JP7431871B2 - Polyolefin crosslinked foam and its manufacturing method - Google Patents
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- 239000006260 foam Substances 0.000 title claims description 53
- 229920000098 polyolefin Polymers 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 84
- 229910021529 ammonia Inorganic materials 0.000 claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 64
- 238000005187 foaming Methods 0.000 description 63
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 32
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 32
- 235000017557 sodium bicarbonate Nutrition 0.000 description 32
- 239000011521 glass Substances 0.000 description 25
- 239000004604 Blowing Agent Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- 239000004088 foaming agent Substances 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- 239000004156 Azodicarbonamide Substances 0.000 description 9
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 9
- 235000019399 azodicarbonamide Nutrition 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229920005672 polyolefin resin Polymers 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- -1 polypropylene, ethylene-propylene copolymer Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 101100023124 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mfr2 gene Proteins 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Description
本発明は、ポリオレフィン架橋発泡体とその製造方法に関する。 The present invention relates to a polyolefin crosslinked foam and a method for producing the same.
ポリオレフィン架橋発泡体は、耐久性があり、かつ耐薬品性や耐候性に優れるために、住宅の床材や壁材、建築の目地材、自動車の内装材、梱包用部材など衝撃緩衝用途に広く使用されている。
ポリオレフィン架橋発泡体の発泡は、コストや発泡体の厚み制御が容易な熱分解型発泡剤を用いる熱分解発泡で行うのが主流である。熱分解型発泡剤としては、作業性の良好なアゾジカルボンアミド（ＡＤＣＡ）系発泡剤が一般的に用いられている（特許文献１）。
Polyolefin crosslinked foam is durable and has excellent chemical and weather resistance, so it is widely used in shock-absorbing applications such as residential flooring and wall materials, building joints, automobile interior materials, and packaging materials. It is used.
Foaming of crosslinked polyolefin foams is mainly carried out by pyrolytic foaming using a pyrolytic foaming agent, which is easy to control the cost and the thickness of the foam. As a thermally decomposable blowing agent, an azodicarbonamide (ADCA) blowing agent with good workability is generally used (Patent Document 1).
しかし、アゾジカルボンアミド系発泡剤は、分解残渣としてアンモニアが発生するため、梱包用緩衝部材として使用する場合に、電子機器や医療部品、自動車の内装材、ヘッドランプなどを、ポリオレフィン系架橋発泡体に残留するアンモニアによって汚染、腐食させる問題がある。例えば、ヘッドランプにあっては、アンモニアによって曇る問題がある。さらに、アゾジカルボンアミド（ＡＤＣＡ）は分解温度が２００～２１０℃と高温度であり、発泡体の製造時に金型温度を高温にする必要があった。 However, azodicarbonamide-based foaming agents generate ammonia as a decomposition residue, so when used as packaging cushioning materials, polyolefin-based crosslinked foams are used for electronic devices, medical parts, automobile interior materials, headlamps, etc. There is a problem of contamination and corrosion caused by residual ammonia. For example, headlamps have the problem of fogging due to ammonia. Furthermore, azodicarbonamide (ADCA) has a high decomposition temperature of 200 to 210° C., so it was necessary to raise the mold temperature to a high temperature during foam production.
ポリオレフィン系架橋発泡体に残留するアンモニアの影響を抑えるために、アンモニア吸着剤を含有させてアンモニア濃度を２００ｐｐｍ～１０００ｐｐｍに減らしたオレフィン系架橋発泡体が提案されている（特許文献２）。 In order to suppress the influence of ammonia remaining in the polyolefin crosslinked foam, an olefin crosslinked foam containing an ammonia adsorbent to reduce the ammonia concentration to 200 ppm to 1000 ppm has been proposed (Patent Document 2).
しかし、アンモニア濃度を２００ｐｐｍ～１０００ｐｐｍに減らしたポリオレフィン系架橋発泡体であっても、残留するアンモニアによる汚染、腐食の問題の解決には不十分であり、更なる解決が求められている。 However, even a polyolefin crosslinked foam with a reduced ammonia concentration of 200 ppm to 1000 ppm is insufficient to solve the problems of contamination and corrosion caused by residual ammonia, and further solutions are required.
本発明は前記の点に鑑みなされたものであって、アンモニアによる汚染、腐食を防ぐことができるポリオレフィン系架橋発泡体とその製造方法の提供を目的とする。 The present invention has been made in view of the above points, and aims to provide a polyolefin crosslinked foam that can prevent contamination and corrosion caused by ammonia, and a method for producing the same.
