WO2017170941A1 - Feuille de mousse en résine de polyoléfine et bande adhésive - Google Patents

Feuille de mousse en résine de polyoléfine et bande adhésive Download PDF

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Publication number
WO2017170941A1
WO2017170941A1 PCT/JP2017/013416 JP2017013416W WO2017170941A1 WO 2017170941 A1 WO2017170941 A1 WO 2017170941A1 JP 2017013416 W JP2017013416 W JP 2017013416W WO 2017170941 A1 WO2017170941 A1 WO 2017170941A1
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WIPO (PCT)
Prior art keywords
polyolefin resin
foam sheet
less
mass
resin foam
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PCT/JP2017/013416
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English (en)
Japanese (ja)
Inventor
麻美 松本
繁季 松木
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2017520991A priority Critical patent/JP6550131B2/ja
Priority to CN201780005106.2A priority patent/CN108431105B/zh
Priority to KR1020187025932A priority patent/KR102078236B1/ko
Publication of WO2017170941A1 publication Critical patent/WO2017170941A1/fr

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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
    • C08J9/10—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 developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • 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
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • 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
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate

Definitions

  • the present invention relates to a polyolefin resin foam sheet and an adhesive tape using the same.
  • a foamed sheet in which a large number of bubbles are formed inside the resin layer has excellent buffering properties, and is therefore widely used as a shock absorber for various electronic devices.
  • the shock absorbing material is used by being disposed between a glass plate constituting the surface of the device and an image display member.
  • Patent Document 1 discloses an adhesive tape based on a polyolefin-based resin.
  • the foam sheet and sealing material used in such applications need to be thinned and narrowed by downsizing the device, but when used in a position close to a light emitting part such as a backlight of a display device, There has been a problem that the light passes through the thin part of the foam sheet and the sealing material and leaks to the outside of the device.
  • a method for solving this problem a method of lowering the expansion ratio of the foamed sheet or a method of increasing the thickness of the foamed sheet can be considered.
  • the flexibility of the foamed sheet is lost or a small electronic device is used.
  • the present invention has been made in view of the above-described conventional circumstances, and provides a polyolefin resin foam sheet having excellent light shielding properties and excellent flexibility, and an adhesive tape using the same. Objective.
  • the gist of the present invention is the following [1] to [2].
  • [1] A polyolefin resin foam sheet obtained by foaming a polyolefin resin composition containing a polyolefin resin and a pigment, having a 25% compression stress of 80 to 1400 kPa and a pigment content of 0.60 with respect to 100 parts by mass of the resin.
  • a polyolefin-based resin foam sheet having a content of ⁇ 10.00 parts by mass, a density of 0.10 to 0.60 g / cm 3 , and a gel fraction of 25 to 60% by mass.
  • An adhesive tape in which an adhesive layer is provided on at least one surface of the polyolefin resin foam sheet described in [1].
  • the polyolefin resin foam sheet of the present invention (hereinafter also referred to as “foam sheet”) is a polyolefin resin foam sheet obtained by foaming a polyolefin resin composition containing a polyolefin resin and a pigment, and has a 25% compression stress. Is 80 to 1400 kPa, the pigment is 0.60 to 10.00 parts by mass with respect to 100 parts by mass of the resin, the density is 0.10 to 0.60 g / cm 3 , and the gel fraction is 25 to 60% by mass. It is what is.
  • the 25% compressive stress of the foamed sheet of the present invention is 80 kPa or more, preferably 90 kPa or more, more preferably 100 kPa or more, and 1400 kPa or less, preferably 1200 kPa or less, more preferably 1000 kPa or less, more preferably 900 kPa or less, Still more preferably, it is 800 kPa or less, More preferably, it is 700 kPa or less, More preferably, it is 600 kPa or less, More preferably, it is 550 kPa or less.
  • 25% compression stress is equal to or higher than the lower limit, the impact absorbability is improved, and when it is equal to or lower than the upper limit, the flexibility of the foamed sheet is improved.
  • the adhesive tape is used, the followability to the adherend is good. This makes it difficult for water and air to enter the electronic device.
  • 25% compressive stress can be measured according to the method as described in the Example mentioned later.
  • An organic pigment and an inorganic pigment can be used.
  • the organic pigment include azo pigments, diazo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments.
  • the inorganic pigment include carbon black, metal oxide, metal sulfide, and metal chloride. These pigments may be used alone or in combination of two or more.
  • the amount of the pigment relative to 100 parts by mass of the polyolefin resin is 0.60 parts by mass or more, preferably 0.70 parts by mass or more, more preferably 0.80 parts by mass or more, from the viewpoint of improving the light shielding properties of the foamed sheet.
  • it is 0.90 parts by mass or more, more preferably 1.00 parts by mass or more, and from the viewpoint of preventing a decrease in flexibility of the foamed sheet, it is 10.00 parts by mass or less, preferably 5.00 parts by mass.
  • it is more preferably 3.00 parts by mass or less, and still more preferably 1.50 parts by mass.
  • the density of the foamed sheet of the present invention from the viewpoint of improving the light-blocking foam sheet, 0.10 g / cm 3 or higher, preferably 0.15 g / cm 3 or more, more preferably 0.20 g / cm 3 or more, further Preferably it is 0.25 g / cm 3 or more, more preferably 0.30 g / cm 3 or more, still more preferably 0.35 g / cm 3 or more, and from the viewpoint of preventing a decrease in flexibility of the foam sheet, 0.60 g / cm 3 or less, preferably 0.55 g / cm 3 or less, more preferably 0.50 g / cm 3 or less, more preferably 0.45 g / cm 3 or less, even more preferably 0.40 g / cm 3 It is as follows.
  • the expansion ratio of the foam sheet of the present invention can be defined by the reciprocal of the density of the foam sheet, preferably 1.5 cm 3 / g or more, more preferably 1.6 cm 3 / g or more, and still more preferably 1.7 cm. 3 / g or more, even more preferably at 1.8 cm 3 / g or more, and preferably 10.0 cm 3 / g or less, more preferably 8.0 cm 3 / g or less, more preferably 7.0 cm 3 / g or less, still more preferably 6.0 cm 3 / g or less, still more preferably 5.5 cm 3 / g or less, still more preferably 5.0 cm 3 / g or less.
  • the expansion ratio is within the above range, the light shielding property of the foamed sheet can be improved, and the shock absorbing property and the step following property of the foamed sheet can be easily secured.
  • the foam sheet of the present invention is crosslinked from the viewpoint of reducing the average cell diameter in the ZD direction, and the gel fraction is 25% by mass or more, preferably 30% by mass or more, more preferably 35% by mass or more. And it is 60 mass% or less, Preferably it is 55 mass% or less, More preferably, it is 53 mass% or less.
  • the gel fraction is equal to or higher than the lower limit, sufficient cross-linking is formed, and a foamed sheet having a small average cell diameter can be obtained by foaming this. Moreover, it becomes easy to ensure the softness
  • a gel fraction can be measured according to the method as described in the Example mentioned later.
  • the average cell diameter in the MD direction in the foamed sheet of the present invention is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, still more preferably 25 ⁇ m or more, from the viewpoint of improving the light shielding property, flexibility, and step following ability of the foamed sheet. More preferably 30 ⁇ m or more, still more preferably 32 ⁇ m or more, and preferably 150 ⁇ m or less, more preferably 140 ⁇ m or less, still more preferably 135 ⁇ m or less, even more preferably 130 ⁇ m or less, even more preferably 125 ⁇ m or less, more More preferably, it is 120 micrometers or less, More preferably, it is 115 micrometers or less.
  • the average bubble diameter in the MD direction is equal to or greater than the lower limit, flexibility and step following ability are improved.
  • the light shielding property of a foam sheet improves that the average bubble of MD direction is below the said upper limit.
  • the average cell diameter in the TD direction in the foamed sheet of the present invention is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, still more preferably 25 ⁇ m or more, from the viewpoint of improving the light shielding property, flexibility, and step following property of the foamed sheet. More preferably 30 ⁇ m or more, still more preferably 35 ⁇ m or more, still more preferably 38 ⁇ m or more, and preferably 250 ⁇ m or less, more preferably 210 ⁇ m or less, still more preferably 170 ⁇ m or less, even more preferably 130 ⁇ m or less, more More preferably, it is 125 micrometers or less, More preferably, it is 120 micrometers or less, More preferably, it is 115 micrometers or less.
  • the average bubble diameter in the MD direction is equal to or greater than the lower limit, flexibility and step following ability are improved.
  • the light shielding property of a foam sheet improves that the average bubble of MD direction is below the said upper limit.
  • the average cell diameter in the ZD direction in the foamed sheet of the present invention is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and even more preferably 9 ⁇ m or more, from the viewpoint of improving the light shielding properties, flexibility, and step following ability of the foamed sheet. More preferably, it is 11 ⁇ m or more, more preferably 13 ⁇ m or more, still more preferably 15 ⁇ m or more, and preferably 60 ⁇ m or less, more preferably 55 ⁇ m or less, still more preferably 50 ⁇ m or less, even more preferably 45 ⁇ m or less, more More preferably, it is 40 ⁇ m or less.
  • the average bubble diameter in the ZD direction is equal to or greater than the lower limit, flexibility and step following ability are improved.
  • the light shielding property of a foam sheet improves that the average bubble of a ZD direction is below the said upper limit.
  • the maximum cell diameter in the MD direction in the foamed sheet of the present invention is preferably 30 ⁇ m or more, more preferably 40 ⁇ m or more, and even more preferably 50 ⁇ m or more, from the viewpoint of improving the light shielding property, flexibility, and step following ability of the foamed sheet. And preferably 400 ⁇ m or less, more preferably 350 ⁇ m or less, and still more preferably 300 ⁇ m or less.
  • the maximum bubble diameter in the MD direction is equal to or greater than the lower limit, flexibility and step following ability are improved.
  • the light shielding property of a foam sheet improves that the largest bubble of MD direction is below the said upper limit.
  • the maximum cell diameter in the TD direction in the foamed sheet of the present invention is preferably 80 ⁇ m or more, more preferably 90 ⁇ m or more, and still more preferably 100 ⁇ m or more, from the viewpoint of improving the light shielding property, flexibility, and step following ability of the foamed sheet. And preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less, and still more preferably 400 ⁇ m or less.
  • the maximum bubble diameter in the TD direction is equal to or greater than the lower limit, flexibility and step following ability are improved.
  • the light shielding property of a foam sheet improves that the largest bubble of TD direction is below the said upper limit.
  • the maximum cell diameter in the ZD direction in the foamed sheet of the present invention is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more, from the viewpoint of improving the light shielding properties, flexibility, and step following ability of the foamed sheet. And preferably 150 ⁇ m or less, more preferably 140 ⁇ m or less, and still more preferably 130 ⁇ m or less.
  • the maximum bubble diameter in the ZD direction is equal to or greater than the lower limit value, flexibility and step following ability are improved.
  • the light-shielding property of a foam sheet improves that the largest bubble of a ZD direction is below the said upper limit.
  • MD means “Machine Direction” and means a direction that coincides with the extrusion direction of the polyolefin-based resin foam sheet.
  • TD means Transverse Direction, which means a direction perpendicular to MD and parallel to the foam sheet.
  • ZD means Thickness Direction, which is a direction perpendicular to both MD and TD.
  • the said average bubble diameter can be measured according to the method of the Example mentioned later.
  • the thickness of the foam sheet of the present invention is preferably 0.020 mm or more, more preferably 0.030 mm or more, and further preferably 0.040 mm or more, from the viewpoint of improving the light shielding properties, flexibility, and step following ability of the foam sheet. More preferably, it is 0.050 mm or more, and preferably 0.38 mm or less, more preferably 0.35 mm or less, still more preferably 0.32 mm or less, and still more preferably 0.30 mm or less.
  • the thickness of the foamed sheet is not less than the lower limit, the light shielding properties and strength of the foamed sheet can be improved.
  • the thickness of the foamed sheet is not more than the above upper limit value, it can be used inside a thin electronic device, and the flexibility and the step following ability can be further improved.
  • the average number of cells per 0.5 mm in the MD direction of the foamed sheet of the present invention is preferably 2 or more, more preferably 3 or more, from the viewpoint of improving the light shielding properties, flexibility, and step following ability of the foamed sheet. 4 or more, and preferably 20 or less, more preferably 18 or less, still more preferably 17 or less, still more preferably 15 or less, still more preferably 13 or less, and even more.
  • the number is preferably 11 or less, more preferably 9 or less, and still more preferably 8 or less.
  • the average number of bubbles per 0.5 mm in the TD direction of the foamed sheet of the present invention is preferably 1 or more, more preferably 2 from the viewpoint of improving the light shielding property, flexibility, and step following ability of the foamed sheet. More preferably 3 or more, and preferably 18 or less, more preferably 16 or less, still more preferably 14 or less, still more preferably 12 or less, even more preferably 10 or less, More preferably, it is 8 or less.
  • the average number of bubbles per 0.5 mm in the ZD direction of the foamed sheet of the present invention is preferably 1 or more, more preferably 2 or more, from the viewpoint of improving the light shielding property, flexibility, and step following ability of the foamed sheet.
  • the number is more preferably 3 or more, and preferably 13 or less, more preferably 11 or less, still more preferably 9 or less, still more preferably 8 or less, and still more preferably 6 or less.
  • the average number of bubbles per 0.5 mm of the foamed sheet is equal to or more than the lower limit, the light shielding property of the foamed sheet can be improved.
  • it can use for the inside of a thin electronic device as the average number of bubbles per 0.5 mm is below the said upper limit, and also a softness
  • the average number of bubbles per 0.5 mm can be measured according to the method of the example described later.
  • the foam sheet of the present invention preferably has closed cells.
  • the bubbles are closed cells, the amount of deformation of the bubbles can be suppressed when subjected to an impact, the amount of deformation of the foamed sheet with respect to the impact can be suppressed, and as a result, the impact absorbability can be further improved.
  • the closed cell ratio is preferably 70 to 100%, more preferably 80 to 100%, and still more preferably 90 to 100% in order to further improve the impact absorbability.
  • the movement of the air inside a foam sheet is restrict
  • the closed cell rate means what was measured based on ASTM D2856 (1998).
  • polyolefin resin examples of the polyolefin resin used to form the foamed sheet include a polyethylene resin, a polypropylene resin, or a mixture thereof.
  • the polyethylene resin may be an ethylene homopolymer, but is obtained by copolymerizing ethylene with a small amount (for example, 30% by mass or less, preferably 10% by mass or less of the total monomers) of ⁇ -olefin as required.
  • Polyethylene resins are preferred, and among them, linear low density polyethylene is preferred.
  • ⁇ -olefin constituting the polyethylene resin examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. . Of these, ⁇ -olefins having 4 to 10 carbon atoms are preferred.
  • the polyethylene resin an ethylene-vinyl acetate copolymer is also preferable.
  • the ethylene-vinyl acetate copolymer is usually a copolymer containing 50% by mass or more of ethylene units.
  • the polyethylene-based resin preferably has a low density in order to increase the flexibility of the foamed sheet and increase the shock absorption.
  • the density of the polyethylene resin particularly preferably from 0.920 g / cm 3 or less, more preferably 0.880 ⁇ 0.915g / cm 3, more preferably 0.885 ⁇ 0.910g / cm 3. The density is measured according to ASTM D792.
  • polypropylene resin examples include a propylene homopolymer, a propylene-ethylene copolymer containing 50% by mass or more of propylene units, and a propylene- ⁇ -olefin copolymer. These may be used alone or in combination of two or more.
  • Specific examples of the ⁇ -olefin constituting the propylene- ⁇ -olefin copolymer include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Of these, ⁇ -olefins having 6 to 12 carbon atoms are preferred.
  • Polyolefin resins in the present invention include polyethylene resins and polypropylene resins polymerized by using metallocene compounds, Ziegler-Natta compounds, chromium oxide compounds, etc. as catalysts from the viewpoint of improving flexibility and impact absorption. Or a mixture thereof, and among the polyethylene resins, linear low density polyethylene is more preferable.
  • the content is preferably 40% by mass or more of the entire polyolefin resin, 50 mass% or more is more preferable, 60 mass% or more is still more preferable, and 100 mass% is still more preferable.
  • Suitable metallocene compounds include compounds such as bis (cyclopentadienyl) metal complexes having a structure in which a transition metal is sandwiched between ⁇ -electron unsaturated compounds. More specifically, tetravalent transition metals such as titanium, zirconium, nickel, palladium, hafnium, and platinum have one or more cyclopentadienyl rings or their analogs as ligands (ligands). The compound to be mentioned is mentioned. Such metallocene compounds have uniform active site properties and each active site has the same activity. A polymer synthesized using a metallocene compound has high uniformity such as molecular weight, molecular weight distribution, composition, and composition distribution.
  • Examples of the ligand include a cyclopentadienyl ring and an indenyl ring. These cyclic compounds may be substituted with a hydrocarbon group, a substituted hydrocarbon group or a hydrocarbon-substituted metalloid group.
  • Examples of the hydrocarbon group include a methyl group, an ethyl group, various propyl groups, various butyl groups, various amyl groups, various hexyl groups, 2-ethylhexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Various cetyl groups, phenyl groups and the like.
  • the “various” means various isomers including n-, sec-, tert-, and iso-. Moreover, what polymerized the cyclic compound as an oligomer may be used as a ligand. In addition to ⁇ -electron unsaturated compounds, monovalent anion ligands such as chlorine and bromine or divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, aryls Phosphide or the like may be used.
  • monovalent anion ligands such as chlorine and bromine or divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, aryls Phosphide or the like may be used.
  • metallocene compounds containing tetravalent transition metals and ligands include, for example, cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopentadienyl) titanium dichloride, dimethyl And silyltetramethylcyclopentadienyl-t-butylamidozirconium dichloride.
  • the metallocene compound exhibits an action as a catalyst in the polymerization of various olefins by combining with a specific cocatalyst (co-catalyst).
  • specific cocatalyst include methylaluminoxane (MAO) and boron compounds.
  • the proportion of the cocatalyst used with respect to the metallocene compound is preferably 100,000 to 1,000,000 mole times, more preferably 50 to 5,000 mole times.
  • the Ziegler-Natta compound is a triethylaluminum-titanium tetrachloride solid composite, which is obtained by reducing titanium tetrachloride with an organoaluminum compound and then treating with various electron donors and electron acceptors.
  • a method of combining a composition, an organoaluminum compound, and an aromatic carboxylic acid ester see JP-A 56-1000080, JP-A 56-120712, JP-A 58-104907), halogens Method of supported catalyst in which magnesium tetrachloride is brought into contact with magnesium tetrachloride and various electron donors (see JP-A-57-63310, JP-A-63-43915, JP-A-63-83116), etc. What was manufactured by is preferable.
  • the polyolefin resin a resin other than the above-described polyolefin resin can be used in combination. Furthermore, you may mix the various additives mentioned later and other arbitrary components with polyolefin resin.
  • optional components contained in the foamed sheet include resins and rubbers other than polyolefin-based resins. These are a total of less content than polyolefin-based resins, and are usually 50 parts per 100 parts by mass of polyolefin-based resin. It is about 30 parts by mass or less, preferably about 30 parts by mass or less.
  • the foam sheet of the present invention can be produced by foaming a polyolefin resin composition by a general method. There is no restriction
  • Step (1) Polyolefin resin, pigment, pyrolyzable foaming agent, and other additives are supplied to an extruder, melt-kneaded, and extruded into a sheet using the extruder, thereby forming a sheet-like polyolefin Step of obtaining the resin composition
  • Step (2) Step of crosslinking the sheet-shaped polyolefin resin composition
  • Step (3) Heating the crosslinked sheet-shaped polyolefin resin composition to thermally decompose foaming agent
  • a manufacturing method of a crosslinked polyolefin resin foamed sheet it is also possible to manufacture by a method described in International Publication No. 2005/007731.
  • the pyrolytic foaming agent is not particularly limited, and examples thereof include azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl semicarbazide and the like. Of these, azodicarbonamide is preferred.
  • a thermal decomposition type foaming agent may be used individually or in combination of 2 or more types.
  • the content of the thermally decomposable foaming agent in the polyolefin resin composition is preferably 1 to 12 parts by mass and more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the foamability of the polyolefin resin composition is improved, and it becomes easier to obtain a polyolefin resin foam sheet having a desired foaming ratio, as well as tensile strength and compression recovery. Improves.
  • Examples of other additives used in the step (1) include a decomposition temperature adjusting agent, a crosslinking aid, and an antioxidant.
  • the decomposition temperature adjusting agent is blended to lower the decomposition temperature of the pyrolytic foaming agent or to increase or adjust the decomposition rate.
  • Specific examples of the compound include zinc oxide, zinc stearate, urea and the like.
  • the decomposition temperature adjusting agent is blended in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin, for example, in order to adjust the surface state of the foam sheet.
  • a polyfunctional monomer can be used as a crosslinking aid.
  • the ionizing radiation dose to be irradiated in the step (2) described later can be reduced, thereby preventing the resin molecules from being cut and deteriorated by the irradiation of ionizing radiation. can do.
  • Specific examples of the crosslinking aid include one molecule such as trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimellitic acid triallyl ester, 1,2,4-benzenetricarboxylic acid triallyl ester, triallyl isocyanurate, and the like.
  • Two compounds in one molecule such as a compound having three functional groups, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, divinylbenzene, etc.
  • Examples thereof include compounds having a functional group, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, ethyl vinyl benzene, neopentyl glycol dimethacrylate, lauryl methacrylate, stearyl methacrylate and the like.
  • These crosslinking aids are used alone or in combination of two or more.
  • the addition amount of the crosslinking aid is preferably 0.2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin component.
  • the addition amount is 0.2 parts by mass or more, it is possible to stably obtain a foam sheet having a gel fraction desired by the foam sheet, and when it is 10 parts by mass or less, the gel fraction of the foam sheet can be controlled. It becomes easy.
  • the antioxidant include phenolic antioxidants such as 2,6-di-t-butyl-p-cresol.
  • the method for foaming the polyolefin resin composition is not particularly limited.
  • the method of heating the polyolefin resin composition with hot air the method of heating with infrared rays, the method of heating with a salt bath, or the method of heating with an oil bath. Etc., and these may be used in combination.
  • the foaming of the polyolefin-based resin composition is not limited to an example using a pyrolytic foaming agent, and physical foaming with butane gas or the like may be used.
  • Examples of the method for crosslinking the polyolefin resin composition include a method in which an organic peroxide is blended in advance with the polyolefin resin composition, and the organic peroxide is decomposed by heating the polyolefin resin composition. It is done.
  • Examples of the organic peroxide used for crosslinking include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and the like. It is done. These may be used alone or in combination of two or more.
  • the addition amount of the organic peroxide is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the amount of the organic peroxide added is within the above range, the crosslinking of the polyolefin resin composition is likely to proceed, and the amount of decomposition residue of the organic peroxide is suppressed in the obtained crosslinked polyolefin resin foam sheet. can do.
  • Examples of the method for crosslinking the polyolefin resin composition include a method of irradiating the polyolefin resin composition with ionizing radiation such as electron beam, ⁇ ray, ⁇ ray, and ⁇ ray.
  • the dose of ionizing radiation is preferably 5 to 200 kGy, more preferably 30 to 120 kGy so that the gel fraction is 25 to 60% by mass.
  • a method of irradiating ionizing radiation is preferable from the viewpoint of homogeneous crosslinking.
  • the polyolefin resin foam sheet of the present invention is preferably stretched in one or both of the MD direction and the TD direction.
  • stretched in one or both of the MD direction and the TD direction the average cell diameter in the ZD direction is reduced, and heat is hardly transmitted by increasing the distance between the thermally conductive resin portions, thereby improving the heat insulation.
  • the stretching may be performed after foaming the polyolefin-based resin composition to obtain a foamed sheet, or may be performed while foaming the polyolefin-based resin composition.
  • the foamed sheet may be heated again to be in a molten or softened state and then stretched.
  • the draw ratio in the MD direction of the foamed sheet is preferably 1.1 to 3.2 times, and more preferably 1.3 to 3.0 times.
  • the draw ratio in the MD direction of the foamed sheet is set to the above lower limit value or more, the flexibility and tensile strength of the foamed sheet are likely to be good.
  • the upper limit value is not exceeded, the foamed sheet is prevented from breaking during stretching, or the foaming gas escapes from the foamed sheet being foamed and the foaming ratio is reduced, thereby reducing the flexibility and tensile strength of the foamed sheet. It becomes good and it becomes easy to make the quality uniform.
  • the draw ratio in the TD direction of the foamed sheet is preferably 1.3 to 3.8 times, and more preferably 1.5 to 3.5 times.
  • the pressure-sensitive adhesive tape of the present invention uses the foamed sheet according to the present invention as a base material, and is provided with a pressure-sensitive adhesive layer on one side or both sides of the foamed sheet.
  • the thickness of the adhesive tape is usually 0.03 to 2.0 mm, preferably 0.05 to 1.0 mm.
  • the thickness of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape is preferably 5 to 200 ⁇ m, more preferably 7 to 150 ⁇ m, still more preferably 10 to 100 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape is 5 to 200 ⁇ m, it is possible to reduce the thickness of the pressure-sensitive adhesive tape and contribute to the miniaturization and thickness reduction of the electronic device itself in which the pressure-sensitive adhesive tape is used. Can do.
  • an adhesive which comprises the adhesive layer provided in one side or both surfaces of a foam sheet For example, an acrylic adhesive, a urethane type adhesive, a rubber-type adhesive, etc. are used.
  • a method of applying a pressure-sensitive adhesive to the foamed sheet and laminating the pressure-sensitive adhesive layer on the foamed sheet for example, a method of applying the pressure-sensitive adhesive using a coating machine such as a coater on at least one surface of the foamed sheet, Examples thereof include a method of spraying and applying a pressure-sensitive adhesive using a spray on at least one surface of the foamed sheet, a method of applying a pressure-sensitive adhesive using a brush on one surface of the foamed sheet, and the like.
  • the pressure-sensitive adhesive tape using the foam sheet of the present invention is an impact absorbing material that prevents an impact applied to an electronic component built in an electronic device body such as a mobile phone or a video camera, and dust or dirt in the electronic device body. It can be used as a sealing material that prevents moisture and the like from entering.
  • ⁇ Density and expansion ratio> The density of the foamed sheets obtained in Examples and Comparative Examples was measured according to JIS K7222, and the reciprocal number was taken as the foaming ratio.
  • the 25% compressive stress was measured in accordance with JIS K6767 for a polyolefin resin foam sheet. In the present invention, it is preferable that the 25% compressive stress is smaller from the viewpoint of improving flexibility and step following ability.
  • a foam sample for measurement was prepared by cutting the foam sheet obtained in each of the examples and comparative examples into 50 mm squares. This was immersed in liquid nitrogen for 1 minute, and then cut with a razor blade in the thickness direction along the MD direction, the TD direction, and the ZD direction. This cross section was taken with a digital microscope (Keyence Co., Ltd. “VHX-900”), and a 200x magnified photograph was taken. All independent sections existing on the cut surface for a length of 2 mm in each of the MD and TD directions. The bubble diameter was measured about the bubble, and the operation was repeated 5 times.
  • the bubble diameter of closed cells present in a 2 mm ⁇ 2 mm square was measured, and the operation was repeated 5 times. And the average value of all the bubbles of each direction was made into the average bubble diameter of MD direction, TD direction, and ZD direction, and the largest bubble diameter in the measured bubble diameter was made into the largest bubble diameter.
  • Total light transmittance The total light transmittance was measured with a haze meter (“NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd.). The total light transmittance was measured for each of the ZD, MD, and TD directions of the foam sheet. In the MD and TD directions, after punching to a width of 0.5 mm and a length of 25 mm, stacking is performed until the thickness reaches 5 mm or more, fixing both ends of 25 mm so that there is no gap, and a width direction of 0.5 mm Measured against.
  • Example 1 Linear low-density polyethylene (exon chemical “Exact3027”, density: 0.900 g / cm 3 ) 100 parts by mass as a polyolefin resin, pigment (Daiichi Seika Kogyo Co., Ltd., AP-091979) 1.13 Parts by mass, 2.1 parts by mass of azodicarbonamide as a pyrolytic foaming agent, 1 part by mass of zinc oxide as a decomposition temperature adjusting agent, and 2,6-di-t-butyl-p-cresol as an antioxidant After 0.5 parts by mass was supplied to an extruder and melt-kneaded at 130 ° C., the polyolefin resin composition was extruded into a long sheet having a thickness of about 0.3 mm.
  • the long sheet-like polyolefin resin composition is crosslinked by irradiating 70 kGy of an electron beam with an acceleration voltage of 500 kV on both sides thereof, and then continuously in a foaming furnace maintained at 250 ° C. by hot air and an infrared heater.
  • the foamed sheet having a thickness of 0.14 mm was obtained by foaming by heating and foaming and stretching the MD with a stretching ratio of 1.3 times and a TD with a stretching ratio of 2.0.
  • Table 1 shows the evaluation results of the obtained foamed sheet.
  • Example 2-8 Comparative Examples 1-8
  • the composition of the polyolefin-based resin composition was changed as shown in Tables 1 and 2, and the dose at the time of crosslinking was adjusted to the gel fractions in Tables 1 and 2, and the MD and TD draw ratios were 1.
  • the same operation as in Example 1 was carried out except that it was adjusted to 2 times to 4.0 times.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une feuille de mousse en résine de polyoléfine formée par moussage d'une composition de résine de polyoléfine contenant une résine de polyoléfine et un pigment, la contrainte de compression à 25 % étant de 80 à 1 400 kPa, la teneur en pigment étant comprise entre 0,60 et 10,00 parties en masse pour 100 parties en masse de résine, la densité étant comprise entre 0,10 et 0,60 g/cm3, et la fraction de gel étant comprise entre 25 et 60 % en masse.
PCT/JP2017/013416 2016-03-30 2017-03-30 Feuille de mousse en résine de polyoléfine et bande adhésive WO2017170941A1 (fr)

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JP2017520991A JP6550131B2 (ja) 2016-03-30 2017-03-30 ポリオレフィン系樹脂発泡シート及び粘着テープ
CN201780005106.2A CN108431105B (zh) 2016-03-30 2017-03-30 聚烯烃系树脂发泡片和胶带
KR1020187025932A KR102078236B1 (ko) 2016-03-30 2017-03-30 폴리올레핀계 수지 발포 시트 및 점착 테이프

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JP2020055917A (ja) * 2018-09-28 2020-04-09 積水化学工業株式会社 架橋ポリオレフィン系樹脂発泡体
WO2020195676A1 (fr) * 2019-03-26 2020-10-01 東レ株式会社 Feuille de résine à base de polyoléfine expansée
WO2021025007A1 (fr) * 2019-08-05 2021-02-11 株式会社ジェイエスピー Corps de coussin pour assise

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KR102078236B1 (ko) 2020-02-17
CN110790972A (zh) 2020-02-14
JP2019178341A (ja) 2019-10-17
CN108431105B (zh) 2021-06-29
JP6665340B2 (ja) 2020-03-13
JP6665336B2 (ja) 2020-03-13
JP6550131B2 (ja) 2019-07-24
CN110746678B (zh) 2020-12-08
JP2019218563A (ja) 2019-12-26
CN110746678A (zh) 2020-02-04
JPWO2017170941A1 (ja) 2018-12-06
KR20180127337A (ko) 2018-11-28
CN108431105A (zh) 2018-08-21

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