPO products used in the foam sheet of the present invention include, for example, olefin-based thermoplastic elastomers manufactured by Prime Polymer Co., Ltd. (product name: Prime TPO, model number: E-2710, MFR: 2.8 g / 10). Minutes).
  • the content of TPO in the resin component of the resin composition (C) is determined from the viewpoint of increasing the interlayer strength of the foam sheet at a temperature of 23 ° C. and making it easier to adjust the 25% compression strength within a predetermined range. It is preferably 5 to 45 parts by mass, more preferably 10 to 40 parts by mass, still more preferably 15 to 35 parts by mass, and particularly preferably 25 to 35 parts by mass with respect to 100 parts by mass of the component. ..
  • the resin (A) contains a polypropylene-based resin, it becomes easy to reduce the heat shrinkage of the foam sheet at a temperature of 90 ° C. Further, when the resin (A) further contains an ethylene-propylene random copolymer rubber and an olefin-based thermoplastic elastomer (TPO), the compatibility between the polypropylene-based resin and the ethylene-propylene random copolymer rubber is improved, and the compatibility is improved. The interlayer strength at a temperature of 23 ° C. is increased, and the 25% compression strength can be easily adjusted within a predetermined range. From this point of view, the resin (A) preferably contains a polypropylene resin, an ethylene-propylene random copolymer rubber, and an olefin thermoplastic elastomer (TPO).
  • the resin composition (C) preferably further contains a polyethylene-based resin (B).
  • a polyethylene-based resin (B) examples include low-density polyethylene-based resin, medium-density polyethylene-based resin, high-density polyethylene-based resin, and linear low-density polyethylene-based resin. Among these, linear low-density polyethylene-based resin is used. Resin (LLDPE) is preferred.
  • Linear low density polyethylene resin density of 0.910 g / cm 3 or more 0.950 g / cm 3 less than the polyethylene, preferably those density of 0.910 ⁇ 0.940g / cm 3. Since the foam contains a low-density linear low-density polyethylene resin, the processability when processing the resin composition into a foam and the moldability when molding the foam into a molded body are improved. It tends to be good.
  • the density of the resin is measured according to JIS K7112.
  • the linear low-density polyethylene usually contains ethylene as a main component (80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more of all the monomers), and is a copolymer of ethylene and a small amount of ⁇ -olefin. It is a polymer.
  • examples of the ⁇ -olefin include those having 3 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and specifically, 1-butene, 1-pentene, 1-hexene and 4-methyl-1. -Pentene, 1-heptene, 1-octene and the like can be mentioned.
  • these ⁇ -olefins can be used alone or in combination of two or more. Further, these polyethylene-based resins may be used alone or in combination of two or more.
  • the content of the polyethylene-based resin (B) in the resin composition (C) is preferably 1 to 45 parts by mass with respect to 100 parts by mass of the resin component. , More preferably 3 to 25 parts by mass, and even more preferably 4 to 12 parts by mass.
  • the resin composition (C) may contain a resin component other than the polypropylene resin, the ethylene-propylene random copolymer rubber, the olefin thermoplastic elastomer, and the polyethylene resin as long as the object of the present invention is not impaired.
  • resin components include ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene- (meth) alkylacrylate copolymers, and modified copolymers obtained by copolymerizing these with maleic anhydride. Examples include copolymers.
  • the total content of the based resin (B) is preferably 70 to 99% by mass, more preferably 80 to 98% by mass.
  • the resin composition (C) usually contains a cross-linking aid and a foaming agent as additives in addition to the olefin-based resin. Further, the resin composition (C) may further contain a decomposition temperature adjusting agent. Further, the resin composition (C) preferably contains an antioxidant.
  • Crosslinking aid A polyfunctional monomer can be used as the crosslinking aid.
  • trifunctional (meth) acrylate compounds such as trimethylolpropane trimethacrylate and trimethylolpropanetriacrylate, trimellitic acid triallyl ester, 1,2,4-benzenetricarboxylic acid triallyl ester, triallyl isocyanurate and the like.
  • Bifunctional compounds such as compounds having three functional groups in one molecule, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, neopentyl glycol dimethacrylate, etc.
