JP2021011551A - Foam and method for producing the same - Google Patents
Foam and method for producing the same Download PDFInfo
- Publication number
- JP2021011551A JP2021011551A JP2019127143A JP2019127143A JP2021011551A JP 2021011551 A JP2021011551 A JP 2021011551A JP 2019127143 A JP2019127143 A JP 2019127143A JP 2019127143 A JP2019127143 A JP 2019127143A JP 2021011551 A JP2021011551 A JP 2021011551A
- Authority
- JP
- Japan
- Prior art keywords
- foam
- zirconium oxide
- mass
- resin
- resin component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000006260 foam Substances 0.000 title claims abstract description 136
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 73
- 239000011347 resin Substances 0.000 claims abstract description 73
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000005187 foaming Methods 0.000 claims abstract description 31
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 28
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 15
- 239000011342 resin composition Substances 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 24
- 229920005672 polyolefin resin Polymers 0.000 claims description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 9
- 229920005678 polyethylene based resin Polymers 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 239000011800 void material Substances 0.000 claims description 3
- 229920013716 polyethylene resin Polymers 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 5
- 230000003139 buffering effect Effects 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 35
- 239000010410 layer Substances 0.000 description 29
- -1 polyethylene Polymers 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 239000004088 foaming agent Substances 0.000 description 20
- 150000001336 alkenes Chemical class 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229920001684 low density polyethylene Polymers 0.000 description 15
- 239000004702 low-density polyethylene Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 12
- 238000004898 kneading Methods 0.000 description 11
- 239000002667 nucleating agent Substances 0.000 description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 11
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000010097 foam moulding Methods 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000001282 iso-butane Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 239000012753 anti-shrinkage agent Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
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- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
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- 229920005673 polypropylene based resin Polymers 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 239000000243 solution Substances 0.000 description 3
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- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
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- 238000000921 elemental analysis Methods 0.000 description 2
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- 229920001903 high density polyethylene Polymers 0.000 description 2
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- 239000010954 inorganic particle Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
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- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
本発明は、温感性および緩衝性を有する発泡体およびその製造方法に関する。 The present invention relates to a foam having warmth and cushioning properties and a method for producing the same.
生活用品（こたつ敷き、キッチンマットなど）、アウトドア用品、防災グッズ、ペット用品、寝装寝具用品などの分野において、温感性（暖かさを付与可能な特性）と緩衝性（クッション性）とを備えた温感グッズとして、アルミ箔を貼り合わせた発泡シートが汎用されている。この発泡シートの利用方法としては、熱源である近赤外線や遠赤外線を反射させて温感性を発現する方法などが挙げられる。 In the fields of daily necessities (kotatsu mats, kitchen mats, etc.), outdoor products, disaster prevention goods, pet products, bedding and bedding products, it has warmth (characteristics that can give warmth) and cushioning (cushioning). Foam sheets with aluminum foil bonded to them are widely used as warm goods. Examples of the method of using this foam sheet include a method of expressing warmth by reflecting near infrared rays and far infrared rays which are heat sources.
特開２０１９−３８１９８号公報（特許文献１）には、フェノール樹脂発泡層と、この発泡層の少なくとも一方の面に、可撓性面材を介して設けられた表層とを備え、前記表層が、保護層で被覆された金属層である発泡樹脂積層板が開示されている。この文献には、フェノール樹脂発泡層は、断熱材として、種々の分野で採用されていることが記載され、実施例では、勾配のある屋根に設置され、作業性が向上したことが記載されている。 Japanese Unexamined Patent Publication No. 2019-38198 (Patent Document 1) includes a phenol resin foam layer and a surface layer provided on at least one surface of the foam layer via a flexible surface material, and the surface layer is provided. , A foamed resin laminate which is a metal layer coated with a protective layer is disclosed. This document describes that the phenolic resin foam layer is used as a heat insulating material in various fields, and in the examples, it is described that it is installed on a sloped roof to improve workability. There is.
特開２０１７−１４１３４２号公報（特許文献２）には、熱可塑性樹脂とエラストマーとを含み、スキン領域およびコア領域からなる発泡体が開示されている。この文献には、発泡成形体が含んでいてもよい任意の成分である充填材として、多数の無機化合物が例示されているが、粒径は記載されておらず、実施例でも配合されていない。 Japanese Unexamined Patent Publication No. 2017-141342 (Patent Document 2) discloses a foam containing a thermoplastic resin and an elastomer and consisting of a skin region and a core region. In this document, a large number of inorganic compounds are exemplified as a filler which is an arbitrary component which may be contained in the foam molded product, but the particle size is not described and is not blended in the examples. ..
特開２０１９−３８９９７号公報（特許文献３）には、電子機器の放熱に利用される樹脂シートとして、粘着剤層付発泡樹脂シートが開示されている。この文献には、粘着剤層として、平均粒子径０．１μｍ以上５μｍ未満の第１の熱伝導性粒子および平均粒子径５〜３０μｍの第２の熱伝導性粒子を含む熱伝導性粘着剤が記載され、粘着剤層が発泡体であってもよいと記載されている。実施例では、粘着剤層として、平均粒子径１μｍの水酸化アルミニウム粉末および平均粒子径８μｍの水酸化アルミニウム粉末を含む非発泡の粘着剤層が調製されている。 Japanese Unexamined Patent Publication No. 2019-38997 (Patent Document 3) discloses a foamed resin sheet with an adhesive layer as a resin sheet used for heat dissipation of an electronic device. In this document, as the pressure-sensitive adhesive layer, a heat-conductive pressure-sensitive adhesive containing a first heat-conductive particle having an average particle diameter of 0.1 μm or more and less than 5 μm and a second heat-conductive particle having an average particle diameter of 5 to 30 μm is described. It is stated that the pressure-sensitive adhesive layer may be a foam. In the example, as the pressure-sensitive adhesive layer, a non-foaming pressure-sensitive adhesive layer containing aluminum hydroxide powder having an average particle diameter of 1 μm and aluminum hydroxide powder having an average particle diameter of 8 μm is prepared.
一方では、発泡樹脂そのものに温感性を与えるため、遠赤外線を放射する金属酸化物などを添加した発泡シートも提案されている。 On the other hand, in order to give warmth to the foamed resin itself, a foamed sheet to which a metal oxide or the like that emits far infrared rays is added has also been proposed.
実用新案登録第３１１３６７８号公報（特許文献４）には、ポリエチレン樹脂に、酸化アルミニウムまたは酸化チタンまたは酸化ジルコニウムの単独、あるいはこれらの併用が混合され、かつ表面がシート状の架橋発泡体を少なくとも有する構造の血流増進用シートが開示されている。 In Utility Model Registration No. 3113678 (Patent Document 4), polyethylene resin is mixed with aluminum oxide, titanium oxide, or zirconium oxide alone or in combination thereof, and has at least a sheet-like crosslinked foam on the surface. A structural blood flow enhancing sheet is disclosed.
特開２００３−３２７７３３号公報（特許文献５）には、無機系天然鉱物コロマナイトを焼成して焼成コロマナイトを作成する第１のステップと、前記焼成コロマナイトを５部程度、金属酸化物を１０部〜２０部、ポリエチレン樹脂を１００部の割合で混ぜ、これに少なくとも発泡剤を加えて混練し発泡させてポリエチレンフォームを得る第２のステップと、前記第２のステップにより得られたポリエチレンフォームを任意の厚みにスライスしてシートを作成する第３のステップとを含むことを特徴とするシートの製造方法が開示されている。 Japanese Patent Application Laid-Open No. 2003-327733 (Patent Document 5) describes the first step of calcining an inorganic natural mineral coromanite to produce calcined coromanite, and about 5 parts of the calcined coromanite and 10 parts of a metal oxide. A second step of mixing 20 parts and 100 parts of polyethylene resin, adding at least a foaming agent to the mixture, kneading and foaming to obtain polyethylene foam, and any of the polyethylene foams obtained by the second step. A method for producing a sheet is disclosed, which comprises a third step of slicing to a thickness to prepare a sheet.
特表２００４−５１８７９３号公報（特許文献６）には、ビヒクル中に約１００ｎｍ未満の表面修飾ナノ粒子を含む発泡組成物が開示されている。実施例では、前記表面修飾ナノ粒子として、シランカップリング剤で修飾されたナノシリカが使用されている。 Japanese Patent Application Laid-Open No. 2004-518793 (Patent Document 6) discloses a foaming composition containing surface-modified nanoparticles having a size of less than about 100 nm in a vehicle. In the examples, nanosilica modified with a silane coupling agent is used as the surface-modified nanoparticles.
しかし、特許文献１〜３のいずれにも、発泡体を温感グッズとして利用することは記載されていない。 However, neither of Patent Documents 1 to 3 describes that the foam is used as a warming goods.
また、特許文献１の発泡体を温感グッズとして利用した場合、発泡体に金属箔を貼り合わせているため、柔軟性および取り扱い性が低い上に、シート形状以外の異形形状に成形するのが困難である。 Further, when the foam of Patent Document 1 is used as a warmth goods, since the metal foil is attached to the foam, the flexibility and handleability are low, and the foam is molded into a deformed shape other than the sheet shape. Have difficulty.
一方、特許文献２および３では、充填材または熱伝導剤として無機粒子を発泡体に配合することは記載されているものの、前記無機粒子を配合した発泡体は調製されていない。 On the other hand, although Patent Documents 2 and 3 describe that inorganic particles are blended into a foam as a filler or a heat conductive agent, a foam containing the inorganic particles has not been prepared.
特許文献４および５では、多量の金属酸化物を含むため、発泡体の機械的特性が低下する上に、金属酸化物の粒径が不明である。加えて、特許文献５では、いわゆる型枠発泡した発泡体であるため、発泡原料の混練が困難であり、金属酸化物が均一に分散された発泡体も得られない。 In Patent Documents 4 and 5, since a large amount of metal oxide is contained, the mechanical properties of the foam are deteriorated, and the particle size of the metal oxide is unknown. In addition, in Patent Document 5, since it is a so-called form-foamed foam, it is difficult to knead the foaming raw material, and a foam in which the metal oxide is uniformly dispersed cannot be obtained.
また、特許文献６および７では、発泡倍率が不明である上に、温感性について記載されていない。さらに、特許文献７の用途では低発泡体が多い。 Further, in Patent Documents 6 and 7, the foaming ratio is unknown and the warmth is not described. Further, in the use of Patent Document 7, there are many low foams.
従って、本発明の目的は、温感性と緩衝性（クッション性）とを両立できる発泡体およびその製造方法を提供することにある。 Therefore, an object of the present invention is to provide a foam having both warmth and cushioning properties (cushioning properties) and a method for producing the same.
本発明の他の目的は、各種の三次元形状に容易に成形できる発泡体およびその製造方法を提供することにある。 Another object of the present invention is to provide a foam that can be easily molded into various three-dimensional shapes and a method for producing the same.
本発明のさらに他の目的は、柔軟性に優れ、肌触りにも優れる発泡体およびその製造方法を提供することにある。 Still another object of the present invention is to provide a foam having excellent flexibility and excellent touch, and a method for producing the same.
本発明の別の目的は、機械的特性に優れ、保温性も有している発泡体およびその製造方法を提供することにある。 Another object of the present invention is to provide a foam having excellent mechanical properties and heat retention, and a method for producing the same.
本発明者らは、前記課題を達成するため鋭意検討した結果、発泡体中に少量の酸化ジルコニウムを微分散させることにより、単純で均質な構造であっても、温感性を発現でき、かつ緩衝性（クッション性）も損なわないことを見出し、本発明を完成した。 As a result of diligent studies to achieve the above-mentioned problems, the present inventors can express warmth and cushion even a simple and homogeneous structure by finely dispersing a small amount of zirconium oxide in the foam. The present invention has been completed by finding that the property (cushioning property) is not impaired.
すなわち、本発明の発泡体は、熱可塑性樹脂および／またはその架橋体からなる樹脂成分と、酸化ジルコニウムとを含む発泡体であって、前記酸化ジルコニウムの割合は前記樹脂成分１００質量部に対して０．０１〜８質量部であり、前記樹脂成分（マトリックス）中に前記酸化ジルコニウムが分散相として分散し、かつ前記分散相の平均径が１０μｍ以下である。前記発泡体の発泡倍率は１０倍以上であってもよい。前記熱可塑性樹脂はオレフィン系樹脂を含んでいてもよい。前記樹脂成分はポリエチレン系樹脂であってもよい。前記発泡体は、酸化ケイ素（特に、シリカゲル）をさらに含んでいてもよい。前記酸化ジルコニウムは、空隙の壁面および／またはスキン層付近に局在化していてもよい。前記発泡体は、熱を放出可能な温感発泡体であってもよい。 That is, the foam of the present invention is a foam containing a resin component composed of a thermoplastic resin and / or a crosslinked product thereof and zirconium oxide, and the ratio of the zirconium oxide to 100 parts by mass of the resin component is It is 0.01 to 8 parts by mass, the zirconium oxide is dispersed as a dispersed phase in the resin component (matrix), and the average diameter of the dispersed phase is 10 μm or less. The foaming ratio of the foam may be 10 times or more. The thermoplastic resin may contain an olefin resin. The resin component may be a polyethylene-based resin. The foam may further contain silicon oxide (particularly silica gel). The zirconium oxide may be localized near the wall surface of the void and / or the skin layer. The foam may be a warm foam capable of releasing heat.
本発明には、原料樹脂成分および酸化ジルコニウムを含む発泡性樹脂組成物を発泡成形する前記発泡体の製造方法も含まれる。前記発泡性樹脂組成物は、マトリックスとしての原料樹脂成分中に酸化ジルコニウムが分散した分散相を有していてもよい。前記分散相の平均径は１００ｎｍ以下であってもよい。前記発泡性樹脂組成物は、マトリックスとしての第１の原料樹脂成分中に酸化ジルコニウムが分散相として分子または原子単位で分散したマスターバッチと、第２の原料樹脂成分との組み合わせであってもよい。 The present invention also includes a method for producing the foam, which is obtained by foam-molding a foamable resin composition containing a raw material resin component and zirconium oxide. The foamable resin composition may have a dispersed phase in which zirconium oxide is dispersed in a raw material resin component as a matrix. The average diameter of the dispersed phase may be 100 nm or less. The foamable resin composition may be a combination of a masterbatch in which zirconium oxide is dispersed as a dispersed phase in a first raw material resin component as a matrix in molecular or atomic units, and a second raw material resin component. ..
本発明では、発泡体中で少量の酸化ジルコニウムが微分散しているため、発泡体とは別に温感性を発現させるための層を形成する必要がなく、単純で均質な構造（簡単な単層構造）であっても、温感性と緩衝性（クッション性）とを両立できる。また、各種の三次元形状に容易に成形できるとともに、柔軟性に優れ、肌触りも向上できる。また、少量の酸化ジルコニウムが微分散しているため、機械的特性にも優れている。さらに、アルミ箔などの反射によって温感性を発現するのではなく、酸化ジルコニウムによって遠赤外線を吸収して放出するため、保温性も有している。 In the present invention, since a small amount of zirconium oxide is finely dispersed in the foam, it is not necessary to form a layer for expressing warmth separately from the foam, and a simple and homogeneous structure (simple single layer) is not required. Even with the structure), both warmth and cushioning (cushioning) can be achieved. In addition, it can be easily molded into various three-dimensional shapes, has excellent flexibility, and can be improved in touch. In addition, since a small amount of zirconium oxide is finely dispersed, it has excellent mechanical properties. Furthermore, it also has heat retention because it absorbs and emits far infrared rays by zirconium oxide, instead of expressing warmth by reflection of aluminum foil or the like.
［樹脂成分］
本発明の発泡体は、樹脂成分として、熱可塑性樹脂またはその架橋体を含む。
[Resin component]
The foam of the present invention contains a thermoplastic resin or a crosslinked product thereof as a resin component.
熱可塑性樹脂としては、例えば、オレフィン系樹脂、スチレン系樹脂、塩化ビニル系樹脂、酢酸ビニル系樹脂、ポリビニルアルコール系樹脂、アクリル系樹脂、ポリアセタール系樹脂、ポリエステル系樹脂、ポリカーボネート樹脂、ポリアミド系樹脂、これらの樹脂の構成成分を含む熱可塑性エラストマーなどが挙げられる。これら熱可塑性樹脂は、単独でまたは二種以上組み合わせて使用できる。これらの熱可塑性樹脂のうち、オレフィン系樹脂を含む熱可塑性樹脂が好ましい。 Examples of the thermoplastic resin include olefin resins, styrene resins, vinyl chloride resins, vinyl acetate resins, polyvinyl alcohol resins, acrylic resins, polyacetal resins, polyester resins, polycarbonate resins, and polyamide resins. Examples thereof include thermoplastic elastomers containing constituents of these resins. These thermoplastic resins can be used alone or in combination of two or more. Among these thermoplastic resins, a thermoplastic resin containing an olefin resin is preferable.
オレフィン系樹脂は、オレフィン単位を主成分とする重合体であればよく、オレフィン系樹脂にはオレフィンの単独または共重合体が含まれる。 The olefin-based resin may be a polymer containing an olefin unit as a main component, and the olefin-based resin contains an olefin alone or a copolymer.
オレフィンとしては、例えば、エチレン、１−プロピレン、１−ブテン、イソブテン、１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセンなどのＣ２−２０α−直鎖状オレフィン；３−メチル−１−ブテン、２−メチル−１−ペンテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、４−エチル−１−ヘキセン、３−エチル−１−ヘキセンなどのＣ２−２０α−分岐鎖状オレフィン；シクロブテン、シクロペンテン、シクロヘプテン、シクロオクテンなどのＣ４−１２シクロオレフィン；２−ノルボルネン、５−メチル−２−ノルボルネン、５，５−ジメチル−２−ノルボルネンなどの多環式オレフィンなどが挙げられる。 Examples of the olefin include ethylene, 1-propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene. C 2-20 α-linear olefins such as 1-ehexene; 3-methyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc. C 2-20 α-branched chain olefins; C 4-12 cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cyclooctene; 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene Examples thereof include polycyclic olefins such as.
これらのオレフィンは、単独でまたは二種以上組み合わせて使用できる。これらのうち、α−Ｃ２−８オレフィンが好ましく、α−Ｃ２−４オレフィンがさらに好ましく、エチレンおよび／またはプロピレンが最も好ましい。 These olefins can be used alone or in combination of two or more. Of these, α-C 2-8 olefins are preferred, α-C 2-4 olefins are even more preferred, and ethylene and / or propylene are most preferred.
オレフィン系樹脂は、前記オレフィンと共重合性単量体との共重合体であってもよい。共重合性単量体としては、例えば、エチレン性不飽和カルボン酸類、（メタ）アクリル酸エステル、カルボン酸ビニルエステル、重合性ニトリル化合物、芳香族ビニル、共役ジエン類、非共役ジエン類などが挙げられる。 The olefin-based resin may be a copolymer of the olefin and a copolymerizable monomer. Examples of the copolymerizable monomer include ethylenically unsaturated carboxylic acids, (meth) acrylic acid esters, carboxylic acid vinyl esters, polymerizable nitrile compounds, aromatic vinyls, conjugated dienes, and non-conjugated dienes. Be done.
エチレン性不飽和カルボン酸類としては、エチレン系不飽和カルボン酸およびその酸無水物を利用でき、例えば、（メタ）アクリル酸、（無水）マレイン酸、フマル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸、メサコン酸、アンゲリカ酸などが挙げられる。 As the ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acids and their acid anhydrides can be used, for example, (meth) acrylic acid, (maleic anhydride), fumaric acid, itaconic acid, citraconic acid, crotonic acid, and the like. Examples thereof include isocrotonic acid, mesaconic acid, and angelic acid.
（メタ）アクリル酸エステルとしては、例えば、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチルなどの（メタ）アクリル酸Ｃ１−６アルキルエステル、グリシジル（メタ）アクリレートなどが挙げられる。 Examples of the (meth) acrylic acid ester include (meth) acrylic acid C 1-6 alkyl esters such as methyl acrylate, ethyl acrylate and methyl methacrylate, and glycidyl (meth) acrylate.
カルボン酸ビニルエステルとしては、例えば、酢酸ビニル、プロピオン酸ビニルなどの飽和カルボン酸ビニルエステルなどが挙げられる。 Examples of the carboxylic acid vinyl ester include saturated carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate.
重合性ニトリル化合物としては、例えば、（メタ）アクリロニトリルなどが挙げられる。 Examples of the polymerizable nitrile compound include (meth) acrylonitrile.
芳香族ビニル類としては、例えば、スチレン、ビニルトルエン、α−メチルスチレンなどが挙げられる。 Examples of aromatic vinyls include styrene, vinyltoluene, α-methylstyrene and the like.
共役ジエン類としては、例えば、ブタジエン、イソプレン、ペンタジエン、２，３−ジメチルブタジエンなどが挙げられる。 Examples of the conjugated diene include butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene.
非共役ジエン類としては、例えば、１，４−ヘキサジエン、１，６−オクタジエン、２−メチル−１，５−ヘキサジエン、４−メチル−１，４−ヘキサジエン、５−メチル−１，４−ヘキサジエン、ジシクロペンタジエン、５−ビニルノルボルネン、５−エチリデン−２−ノルボルネンなどが挙げられる。 Examples of non-conjugated dienes include 1,4-hexadiene, 1,6-octadien, 2-methyl-1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene. , Dicyclopentadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene and the like.
これらの共重合性単量体は、単独でまたは二種以上組み合わせて使用できる。共重合性単量体の割合は、全単量体中０〜５０モル％、好ましくは０．１〜３０モル％、さらに好ましくは１〜１０モル％である。 These copolymerizable monomers can be used alone or in combination of two or more. The proportion of the copolymerizable monomer is 0 to 50 mol%, preferably 0.1 to 30 mol%, and more preferably 1 to 10 mol% of the total monomers.
前記共重合体（オレフィン同士の共重合体およびオレフィンと共重合性単量体との共重合体）には、ランダム共重合体、交互共重合体、ブロック共重合体、グラフト共重合体が含まれるが、通常、ランダム共重合体または交互共重合体である。 The copolymers (copolymers of olefins and copolymers of olefins and copolymerizable monomers) include random copolymers, alternate copolymers, block copolymers, and graft copolymers. However, it is usually a random copolymer or an alternating copolymer.
これらのオレフィン系樹脂は、単独でまたは二種以上組み合わせて使用できる。これらのオレフィン系樹脂のうち、発泡性などの点から、ポリエチレン系樹脂、ポリプロピレン系樹脂などのポリＣ２−３オレフィン系樹脂（特にポリエチレン系樹脂）が好ましい。 These olefin resins can be used alone or in combination of two or more. Among these olefin-based resins, poly-C 2-3 olefin-based resins (particularly polyethylene-based resins) such as polyethylene-based resins and polypropylene-based resins are preferable from the viewpoint of foamability and the like.
ポリエチレン系樹脂としては、例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）などのエチレンの単独重合体；エチレン−プロピレン共重合体、エチレン−ブテン−１共重合体、エチレン−プロピレン−ブテン−１共重合体、エチレン−（４−メチルペンテン−１）共重合体、エチレン−酢酸ビニル共重合体（ＥＶＡ樹脂）、エチレン−メチルメタクリレート共重合体などのエチレンを主成分とする共重合体などが挙げられる。これらのポリエチレン系樹脂は、単独でまたは二種以上組み合わせて使用できる。これらのポリエチレン系樹脂のうち、発泡性などの点から、ＬＤＰＥ、ＬＬＤＰＥ、ＥＶＡ樹脂などが好ましい。 Examples of the polyethylene-based resin include homopolymers of ethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE); both ethylene and propylene. Polymer, ethylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene- (4-methylpentene-1) copolymer, ethylene-vinyl acetate copolymer (EVA resin), ethylene -Examples include a polyethylene-based copolymer such as a methyl methacrylate copolymer. These polyethylene-based resins can be used alone or in combination of two or more. Among these polyethylene-based resins, LDPE, LLDPE, EVA resin and the like are preferable from the viewpoint of foamability and the like.
ポリエチレン系樹脂の数平均分子量は、例えば１万〜３０万、好ましくは１．５万〜２０万、さらに好ましくは２万〜１０万である。なお、分子量は、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）において、測定温度１４０℃で、溶媒としてオルトジクロロベンゼン、およびカラム（Ｓｈｏｄｅｘ ＧＰＣ ＡＤ−８０６ＭＳ）を用いて、ポリスチレンを基準とするユニバーサルキャリブレーションにより測定できる。 The number average molecular weight of the polyethylene resin is, for example, 10,000 to 300,000, preferably 15,000 to 200,000, and more preferably 20,000 to 100,000. The molecular weight is universally calibrated based on polystyrene in a gel permeation chromatography method (GPC method) at a measurement temperature of 140 ° C. using orthodichlorobenzene as a solvent and a column (Shodex GPC AD-806MS). Can be measured by.
ポリエチレン系樹脂のメルトフローレート（ＭＦＲ）は、ＪＩＳ Ｋ７２１０に準じた方法（１９０℃、荷重２１．２Ｎ）で、０．１ｇ／１０分以上であってもよく、例えば０．１〜６０ｇ／１０分、好ましくは０．２〜２５ｇ／１０分、さらに好ましくは０．２５〜８ｇ／１０分、最も好ましくは０．３〜５ｇ／１０分である。ＭＦＲが大きすぎると、発泡性や強度などが低下する虞があり、逆に小さすぎても、発泡性が低下する虞がある。一般的にＭＦＲが大きくなると、溶融張力の低下により破泡し易くなることが知られているが、ＭＦＲの下限も前記範囲に調整することにより、発泡性を向上できる。 The melt flow rate (MFR) of the polyethylene resin may be 0.1 g / 10 minutes or more by a method (190 ° C., load 21.2 N) according to JIS K7210, for example, 0.1 to 60 g / 10. Minutes, preferably 0.2 to 25 g / 10 minutes, more preferably 0.25 to 8 g / 10 minutes, most preferably 0.3 to 5 g / 10 minutes. If the MFR is too large, the foamability and strength may decrease, and conversely, if the MFR is too small, the foamability may decrease. Generally, it is known that when the MFR is increased, the foam is likely to break due to the decrease in the melt tension, but the foamability can be improved by adjusting the lower limit of the MFR to the above range.
ポリエチレン系樹脂の融点（ＤＳＣ法）は、例えば８０〜１５０℃、好ましくは９０〜１４０℃、さらに好ましくは１００〜１３０℃である。ポリエチレン系樹脂のビカット軟化点は、例えば７０〜１４０℃、好ましくは８０〜１３０℃、さらに好ましくは９０〜１２０℃である。 The melting point (DSC method) of the polyethylene resin is, for example, 80 to 150 ° C., preferably 90 to 140 ° C., and more preferably 100 to 130 ° C. The bicut softening point of the polyethylene resin is, for example, 70 to 140 ° C., preferably 80 to 130 ° C., and more preferably 90 to 120 ° C.
ポリプロピレン系樹脂としては、例えば、プロピレンの単独重合体であるポリプロピレン；プロピレン−エチレン共重合体、プロピレン−（メタ）アクリル酸共重合体、プロピレン−エチレン−ブテン−１などのプロピレンを主成分とする共重合体などが挙げられる。これらのポリプロピレン系樹脂は、単独でまたは二種以上組み合わせて使用できる。これらのポリプロピレン系樹脂のうち、ポリプロピレン、プロピレン−エチレン共重合体などが好ましい。 The polypropylene-based resin contains, for example, polypropylene, which is a homopolymer of propylene; propylene such as a propylene-ethylene copolymer, a propylene- (meth) acrylic acid copolymer, and propylene-ethylene-butene-1 as a main component. Examples thereof include copolymers. These polypropylene-based resins can be used alone or in combination of two or more. Among these polypropylene-based resins, polypropylene, propylene-ethylene copolymer and the like are preferable.
ポリプロピレン系樹脂の数平均分子量は、例えば１万〜５０万、好ましくは１．５万〜３０万、さらに好ましくは２万〜１０万である。なお、ポリプロピレン系樹脂の数平均分子量は、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）により測定できる。前記ポリプロピレン系樹脂の数平均分子量は、前記ポリエチレン系樹脂の数平均分子量の測定方法と同じ条件で測定できる。 The number average molecular weight of the polypropylene resin is, for example, 10,000 to 500,000, preferably 15,000 to 300,000, and more preferably 20,000 to 100,000. The number average molecular weight of the polypropylene resin can be measured by a gel permeation chromatography method (GPC method). The number average molecular weight of the polypropylene resin can be measured under the same conditions as the method for measuring the number average molecular weight of the polyethylene resin.
ポリプロピレン系樹脂の融点（ＤＳＣ法）は、例えば１２０〜１８０℃、好ましくは１３０〜１７５℃、さらに好ましくは１４０〜１７０℃である。ポリプロピレン系樹脂のビカット軟化点は、例えば１１０〜１７０℃、好ましくは１２０〜１６５℃、さらに好ましくは１３０〜１６０℃である。 The melting point (DSC method) of the polypropylene resin is, for example, 120 to 180 ° C, preferably 130 to 175 ° C, and more preferably 140 to 170 ° C. The Vicat softening point of the polypropylene resin is, for example, 110 to 170 ° C., preferably 120 to 165 ° C., and more preferably 130 to 160 ° C.
ポリプロピレン系樹脂のＭＦＲは、ＪＩＳ Ｋ７２１０に準じた方法（２３０℃、荷重２１．２Ｎ）で、０．１ｇ／１０分以上であってもよく、例えば０．１〜５０ｇ／１０分、好ましくは０．２〜３０ｇ／１０分、さらに好ましくは０．２５〜１０ｇ／１０分、最も好ましくは０．３〜５ｇ／１０分である。ＭＦＲが小さすぎても、逆に大きすぎても、発泡性や強度などが低下する虞がある。 The MFR of the polypropylene resin may be 0.1 g / 10 minutes or more by a method according to JIS K7210 (230 ° C., load 21.2 N), for example, 0.1 g / 10 minutes, preferably 0. .2 to 30 g / 10 minutes, more preferably 0.25 to 10 g / 10 minutes, most preferably 0.3 to 5 g / 10 minutes. If the MFR is too small or too large, the foamability and strength may decrease.
熱可塑性樹脂がオレフィン系樹脂を含む場合、熱可塑性樹脂は、オレフィン系樹脂単独であってもよく、オレフィン系樹脂とオレフィン系樹脂以外の熱可塑性樹脂（他の熱可塑性樹脂）との組み合わせであってもよい。オレフィン系樹脂と組み合わせる他の熱可塑性樹脂としては、発泡体の剛性を向上できる点から、スチレン系樹脂が好ましく、発泡体の柔軟性を向上できる点から、熱可塑性エラストマー（例えば、オレフィン系熱可塑性エラストマー、スチレン系熱可塑性エラストマーなど）が好ましい。 When the thermoplastic resin contains an olefin resin, the thermoplastic resin may be an olefin resin alone, or may be a combination of the olefin resin and a thermoplastic resin other than the olefin resin (other thermoplastic resin). You may. As another thermoplastic resin to be combined with the olefin resin, a styrene resin is preferable from the viewpoint of improving the rigidity of the foam, and a thermoplastic elastomer (for example, olefin thermoplastic) can be improved from the viewpoint of improving the flexibility of the foam. Elastomers, styrene-based thermoplastic elastomers, etc.) are preferable.
オレフィン系樹脂と他の熱可塑性樹脂との質量割合は、オレフィン系樹脂／他の熱可塑性樹脂＝１００／０〜１０／９０（例えば１００／０〜５０／５０）程度の範囲から選択でき、他の熱可塑性樹脂と組み合わせる場合、オレフィン系樹脂／他の熱可塑性樹脂＝９９／１〜３０／７０、好ましくは９８／２〜５０／５０、さらに好ましくは９５／５〜７０／３０、最も好ましくは９３／７〜８０／２０である。オレフィン系樹脂の割合は、熱可塑性樹脂中５０質量％以上が好ましく、さらに好ましくは８０質量％以上（特に９０質量％以上）であり、１００質量％（オレフィン系樹脂のみ）であってもよい。オレフィン系樹脂の割合が少なすぎると、発泡性が低下する虞がある。 The mass ratio of the olefin resin to the other thermoplastic resin can be selected from the range of olefin resin / other thermoplastic resin = 100/0 to 10/90 (for example, 100/0 to 50/50). When combined with the thermoplastic resin of, olefin resin / other thermoplastic resin = 99/1 to 30/70, preferably 98/2 to 50/50, more preferably 95/5 to 70/30, most preferably. It is 93/7 to 80/20. The proportion of the olefin-based resin is preferably 50% by mass or more, more preferably 80% by mass or more (particularly 90% by mass or more), and 100% by mass (only the olefin-based resin) in the thermoplastic resin. If the proportion of the olefin resin is too small, the foamability may decrease.
樹脂成分は、耐久性などが要求される用途では、熱可塑性樹脂の架橋体であってもよい。架橋体は、熱可塑性樹脂の種類に応じて慣用の架橋体を利用できる。熱可塑性樹脂がオレフィン系樹脂である場合、架橋体は、慣用のオレフィン樹脂架橋体、例えば、水架橋体、化学架橋体、放射線架橋体、電子線架橋体であってもよい。これらのうち、架橋性や生産性などの点から、水架橋体が好ましい。 The resin component may be a crosslinked body of a thermoplastic resin in applications where durability or the like is required. As the crosslinked body, a conventional crosslinked body can be used depending on the type of the thermoplastic resin. When the thermoplastic resin is an olefin resin, the crosslinked product may be a conventional olefin resin crosslinked product, for example, a water crosslinked product, a chemical crosslinked product, a radiation crosslinked product, or an electron beam crosslinked product. Of these, a water crosslinked product is preferable from the viewpoint of crosslinkability and productivity.
水架橋体は、水架橋可能な加水分解縮合性のシリル基（水架橋性シリル基）を有するオレフィン系樹脂の水架橋体であればよく、主鎖を構成する単量体として、加水分解縮合性のシリル基を有する単量体を用いて得られた重合体の架橋体であってもよく、オレフィン系樹脂の主鎖に加水分解縮合性のシリル基を有する単量体をグラフト重合させた重合体であってもよい。このようなオレフィン系樹脂の水架橋体としては、例えば、特開２０１６−３７５５１号公報、特開２０１６−３７５５２号公報に記載の水架橋体などを利用できる。 The water-crosslinked product may be a water-crosslinked product of an olefin resin having a hydrocrosslinkable silyl group (hydrocrosslinkable silyl group), and is hydrolyzed and condensed as a monomer constituting the main chain. It may be a crosslinked product of a polymer obtained by using a monomer having a sex silyl group, and a monomer having a hydrolysis condensable silyl group is graft-polymerized on the main chain of an olefin resin. It may be a polymer. As the water-crosslinked product of such an olefin resin, for example, the water-crosslinked product described in JP-A-2016-37551 and JP-A-2016-37552 can be used.
［酸化ジルコニウム］
本発明の発泡体は、発泡体に温感性を付与できる酸化ジルコニウム（ジルコニアまたは二酸化ジルコニウム）を含む。酸化ジルコニウムは、遠赤外線を吸収して放出する作用を有するため、発泡体に保温性などの温感性を付与できる。また、本発明では、樹脂成分中に分散相として酸化ジルコニウムを含むことにより、発泡体の緩衝性、柔軟性を損なうことなく、温感性を付与できる。特に、マトリックスとしての樹脂成分中に酸化ジルコニウムが分散相として微分散することにより、少量であっても、発泡体に対して、高い温感性を付与できるとともに、高い発泡性および機械的特性も付与できる。
[Zirconium oxide]
The foam of the present invention contains zirconium oxide (zirconia or zirconium dioxide) that can impart warmth to the foam. Since zirconium oxide has a function of absorbing and emitting far infrared rays, it is possible to impart warmth such as heat retention to the foam. Further, in the present invention, by including zirconium oxide as a dispersed phase in the resin component, warmth can be imparted without impairing the cushioning property and flexibility of the foam. In particular, by finely dispersing zirconium oxide as a dispersed phase in the resin component as a matrix, it is possible to impart high warmth to the foam even in a small amount, and also impart high foamability and mechanical properties. it can.
マトリックス中で微分散した分散相（酸化ジルコニウム）の平均径は１０μｍ以下（例えば０．０１〜１０μｍ程度）であればよく、例えば０．１〜５μｍ、好ましくは０．３〜３μｍ、さらに好ましくは０．５〜２μｍ、最も好ましくは１〜１．５μｍである。分散相の平均径は、ナノメータサイズであってもよく、例えば１００ｎｍ以下であってもよく、好ましくは５０ｎｍ以下、さらに好ましくは３０ｎｍ以下（例えば０．１〜１０ｎｍ程度）であってもよい。なお、分散相が異方形状である場合、各分散相の径は、長径と短径との平均値を意味する。 The average diameter of the dispersed phase (zirconium oxide) finely dispersed in the matrix may be 10 μm or less (for example, about 0.01 to 10 μm), for example, 0.1 to 5 μm, preferably 0.3 to 3 μm, and more preferably 0.3 to 3 μm. It is 0.5 to 2 μm, most preferably 1 to 1.5 μm. The average diameter of the dispersed phase may be nanometer size, for example, 100 nm or less, preferably 50 nm or less, and more preferably 30 nm or less (for example, about 0.1 to 10 nm). When the dispersed phase has an anisotropic shape, the diameter of each dispersed phase means the average value of the major axis and the minor axis.
さらに、マトリックス中で微分散した分散相（酸化ジルコニウム）は、温感性を向上できる点から、空隙の壁面および／またはスキン層付近に局在化しているのが好ましい。 Further, the dispersed phase (zirconium oxide) finely dispersed in the matrix is preferably localized near the wall surface of the void and / or the skin layer from the viewpoint of improving the warmth.
本明細書および特許請求の範囲において、分散相の平均径および分散状態は、走査型電子顕微鏡（ＳＥＭ）の観察及びエネルギー分散型Ｘ線分光器による元素分析（ＥＤＳ元素分析）に基づいて測定でき、詳細には、後述の実施例に記載の方法で測定できる。 Within the scope of this specification and patent claims, the average diameter and dispersed state of the dispersed phase can be measured based on observation by a scanning electron microscope (SEM) and elemental analysis by an energy dispersive X-ray spectrometer (EDS elemental analysis). , In detail, it can be measured by the method described in Examples described later.
酸化ジルコニウムは、温感性や分散性などの点から、表面処理されていない酸化ジルコニウムが好ましい。 As the zirconium oxide, unsurface-treated zirconium oxide is preferable from the viewpoint of warmth and dispersibility.
本発明では、酸化ジルコニウムの割合は、比較的少量であるため、発泡体の発泡性や機械特性を向上できる。具体的には、発泡体中の酸化ジルコニウムの割合は１０質量％以下（例えば０．００１〜１０質量％程度）であってもよいが、少量でも機能性を発現できるため、発泡体本来の前記特性を向上させる観点から、５質量％以下（例えば０．０１〜５質量％）であってもよく、例えば０．０３〜５質量％（例えば０．０５〜４質量％）、好ましくは０．１〜３質量％（例えば０．２〜２質量％）、さらに好ましくは０．３〜１．５質量％、最も好ましくは０．５〜１質量％である。酸化ジルコニウムの割合は、樹脂成分１００質量部に対して０．０１〜８質量部であり、好ましくは０．０１〜５質量部、さらに好ましくは０．１〜３質量部、より好ましくは０．３〜２質量部、最も好ましくは０．５〜１．５質量部である。酸化ジルコニウムの割合が多すぎると、発泡体の発泡性や機械的特性が低下する虞がある。 In the present invention, since the proportion of zirconium oxide is relatively small, the foamability and mechanical properties of the foam can be improved. Specifically, the proportion of zirconium oxide in the foam may be 10% by mass or less (for example, about 0.001 to 10% by mass), but since functionality can be exhibited even in a small amount, the original foam From the viewpoint of improving the characteristics, it may be 5% by mass or less (for example, 0.01 to 5% by mass), for example, 0.03 to 5% by mass (for example, 0.05 to 4% by mass), preferably 0. It is 1 to 3% by mass (for example, 0.2 to 2% by mass), more preferably 0.3 to 1.5% by mass, and most preferably 0.5 to 1% by mass. The ratio of zirconium oxide is 0.01 to 8 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and more preferably 0. parts by mass with respect to 100 parts by mass of the resin component. It is 3 to 2 parts by mass, most preferably 0.5 to 1.5 parts by mass. If the proportion of zirconium oxide is too high, the foamability and mechanical properties of the foam may deteriorate.
［酸化ケイ素］
本発明の発泡体は、樹脂成分および酸化ジルコニウムに加えて、酸化ジルコニウムの分散性を向上できる点から、酸化ケイ素（シリカまたは二酸化ケイ素）をさらに含んでいてもよい。
[Silicon oxide]
In addition to the resin component and zirconium oxide, the foam of the present invention may further contain silicon oxide (silica or silicon dioxide) from the viewpoint of improving the dispersibility of zirconium oxide.
酸化ケイ素（シリカ）としては、例えば、フュームドシリカなどの乾式シリカ（乾式法ホワイトカーボン）；コロイダルシリカ、シリカゲル、沈降シリカなどの湿式シリカ（湿式法ホワイトカーボン）などが挙げられる。これらの酸化ケイ素は、単独でまたは二種以上組み合わせて使用できる。酸化ケイ素は、表面処理されたシリカであってもよい。これらのシリカのうち、シリカゲルが好ましく、Ｂ型シリカゲルが特に好ましい。 Examples of silicon oxide (silica) include dry silica (dry white carbon) such as fumed silica; wet silica (wet white carbon) such as colloidal silica, silica gel, and precipitated silica. These silicon oxides can be used alone or in combination of two or more. The silicon oxide may be surface-treated silica. Of these silica gels, silica gel is preferable, and B-type silica gel is particularly preferable.
酸化ケイ素の粒径は、篩分け法によるメッシュ通過粒子として、例えば１０００μｍ以下、好ましくは５００μｍ以下、さらに好ましくは１００μｍ以下、最も好ましくは５０μｍ以下である。シリカの粒径が大きすぎると、発泡体の機械的特性が低下する虞がある。 The particle size of silicon oxide is, for example, 1000 μm or less, preferably 500 μm or less, more preferably 100 μm or less, and most preferably 50 μm or less as the mesh-passing particles by the sieving method. If the particle size of silica is too large, the mechanical properties of the foam may deteriorate.
酸化ケイ素は、非多孔質または多孔質のいずれであってもよいが、ＢＥＴ法による窒素吸着比表面積は、例えば１００〜１０００ｍ２／ｇ、好ましくは２００〜８００ｍ２／ｇ、さらに好ましくは３００〜７００ｍ２／ｇ、最も好ましくは４００〜６００ｍ２／ｇである。比表面積が大きすぎると、均一に分散するのが困難となる虞があり、比表面積が小さすぎると、発泡体の機械的特性が低下する虞がある。 The silicon oxide may be either non-porous or porous, but the nitrogen adsorption specific surface area by the BET method is, for example, 100 to 1000 m 2 / g, preferably 200 to 800 m 2 / g, and more preferably 300 to 300. 700m 2 / g, most preferably 400-600m 2 / g. If the specific surface area is too large, it may be difficult to disperse uniformly, and if the specific surface area is too small, the mechanical properties of the foam may deteriorate.
酸化ケイ素の割合は、酸化ジルコニウム１００質量部に対して１０質量部以上であってもよく、例えば１０〜５０００質量部、好ましくは５０〜３０００質量部、さらに好ましくは１００〜１０００質量部、より好ましくは２００〜５００質量部、最も好ましくは２５０〜４００質量部である。酸化ケイ素の割合が少なすぎると、酸化ジルコニウムの分散性を向上させる効果が低下する虞がある。 The ratio of silicon oxide may be 10 parts by mass or more with respect to 100 parts by mass of zirconium oxide, for example, 10 to 5000 parts by mass, preferably 50 to 3000 parts by mass, and more preferably 100 to 1000 parts by mass. Is 200 to 500 parts by mass, most preferably 250 to 400 parts by mass. If the proportion of silicon oxide is too small, the effect of improving the dispersibility of zirconium oxide may be reduced.
［発泡剤］
本発明の発泡体は、前記樹脂成分および酸化ジルコニウムを含む発泡性樹脂組成物を発泡して得られ、発泡性樹脂組成物は、発泡剤を含んでいてもよい。
[Blowing agent]
The foam of the present invention is obtained by foaming a foamable resin composition containing the resin component and zirconium oxide, and the foamable resin composition may contain a foaming agent.
発泡剤としては、慣用の発泡剤を使用でき、分解性発泡剤（化学発泡剤）であってもよいが、簡便な方法で、発泡倍率を向上できる点から、揮発性発泡剤（物理発泡剤）が好ましい。揮発性発泡剤としては、例えば、無機系発泡剤（窒素、二酸化炭素、酸素、空気、水など）、有機系発泡剤（脂肪族炭化水素、脂環族炭化水素、芳香族炭化水素、塩素化炭化水素、フッ化炭化水素、アルコール類、エーテル類、アルデヒド類、ケトン類など）などが挙げられる。これらのうち、安価で毒性が低い点から、ブタン（ｎ−ブタン、イソブタンなど）やペンタン（ｎ−ペンタン、イソペンタンなど）などの低級脂肪族炭化水素が汎用される。 As the foaming agent, a conventional foaming agent can be used, and a degradable foaming agent (chemical foaming agent) may be used, but a volatile foaming agent (physical foaming agent) can be used because the foaming ratio can be improved by a simple method. ) Is preferable. Examples of the volatile foaming agent include inorganic foaming agents (nitrogen, carbon dioxide, oxygen, air, water, etc.) and organic foaming agents (aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorination). Hydrocarbons, fluorinated hydrocarbons, alcohols, ethers, aldehydes, ketones, etc.) and the like. Of these, lower aliphatic hydrocarbons such as butane (n-butane, isobutane, etc.) and pentane (n-pentane, isopentane, etc.) are widely used because they are inexpensive and have low toxicity.
発泡剤の割合は、樹脂成分１００質量部に対して、例えば０．０１〜３０質量部、好ましくは０．１〜２５質量部、さらに好ましくは１〜２０質量部、最も好ましくは５〜１５質量部である。 The ratio of the foaming agent is, for example, 0.01 to 30 parts by mass, preferably 0.1 to 25 parts by mass, more preferably 1 to 20 parts by mass, and most preferably 5 to 15 parts by mass with respect to 100 parts by mass of the resin component. It is a department.
［発泡核剤］
本発明の発泡体は、発泡核剤をさらに含んでいてもよい。発泡核剤としては、例えば、ケイ素化合物（タルク、シリカ、ゼオライトなど）、無機酸塩（重炭酸ナトリウム、炭酸カルシウム、炭酸マグネシウム、炭酸水素ナトリウム、炭酸アンモニウムなどの炭酸塩または炭酸水素塩など）、有機酸またはその塩（クエン酸、クエン酸ナトリウム、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸亜鉛など）、金属酸化物（酸化亜鉛、酸化チタン、酸化アルミニウムなど）、金属水酸化物（水酸化アルミニウムなど）などが挙げられる。これらの発泡核剤は、単独でまたは二種以上組み合わせて使用できる。
[Effervescent nucleating agent]
The foam of the present invention may further contain a foam nucleating agent. Examples of the foam nucleating agent include silicon compounds (talc, silica, zeolite, etc.), inorganic acid salts (carbonate or hydrogen carbonate such as sodium bicarbonate, calcium carbonate, magnesium carbonate, sodium hydrogen carbonate, ammonium carbonate, etc.). Organic acids or salts thereof (citrate, sodium citrate, calcium stearate, aluminum stearate, zinc stearate, etc.), metal oxides (zinc oxide, titanium oxide, aluminum oxide, etc.), metal hydroxides (aluminum hydroxide, etc.) ) And so on. These effervescent nucleating agents can be used alone or in combination of two or more.
発泡核剤の割合は、樹脂成分１００質量部に対して、例えば０．０１〜１０質量部、好ましくは０．０５〜５質量部、さらに好ましくは０．１〜３質量部、最も好ましくは０．５〜２質量部である。 The ratio of the foam nucleating agent is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and most preferably 0, with respect to 100 parts by mass of the resin component. .5-2 parts by mass.
［収縮防止剤］
本発明の発泡体は、収縮防止剤をさらに含んでいてもよい。収縮防止剤としては、例えば、脂肪酸エステル（パルミチン酸モノないしトリグリセリド、ステアリン酸モノないしトリグリセリドなどのＣ８−２４脂肪酸と多価アルコールとのエステルなど）、脂肪酸アミド（パルミチン酸アミド、ステアリン酸アミドなどのＣ８−２４脂肪酸アミドなど）などが挙げられる。これらの収縮防止剤は、単独でまたは二種以上組み合わせて使用できる。
[Shrink inhibitor]
The foam of the present invention may further contain an antioxidant. Examples of the shrinkage inhibitor include fatty acid esters (esters of C8-24 fatty acids such as palmitic acid mono or triglyceride, stearic acid mono or triglyceride and polyhydric alcohols), fatty acid amides (palmitic acid amides, stearic acid amides, etc.). C 8-24 fatty acid amide, etc.) and the like. These anti-shrinkage agents can be used alone or in combination of two or more.
収縮防止剤の割合は、樹脂成分１００質量部に対して、例えば０．０１〜３０質量部、好ましくは０．０５〜２０質量部、さらに好ましくは０．１〜１０質量部、最も好ましくは１〜５質量部である。 The ratio of the shrinkage inhibitor is, for example, 0.01 to 30 parts by mass, preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and most preferably 1 with respect to 100 parts by mass of the resin component. ~ 5 parts by mass.
［他の添加剤］
本発明の発泡体は、他の添加剤として、慣用の添加剤をさらに含んでいてもよい。慣用の添加剤としては、着色剤（染料や顔料など）、表面平滑剤、気泡調整剤、安定剤（酸化防止剤、熱安定化剤、紫外線吸収剤など）、粘度調節剤、相溶化剤、分散剤、帯電防止剤、ブロッキング防止剤、防曇剤、充填剤（炭酸カルシウム、炭素繊維など）、滑剤、離型剤、潤滑剤、衝撃改良剤、可塑剤、難燃剤、バイオサイド（殺菌剤、静菌剤、抗かび剤、防腐剤、防虫剤など）、坑アレルギー剤、消臭剤などが挙げられる。これら慣用の添加剤は、単独でまたは二種以上組み合わせて使用できる。
[Other additives]
The foam of the present invention may further contain a conventional additive as another additive. Conventional additives include colorants (dye, pigment, etc.), surface smoothers, bubble conditioners, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), viscosity modifiers, compatibilizers, etc. Dispersants, antistatics, antiblocking agents, antifogging agents, fillers (calcium carbonate, carbon fibers, etc.), lubricants, mold release agents, lubricants, impact improvers, plasticizers, flame retardants, biosides (bactericidal agents) , Bacteriostatic agents, antifungal agents, preservatives, insect repellents, etc.), anti-allergic agents, deodorants, etc. These conventional additives can be used alone or in combination of two or more.
他の添加剤の合計割合は、樹脂成分１００質量部に対して、例えば０．０１〜３０質量部、好ましくは０．０５〜２０質量部、さらに好ましくは０．１〜１０質量部、最も好ましくは１〜５質量部である。 The total ratio of the other additives is, for example, 0.01 to 30 parts by mass, preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, most preferably, with respect to 100 parts by mass of the resin component. Is 1 to 5 parts by mass.
［発泡体の特性］
本発明の発泡体は、発泡性が低下することを理由に従来は積極的に添加されていなかった無機化合物を含んでいるにも拘わらず、発泡性を向上できる。具体的な発泡倍率は、３倍以上（特に１０倍以上）であればよく、例えば３〜１００倍、好ましくは５〜８０倍、さらに好ましくは１０〜５０倍、より好ましくは１５〜４０倍、最も好ましくは２０〜３０倍である。発泡倍率が低すぎると、緩衝性や柔軟性が低下する虞がある。
[Characteristics of foam]
The foam of the present invention can improve the foamability even though it contains an inorganic compound which has not been positively added in the past because of the decrease in foamability. The specific foaming ratio may be 3 times or more (particularly 10 times or more), for example, 3 to 100 times, preferably 5 to 80 times, more preferably 10 to 50 times, and more preferably 15 to 40 times. Most preferably, it is 20 to 30 times. If the foaming ratio is too low, the cushioning property and flexibility may decrease.
本発明の発泡体は、独立気泡および／または連続気泡構造を有しており、少なくとも独立気泡構造を含むのが好ましく、気泡全体（連続気泡と独立気泡との合計）に対する連続気泡の割合である連続気泡率は９０体積％以下であってもよく、例えば０．１〜９０体積％、好ましくは１〜８０体積％、さらに好ましくは３〜５０体積％、最も好ましくは５〜４０体積％である。連続気泡率が高すぎると、発泡体の機械的特性が低下する虞がある。本発明では、酸化ジルコニウムが熱可塑性樹脂中に微分散しているため、独立発泡が困難な無機化合物である酸化ジルコニウムを用いているにも拘わらず、このような高い独立気泡率を実現できる。一方、柔軟性が要求される用途では、連続気泡率の高い発泡体であってもよく、例えば連続気泡率が９０体積％を超える発泡体であってもよい。連続気泡率は、例えば、マスターバッチ以外の樹脂成分の組成を変更することによって調整してもよい。 The foam of the present invention has a closed cell structure and / or an open cell structure, and preferably contains at least a closed cell structure, which is the ratio of open cells to the total cells (total of open cells and closed cells). The open cell ratio may be 90% by volume or less, for example, 0.1 to 90% by volume, preferably 1 to 80% by volume, more preferably 3 to 50% by volume, and most preferably 5 to 40% by volume. .. If the open cell ratio is too high, the mechanical properties of the foam may deteriorate. In the present invention, since zirconium oxide is finely dispersed in the thermoplastic resin, such a high closed cell ratio can be realized even though zirconium oxide, which is an inorganic compound that is difficult to independently foam, is used. On the other hand, in applications where flexibility is required, a foam having a high open cell ratio may be used, and for example, a foam having an open cell ratio of more than 90% by volume may be used. The open cell ratio may be adjusted, for example, by changing the composition of the resin component other than the masterbatch.
本発明の発泡体の平均気泡径は、例えば０．２〜２ｍｍ、好ましくは０．３〜１．８ｍｍ、さらに好ましくは０．４〜１．６ｍｍ、最も好ましくは０．５〜１．３ｍｍである。平均気泡径が小さすぎると、発泡倍率を高くするのが困難となる虞があり、大きすぎると、機械的特性が低下する虞がある。 The average cell diameter of the foam of the present invention is, for example, 0.2 to 2 mm, preferably 0.3 to 1.8 mm, more preferably 0.4 to 1.6 mm, and most preferably 0.5 to 1.3 mm. is there. If the average cell diameter is too small, it may be difficult to increase the foaming ratio, and if it is too large, the mechanical properties may deteriorate.
本発明の発泡体は、表面にスキン層を有するのが好ましく、全表面に対するスキン層の被覆率は６０面積％以上（特に８０面積％以上）であってもよく、好ましくは９０面積％以上であってもよく、１００面積％（全表面がスキン層）であってもよい。スキン層は、発泡体の表面において、略均一な厚みで延びる非発泡層を意味する。 The foam of the present invention preferably has a skin layer on the surface, and the coverage of the skin layer on the entire surface may be 60 area% or more (particularly 80 area% or more), preferably 90 area% or more. It may be 100 area% (the entire surface is a skin layer). The skin layer means a non-foamed layer extending with a substantially uniform thickness on the surface of the foam.
スキン層の平均厚みは、０．００１〜１ｍｍ程度の範囲から選択でき、例えば０．００５〜０．１ｍｍ、好ましくは０．００８〜０．０５ｍｍ、さらに好ましくは０．０１〜０．０３ｍｍ、最も好ましくは０．０１２〜０．０２５ｍｍである。スキン層の平均厚みが薄すぎると、取り扱い性が低下する虞があり、逆に厚すぎると、発泡性が低下する虞がある。 The average thickness of the skin layer can be selected from the range of about 0.001 to 1 mm, for example, 0.005 to 0.1 mm, preferably 0.008 to 0.05 mm, more preferably 0.01 to 0.03 mm, most preferably. It is preferably 0.012 to 0.025 mm. If the average thickness of the skin layer is too thin, the handleability may be lowered, and conversely, if it is too thick, the foamability may be lowered.
なお、本明細書および特許請求の範囲において、発泡倍率、連続気泡率、平均気泡径およびスキン層の平均厚みは、後述の実施例に記載の方法で測定できる。 In the present specification and claims, the expansion ratio, the open cell ratio, the average cell diameter and the average thickness of the skin layer can be measured by the methods described in Examples described later.
本発明の発泡体は、熱を放出可能な温感発泡体であってもよい。特に、本発明の温感発泡体は、波長１０μｍ以上の遠赤外線の吸収および放出性に優れており、なかでも波長１０〜２０μｍ程度の遠赤外線の吸収および放出性に優れているため、人体に対して暖かさを有効に付与できる。 The foam of the present invention may be a warm foam capable of releasing heat. In particular, the warm foam of the present invention is excellent in absorption and emission of far infrared rays having a wavelength of 10 μm or more, and particularly excellent in absorption and emission of far infrared rays having a wavelength of about 10 to 20 μm, so that it is suitable for the human body. On the other hand, warmth can be effectively given.
［発泡体の製造方法］
本発明の発泡体の製造方法は、原料樹脂成分（未発泡の熱可塑性樹脂）および酸化ジルコニウムを含む発泡性樹脂組成物を発泡成形する方法であればよく、慣用の方法を利用できるが、通常、前記樹脂組成物を溶融混練し、発泡成形する方法を利用できるが、発泡性樹脂組成物として、原料樹脂成分中に酸化ジルコニウムが微分散した発泡性樹脂組成物を用いるのが好ましい。
[Manufacturing method of foam]
The method for producing the foam of the present invention may be any method as long as it is a method of foam-molding a foamable resin composition containing a raw material resin component (unfoamed thermoplastic resin) and zirconium oxide, and a conventional method can be used. Although a method of melt-kneading the resin composition and foam molding can be used, it is preferable to use a foamable resin composition in which zirconium oxide is finely dispersed in the raw material resin component as the foamable resin composition.
発泡性樹脂組成物中に微分散している酸化ジルコニウムの平均径は、１００ｎｍ未満であってもよく、好ましくは５０ｎｍ以下、さらに好ましくは３０ｎｍ以下（例えば０．１〜１０ｎｍ程度）であってもよく、分散相は分子または原子単位でマトリックス中に分散するのが特に好ましい。本発明では、発泡前の樹脂組成物として、このように酸化ジルコニウムが微分散した組成物を用いるため、得られた発泡体においても、酸化ジルコニウムを微分散できるとともに、酸化ジルコニウムを空隙の壁面および／またはスキン層付近に局在化できる。 The average diameter of zirconium oxide finely dispersed in the foamable resin composition may be less than 100 nm, preferably 50 nm or less, and more preferably 30 nm or less (for example, about 0.1 to 10 nm). Often, the dispersed phase is particularly preferably dispersed in the matrix on a molecular or atomic basis. In the present invention, since the composition in which zirconium oxide is finely dispersed is used as the resin composition before foaming, zirconium oxide can be finely dispersed even in the obtained foam, and zirconium oxide can be finely dispersed on the wall surface of the voids. / Or can be localized near the skin layer.
酸化ジルコニウムが微分散した発泡性樹脂組成物の調製方法としては、酸化ジルコニウムを溶媒に溶解または分散させた状態で、加熱した前記原料樹脂成分（特にオレフィン系樹脂）と混合し、前記原料樹脂成分が溶融した状態の樹脂組成物から前記溶媒を気体の状態で除去することにより得られる。原料の酸化ジルコニウムは、ナノメータサイズであってもよい。酸化ジルコニウムを溶解または分散する溶媒としては、例えば、水、水性有機溶媒（例えば、エタノール、イソプロパノールなどの低級アルコール、アセトンなどのケトンなど）などが挙げられる。これらの溶媒のうち、水が好ましい。水分散液の濃度は、例えば１０〜５０質量％、好ましくは２０〜４０質量％程度である。酸化ケイ素をさらに含む場合は、酸化ジルコニウム分散液とともに、または別々に、酸化ケイ素をドライブレンドで混合してもよい。詳細には、酸化ジルコニウムが微分散した発泡性樹脂組成物は、特開２０１６−２１６５７３号公報に記載の方法で調製でき、例えば、酸化ジルコニウムを前記溶媒に分散した溶液と、前記原料樹脂成分とを押出機（例えば、一軸またはベント式二軸押出機など）に供給した後、溶融した原料樹脂成分および前記溶液は、複数枚の回転可能な混練プレートを有する混練分散部に送られる。混練分散部では、溶融した原料樹脂成分と前記溶液とは、回転する混練プレートにより、均一に混合された後、減圧ラインから溶媒が気体の状態で除去されることにより、前記原料樹脂成分中に酸化ジルコニウムが平均分散径１００ｎｍ未満で微分散した発泡性樹脂組成物が調製される。 As a method for preparing a foamable resin composition in which zirconium oxide is finely dispersed, zirconium oxide is dissolved or dispersed in a solvent and mixed with a heated raw material resin component (particularly an olefin resin) to prepare the raw material resin component. It is obtained by removing the solvent in a gaseous state from the resin composition in a molten state. The raw material zirconium oxide may be of nanometer size. Examples of the solvent that dissolves or disperses zirconium oxide include water, an aqueous organic solvent (for example, a lower alcohol such as ethanol and isopropanol, a ketone such as acetone, and the like). Of these solvents, water is preferred. The concentration of the aqueous dispersion is, for example, 10 to 50% by mass, preferably about 20 to 40% by mass. If silicon oxide is further included, silicon oxide may be mixed in a dry blend with or separately from the zirconium oxide dispersion. Specifically, the effervescent resin composition in which zirconium oxide is finely dispersed can be prepared by the method described in JP-A-2016-216573. For example, a solution in which zirconium oxide is dispersed in the solvent and the raw material resin component are used. Is fed to an extruder (eg, a single-screw or bent twin-screw extruder), and then the molten raw material resin component and the solution are sent to a kneading dispersion having a plurality of rotatable kneading plates. In the kneading and dispersing portion, the melted raw material resin component and the solution are uniformly mixed by a rotating kneading plate, and then the solvent is removed from the decompression line in a gaseous state into the raw material resin component. A foamable resin composition in which zirconium oxide is finely dispersed with an average dispersion diameter of less than 100 nm is prepared.
得られた発泡性樹脂組成物は、そのまま発泡成形に供してもよいが、マスターバッチとして発泡成形に供してもよい。発泡性樹脂組成物がマスターバッチとして利用される場合には、溶媒が除去された樹脂組成物は、さらに冷却してペレットなどの形態に調製してもよい。 The obtained foamable resin composition may be subjected to foam molding as it is, or may be subjected to foam molding as a master batch. When the foamable resin composition is used as a masterbatch, the resin composition from which the solvent has been removed may be further cooled and prepared in the form of pellets or the like.
マスターバッチとして供される場合、第１の原料樹脂成分（特に、第１のオレフィン系樹脂）中に酸化ジルコニウムが平均分散径１００ｎｍ未満で微分散したマスターバッチと、残部の原料樹脂成分である第２の原料樹脂成分（特に第２のオレフィン系樹脂）とは、慣用の溶融混練機、例えば、一軸またはベント式二軸押出機などを用いて溶融混練してもよい。また、マスターバッチと第２の原料樹脂成分との溶融混練において、他の成分（発泡剤および必要に応じて発泡核剤、添加剤など）を配合してもよい。酸化ジルコニウムが微分散した発泡性樹脂組成物の溶融混練は、慣用の溶融混練機、例えば、一軸またはベント式二軸押出機などを用いて溶融混練してもよい。また、溶融混練に先だって、慣用の方法、例えば、混合機（タンブラー、Ｖ型ブレンダー、ヘンシェルミキサー、ナウタミキサー、リボンミキサー、メカノケミカル装置、押出混合機など）を用いて、前記マスターバッチと、第２の原料樹脂成分と、他の成分（発泡剤及び必要に応じて発泡核剤、添加剤など）とを予備混合してもよい。 When provided as a masterbatch, a masterbatch in which zirconium oxide is finely dispersed in a first raw material resin component (particularly, a first olefin resin) with an average dispersion diameter of less than 100 nm, and a remaining raw material resin component. The raw material resin component (particularly the second olefin resin) of 2 may be melt-kneaded using a conventional melt-kneader, for example, a uniaxial or bent twin-screw extruder. Further, in the melt-kneading of the master batch and the second raw material resin component, other components (foaming agent and, if necessary, foaming nucleating agent, additive, etc.) may be blended. The melt-kneading of the foamable resin composition in which zirconium oxide is finely dispersed may be melt-kneaded using a conventional melt-kneader, for example, a uniaxial or bent twin-screw extruder. In addition, prior to melt-kneading, a conventional method, for example, a mixer (tumbler, V-type blender, Henschel mixer, Nauta mixer, ribbon mixer, mechanochemical device, extrusion mixer, etc.) is used to perform the masterbatch and the first. The raw material resin component of 2 and other components (foaming agent and, if necessary, foaming nucleating agent, additive, etc.) may be premixed.
発泡成形法としては、慣用の方法、例えば、押出成形法（例えば、Ｔダイ法、インフレーション法など）、射出成形法などが使用できる。これらのうち、高い発泡性を有する発泡体を高い生産性で製造できる点から、押出成形法が好ましい。 As the foam molding method, a conventional method, for example, an extrusion molding method (for example, a T-die method, an inflation method, etc.), an injection molding method, or the like can be used. Of these, the extrusion molding method is preferable because a foam having high foamability can be produced with high productivity.
押出成形法において、押出機としては、例えば、単軸押出機（例えば、ベント式押出機など）、二軸押出機（例えば、同方向二軸押出機、異方向二軸押出機など）などが利用でき、発泡条件を調整し易く、高発泡率を実現できる点から、タンデム押出機などの多段押出機が好ましい。 In the extrusion molding method, examples of the extruder include a single-screw extruder (for example, a vent type extruder) and a twin-screw extruder (for example, a simultaneous twin-screw extruder and a different-direction twin-screw extruder). A multi-stage extruder such as a tandem extruder is preferable because it can be used, the foaming conditions can be easily adjusted, and a high foaming rate can be realized.
押出成形法において、発泡剤を導入する方法は特に限定されず、分解性発泡剤（化学発泡剤）を予め発泡性樹脂組成物に配合してもよいが、簡便な方法で、発泡倍率を向上できる点から、押出機において揮発性発泡剤（物理発泡剤）を導入するのが好ましい。 In the extrusion molding method, the method of introducing the foaming agent is not particularly limited, and a degradable foaming agent (chemical foaming agent) may be mixed in advance with the foamable resin composition, but the foaming ratio is improved by a simple method. From the possible points, it is preferable to introduce a volatile foaming agent (physical foaming agent) in the extruder.
口金の吐出口（ダイのリップ）の形状は、特に制限されず目的の形態に応じて選択でき、例えば、棒状、紐状などの一次元的形状、シート状、フィルム状、二次元網目（ネット）状などの二次元的形状、ブロック状、板状、柱状、スリット状、Ｌ字状、コ型状、パイプ状またはリング状などの三次元的形状であってもよい。 The shape of the discharge port (die lip) of the base is not particularly limited and can be selected according to the desired shape. For example, a one-dimensional shape such as a rod shape or a string shape, a sheet shape, a film shape, or a two-dimensional mesh (net). It may be a two-dimensional shape such as a) shape, a block shape, a plate shape, a columnar shape, a slit shape, an L shape, a U shape, a pipe shape, or a ring shape.
押出発泡された発泡体は、慣用の方法、例えば、冷却器を用いた冷却方法で冷却してもよい。冷却器を用いた冷却方法において、冷却媒体としては、圧縮エアー、水（冷却水）、空気（ブロア）などの冷却媒体が挙げられる。冷却方法としては、圧縮エアーを噴射する方法、ブロアで冷却する方法、水を噴霧して冷却する方法、冷却ジャケットを用いて冷却する方法などが挙げられる。冷却媒体の温度は、例えば０〜６０℃、好ましくは５〜５５℃、さらに好ましくは１０〜５０℃である。 The extruded foam may be cooled by a conventional method, for example, a cooling method using a cooler. In the cooling method using a cooler, examples of the cooling medium include cooling media such as compressed air, water (cooling water), and air (blower). Examples of the cooling method include a method of injecting compressed air, a method of cooling with a blower, a method of spraying water to cool, and a method of cooling using a cooling jacket. The temperature of the cooling medium is, for example, 0 to 60 ° C, preferably 5 to 55 ° C, and more preferably 10 to 50 ° C.
圧縮エアーを噴射する方法において、エアーの圧力は、例えば０．１〜１０ＭＰａ、好ましくは０．２〜５ＭＰａ、さらに好ましくは０．３〜１ＭＰａである。圧縮エアーの噴射量は、例えば１００〜１０００リットル／分、好ましくは２００〜５００リットル／分、さらに好ましくは２５０〜４００リットル／分である。 In the method of injecting compressed air, the pressure of air is, for example, 0.1 to 10 MPa, preferably 0.2 to 5 MPa, and more preferably 0.3 to 1 MPa. The injection amount of compressed air is, for example, 100 to 1000 liters / minute, preferably 200 to 500 liters / minute, and more preferably 250 to 400 liters / minute.
なお、樹脂成分が熱可塑性樹脂の架橋体である場合、得られた押出発泡体は架橋工程に供してもよい。水架橋体における架橋工程では、空気中の水分によりシリル変性ポリオレフィンを水架橋してもよい。架橋処理は、非加熱状態（１５〜２５程度の室温）で架橋させてもよいが、生産性を向上させるために、加熱して架橋してもよい。加熱温度は、例えば４０〜１００℃、好ましくは５０〜８０℃、さらに好ましくは５５〜７０℃である。 When the resin component is a crosslinked product of a thermoplastic resin, the obtained extruded foam may be subjected to a cross-linking step. In the cross-linking step in the water-crosslinked product, the silyl-modified polyolefin may be water-crosslinked with moisture in the air. The cross-linking treatment may be carried out in a non-heated state (room temperature of about 15 to 25), but may be cross-linked by heating in order to improve productivity. The heating temperature is, for example, 40 to 100 ° C, preferably 50 to 80 ° C, and more preferably 55 to 70 ° C.
また、必要により、得られた発泡体（特に、シート状発泡体）を二次加工［例えば、真空成形、圧空成形、真空圧空成形、マッチモールド成形などの熱成形（例えば、金型を用いる熱成形）］してもよい。 Further, if necessary, the obtained foam (particularly, sheet-like foam) is subjected to secondary processing [for example, thermoforming such as vacuum forming, compressed air forming, vacuum forming, match molding (for example, heat using a mold). Molding)] may be used.
なお、発泡成形または二次加工もしくは成形温度は、例えば７０〜３００℃、好ましくは８０〜２８０℃、さらに好ましくは８５〜２６０℃程度であってもよい。 The foam molding or secondary processing or molding temperature may be, for example, 70 to 300 ° C, preferably 80 to 280 ° C, and more preferably about 85 to 260 ° C.
発泡体の形状は、用途に応じて任意の形状に適宜選択でき、例えば、棒状、シート状、三次元形状などであってもよい。 The shape of the foam can be appropriately selected from any shape depending on the intended use, and may be, for example, a rod shape, a sheet shape, or a three-dimensional shape.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。実施例および比較例で用いた原料は以下の通りであり、得られた発泡体の特性は以下の方法で評価した。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The raw materials used in Examples and Comparative Examples were as follows, and the characteristics of the obtained foam were evaluated by the following methods.
［原料］
ＬＤＰＥ：低密度ポリエチレン、日本ポリエチレン（株）製「ノバテック（登録商標）ＬＤ ＬＦ６４０ＭＡ」、ＭＦＲ５ｇ／１０分
イソブタン（発泡剤）：市販品
発泡核剤：タルク、平均粒子径１５μｍ
収縮防止剤：ベーリンガーインゲルハイムケミカルズ（株）製「アクティベックス３２５」
酸化ジルコニウム：堺化学工業（株）製「ＳＺＲ−Ｗ」、平均粒径３ｎｍ
シリカ：豊田化工（株）製「トヨタシリカゲルＢ白４００下」、粒径３７μｍ以下（篩分け法によるメッシュ通過粒子）、ＢＥＴ比表面積４５０ｍ２／ｇ。
[material]
LDPE: Low-density polyethylene, "Novatec (registered trademark) LD LF640MA" manufactured by Japan Polyethylene Corporation, MFR 5 g / 10 minutes Isobutane (foaming agent): Commercial product Foaming nucleating agent: talc, average particle size 15 μm
Anti-shrinkage agent: "Activex 325" manufactured by Boehringer Ingelheim Chemicals Co., Ltd.
Zirconium oxide: "SZR-W" manufactured by Sakai Chemical Industry Co., Ltd., average particle size 3 nm
Silica: "Toyota silica gel B white 400 under" manufactured by Toyota Kako Co., Ltd., particle size 37 μm or less (mesh-passing particles by sieving method), BET specific surface area 450 m 2 / g.
［発泡体の目付］
直径７４ｍｍ、内径７０ｍｍの円筒状の発泡体を１ｍで切断し、電子比重計（ミラージュ貿易社製「ＭＤ２００Ｓ」）を用い、測定した（ｎ＝３）。
[Metsuke of foam]
A cylindrical foam having a diameter of 74 mm and an inner diameter of 70 mm was cut at 1 m and measured using an electronic hydrometer (“MD200S” manufactured by Mirage Trading Co., Ltd.) (n = 3).
［発泡倍率］
発泡倍率は、以下の式に基づいて算出した。
[Expansion magnification]
The foaming ratio was calculated based on the following formula.
発泡倍率（倍）＝発泡体用樹脂組成物の密度／発泡体の見掛け密度。 Foaming magnification (times) = Density of resin composition for foam / Apparent density of foam.
［連続気泡率］
実施例および比較例で得られた発泡体を、予め質量を測定し、水中に静置した後、−４００ｍｍＨｇ（ゲージ圧）の減圧下に１分間放置して、連続気泡構造の中に水を浸透させた。減圧状態から大気圧力に戻し、発泡体の表面に付着した水を除去して質量を測定した後、下記式（１）により連続気泡率を算出した。
[Continuous bubble ratio]
The foams obtained in Examples and Comparative Examples were mass-measured in advance, allowed to stand in water, and then left to stand under reduced pressure of −400 mmHg (gauge pressure) for 1 minute to allow water to enter the open cell structure. Infiltrated. After returning from the reduced pressure state to the atmospheric pressure, removing the water adhering to the surface of the foam and measuring the mass, the open cell ratio was calculated by the following formula (1).
連続気泡率（％）＝｛(ｗ２−ｗ１)／ｄ３｝／(ｗ１／ｄ１−ｗ１／ｄ２)×100 (１)
（式中、ｗ２は吸水後の発泡体質量、ｗ１は吸水前の発泡体質量、ｄ１は発泡体の見掛密度、ｄ２は発泡体に使用されている樹脂組成物の見掛密度、ｄ３は測定時の水の密度を示す）。
Continuous bubble ratio (%) = {(w 2- w 1 ) / d 3 } / (w 1 / d 1- w 1 / d 2 ) × 100 (1)
(In the formula, w 2 is the mass of the foam after water absorption, w 1 is the mass of the foam before water absorption, d 1 is the apparent density of the foam, and d 2 is the apparent density of the resin composition used for the foam. Density, d 3 indicates the density of water at the time of measurement).
［気泡径（セルサイズ）］
発泡体の断面を走査型電子顕微鏡（（株）日立製作所製「Ｓ−４８００」）またはデジタル顕微鏡（スカラ（株）製）で観察し、ＴＤ方向断面の気泡径およびＭＤ方向断面の気泡径を、それぞれ任意の１０箇所で測定し、それら２０箇所の平均値を気泡径とした。また、各々の気泡径は、長径と短径との平均値とした。
[Bubble diameter (cell size)]
Observe the cross section of the foam with a scanning electron microscope (“S-4800” manufactured by Hitachi, Ltd.) or a digital microscope (manufactured by SCARA Co., Ltd.), and determine the cell diameter in the TD direction and the bubble diameter in the MD direction. , Each of which was measured at an arbitrary 10 points, and the average value of those 20 points was taken as the bubble diameter. The diameter of each bubble was taken as the average value of the major axis and the minor axis.
［発泡体のスキン層の平均厚み］
電子顕微鏡（スカラ（株）製）およびファイリング＆２次元計測ソフトウェア（（株）アートレイ製「ＡＲ−ＣＮＶＭＦ」）を用いて、ＴＤ方向のスキン層の厚みを任意の１０箇所で測定し、平均値をスキン層の平均厚みとした。
[Average thickness of foam skin layer]
Using an electron microscope (manufactured by SCARA Co., Ltd.) and filing & two-dimensional measurement software (manufactured by Artley Co., Ltd. "AR-CNVMF"), the thickness of the skin layer in the TD direction was measured at any 10 points, and the average value was obtained. Was taken as the average thickness of the skin layer.
［温感性］
発泡体を直径３ｃｍの円形に切り取り試料を作製して、フーリエ変換赤外分光分析装置（パーキンエルマー社製「FT-IR SpectrumOne Frontier T」）を用い、測定温度４０℃で遠赤外線分光放射率を測定した。
[Warmness]
A sample is prepared by cutting the foam into a circle with a diameter of 3 cm, and the far-infrared spectroscopic emissivity is measured at a measurement temperature of 40 ° C. using a Fourier transform infrared spectroscopic analyzer (“FT-IR SpectrumOne Frontier T” manufactured by Perkin Elmer). It was measured.
比較例１
ＬＤＰＥ１００質量部、発泡核剤１．７５質量部および収縮防止剤３．０質量部を含む樹脂組成物を押出機に投入し、この押出機の途中からイソブタンガス８．０質量部を注入した後、発泡適正温度まで冷却し、先端に取り付けたリング形状の金型から押出し、発泡体を得た。得られた発泡体は、幅１０８ｍｍ、厚み１．８３ｍｍの筒状であり、目付１５ｇ／ｍ、発泡倍率２４．５倍、連続気泡率８．８％、セルサイズ１．０７ｍｍ、スキン層の平均厚み０．０２０ｍｍであった。
Comparative Example 1
A resin composition containing 100 parts by mass of LDPE, 1.75 parts by mass of foam nucleating agent and 3.0 parts by mass of shrinkage inhibitor is put into an extruder, and 8.0 parts by mass of isobutane gas is injected from the middle of the extruder. The foam was cooled to an appropriate foaming temperature and extruded from a ring-shaped mold attached to the tip to obtain a foam. The obtained foam has a tubular shape with a width of 108 mm and a thickness of 1.83 mm, a basis weight of 15 g / m, a foaming ratio of 24.5 times, an open cell ratio of 8.8%, a cell size of 1.07 mm, and an average of skin layers. The thickness was 0.020 mm.
実施例１
（酸化ジルコニウム含有マスターバッチの調製）
酸化ジルコニウム３質量部、シリカ１０質量部を、酸化ジルコニウムは３０質量％濃度のスラリーで、シリカはドライブレンドで、ＬＤＰＥ１００質量部に添加して、押し出し機（特開２０１６−２１６５７３号公報記載の押し出し機）に供給し、温度１５０〜１６０℃の条件で、溶融混練した。溶融混練部では複数枚の混練プレートが回転しており、ここでポリマーと水に分散させた機能剤は均一混合され、次いで真空（負圧）にすることで同時に水分を取り除いた。水分を除去された溶融混練物は、押出部に供給されて押し出され、冷却後、取り出され、ペレタイザーでペレット化し、酸化ジルコニウム含有マスターバッチを得た。
Example 1
(Preparation of masterbatch containing zirconium oxide)
3 parts by mass of zirconium oxide and 10 parts by mass of silica are added to 100 parts by mass of LDPE with zirconium oxide in a slurry having a concentration of 30% by mass and silica in a dry blend, and an extruder (Japanese Patent Laid-Open No. 2016-216573) is used for extrusion. It was supplied to the machine) and melt-kneaded at a temperature of 150 to 160 ° C. In the melt-kneading section, a plurality of kneading plates are rotated, and the polymer and the functional agent dispersed in water are uniformly mixed there, and then a vacuum (negative pressure) is applied to remove water at the same time. The melt-kneaded product from which water had been removed was supplied to an extrusion section, extruded, cooled, and then taken out and pelletized with a pelletizer to obtain a zirconium oxide-containing masterbatch.
（発泡体の製造）
ＬＤＰＥ９０質量部、酸化ジルコニウム含有マスターバッチ１０質量部、発泡核剤１．７５質量部および収縮防止剤３．０質量部を含む樹脂組成物を押出機に投入し、この押出機の途中からイソブタンガス８．０質量部を注入した後、発泡適正温度まで冷却し、先端に取り付けたリング形状の金型から押出し、発泡体を得た。得られた発泡体は、幅９７ｍｍ、厚み２．３７ｍｍの筒状であり、目付１５．８ｇ／ｍ、発泡倍率２４．５倍、連続気泡率５．５％、セルサイズ１．４５ｍｍ、スキン層の平均厚み０．０１５ｍｍであった。
(Manufacturing of foam)
A resin composition containing 90 parts by mass of LDPE, 10 parts by mass of a masterbatch containing zirconium oxide, 1.75 parts by mass of a foam nucleating agent and 3.0 parts by mass of an anti-shrinkage agent was put into an extruder, and isobutane gas was introduced from the middle of the extruder. After injecting 8.0 parts by mass, the mixture was cooled to an appropriate foaming temperature and extruded from a ring-shaped mold attached to the tip to obtain a foam. The obtained foam has a tubular shape with a width of 97 mm and a thickness of 2.37 mm, a basis weight of 15.8 g / m, a foaming magnification of 24.5 times, an open cell ratio of 5.5%, a cell size of 1.45 mm, and a skin layer. The average thickness was 0.015 mm.
実施例２
ＬＤＰＥ９０質量部および酸化ジルコニウム含有マスターバッチ１０質量部の代わりに、ＬＤＰＥ８０質量部および酸化ジルコニウム含有マスターバッチ２０質量部を用いる以外は実施例１と同様の方法で発泡体を製造した。得られた発泡体は、幅９８ｍｍ、厚み２．１４ｍｍの筒状であり、目付１６．２ｇ／ｍ、発泡倍率２３．０倍、連続気泡率５．０％、セルサイズ１．００ｍｍ、スキン層の平均厚み０．０１８ｍｍであった。
Example 2
A foam was produced in the same manner as in Example 1 except that 80 parts by mass of LDPE and 20 parts by mass of the masterbatch containing zirconium oxide were used instead of 90 parts by mass of LDPE and 10 parts by mass of the masterbatch containing zirconium oxide. The obtained foam has a tubular shape with a width of 98 mm and a thickness of 2.14 mm, a basis weight of 16.2 g / m, a foaming ratio of 23.0 times, an open cell ratio of 5.0%, a cell size of 1.00 mm, and a skin layer. The average thickness was 0.018 mm.
実施例３
ＬＤＰＥ９０質量部および酸化ジルコニウム含有マスターバッチ１０質量部の代わりに、ＬＤＰＥ７０質量部および酸化ジルコニウム含有マスターバッチ３０質量部を用いる以外は実施例１と同様の方法で発泡体を製造した。得られた発泡体は、幅１００ｍｍ、厚み２．１３ｍｍの筒状であり、目付１８．０ｇ／ｍ、発泡倍率１７．７倍、連続気泡率８．３％、セルサイズ１．１４ｍｍ、スキン層の平均厚み０．０１８ｍｍであった。
Example 3
A foam was produced in the same manner as in Example 1 except that 70 parts by mass of LDPE and 30 parts by mass of the masterbatch containing zirconium oxide were used instead of 90 parts by mass of LDPE and 10 parts by mass of the masterbatch containing zirconium oxide. The obtained foam has a tubular shape with a width of 100 mm and a thickness of 2.13 mm, a basis weight of 18.0 g / m, a foaming ratio of 17.7 times, an open cell ratio of 8.3%, a cell size of 1.14 mm, and a skin layer. The average thickness was 0.018 mm.
実施例４
（酸化ジルコニウム含有マスターバッチの調製）
シリカの使用量を３０質量部に変更する以外は実施例１と同様の方法で酸化ジルコニウム含有マスターバッチを得た。
Example 4
(Preparation of masterbatch containing zirconium oxide)
A zirconium oxide-containing masterbatch was obtained in the same manner as in Example 1 except that the amount of silica used was changed to 30 parts by mass.
（発泡体の製造）
ＬＤＰＥ９０質量部、酸化ジルコニウム含有マスターバッチ１０質量部、発泡核剤１．７５質量部および収縮防止剤３．０質量部を含む樹脂組成物を押出機に投入し、この押出機の途中からイソブタンガス７．７質量部を注入した後、発泡適正温度まで冷却し、先端に取り付けたリング形状の金型から押出し、発泡体を得た。得られた発泡体は、幅９３ｍｍ、厚み１．４９ｍｍの筒状であり、目付１５．０ｇ／ｍ、発泡倍率１７．７倍、連続気泡率３．３％、セルサイズ１．２０ｍｍ、スキン層の平均厚み０．０１９ｍｍであった。
(Manufacturing of foam)
A resin composition containing 90 parts by mass of LDPE, 10 parts by mass of a masterbatch containing zirconium oxide, 1.75 parts by mass of a foam nucleating agent and 3.0 parts by mass of an anti-shrinkage agent was put into an extruder, and isobutane gas was introduced from the middle of the extruder. After injecting 7.7 parts by mass, the mixture was cooled to an appropriate foaming temperature and extruded from a ring-shaped mold attached to the tip to obtain a foam. The obtained foam has a tubular shape with a width of 93 mm and a thickness of 1.49 mm, a basis weight of 15.0 g / m, a foaming ratio of 17.7 times, an open cell ratio of 3.3%, a cell size of 1.20 mm, and a skin layer. The average thickness was 0.019 mm.
実施例５
ＬＤＰＥ９０質量部および酸化ジルコニウム含有マスターバッチ１０質量部の代わりに、ＬＤＰＥ８０質量部および酸化ジルコニウム含有マスターバッチ２０質量部を用いる以外は実施例４と同様の方法で発泡体を製造した。得られた発泡体は、幅６２ｍｍ、厚み１．６６ｍｍの筒状であり、目付１３．６ｇ／ｍ、発泡倍率１４．７倍、連続気泡率９．０％、セルサイズ１．２４ｍｍ、スキン層の平均厚み０．０１７ｍｍであった。
Example 5
A foam was produced in the same manner as in Example 4 except that 80 parts by mass of LDPE and 20 parts by mass of the masterbatch containing zirconium oxide were used instead of 90 parts by mass of LDPE and 10 parts by mass of the masterbatch containing zirconium oxide. The obtained foam has a tubular shape with a width of 62 mm and a thickness of 1.66 mm, a basis weight of 13.6 g / m, a foaming ratio of 14.7 times, an open cell ratio of 9.0%, a cell size of 1.24 mm, and a skin layer. The average thickness was 0.017 mm.
比較例１および実施例１、３および５で得られた発泡体の温感性（遠赤外線の放射率）を評価した結果を表１に示す。 Table 1 shows the results of evaluating the warmth (emissivity of far infrared rays) of the foams obtained in Comparative Example 1 and Examples 1, 3 and 5.
表１の結果から明らかなように、実施例の発泡体は、比較例１の発泡体よりも遠赤外線の放射率が高い。 As is clear from the results in Table 1, the foam of Example has a higher emissivity of far infrared rays than the foam of Comparative Example 1.
本発明の発泡体は、温感性と緩衝性とを要求される各種の用途、例えば、生活用品（こたつ敷き、キッチンマット、クッションなど）、アウトドア用品（テント、野外用マットなど）、防災グッズ（カプセルテント、防寒用ジャケットなど）、ペット用品（籠、バスケットなど）、寝装寝具用品（敷布団、マットレスパッドなど）などに利用できる。 The foam of the present invention has various uses that require warmth and cushioning properties, such as daily necessities (kotatsu mattress, kitchen mat, cushion, etc.), outdoor products (tent, outdoor mat, etc.), disaster prevention goods (for example,). It can be used for capsule tents, cold protection jackets, etc.), pet supplies (baskets, baskets, etc.), bedding supplies (mattresses, mattress pads, etc.).
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| JP2018513252A (en) * | 2015-04-15 | 2018-05-24 | ダウ グローバル テクノロジーズ エルエルシー | Insulating foam having vertically elongated bubbles |
| US20190144624A1 (en) * | 2017-08-18 | 2019-05-16 | Owens Corning Intellectual Capital, Llc | Infrared attenuation agent blends |
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