第１の態様は、密度が２０～１６０ｋｇ／ｍ３、アンモニア濃度が０ｐｐｍ～１００ｐｐｍ、ガラス霞度が５％以下であるポリオレフィン系架橋発泡体に係る。 The first embodiment relates to a polyolefin crosslinked foam having a density of 20 to 160 kg/m 3 , an ammonia concentration of 0 ppm to 100 ppm, and a glass haze of 5% or less.
第２の態様は、第１の態様において、発泡剤は重曹及びｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの併用であることを特徴とする。 The second aspect is characterized in that in the first aspect , the blowing agent is a combination of baking soda and p,p'-oxybisbenzenesulfonyl hydrazide.
第３の態様は、密度が２０～１６０ｋｇ／ｍ３、アンモニア濃度が０ｐｐｍ～１００ｐｐｍ、ガラス霞度が５％以下であるポリオレフィン系架橋発泡体の製造方法であって、発泡剤として重曹とｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドを、重曹の量よりもｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの量を大にして併用し、一段発泡または二段発泡によって発泡倍率６～４０倍で発泡させることを特徴とするポリオレフィン系架橋発泡体の製造方法に係る。 A third aspect is a method for producing a polyolefin crosslinked foam having a density of 20 to 160 kg/m 3 , an ammonia concentration of 0 ppm to 100 ppm, and a glass haze of 5% or less, comprising baking soda as a blowing agent, p. P'-oxybisbenzenesulfonyl hydrazide is used in combination with p,p'-oxybisbenzenesulfonyl hydrazide in a larger amount than the amount of baking soda, and foaming is performed at a foaming ratio of 6 to 40 times by one-stage foaming or two-stage foaming. The present invention relates to a method for producing a polyolefin crosslinked foam, characterized in that:
第４の態様は、第３の態様において、前記発泡剤は、ｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの量／重曹の量＝５．５／４．５～７７／２３であることを特徴とする。 A fourth aspect is the third aspect , wherein the blowing agent has a ratio of p,p'-oxybisbenzenesulfonyl hydrazide amount/baking soda amount = 5.5/4.5 to 77/23. shall be.
第５の態様は、第３または第４の態様において、前記発泡剤は、ポリオレフィン系樹脂１００重量部に対して３．０～３５重量部であることを特徴とする。 A fifth aspect is the third or fourth aspect , wherein the blowing agent is 3.0 to 35 parts by weight based on 100 parts by weight of the polyolefin resin.
本発明によれば、残留するアンモニアによる汚染、腐食を防ぐことができるポリオレフィン系架橋発泡体が得られる。 According to the present invention, a polyolefin crosslinked foam can be obtained that can prevent contamination and corrosion caused by residual ammonia.
本発明のポリオレフィン系架橋発泡体は、住宅の床材や壁材、建築の目地材、自動車の内装材、梱包用部材など衝撃緩衝用途に好適なものであり、密度（ＪＩＳ Ｋ ６７６７準拠）が２０～１６０ｋｇ／ｍ３、アンモニア濃度は０ｐｐｍ～１００ｐｐｍ、ガラス霞度（ＩＳＯ６４５２準拠）が５％以下である。アンモニア濃度は、丸底フラスコ５００ｃｃにサンプルを０．１ｇ投入し、８０℃のオーブン中に２時間放置した後、取り出して放冷し、アンモニア検知管（ガステック製）にて測定した。 The polyolefin crosslinked foam of the present invention is suitable for shock-absorbing applications such as flooring and wall materials of houses, joint materials of buildings, interior materials of automobiles, and packaging materials, and has a density (according to JIS K 6767). 20 to 160 kg/m 3 , ammonia concentration is 0 ppm to 100 ppm, and glass haze (according to ISO 6452) is 5% or less. The ammonia concentration was measured by putting 0.1 g of the sample into a 500 cc round bottom flask, leaving it in an oven at 80° C. for 2 hours, then taking it out, allowing it to cool, and measuring it with an ammonia detection tube (manufactured by Gastech).
ポリオレフィン系架橋発泡体を、例えば梱包用緩衝部材として使用した場合、ポリオレフィン系架橋発泡体の密度が低すぎると、発泡体が柔軟化されすぎて形状が保持できず緩衝材として好ましくない結果となる。一方、密度が高過ぎると発泡体は硬くなって柔軟性にかけ緩衝材として好ましくない結果となる。このため、密度は２０～１６０ｋｇ／ｍ３が好ましい。
また、ポリオレフィン系架橋発泡体のアンモニア濃度が高すぎると、梱包した製品に対する汚染、腐食の問題が大きくなるため、アンモニア濃度は０ｐｐｍ～１００ｐｐｍが好ましい。
ポリオレフィン系架橋発泡体のガラス霞度が高すぎると、梱包したヘッドランプに曇りを生じ易くなるため、ガラス霞度は５％以下が好ましい。
When a polyolefin crosslinked foam is used, for example, as a cushioning material for packaging, if the density of the polyolefin crosslinked foam is too low, the foam becomes too flexible and cannot hold its shape, resulting in an undesirable result as a cushioning material. . On the other hand, if the density is too high, the foam will become hard and flexible, resulting in an undesirable use as a cushioning material. Therefore, the density is preferably 20 to 160 kg/m 3 .
Further, if the ammonia concentration in the polyolefin crosslinked foam is too high, problems of contamination and corrosion of the packaged product will increase, so the ammonia concentration is preferably 0 ppm to 100 ppm.
If the glass haze of the polyolefin crosslinked foam is too high, the packaged headlamp is likely to fog up, so the glass haze is preferably 5% or less.
ポリレフィン系架橋発泡体を形成するポリオレフィン系樹脂としては、低密度、中密度、高密度、直鎖状低密度などのポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体、エチレン－ブテン共重合体、エチレン－酢酸ビニル共重合体、エチレンとメチル、エチル、プロピル若しくはブチルの各アクリル酸エステル（このエステルの含有量；４５モル％以内）との共重合体、又はこれらのそれぞれ塩素含有率６０重量％まで塩素化したもの等を挙げることができる。特に低密度のポリエチレンが好ましい。 Examples of polyolefin resins forming crosslinked polyolefin foams include low density, medium density, high density, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene- Vinyl acetate copolymers, copolymers of ethylene and each acrylic ester of methyl, ethyl, propyl, or butyl (content of this ester: within 45 mol%), or chlorine content of each of these up to 60% by weight. Examples include those that have been transformed into Particularly preferred is low density polyethylene.
ポリオレフィン系架橋樹脂発泡体は、一段発泡または二段発泡によって製造される。一段発泡では、ポリオレフィン系樹脂と発泡剤を含む発泡性樹脂組成物を発泡型に充填し、加熱加圧して発泡剤を分解させた後、発泡型を開放して発泡させることにより、所望のポリオレフィン系架橋樹脂発泡体を得る。二段発泡では、ポリオレフィン系樹脂と発泡剤を含む発泡性樹脂組成物を一次発泡型に充填し、加熱加圧させることにより一次発泡させて一次発泡体を形成し、次に一次発泡体の外形よりも内面形状の大きい二次発泡型に一次発泡体を収容し、常圧下加熱することにより二次発泡させて所望のポリオレフィン系架橋発泡体を得る。二段発泡では、一段発泡よりも発泡倍率の高い発泡体が得られる。 Polyolefin crosslinked resin foams are produced by one-stage foaming or two-stage foaming. In one-stage foaming, a foamable resin composition containing a polyolefin resin and a blowing agent is filled into a foaming mold, heated and pressurized to decompose the foaming agent, and then the foaming mold is opened and foamed to form the desired polyolefin. A crosslinked resin foam is obtained. In two-stage foaming, a foamable resin composition containing a polyolefin resin and a blowing agent is filled into a primary foaming mold, heated and pressurized to cause primary foaming to form a primary foam, and then the external shape of the primary foam is The primary foam is housed in a secondary foaming mold having an inner surface larger than that of the primary foam, and is heated under normal pressure to cause secondary foaming to obtain a desired polyolefin crosslinked foam. Two-stage foaming provides a foam with a higher expansion ratio than single-stage foaming.
発泡剤としては、重曹（炭酸水素ナトリウム）とｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジド（ＯＢＳＨ）が併用される。重曹単独では、ポリオレフィン系架橋発泡体の発泡後に収縮を生じ易くなり、一方、ｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジド単独では、発泡不足を生じ易くなる。重曹とｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドを併用することにより、発泡後の収縮や発泡不足を生じ難くできる。重曹の量（重量部）とