WO2021106910A1 - Mousse de résine - Google Patents

Mousse de résine Download PDF

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Publication number
WO2021106910A1
WO2021106910A1 PCT/JP2020/043759 JP2020043759W WO2021106910A1 WO 2021106910 A1 WO2021106910 A1 WO 2021106910A1 JP 2020043759 W JP2020043759 W JP 2020043759W WO 2021106910 A1 WO2021106910 A1 WO 2021106910A1
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Prior art keywords
resin foam
resin
weight
polyolefin
foam
Prior art date
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PCT/JP2020/043759
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English (en)
Japanese (ja)
Inventor
清明 児玉
齋藤　誠
Original Assignee
日東電工株式会社
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Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to JP2021561441A priority Critical patent/JPWO2021106910A1/ja
Priority to KR1020227017000A priority patent/KR20220106752A/ko
Priority to CN202080075113.1A priority patent/CN114616278A/zh
Publication of WO2021106910A1 publication Critical patent/WO2021106910A1/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
    • C08J9/12—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 physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • 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
    • C08J9/12—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 physical 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
    • 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
    • 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
    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene

Definitions

  • the present invention relates to a resin foam.
  • Cushion material is often used to protect the screen of electronic devices and the substrate. In recent years, it has been required to narrow the clearance of the portion where the cushion material is arranged in accordance with the tendency of thinning of electronic devices. Furthermore, studies on flexible electronic devices using organic EL panels are also in progress. In such an electronic device, a load of action different from that of the conventional rigid LCD panel is applied.
  • Examples of the cushioning material include members having a foamed structure, and as a method for obtaining a foam having a fine bubble structure, an inert gas is dissolved in a polymer under high pressure, and then the pressure is rapidly reduced to form a foamed structure.
  • a method of forming has been proposed (Cited Document 1). Attempts have also been made to improve the shock absorption of the foamed member (Cited Documents 2 and 3).
  • the equipment used in conventional rigid displays but also the equipment used in flexible displays and the equipment used by bending the flexible display have a high level of impact resistance.
  • a foamed member that has been realized and is thinly constructed has not been obtained.
  • An object of the present invention is to provide a resin foam having excellent shock absorption even if it is thin.
  • the resin foam of the present invention has an apparent density of 0.02 g / cm 3 to 0.30 g / cm 3 , a 25% compression load of 90 kPa or less, and an elastic strain energy during compression of 10 kPa or more. It has a bubble structure.
  • the resin foam has an average cell diameter of 10 ⁇ m to 200 ⁇ m.
  • the resin foam has a bubble ratio of 30% or more.
  • the resin foam has a coefficient of variation of bubble diameter of 0.5 or less.
  • the resin foam has a non-foam bending stress of 5 MPa or more.
  • the resin foam further comprises a filler.
  • the filler is an inorganic material.
  • the filler is organic.
  • the resin foam comprises a polyolefin-based resin.
  • the polyolefin-based resin is a mixture of a polyolefin other than the polyolefin-based elastomer and a polyolefin-based elastomer.
  • the resin foam has a hot melt layer on one or both sides.
  • a foamed member is provided. This foamed member has a resin foamed layer and an adhesive layer arranged on at least one side of the resin foamed layer, and the resin foamed layer is the resin foam.
  • the present invention it is possible to provide a resin foam having excellent shock absorption even if it is thin.
  • the resin foam of the present invention exhibits excellent shock absorption even when combined with a flexible sheet.
  • the resin foam of the present invention has an apparent density of 0.02 g / cm 3 to 0.30 g / cm 3 , a 25% compression load of 90 kPa or less, and an elastic strain energy during compression of 10 kPa or more.
  • the resin foam of the present invention has a bubble structure (cell structure). Examples of the cell structure (cell structure) include a closed cell structure, an open cell structure, and a semi-continuous semi-closed cell structure (a bubble structure in which a closed cell structure and an open cell structure are mixed).
  • the cell structure of the resin foam is preferably a continuous cell structure or a semi-continuous semi-closed cell structure, and more preferably a semi-continuous semi-closed cell structure.
  • the resin foam of the present invention is obtained by foaming the resin composition.
  • the resin composition is a composition containing at least the resin constituting the resin foam.
  • the apparent density of the resin foam of the present invention is 0.02 g / cm 3 to 0.30 g / cm 3 . Within such a range, a resin foam having excellent flexibility and stress dispersibility can be obtained.
  • the apparent density of the resin foam of the present invention is preferably 0.03g / cm 3 ⁇ 0.28g / cm 3, more preferably from 0.04g / cm 3 ⁇ 0.25g / cm 3, particularly preferably Is 0.05 g / cm 3 to 0.20 g / cm 3 , and most preferably 0.07 g / cm 3 to 0.15 g / cm 3 . Within such a range, the above effect becomes remarkable. The method for measuring the apparent density will be described later.
  • the 25% compressive load of the resin foam of the present invention is 90 kPa or less. If the resin foam has a 25% compressive load in such a range, the load on the applied member can be reduced. More specifically, when the resin foam is applied to a portion having a narrow clearance by compressing it to some extent, the resin foam of the present invention can reduce the stress applied to other members. For example, when the resin foam is applied to the display member, the stress applied to the display member can be relaxed and dispersed, which is useful from the viewpoint of reducing color unevenness and protecting the member.
  • the 25% compressive load of the resin foam of the present invention is preferably 80 kPa or less, more preferably 75 kPa or less, and further preferably 55 kPa or less.
  • the 25% compressive load of the resin foam of the present invention is preferably as small as possible, but the lower limit thereof is, for example, 10 kPa, preferably 5 kPa, more preferably 1 kPa, and particularly preferably 0.1 kPa. is there.
  • the method for measuring the 25% compressive load will be described later.
  • the elastic strain energy of the resin foam of the present invention during compression is 10 kPa or more.
  • “Elastic strain energy during compression” means the total amount of compression repulsive force when the resin foam is compressed by 10%.
  • the "elastic strain energy during compression” was determined by a compression test (test temperature: 23 ° C., sample size: 10 mm x 10 mm, compression rate: 10 mm / min) according to JIS K 6767. When the compression rate (%) and the compression repulsive force (kPa) are measured, it is obtained from the compression ss curve with the x-axis as the compression rate (%) and the y-axis as the compression repulsive force (kPa), and the compression rate is 0%.
  • the elastic strain energy of the resin foam of the present invention during compression is preferably 20 kPa or more, more preferably 28 kPa or more, still more preferably 35 kPa or more, still more preferably 50 kPa or more, still more preferably 80 kPa or more.
  • the above is particularly preferable, 100 kPa or more, and most preferably 150 kPa or more. Within such a range, the above effect becomes remarkable.
  • the upper limit of the elastic strain energy during compression of the resin foam of the present invention is, for example, 500 kPa (preferably 800 kPa).
  • a resin foam having excellent flexibility, stress dispersibility and impact resistance can be obtained by setting the apparent density, 25% compressive load and elastic strain energy during compression within the above ranges. Further, a resin foam that satisfies all of the above characteristics is a combination with a member (for example, an organic EL panel, a resin base material) that exhibits excellent impact resistance while being a thin layer and has flexibility. Demonstrates excellent impact resistance.
  • a member for example, an organic EL panel, a resin base material
  • the thickness of the resin foam of the present invention is preferably 30 ⁇ m to 5000 ⁇ m, more preferably 35 ⁇ m to 4000 ⁇ m, further preferably 40 ⁇ m to 3000 ⁇ m, still more preferably 45 ⁇ m to 2000 ⁇ m, still more preferably 50 ⁇ m to 50 ⁇ m. It is 1000 ⁇ m, and particularly preferably 55 ⁇ m to 500 ⁇ m.
  • the resin foam of the present invention exhibits excellent impact resistance even though it is a thin layer. Further, when the thickness of the resin foam is within the above range, a fine and uniform bubble structure can be formed, which is advantageous in that excellent shock absorption can be exhibited.
  • the elongation at break of the resin foam of the present invention at 25 ° C. is preferably 120% or less, more preferably 110% or less, further preferably 100% or less, and particularly preferably 90% or less. Within such a range, a resin foam having excellent flexibility and stress dispersibility can be obtained. If the elongation at break is small, the deformation of the cell wall of the resin foam becomes small when a load is applied to the resin foam. For example, when a filler is added, the resin foam constitutes the resin foam. Slip is likely to occur at the interface between the resin and the filler, and the load can be further relaxed. On the other hand, if the breaking elongation is too large, the deformation of the cell wall of the resin foam becomes large, and it may be difficult to relax the load. The elongation at break can be measured according to JIS K 6767.
  • the average cell diameter (average cell diameter) of the resin foam is preferably 10 ⁇ m to 200 ⁇ m, more preferably 15 ⁇ m to 180 ⁇ m, further preferably 20 ⁇ m to 150 ⁇ m, and particularly preferably 23 ⁇ m to 120 ⁇ m. It is particularly preferably 25 ⁇ m to 100 ⁇ m, and most preferably 30 ⁇ m to 80 ⁇ m. Within such a range, a resin foam having more excellent flexibility and stress dispersibility can be obtained. In addition, it is possible to obtain a resin foam having excellent compression recovery and resistance to repeated impacts. The method for measuring the average cell diameter will be described later.
  • the aspect ratio of bubbles contained in the resin foam is preferably 1.5 or more. Within such a range, a resin foam having excellent thickness recovery can be obtained.
  • the aspect ratio of the bubbles constituting the resin foam is preferably 2.0 or more, and more preferably 2.5 or more. Within such a range, the above effect becomes remarkable.
  • the upper limit of the aspect ratio of the bubbles constituting the resin foam is preferably 8, more preferably 6, and even more preferably 5. Within such a range, a resin foam having excellent shock absorption can be obtained.
  • the "aspect ratio of bubbles contained in the resin foam” is the aspect ratio of individual bubbles existing in a predetermined area (3 mm 2) in the cross section of the resin foam at randomly selected locations. Means the average value.
  • the specific method for obtaining the "aspect ratio of bubbles contained in the resin foam” is as follows. -The resin foam is cut using a razor blade in the TD (direction orthogonal to the flow direction) and in the direction perpendicular to the main surface of the resin foam (thickness direction), and within a predetermined area (3 mm 2 ). Is observed at a magnification of 100 times. The length of one bubble in the thickness direction and the length of TD are measured.
  • the coefficient of variation of the bubble diameter (cell diameter) of the resin foam of the present invention is preferably 0.5 or less, more preferably 0.48 or less, still more preferably 0.45 or less, and particularly preferably 0.45 or less. It is 0.43 or less, most preferably less than 0.4. Within such a range, it is possible to obtain a resin foam in which deformation due to impact becomes uniform, local stress load is prevented, stress dispersibility is excellent, and impact resistance is particularly excellent.
  • the bubble ratio (cell ratio) of the resin foam of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 80% or more. Within such a range, a resin foam having a small repulsive stress during compression can be obtained. Such a resin foam can reduce the stress applied to other members when the resin foam is applied by compressing it to a place having a narrow clearance. For example, when the resin foam is applied to the display member, the stress applied to the display member can be relaxed and dispersed, which is useful from the viewpoint of reducing color unevenness and protecting the member.
  • the upper limit of the bubble ratio is, for example, 99% or less. The method for measuring the bubble ratio will be described later.
  • the thickness of the bubble wall (cell wall) of the resin foam of the present invention is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.3 ⁇ m to 8 ⁇ m, still more preferably 0.5 ⁇ m to 5 ⁇ m, and particularly. It is preferably 0.7 ⁇ m to 4 ⁇ m, and most preferably 1 ⁇ m to 2.8 ⁇ m. Within such a range, a resin foam having more excellent flexibility and stress dispersibility can be obtained. If the thickness of the bubble wall is too thin, the resin foam is easily deformed by a load, and a sufficient stress dispersion effect may not be obtained. If the thickness of the bubble wall is too thick, the resin foam is less likely to be deformed by a load, and when used in a gap between devices, the step followability may be deteriorated. The method for measuring the thickness of the bubble wall will be described later.
  • the ratio of the closed cell structure in the cell structure is preferably 40% or less, more preferably 30% or less.
  • the self-foaming ratio of the resin foam is, for example, in an environment of a temperature of 23 ° C. and a humidity of 50%, the object to be measured is submerged in water, the mass thereof is measured thereafter, and then in an oven at 80 ° C. After sufficiently drying, the mass is measured again to obtain the determination. Further, since open cells can retain water, the mass thereof can be measured and obtained as open cells.
  • the non-foaming bending stress of the resin foam of the present invention is preferably 5 MPa or more, more preferably larger than 5 MPa, more preferably 7 MPa or more, still more preferably 10 MPa or more. Within such a range, a large amount of energy is required to deform the bubble wall (cell wall) of the resin foam, and a resin foam having excellent shock absorption can be obtained.
  • the resin foam of the present invention can improve impact resistance (impact absorption) by appropriately reducing the flexibility, which has been regarded as important in cushioning materials, and balancing it with other characteristics. ..
  • the resin foam of the present invention that exhibits shock absorption due to an action different from the conventional one is particularly useful in a configuration in which the impact propagates in a narrow range (a configuration in which the impact does not easily spread in the plane direction), for example. , Especially useful when applied to flexible members (eg, members made of resin).
  • the upper limit of the non-foam bending stress is preferably 20 MPa, more preferably 15 MPa. Within such a range, a resin foam having more excellent flexibility and stress dispersibility can be obtained.
  • the “non-foaming bending stress” means the bending stress of the resin molded product a that has been returned to the non-foaming state (bulk) without bubbles by heat-pressing the resin foam.
  • the density of the resin molded body a can be made equal to the density of the resin molded body b before foaming formed by the resin composition described later.
  • the bending stress of the resin molded body a (non-foamed bending stress of the resin foam) can be the same as that of the resin molded body b. The method for measuring the bending stress will be described later.
  • the thickness recovery rate of the resin foam is preferably 65% or more, more preferably 70% or more, and further preferably 75% or more.
  • the thickness recovery rate of the foamed layer is defined by the following formula.
  • the thickness recovery rate of this foam layer is a recovery rate measured by applying a load to a foam sheet with a certain area and compressing it, and is a so-called dent recovery rate measured by locally applying a load and denting only a part of the foam sheet. Is different.
  • Thickness recovery rate (%) ⁇ (thickness 0.5 seconds after decompression) / (initial thickness) ⁇ x 100
  • Initial thickness The thickness of the resin foam before applying a load.
  • Thickness 0.5 seconds after decompression Maintained for 120 seconds with a load of 1000 g / cm 2 applied to the resin foam, decompressed, 0.5 seconds after decompression Thickness of resin foam.
  • any appropriate shape can be adopted depending on the purpose.
  • Such a shape is typically a sheet shape.
  • the resin foam of the present invention may have a hot melt layer on one side or both sides thereof.
  • the resin foam having the hot melt layer is, for example, a resin foam (or a precursor of the resin foam) using a pair of heating rolls heated to a temperature equal to or higher than the melting temperature of the resin composition constituting the resin foam. Can be obtained by rolling.
  • the resin foam of the present invention can be formed by any suitable method as long as the effects of the present invention are not impaired.
  • a typical example of such a method is a method of foaming a resin composition containing a resin material (polymer).
  • the resin foam of the present invention can be typically obtained by foaming a resin composition.
  • the resin composition comprises any suitable resin material (polymer).
  • polymer examples include acrylic resin, silicone resin, urethane resin, polyolefin resin, ester resin, rubber resin and the like.
  • the polymer may be used alone or in combination of two or more.
  • the content ratio of the polymer is preferably 30 parts by weight to 95 parts by weight, more preferably 35 parts by weight to 90 parts by weight, and further preferably 40 parts by weight to 80 parts by weight with respect to 100 parts by weight of the resin composition. It is a part, particularly preferably 40 parts by weight to 60 parts by weight. Within such a range, a resin foam having more excellent flexibility and stress dispersibility can be obtained.
  • a polyolefin resin is used as the polymer.
  • the content ratio of the polyolefin resin is preferably 50 parts by weight to 100 parts by weight, more preferably 70 parts by weight to 100 parts by weight, and further preferably 90 parts by weight to 100 parts by weight with respect to 100 parts by weight of the polymer. It is a part by weight, particularly preferably 95 parts by weight to 100 parts by weight, and most preferably 100 parts by weight.
  • the polyolefin-based resin preferably includes at least one selected from the group consisting of polyolefins and polyolefin-based elastomers, and more preferably, polyolefins and polyolefin-based elastomers are used in combination.
  • polyolefins and polyolefin-based elastomers are used in combination.
  • the polyylene and the polyolefin-based elastomer only one type may be used alone, or two or more types may be used in combination.
  • the term "polyolefin” does not include "polyolefin-based elastomer”.
  • the weight ratio of the polyolefin and the polyolefin-based elastomer is preferably 1/99 to 99/1, more preferably 10/90 to It is 90/10, more preferably 20/80 to 80/20, and particularly preferably 30/70 to 70/30. Within such a range, the effect of the present invention becomes remarkable.
  • any suitable polyolefin can be adopted as long as the effect of the present invention is not impaired.
  • examples of such polyolefins include linear polyolefins and branched-chain (branched-chain) polyolefins.
  • a branched-chain polyolefin is used as the polyolefin-based resin.
  • the polyolefin only the branched polyolefin may be used, or the branched polyolefin and the linear polyolefin may be used in combination.
  • the content ratio of the branched polyolefin is preferably 30 parts by weight to 100 parts by weight, and more preferably 80 parts by weight to 120 parts by weight with respect to 100 parts by weight of the polyolefin.
  • polystyrene resin examples include polymers containing a structural unit derived from ⁇ -olefin.
  • the polyolefin may be composed of only a structural unit derived from an ⁇ -olefin, or may be composed of a structural unit derived from an ⁇ -olefin and a structural unit derived from a monomer other than the ⁇ -olefin.
  • any suitable copolymerization form can be adopted as the copolymerization form thereof. For example, random copolymers, block copolymers and the like can be mentioned.
  • ⁇ -olefins examples include ⁇ -olefins having 2 to 8 carbon atoms (preferably 2 to 6, more preferably 2 to 4) (for example, ethylene, propylene, 1-butene, 1-pentene). , 1-Hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, etc.) are preferred.
  • the ⁇ -olefin may be only one kind or two or more kinds.
  • Examples of the monomer other than the ⁇ -olefin constituting the polyolefin include ethylenically unsaturated monomers such as vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, and vinyl alcohol.
  • the monomer other than the ⁇ -olefin may be only one kind or two or more kinds.
  • polystyrene resin examples include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene (propylene homopolymer), a copolymer of ethylene and propylene, and ethylene and other than ethylene.
  • Examples include a copolymer with a body.
  • a polypropylene-based polymer having a propylene-derived structural unit is used as the polyolefin.
  • the polypropylene-based polymer include polypropylene (propylene homopolymer), a copolymer of ethylene and propylene, a copolymer of propylene and an ⁇ -olefin other than propylene, and preferably polypropylene (propylene homopolymer). ).
  • the polypropylene-based polymer only one type may be used alone, or two or more types may be used in combination.
  • the melt flow rate (MFR) of the polyolefin at a temperature of 230 ° C. is preferably 0.2 g / 10 min to 10 g / 10 min, and more preferably 0.25 g / 10 in that the effects of the present invention can be more exhibited. Minutes to 5 g / 10 minutes, more preferably 0.3 g / 10 minutes to 3 g / 10 minutes, and particularly preferably 0.35 g / 10 minutes to 1.5 g / 10 minutes.
  • the melt flow rate (MFR) refers to an MFR measured at a temperature of 230 ° C. and a load of 2.16 kgf based on ISO1133 (JIS-K-7210).
  • melt flow rate (MFR) at a temperature of 230 ° C. is preferably 0.2 g / 10 minutes or more and less than 0.7 g / 10 minutes (more preferably 0.2 g / 10 minutes to 0.65 g / 10 minutes).
  • the polyolefin and melt flow rate (MFR) at a temperature of 230 ° C. are preferably 0.7 g / 10 min to 10 g / 10 min (more preferably 0.7 g / 10 min to 5 g / 10 min, and even more preferably 0.
  • the melt flow rate (MFR) at a temperature of 230 ° C. is preferably 0.
  • the polyolefin of 2 g / 10 minutes or more and less than 0.7 g / 10 minutes (more preferably 0.2 g / 10 minutes to 0.65 g / 10 minutes) and the melt flow rate (MFR) at a temperature of 230 ° C. are preferably 0.7 g.
  • the weight ratio of 10 minutes to 1.5 g / 10 minutes, most preferably 0.7 g / 10 minutes to 1.3 g / 10 minutes) with the polyolefin is preferably 1/99 to 99/1. , More preferably 10/90 to 90/10, further preferably 20/80 to 80/20, particularly preferably 30/70 to 70/30, and most preferably 40/60 to 60/40. Is.
  • polystyrene resin As the polyolefin, a commercially available product may be used, for example, “E110G” (manufactured by Prime Polymer Co., Ltd.), “EA9” (manufactured by Japan Polypropylene Corporation), “EA9FT” (manufactured by Japan Polypropylene Corporation), “E-”. Examples thereof include “185G” (manufactured by Prime Polymer Co., Ltd.), "WB140HMS” (manufactured by Borealis), and "WB135HMS” (manufactured by Borealis).
  • any suitable polyolefin-based elastomer can be adopted as long as the effects of the present invention are not impaired.
  • examples of such polyolefin-based elastomers include ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-vinyl acetate copolymers, polybutene, polyisobutylene, chlorinated polyethylene, and polyolefin components and rubber components.
  • thermoplastic olefin-based elastomer such as an elastomer in which is physically dispersed, or an elastomer having a structure in which a polyolefin component and a rubber component are microphase-separated; a resin component A (olefin) forming a matrix.
  • a mixture containing a system resin component A) and a rubber component B forming a domain is dynamically heat-treated in the presence of a cross-linking agent, and cross-linked rubber particles are contained in the resin component A which is a matrix (sea phase).
  • TPV dynamically crosslinked thermoplastic olefin-based elastomer
  • TPV dynamically crosslinked thermoplastic olefin-based elastomer
  • the polyolefin-based elastomer preferably contains a rubber component.
  • rubber components include JP-A-08-302111, JP-A-2010-241934, JP-A-2008-024882, JP-A-2000-007858, JP-A-2006-052277, and JP-A.
  • Examples thereof include those described in Japanese Patent Application Laid-Open No. 2012-072306, Japanese Patent Application Laid-Open No. 2012-057068, Japanese Patent Application Laid-Open No. 2010-2418997, Japanese Patent Application Laid-Open No. 2009-067969, and Japanese Patent Application Laid-Open No. 03/002654.
  • the elastomer having a structure in which the polyolefin component and the olefin rubber component are microphase-separated include polypropylene resin (PP) and an elastomer composed of polypropylene resin (PP) and ethylene-propylene rubber (EPM). Examples thereof include an elastomer composed of ethylene-propylene-diene rubber (EPDM).
  • the weight ratio of the polyolefin component and the olefin rubber component is preferably 90/10 to 10/90, and more preferably 80/20 to 20/80.
  • the dynamically crosslinked thermoplastic olefin elastomer generally has a higher elastic modulus and a smaller compression set than the non-crosslinked thermoplastic olefin elastomer (TPO). As a result, the recoverability is good, and when a foam is used, excellent recoverability can be exhibited.
  • the dynamically crosslinked thermoplastic olefin elastomer is a cross-linking agent containing a mixture containing a resin component A (olefin resin component A) forming a matrix and a rubber component B forming a domain. It is a multiphase polymer having a sea-island structure in which crosslinked rubber particles are finely dispersed as domains (island phases) in the resin component A which is a matrix (sea phase) obtained by dynamically heat-treating in the presence. ..
  • thermoplastic olefin elastomer examples include JP-A-2000-007858, JP-A-2006-052277, JP-A-2012-072306, JP-A-2012-057068, and Japanese Patent Application Laid-Open No. 2012-057068. Examples thereof include those described in Japanese Patent Application Laid-Open No. 2010-2418997, Japanese Patent Application Laid-Open No. 2009-067969, and Re-Table 03/002654.
  • thermoplastic olefin elastomer a commercially available product may be used, for example, “Zeotherm” (manufactured by Zeon Corporation), “Thermoran” (manufactured by Mitsubishi Chemical Corporation), “Sarlink 3245D”. (Manufactured by Toyobo Corporation) and the like.
  • the melt flow rate (MFR) of the polyolefin-based elastomer at a temperature of 230 ° C. is preferably 2 g / 10 min to 15 g / 10 min, more preferably 3 g / 10 min to 10 g / 10 min, and even more preferably 3. It is 5 g / 10 minutes to 9 g / 10 minutes, particularly preferably 4 g / 10 minutes to 8 g / 10 minutes, and most preferably 4.5 g / 10 minutes to 7.5 g / 10 minutes.
  • the melt tension (190 ° C., at break) of the polyolefin-based elastomer is preferably less than 10 cN, and more preferably 5 cN to 9.5 cN.
  • the JIS A hardness of the polyolefin-based elastomer is preferably 30 ° to 95 °, more preferably 35 ° to 90 °, further preferably 40 ° to 88 °, and particularly preferably 45 ° to 85 °. Yes, most preferably 50 ° to 83 °.
  • the JIS A hardness is measured based on ISO7619 (JIS K6253).
  • the resin foam (ie, the resin composition) may further comprise a filler.
  • a filler By containing the filler, it is possible to form a resin foam that requires a large amount of energy to deform the bubble wall (cell wall), and the resin foam exhibits excellent shock absorption. Further, by containing the filler, a fine and uniform bubble structure can be formed, which is also advantageous in that excellent shock absorption can be exhibited.
  • the filler only one kind may be used alone, or two or more kinds may be used in combination.
  • the content ratio of the filler is preferably 10 parts by weight to 150 parts by weight, more preferably 30 parts by weight to 130 parts by weight, still more preferably, with respect to 100 parts by weight of the polymer constituting the resin foam. It is 50 parts by weight to 100 parts by weight. Within such a range, the above effect becomes remarkable.
  • the filler is an inorganic substance.
  • the material constituting the filler which is an inorganic substance include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and boric acid.
  • examples thereof include aluminum whisker, silicon nitride, boron nitride, crystalline silica, amorphous silica, metals (for example, gold, silver, copper, aluminum, nickel), carbon, graphite and the like.
  • the filler is organic.
  • the material constituting the filler which is an organic substance include polymethyl methacrylate (PMMA), polyimide, polyamideimide, polyetheretherketone, polyetherimide, polyesterimide and the like.
  • a flame retardant may be used as the filler.
  • the flame retardant include a bromine-based flame retardant, a chlorine-based flame retardant, a phosphorus-based flame retardant, an antimony-based flame retardant, and the like.
  • a non-halogen-non-antimony flame retardant is used.
  • non-halogen-non-antimony flame retardant examples include compounds containing aluminum, magnesium, calcium, nickel, cobalt, tin, zinc, copper, iron, titanium, boron and the like.
  • examples of such a compound (inorganic compound) include hydrated metal compounds such as aluminum hydroxide, magnesium hydroxide, magnesium oxide / nickel oxide hydrate, and magnesium oxide / zinc oxide hydrate. ..
  • the above-mentioned filler may be subjected to any appropriate surface treatment.
  • the surface treatment include a silane coupling treatment and a stearic acid treatment.
  • the bulk density of the filler is preferably 0.8 g / cm 3 or less, more preferably 0.6 g / cm 3 or less, still more preferably 0.4 g / cm 3 or less, and in particular. It is preferably 0.3 g / cm 3 or less. Within such a range, the filler can be contained with good dispersibility, and the effect of adding the filler can be sufficiently exhibited while reducing the content of the filler.
  • a resin foam having a low filler content is advantageous in that it is highly foamed, flexible, and has excellent stress dispersibility and appearance.
  • the lower limit of the bulk density of the filler is, for example, 0.01 g / cm 3, preferably 0.05 g / cm 3, more preferably 0.1 g / cm 3.
  • the number average particle size (primary particle size) of the filler is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and further preferably 1 ⁇ m or less. Within such a range, the filler can be contained with good dispersibility and a uniform bubble structure can be formed. As a result, a resin foam having excellent stress dispersibility and appearance can be obtained.
  • the lower limit of the number average particle size of the filler is, for example, 0.1 ⁇ m.
  • the number average particle size of the filler can be measured using a particle size distribution meter (MicrotracII, Microtrac Bell Co., Ltd.) using a suspension prepared by mixing 1 g of a filler with 100 g of water as a sample. it can.
  • the specific surface area of the filler is preferably 2 m 2 / g or more, more preferably 4 m 2 / g or more, and further preferably 6 m 2 / g or more. Within such a range, the filler can be contained with good dispersibility and a uniform bubble structure can be formed. As a result, a resin foam having excellent stress dispersibility and appearance can be obtained.
  • the upper limit of the specific surface area of the filler is, for example, 20 m 2 / g.
  • the specific surface area of the filler can be measured by the BET method, that is, by adsorbing a molecule having a known adsorption area to the surface of the filler at a low temperature of liquid nitrogen and measuring the adsorption amount.
  • the resin composition may contain any suitable other components as long as the effects of the present invention are not impaired.
  • Such other components may be only one kind or two or more kinds.
  • Such other components include, for example, rubber, resins other than polymers blended as resin materials, softeners, aliphatic compounds, antioxidants, antioxidants, light stabilizers, weather resistant agents, and ultraviolet absorption.
  • Agents dispersants, plastics, carbons, antistatic agents, surfactants, cross-linking agents, thickeners, rust preventives, silicone compounds, tension modifiers, shrinkage inhibitors, fluidity modifiers, gelling Agents, hardeners, reinforcing agents, foaming agents, foaming nucleating agents, coloring agents (pigments, dyes, etc.), pH adjusting agents, solvents (organic solvents), thermal polymerization initiators, photopolymerization initiators, lubricants, crystal nucleating agents, Examples thereof include crystallization accelerators, solubilizers, surface treatment agents, and dispersion aids.
  • the resin foam of the present invention is typically obtained by foaming a resin composition.
  • foaming method bubble forming method
  • a method usually used for foam molding such as a physical method or a chemical method
  • the resin foam of the present invention may be typically a foam (physical foam) formed by foaming by a physical method, or may be foamed by a chemical method. It may be a body (chemical foam).
  • the physical method is generally one in which a gas component such as air or nitrogen is dispersed in a polymer solution to form bubbles by mechanical mixing (mechanical foam).
  • the chemical method is generally a method of forming a cell by a gas generated by thermal decomposition of a foaming agent added to a polymer base to obtain a foam.
  • the resin composition to be subjected to foam molding can be, for example, a component of any suitable melt-kneading device, for example, an open mixing roll, a non-open Banbury mixer, a single-screw extruder, a twin-screw extruder, or a continuous type. It may be prepared by mixing using any suitable means such as a kneader and a pressure kneader.
  • ⁇ Embodiment 1 for forming the resin foam of the present invention for example, a step of mechanically foaming an emulsion resin composition (an emulsion containing a resin material (polymer) or the like) to foam (step A).
  • a step in which a resin foam is formed through the above can be mentioned.
  • the foaming device include a high-speed shearing device, a vibration device, a pressurized gas discharge device, and the like.
  • a high-speed shearing device is preferable from the viewpoint of reducing the bubble diameter and producing a large capacity.
  • This one embodiment 1 for forming the resin foam of the present invention can be applied to the formation from any resin composition.
  • the solid content concentration of the emulsion is preferably high from the viewpoint of film forming property.
  • the solid content concentration of the emulsion is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more.
  • the bubbles when foamed by mechanical stirring are those in which a gas is incorporated into the emulsion.
  • a gas any suitable gas can be adopted as long as it is inert to the emulsion, as long as the effects of the present invention are not impaired. Examples of such a gas include air, nitrogen, carbon dioxide and the like.
  • the resin foam of the present invention can be obtained by subjecting the emulsion resin composition foamed by the above method (bubble-containing emulsion resin composition) to a substrate and drying it (step B). it can.
  • the base material include a peel-treated plastic film (peeling-treated polyethylene terephthalate film and the like), a plastic film (polyethylene terephthalate film and the like), and the like.
  • Step B any appropriate method can be adopted as the coating method and the drying method as long as the effects of the present invention are not impaired.
  • Step B includes a preliminary drying step B1 in which the bubble-containing emulsion resin composition coated on the substrate is dried at 50 ° C. or higher and lower than 125 ° C., and then a main drying step B2 in which the bubble-containing emulsion resin composition is further dried at 125 ° C. or higher and 200 ° C. or lower. It is preferable to have.
  • the pre-drying step B1 and the main drying step B2 it is possible to prevent the coalescence of bubbles and the bursting of bubbles due to a rapid temperature rise.
  • bubbles are united and burst due to a rapid rise in temperature, so it is of great significance to provide the pre-drying step B1.
  • the temperature in the pre-drying step B1 is preferably 50 ° C. to 100 ° C.
  • the time of the pre-drying step B1 is preferably 0.5 minutes to 30 minutes, more preferably 1 minute to 15 minutes.
  • the temperature in the main drying step B2 is preferably 130 ° C. to 180 ° C. or lower, and more preferably 130 ° C. to 160 ° C.
  • the time of the main drying step B2 is preferably 0.5 minutes to 30 minutes, more preferably 1 minute to 15 minutes.
  • ⁇ Embodiment 2 for forming the resin foam of the present invention there is a mode in which the resin composition is foamed with a foaming agent to form a foam.
  • a foaming agent those usually used for foam molding can be used, and from the viewpoint of environmental protection and low pollution to the foam to be foamed, it is preferable to use a high-pressure inert gas.
  • any suitable inert gas can be adopted as long as it is inert to the resin composition and can be impregnated.
  • examples of such an inert gas include carbon dioxide, nitrogen gas, and air. These gases may be mixed and used. Of these, carbon dioxide is preferable from the viewpoint of a large amount of impregnation into the resin material (polymer) and a high impregnation rate.
  • the inert gas is preferably in a supercritical state. That is, it is particularly preferable to use carbon dioxide in a supercritical state. In the supercritical state, the solubility of the inert gas in the resin composition is further increased, a high concentration of the inert gas can be mixed, and the inert gas becomes high concentration at the time of a sudden pressure drop. Since the number of nuclei generated increases and the density of bubbles formed by the growth of the bubble nuclei becomes higher than in other states even if the porosity is the same, fine bubbles can be obtained.
  • the critical temperature of carbon dioxide is 31 ° C.
  • the critical pressure is 7.4 MPa.
  • a gas impregnation step of impregnating a resin composition containing a resin material (polymer) with an inert gas under high pressure for example, a gas impregnation step of impregnating a resin composition containing a resin material (polymer) with an inert gas under high pressure, the same.
  • a decompression step of lowering the pressure after the step to foam the resin material (polymer) for example, a method of forming the resin material (polymer) through a heating step of growing bubbles by heating if necessary.
  • a preformed unfoamed molded product may be impregnated with an inert gas, or the molten resin composition is impregnated with an inert gas under a pressurized state and then subjected to molding when the pressure is reduced.
  • You may.
  • These steps may be performed by either a batch method or a continuous method. That is, after the resin composition is previously molded into an appropriate shape such as a sheet to form an unfoamed resin molded product, the unfoamed resin molded product is impregnated with a high-pressure gas to release the pressure for foaming. It may be a batch method in which the resin composition is kneaded together with a high-pressure gas under pressure, and the pressure is released at the same time as molding, and molding and foaming may be performed at the same time.
  • a resin sheet for foam molding is produced by extruding the resin composition using an extruder such as a single-screw extruder or a twin-screw extruder.
  • the resin composition is uniformly kneaded using a kneader equipped with blades such as a roller, a cam, a kneader, and a bambari type, and pressed to a predetermined thickness using a hot plate press or the like.
  • a hot plate press or the like.
  • the unfoamed resin molded body thus obtained is placed in a high-pressure container, and a high-pressure inert gas (carbon dioxide or the like in a supercritical state) is injected to impregnate the unfoamed resin molded body with the inert gas.
  • a high-pressure inert gas carbon dioxide or the like in a supercritical state
  • the pressure is released (usually up to atmospheric pressure) to generate bubble nuclei in the resin.
  • the bubble nuclei may be grown as they are at room temperature, but in some cases, they may be grown by heating.
  • known or conventional methods such as a water bath, an oil bath, a hot roll, a hot air oven, far infrared rays, near infrared rays, and microwaves can be adopted.
  • the non-foamed resin molded product to be foamed is not limited to a sheet-like product, and various shapes can be used depending on the intended use. Further, the non-foamed resin molded product to be used for foaming can be produced by extrusion molding, press molding, or other molding method such as injection molding.
  • a heating step of growing bubbles by heating may be provided, if necessary. After the bubbles are grown in this way, the shape may be fixed by rapidly cooling with cold water or the like, if necessary. Further, the high-pressure gas may be introduced continuously or discontinuously. Further, in the kneading impregnation step and the molding depressurization step, for example, an extruder or an injection molding machine can be used.
  • the heating method for growing the bubble nuclei include any suitable method such as a water bath, an oil bath, a hot roll, a hot air oven, far infrared rays, near infrared rays, and microwaves. Any suitable shape may be adopted as the shape of the foam. Examples of such a shape include a sheet shape, a prismatic shape, a cylindrical shape, and a modified shape.
  • the amount of the gas mixed when the resin composition is foam-molded is, for example, preferably 2% by weight to 10% by weight, based on the total amount of the resin composition, in that a highly foamed foam can be obtained. It is preferably 2.5% by weight to 8% by weight, more preferably 3% by weight to 6% by weight.
  • the pressure when the resin composition is impregnated with the inert gas can be appropriately selected in consideration of operability and the like.
  • a pressure is, for example, preferably 6 MPa or more (for example, 6 MPa to 100 MPa), more preferably 8 MPa or more (for example, 8 MPa to 50 MPa).
  • the pressure when carbon dioxide in the supercritical state is used is preferably 7.4 MPa or more from the viewpoint of maintaining the supercritical state of carbon dioxide.
  • the pressure is lower than 6 MPa, the bubble growth during foaming is remarkable, the bubble diameter becomes too large, and a preferable average cell diameter (average cell diameter) may not be obtained.
  • the temperature in the gas impregnation step varies depending on the inert gas used, the type of component in the resin composition, etc., and can be selected in a wide range. Considering operability and the like, the temperature is preferably 10 ° C to 350 ° C.
  • the impregnation temperature is preferably 10 ° C. to 250 ° C., more preferably 40 ° C. to 230 ° C. in the batch type.
  • the impregnation temperature is preferably 60 ° C. to 350 ° C. in the continuous type.
  • the temperature at the time of impregnation is preferably 32 ° C. or higher, more preferably 40 ° C. or higher, in order to maintain the supercritical state.
  • the decompression rate is preferably 5 MPa / sec to 300 MPa / sec in order to obtain uniform fine bubbles.
  • the heating temperature in the heating step is preferably 40 ° C. to 250 ° C., more preferably 60 ° C. to 250 ° C.
  • FIG. 1 is a schematic cross-sectional view of a foaming member according to one embodiment of the present invention.
  • the foaming member 100 has a resin foaming layer 10 and an adhesive layer 20 arranged on at least one side of the resin foaming layer 10.
  • the resin foam layer 10 is composed of the resin foam.
  • the thickness of the pressure-sensitive adhesive layer is preferably 5 ⁇ m to 300 ⁇ m, more preferably 6 ⁇ m to 200 ⁇ m, further preferably 7 ⁇ m to 100 ⁇ m, and particularly preferably 8 ⁇ m to 50 ⁇ m.
  • the foamed member of the present invention can exhibit excellent shock absorption.
  • the pressure-sensitive adhesive layer a layer made of any suitable pressure-sensitive adhesive can be adopted.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include rubber-based pressure-sensitive adhesives (synthetic rubber-based pressure-sensitive adhesives, natural rubber-based pressure-sensitive adhesives, etc.), urethane-based pressure-sensitive adhesives, acrylic urethane-based pressure-sensitive adhesives, acrylic-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives.
  • examples thereof include pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, polyamide-based pressure-sensitive adhesives, epoxy-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, fluorine-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is preferably at least one selected from an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive. Such an adhesive may be only one kind or two or more kinds.
  • the pressure-sensitive adhesive layer may be one layer or two or more layers.
  • the adhesives are, for example, emulsion type adhesives, solvent type adhesives, ultraviolet crosslinked (UV crosslinked) adhesives, electron beam crosslinked (EB crosslinked) adhesives, and heat melt type adhesives. Agents (hot melt type adhesives) and the like can be mentioned.
  • Such an adhesive may be only one kind or two or more kinds.
  • Steam moisture permeability of the adhesive layer is preferably not more than 50 (g / (m 2 ⁇ 24 hr)), more preferably 30 (g / (m 2 ⁇ 24 hr)) or less, more preferably 20 (g / (m 2 ⁇ 24 hr)) or less, particularly preferably 10 (g / (m 2 ⁇ 24 hr)) or less.
  • the foamed sheet of the present invention can stabilize the shock absorption without being affected by moisture.
  • the water vapor permeability can be measured, for example, by a method according to JIS Z 0208 under test conditions of 40 ° C. and a relative humidity of 92%.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer may contain any suitable other component as long as the effect of the present invention is not impaired.
  • Other components include, for example, other polymer components, softeners, antioxidants, hardeners, plasticizers, fillers, antioxidants, thermal polymerization initiators, photopolymerization initiators, UV absorbers, light stabilizers.
  • Colorants pigments, dyes, etc.
  • solvents organic solvents
  • surfactants eg, ionic surfactants, silicone-based surfactants, fluorine-based surfactants, etc.
  • cross-linking agents eg, polyisocyanate-based
  • Cross-linking agents silicone-based cross-linking agents, epoxy-based cross-linking agents, alkyl etherified melamine-based cross-linking agents, etc.
  • the thermal polymerization initiator and the photopolymerization initiator may be included in the material for forming the polymer component.
  • the foamed member of the present invention can be produced by any suitable method.
  • the foamed member of the present invention is produced, for example, by laminating a resin foam layer and a pressure-sensitive adhesive layer, or by laminating a material for forming a pressure-sensitive adhesive layer and a resin foam layer and then forming a pressure-sensitive adhesive layer by a curing reaction or the like. And the method of manufacturing.
  • the resin foam is TD (direction orthogonal to the flow direction) and perpendicular to the main surface of the resin foam (thickness direction).
  • TD direction orthogonal to the flow direction
  • Thickness direction direction orthogonal to the main surface of the resin foam
  • Non-foam bending stress Non-foaming by pressing the resin foam with a vacuum press molding machine (IVM-70: Iwaki Kogyo Co., Ltd.) at a temperature of (melting point + 70 ° C.) and a pressure of 15 MPa for 5 minutes.
  • a foamed resin molded product a was obtained.
  • the resin molded body a was cut into a width of 20 mm and a length of 150 mm to prepare a sample, and this sample was placed on a three-point bending tool having a distance between fulcrums of 100 mm, and the pushing speed was 5 mm / in an environment of 23 ° C. ⁇ 50% RH.
  • a indentation test (manufactured by Shimadzu Corporation, trade name "AG-Xplus”) was performed in min, and the load (g) when the sample was indented by 5 mm was defined as a non-foam bending stress.
  • VHX-2000 Keyence's "VHX-2000” was used to observe a predetermined area (3 mm 2 ) range at a magnification of 100 times, and the length of one bubble in the thickness direction and the length of TD were measured. -Similar measurements were made for all bubbles present within a predetermined area. The aspect ratio of the bubbles was calculated by dividing the length of the TD by the length in the thickness direction, and the same calculation was performed for all the bubbles, and the average value was taken as the "aspect ratio of the bubbles of the resin foam".
  • Example 1 Polypropylene (melt flow rate (MFR) (230 ° C): 0.40 g / 10 min) 65 parts by weight, polyolefin-based elastomer (melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °) 35 parts by weight, water 80 parts by weight of magnesium oxide (trade name "KISUMA 5P” manufactured by Kyowa Chemical Industry Co., Ltd.), 10 parts by weight of carbon (trade name "Asahi # 35" manufactured by Asahi Carbon Co., Ltd.), and 1 part by weight of stearate monoglyceride It was kneaded at a temperature of 200 ° C.
  • the resin foam a is passed between the rolls (the gap between the rolls) in the pair of rolls in which one roll is heated to 200 ° C. to form the resin foam A having a thickness of 0.1 mm. Obtained.
  • the gap between the rolls was set so that the resin foam A having a thickness of 0.1 mm could be obtained.
  • the obtained resin foam A was subjected to the above evaluations (1) to (10). The results are shown in Table 1.
  • Example 2 Polypropylene (melt flow rate (MFR) (230 ° C): 0.40 g / 10 min) 65 parts by weight, polyolefin-based elastomer (melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °) 35 parts by weight, water 80 parts by weight of magnesium oxide (trade name "KISUMA 5P” manufactured by Kyowa Chemical Industry Co., Ltd.), 10 parts by weight of carbon (trade name "Asahi # 35" manufactured by Asahi Carbon Co., Ltd.), and 1 part by weight of stearate monoglyceride It was kneaded at a temperature of 200 ° C.
  • the resin foam b is passed between the rolls (the gap between the rolls) in the pair of rolls in which one roll is heated to 200 ° C. to obtain the resin foam C having a thickness of 0.1 mm. Obtained.
  • the gap between the rolls was set so that the resin foam B having a thickness of 0.1 mm could be obtained.
  • the obtained resin foam B was subjected to the above evaluations (1) to (10). The results are shown in Table 1.
  • Example 3 Polypropylene (melt flow rate (MFR) (230 ° C): 0.40 g / 10 min) 65 parts by weight, polyolefin-based elastomer (melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °) 35 parts by weight, water 120 parts by weight of magnesium oxide (trade name "KISUMA 5P” manufactured by Kyowa Chemical Industry Co., Ltd.), 10 parts by weight of carbon (trade name "Asahi # 35" manufactured by Asahi Carbon Co., Ltd.), and 1 part by weight of stearate monoglyceride It was kneaded at a temperature of 200 ° C.
  • MFR melt flow rate
  • MFR polyolefin-based elastomer
  • the resin foam c is passed between the rolls (the gap between the rolls) in the pair of rolls in which one roll is heated to 200 ° C. to obtain the resin foam C having a thickness of 0.1 mm. Obtained.
  • the gap between the rolls was set so that the resin foam C having a thickness of 0.1 mm could be obtained.
  • the obtained resin foam C was subjected to the above evaluations (1) to (10). The results are shown in Table 1.
  • Example 4 A resin foam D containing polyethylene as a main component was prepared, having an apparent density of 0.3 g / cm 3 , a 25% compression load of 50 N / cm 2, and an elastic strain energy of 26 kPa. This resin foam D was subjected to the above evaluations (1) to (10). The results are shown in Table 1.
  • Example 5 Polypropylene (melt flow rate (MFR) (230 ° C): 0.40 g / 10 min) 60 parts by weight, polyolefin-based elastomer (melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °) 40 parts by weight, water 120 parts by weight of magnesium oxide (trade name "KISUMA 5P” manufactured by Kyowa Chemical Industry Co., Ltd.), 10 parts by weight of carbon (trade name "Asahi # 35" manufactured by Asahi Carbon Co., Ltd.), and 1 part by weight of stearate monoglyceride It was kneaded at a temperature of 200 ° C.
  • MFR melt flow rate
  • MFR polyolefin-based elastomer
  • the resin foam e is passed between the rolls (gap between the rolls) in the pair of rolls in which one roll is heated to 200 ° C. to form a resin foam E having a thickness of 0.1 mm. Obtained.
  • the gap between the rolls was set so that the resin foam E having a thickness of 0.1 mm could be obtained.
  • the obtained resin foam E was subjected to the above evaluations (1) to (10). The results are shown in Table 1.
  • Example 6 Polypropylene (melt flow rate (MFR) (230 ° C): 0.40 g / 10 min) 60 parts by weight, polyolefin-based elastomer (melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °) 40 parts by weight, water 120 parts by weight of magnesium oxide (trade name "KISUMA 5P” manufactured by Kyowa Chemical Industry Co., Ltd.), 10 parts by weight of carbon (trade name "Asahi # 35" manufactured by Asahi Carbon Co., Ltd.), and 1 part by weight of stearate monoglyceride It was kneaded at a temperature of 200 ° C.
  • MFR melt flow rate
  • MFR polyolefin-based elastomer
  • the resin foam j is passed between the rolls (gap between the rolls) in the pair of rolls in which one roll is heated to 200 ° C. to form a resin foam J having a thickness of 0.1 mm. Obtained.
  • the gap between the rolls was set so that the resin foam J having a thickness of 0.1 mm could be obtained.
  • the obtained resin foam J was subjected to the above evaluations (1) to (10). The results are shown in Table 1.
  • the resin foam g is passed between the rolls (the gap between the rolls) in the pair of rolls in which one roll is heated to 200 ° C. to obtain the resin foam G having a thickness of 0.1 mm. Obtained.
  • the gap between the rolls was set so that the resin foam G having a thickness of 0.1 mm could be obtained.
  • the obtained resin foam G was subjected to the above evaluations (1) to (10). The results are shown in Table 1.
  • This foam composition was applied onto a peel-treated PET (polyethylene terephthalate) film (thickness: 38 ⁇ m, trade name “MRF # 38” manufactured by Mitsubishi Plastics Co., Ltd.) at 70 ° C. for 4.5 minutes at 140 ° C. The mixture was dried for 4.5 minutes to obtain a resin foam I (thickness: 0.1 mm). The obtained resin foam I was subjected to the above evaluations (1) to (10). The results are shown in Table 1.
  • the resin foam of the present invention can be suitably used, for example, as a cushioning material for electronic devices.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne une mousse de résine qui est mince et possède une excellente résistance aux chocs.　Une mousse de résine selon la présente invention possède une densité apparente de 0.02 g/cm3 à 0.30 g/cm3, une charge de compression de 25 % de 90 kPa ou moins, une énergie de déformation élastique de 10 kPa ou plus lors de la compression, et une structure de bulles. Dans un mode de réalisation, la mousse de résine présente un diamètre moyen de bulles de 10-200 µm. Dans un mode de réalisation, la mousse de résine comprend une fraction de bulles de 30 % ou plus. Dans un mode de réalisation, la mousse de résine possède un coefficient de variation de diamètre de bulles de 0,5 ou moins.
PCT/JP2020/043759 2019-11-25 2020-11-25 Mousse de résine WO2021106910A1 (fr)

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PCT/JP2020/043760 WO2021106911A1 (fr) 2019-11-25 2020-11-25 Corps alvéolaire en résine
PCT/JP2020/043762 WO2021106913A1 (fr) 2019-11-25 2020-11-25 Mousse de résine
PCT/JP2020/043759 WO2021106910A1 (fr) 2019-11-25 2020-11-25 Mousse de résine
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WO2023139879A1 (fr) * 2022-01-18 2023-07-27 日東電工株式会社 Élément en mousse
WO2023139878A1 (fr) * 2022-01-18 2023-07-27 日東電工株式会社 Élément en mousse
JPWO2023176984A1 (fr) * 2022-03-18 2023-09-21

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JP2013049830A (ja) * 2011-07-29 2013-03-14 Nitto Denko Corp ポリオレフィン系樹脂発泡体用樹脂組成物、ポリオレフィン系樹脂発泡体及び発泡シール材
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WO2021106914A1 (fr) 2021-06-03
CN114585670A (zh) 2022-06-03
KR20220106752A (ko) 2022-07-29
JPWO2021106912A1 (fr) 2021-06-03
JPWO2021106911A1 (fr) 2021-06-03
JPWO2021106913A1 (fr) 2021-06-03
WO2021106911A1 (fr) 2021-06-03
CN114761473A (zh) 2022-07-15
CN114641521A (zh) 2022-06-17
WO2021106912A1 (fr) 2021-06-03
WO2021106913A1 (fr) 2021-06-03
CN114761474A (zh) 2022-07-15
JPWO2021106910A1 (fr) 2021-06-03
CN114616278A (zh) 2022-06-10
JPWO2021106914A1 (fr) 2021-06-03

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