  • Examples thereof include meta) acrylate compounds, compounds having two functional groups in one molecule such as divinylbenzene, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, ethyl vinylbenzene, lauryl methacrylate, and stearyl methacrylate. Of these, trifunctional (meth) acrylate compounds are more preferred, and trimethylolpropane trimethacrylate is even more preferred.
  • the cross-linking aid can be used alone or in combination of two or more. By adding the cross-linking aid to the resin composition (C), it becomes possible to cross-link the resin composition (C) with a small amount of ionizing radiation.
  • the content of the cross-linking aid is preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the resin component from the viewpoint of easy adjustment and control of the degree of cross-linking when foaming the resin composition (C). , 0.5 to 10 parts by mass is more preferable.
  • Examples of the method for foaming the resin composition (C) include a chemical foaming method and a physical foaming method.
  • the chemical foaming method is a method of forming bubbles by the gas generated by the thermal decomposition of the compound added to the resin composition (C)
  • the physical foaming method is a method of forming a low boiling point liquid (foaming agent) into a resin composition (foaming agent). This is a method of impregnating C) and then volatilizing a foaming agent to form cells.
  • the foaming method is not particularly limited, but the chemical foaming method is preferable from the viewpoint of obtaining a uniform closed cell foam sheet.
  • a thermally decomposable foaming agent is preferably used, and for example, an organic or inorganic chemical foaming agent having a decomposition temperature of about 160 to 270 ° C. can be used.
  • the organic foaming agent include azodicarboxylic amides, azodicarboxylic acid metal salts (such as barium azodicarboxylic acid), azo compounds such as azobisisobutyronitrile, and nitroso compounds such as N, N'-dinitrosopentamethylenetetramine.
  • Examples thereof include hydrazine derivatives such as hydrazodicarboxylic amide, 4,4'-oxybis (benzenesulfonyl hydrazide) and toluenesulfonylhydrazide, and semicarbazide compounds such as toluenesulfonyl semicarbazide.
  • hydrazine derivatives such as hydrazodicarboxylic amide, 4,4'-oxybis (benzenesulfonyl hydrazide) and toluenesulfonylhydrazide
  • semicarbazide compounds such as toluenesulfonyl semicarbazide.
  • the inorganic foaming agent examples include ammonium acid, sodium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium borohydride, monosoda anhydrous citrate and the like.
  • azo compounds and nitroso compounds are preferable from the viewpoint of obtaining fine bubbles, and from the viewpoint of economy and safety, azodicarbonamide, azobisisobutyronitrile, N, N'-dinitrosopentamethylene. Tetramine is more preferred, and azodicarbonamide is particularly preferred.
  • the foaming agent can be used alone or in combination of two or more.
  • the amount of the thermal decomposition foaming agent added is preferably 1 to 25 parts by mass, preferably 1.3 to 15 parts by mass, based on 100 parts by mass of the resin component, from the viewpoint of appropriately foaming the foam sheet without bursting. Is more preferable, and 1.5 to 10 parts by mass is further preferable.
  • Decomposition temperature adjusting agent examples include basic magnesium salt, zinc oxide, zinc stearate, urea and the like. These decomposition temperature regulators may be used alone or in combination of two or more. Among these decomposition temperature adjusting agents, a basic magnesium salt is preferable. Further, the preferable basic magnesium as the decomposition temperature adjusting agent is at least one magnesium compound selected from the group consisting of magnesium oxide and magnesium hydroxide.
  • the resin composition (C) may contain only one of magnesium oxide and magnesium hydroxide, or may contain both. However, the resin composition (C) preferably contains both magnesium oxide and magnesium hydroxide.
  • the decomposition temperature of the thermal decomposition foaming agent can be adjusted, thereby adjusting the bubble diameter of the foam sheet with even higher accuracy. Can be done.
  • the foaming agent especially azodicarbonamide
  • the resin composition (C) contains basic magnesium, the occurrence of fogging due to such a sublimated product is prevented. Therefore, in the present invention, when azodicarbonamide is used as the foaming agent, the resin composition (C) preferably contains basic magnesium.
  • the content of the decomposition temperature adjusting agent in the resin composition (C) is preferably 0.03 to 3.0 parts by mass, and more preferably 0.04 to 2.0 parts by mass with respect to 100 parts by mass of the resin component. Parts, more preferably 0.05 to 1.5 parts by mass.
  • antioxidants examples include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, amine-based antioxidants, and the like. Among these, phenolic antioxidants and sulfur-based antioxidants are preferable, and it is more preferable to use a phenolic antioxidant and a sulfur-based antioxidant in combination.
  • the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-.
  • the sulfur-based antioxidant include dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate) and the like.
  • phenolic antioxidants 2,6-di-tert-butyl-p-cresol is preferable, and among these sulfur-based antioxidants, dilaurylthiodipropionate is preferable.
  • These antioxidants can be used alone or in combination of two or more.
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the resin component.
  • the resin composition (C) may contain additives other than the above, such as a flame retardant, a metal damage inhibitor, an antistatic agent, a stabilizer, a filler, and a pigment, if necessary.
  • the foam sheet of the present invention has excellent heat resistance, flexibility, and impact resistance, it is suitable for applications in electronic devices, especially in-vehicle electronic devices.
  • it is suitable for applications in in-vehicle image display devices such as center information displays (CID) and head-up displays (HUD), and is more suitable for applications in in-vehicle image display devices having curved surfaces.
  • CID center information displays
  • HUD head-up displays
  • the foam sheet of the present invention is produced, for example, by melt-kneading the resin composition (C), forming it into a desired shape, and then irradiating it with ionizing radiation to heat-foam the resin composition (C). Can be done. Specifically, a production method having the following steps 1 to 3 is more preferable. Step 1: After melt-kneading each component constituting the resin composition (C), a sheet-shaped resin composition (C) is obtained. Step 2: The resin composition (C) obtained in step 1 is ionizing property.
  • Step 3 Crosslinking by Irradiating Radiation Step 3: A step of heating the resin composition (C) crosslinked in Step 2 to a temperature higher than the decomposition temperature of the pyrolytic foaming agent and foaming the resin composition (C) to obtain a foam sheet.
  • each component constituting the resin composition (C) is supplied to a kneading device, melt-kneaded at a temperature lower than the decomposition temperature of the thermal decomposition foaming agent, and then melt-kneaded the resin composition (C).
  • a kneading device melt-kneaded at a temperature lower than the decomposition temperature of the thermal decomposition foaming agent, and then melt-kneaded the resin composition (C).
  • the kneading device used here include an injection molding machine, an extruder (single-screw extruder, twin-screw extruder, etc.), a Banbury mixer, a general-purpose kneading device such as a roll, and the like.
  • the resin temperature inside the injection molding machine or extruder is preferably 120 to 220 ° C, more preferably 140 to 200 ° C, and even more preferably 150 to 195 ° C.
  • the resin composition (C) formed into a sheet is irradiated with ionizing radiation.
  • the ionizing radiation include electron beam, ⁇ ray, ⁇ ray, ⁇ ray, X ray and the like. Among these, an electron beam is preferable from the viewpoint of productivity and uniform irradiation.
  • the ionizing radiation may be irradiated to only one side of the resin composition (C) formed into a sheet, or to both sides.
  • the acceleration voltage of the ionizing radiation depends on the thickness of the foamable resin composition to be irradiated, but for example, when the thickness is 0.05 to 3 mm, it is preferably 400 to 1200 kV, preferably 500 to 1100 kV.
  • the irradiation dose of the ionizing radiation may be an amount capable of obtaining a desired degree of cross-linking without causing surface roughness or cracks in consideration of the thickness of the foamable resin composition to be irradiated, but is usually used. 0.1 to 10 Mrad is preferable, 0.2 to 5 Mrad is more preferable, and 0.3 to 3 Mrad is more preferable.
  • step 3 after the resin composition (C) is crosslinked by irradiation with ionizing radiation as described above, the resin composition (C) is heated to a temperature higher than the decomposition temperature of the foaming agent and foamed to form a foam sheet.
  • the resin composition (C) After foaming the resin composition (C), or while foaming the resin composition (C), the resin composition (C) may be stretched in either one or both of the MD direction and the CD direction.
  • the temperature at which the resin composition (C) is heated and foamed depends on the decomposition temperature of the thermally decomposable foaming agent used as the foaming agent, but is usually 140 to 300 ° C., preferably 150 to 280 ° C., more preferably 160. ⁇ 260 ° C.
  • the foam sheet of the present invention preferably has a closed cell structure, but may have a closed cell structure containing open cells.
  • the adhesive tape of the present invention is an adhesive tape using the above-mentioned foam sheet of the present invention as a base material, and specifically, the foam sheet of the present invention and at least one surface of the foam sheet of the present invention. It is provided with an adhesive layer provided in.
  • the adhesive tape of the present invention preferably has adhesive layers on both sides of the foam sheet. That is, the adhesive tape of the present invention is preferably a double-sided tape. Further, since the adhesive tape of the present invention can seal the gap even if it has a curved surface, it more reliably prevents dust, moisture, etc. from entering from the outside to the inside of the electronic device having a curved surface. Used for.
  • the adhesive tape of the present invention can be suitably used as a sealing material for electronic devices, and in particular, can be suitably used as a sealing material for in-vehicle electronic devices, and is more suitable as a sealing material for in-vehicle electronic devices having a curved surface. It can be preferably used.
  • the adhesive layer is a layer having adhesiveness at least on the surface opposite to the foam sheet side.
  • the pressure-sensitive adhesive layer include a pressure-sensitive adhesive layer made of a single pressure-sensitive adhesive, and a double-sided tape having pressure-sensitive adhesive layers on both sides of a base material.
  • the pressure-sensitive adhesive layer is preferable from the viewpoint that the pressure-sensitive adhesive tape can be thinned.
  • the thickness of the adhesive layer constituting the adhesive tape is preferably 5 to 200 ⁇ m, more preferably 7 to 150 ⁇ m, still more preferably 10 to 100 ⁇ m.
  • the pressure-sensitive adhesive constituting the pressure-sensitive portion of the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive.
  • Examples of the method of laminating the pressure-sensitive adhesive layer on the foam sheet include a method of transferring the pressure-sensitive adhesive applied to the release paper to the foam sheet, a coater on at least one surface of the foam sheet, and the like. Examples thereof include a method of applying an adhesive using a coating machine.
  • a method of laminating the adhesive layer on the foam sheet for example, a method of spraying and applying the adhesive on at least one surface of the foam sheet by using a spray, one surface of the foam sheet.
  • a method of applying an adhesive using a brush for example, a method of sticking the double-sided tape on the foam sheet can be mentioned.
  • the adhesive tape of the present invention uses a foam sheet having excellent heat resistance, flexibility and impact resistance as a base material, it is suitable for applications in electronic devices, especially in-vehicle electronic devices.
  • it is suitable for applications in in-vehicle image display devices such as center information displays (CID) and head-up displays (HUD).
  • CID center information displays
  • HUD head-up displays
  • the adherend surface is a curved surface
  • the adhesive tape can be adhered following the curved surface, so that the adhesive tape of the present invention is more suitable for use in an in-vehicle image display device having a curved surface.
  • the method for measuring each physical property and the method for evaluating the foam sheet are as follows.
  • FIG. 1 shows a schematic diagram of a test device for evaluating the interlayer strength.
  • a 10 mm square aluminum jig 14 was placed on the adhesive dropping portion, and the foam sheet and the jig 14 were pressure-bonded. After wiping off the adhesive that had squeezed out around the jig 14, a cut 15 was made in the foam sheet along the size of the jig 14. The adhesive was cured by leaving this at room temperature for 30 minutes to prepare a sample for measuring the interlayer strength. Subsequently, a 1 kN load cell was installed in a testing machine provided with a constant temperature bath (“Tencilon universal material testing machine” manufactured by A & D Co., Ltd.) so that tests could be performed in the constant temperature bath.
  • a constant temperature bath (“Tencilon universal material testing machine” manufactured by A & D Co., Ltd.)
  • a sample for measuring the interlayer strength was attached to the testing machine so that the sheet surface of the foam sheet was perpendicular to the tensile direction. After setting the temperature of the constant temperature bath to 23 ° C., the sample was left to stand until the temperature of the sample for interlayer strength measurement reached 23 ° C. Then, one of the jigs was pulled vertically upward at a speed of 100 mm / min, and only the 1 cm square area of the foam sheet was peeled off. The maximum load at this time was measured and used as the first measurement result. The same operation was repeated three times, and the average value was taken as the interlayer strength at 23 ° C. Further, the interlayer strength at 90 ° C.
  • the elongation mm measured by the above method is plotted on the horizontal axis and the load N is plotted on the vertical axis, and the inclination value when the inclination of the plot within the elongation range of 0.5 mm to 5 mm is maximized is the flexural modulus. It was a rate.
  • Ball drop test A ball drop test was conducted according to the following procedure. (I) The foam sheet was punched so as to have a width of 50 mm, a length of 70 mm, and a width of 2 mm on all sides, and an adhesive layer was formed on both sides to prepare a frame-shaped sample. Then, as shown in FIG.
  • the frame-shaped sample 21 was attached to the SUS plate (A) 22 having a width of 70 mm and a length of 95 mm.
  • An acrylic pressure-sensitive adhesive (manufactured by Sekisui Chemical Co., Ltd., model number: # 5782) was used as the pressure-sensitive adhesive layer.
  • FIG. 2B using the sample 21 attached to the SUS plate (A) 22, a 120 mm wide ⁇ 120 mm long SUS plate having a hole 231 having a width of 25 mm ⁇ a length of 50 mm at the center (ii).
  • the SUS plate (A) 22 was attached to the B) 23 so that the SAS plate (A) 22 closed the hole.
  • a jig was prepared in which a SUS cylinder having a diameter of 20 mm and a height of 45 mm was vertically suspended in the center of a SUS plate having a width of 100 mm and a length of 100 mm.
  • the cylinder 252 is on the lower side with respect to the plate 251 so that the tip of the cylinder 252 of the jig 25 is located at the center of the hole of the SUS plate (B) 23.
  • the jig 25 was placed on the SUS plate (A) 22 appearing from the hole 231 of the SUS plate (B) 23.
  • the adhesive layer was acrylic adhesive. An agent (manufactured by Sekisui Chemical Co., Ltd., model number: # 5782) was used.
  • Example 1 40 parts by mass of random PP, 20 parts by mass of EPDM, 35 parts by mass of TPO, 5 parts by mass of LLDPE, 3 parts by mass of cross-linking aid, 3.5 parts by mass of thermally decomposable foaming agent, 1 part by mass of decomposition A temperature control agent and 0.5 parts by mass of an antioxidant were charged into the single shaft extruder. Then, the above-mentioned raw materials were melt-kneaded and extruded at a resin temperature of 180 ° C. to obtain a sheet-shaped resin composition having a thickness of 0.36 mm.
  • the resin composition was crosslinked so as to have a degree of cross-linking of 40% by mass. Then, the crosslinked resin composition was heated in a hot air oven at 250 ° C. for 5 minutes while being stretched to MD and TD, and foamed by the heating to have an apparent density of 0.2 g / cm 3 and a thickness of 0.3 mm. The foam sheet of Example 1 was obtained.
  • Example 2 The blending amount of the pyrolysis foaming agent was changed from 3.5 parts by mass to 3.7 parts by mass, and the degree of cross-linking of the resin composition was changed from 40% by mass to 50% by mass by changing the irradiation dose of the electron beam.
  • a foam sheet of Example 2 having an apparent density of 0.2 g / cm 3 and a thickness of 0.3 mm was obtained by the same production method as that of the foam sheet of Example 1.
  • Example 3 The amount of the pyrolysis foaming agent was changed from 3.5 parts by mass to 3.7 parts by mass, the amount of the cross-linking aid was changed from 3 parts by mass to 4 parts by mass, and the irradiation dose of the electron beam was changed.
  • the degree of cross-linking of the resin composition was changed from 40% by mass to 50% by mass.
  • a foam sheet of Example 3 having an apparent density of 0.2 g / cm 3 and a thickness of 0.3 mm was obtained by the same production method as that of the foam sheet of Example 1.
  • Example 4 The blending amount of the pyrolysis foaming agent was changed from 3.5 parts by mass to 1.6 parts by mass, and the degree of cross-linking of the resin composition was changed from 40% by mass to 50% by mass by changing the irradiation dose of the electron beam.
  • Example 5 The amount of random PP was changed from 40 parts by mass to 60 parts by mass, the amount of TPO was changed from 35 parts by mass to 15 parts by mass, and the amount of pyrolysis foaming agent was changed from 3.5 parts by mass to 7 parts by mass.
  • the degree of cross-linking of the resin composition was changed from 40% by mass to 50% by mass by changing the irradiation dose of the electron beam.
  • a foam sheet of Example 5 having an apparent density of 0.075 g / cm 3 and a thickness of 1.0 mm was obtained by the same production method as that of the foam sheet of Example 1.
  • Example 6> The blending amount of the pyrolysis foaming agent was changed from 3.5 parts by mass to 3.9 parts by mass, and the irradiation dose of the electron beam was changed to change the degree of cross-linking of the resin composition from 40% by mass to 60% by mass.
  • Example 7 The amount of random PP compounded was changed from 40 parts by mass to 60 parts by mass, the amount of TPO compounded was changed from 35 parts by mass to 15 parts by mass, and the amount of pyrolysis foaming agent compounded was changed from 3.5 parts by mass to 7.
  • the degree of cross-linking of the resin composition was changed from 40% by mass to 60% by mass by changing the amount to 3 parts by mass and changing the irradiation dose of the electron beam.
  • a foam sheet of Example 7 having an apparent density of 0.075 g / cm 3 and a thickness of 1.0 mm was obtained by the same production method as that of the foam sheet of Example 1.
  • Example 8> The amount of the pyrolysis foaming agent was changed from 3.5 parts by mass to 4.2 parts by mass, the content of the cross-linking aid was changed from 3 parts by mass to 4 parts by mass, and the irradiation dose of the electron beam was changed. The degree of cross-linking of the resin composition was changed from 40% by mass to 70% by mass.
  • a foam sheet of Example 8 having an apparent density of 0.2 g / cm 3 and a thickness of 0.3 mm was obtained by the same production method as that of the foam sheet of Example 1.
  • Example 9 The blending amount of the pyrolysis foaming agent was changed from 3.5 parts by mass to 1.9 parts by mass, and the degree of cross-linking of the resin composition was changed from 40% by mass to 70% by mass by changing the irradiation dose of the electron beam.
  • Example 10 The degree of cross-linking of the resin composition was changed from 40% by mass to 30% by mass by changing the irradiation dose of the electron beam.
  • a foam sheet of Example 10 having an apparent density of 0.2 g / cm 3 and a thickness of 0.3 mm was obtained by the same production method as that of the foam sheet of Example 1.
  • Tables 1 to 3 show the physical characteristics and evaluation results of the foam sheet.
  • TPO Olefin-based thermoplastic elastomer, manufactured by Prime Polymer Co., Ltd., Product name: Prime TPO, Model number: E-2710, MFR: 2.8 g / 10 minutes, LLDPE: Linear low-density polyethylene, manufactured by Dow Chemical Co., Ltd., Product name: 2036P, MFR: 2.5 g / 10
  • Pyrolytic foaming agent Azo Dicarbonamide Pyrolysis temperature control agent: Magnesium oxide, Magnesium hydroxide Antioxidant: 2,6-di-tert-butyl-p-cresol, dilaurylthiodipropionate
  • the foam sheets of Examples 1 to 10 at least one of the shrinkage rate of MD and the shrinkage rate of TD when the foam sheet was cured at a temperature of 90 ° C. for 1 hour was 5% or less, and 23 ° C.
  • the interlayer strength at the above temperature was 0.80 MPa or more, the thickness was 1.5 mm or less, and the 25% compression strength was 800 kPa or less. Therefore, the result of the falling ball test and the 90 ° C. curved surface followability were good.
  • the foam sheets of Comparative Example 1 and Comparative Example 2 the interlayer strength of the foam sheet at a temperature of 23 ° C. was less than 0.80 MPa, so that the result of the ball drop test was poor.
  • the curved surface followability at a temperature of 90 ° C. was poor.
  • at least one of the shrinkage rate of MD and the shrinkage rate of TD when cured at a temperature of 90 ° C. for 1 hour was larger than 5%, so that the shrinkage rate was higher than 5%.
  • a large heat shrinkage occurred, and therefore the curved surface followability at a temperature of 90 ° C. was poor.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
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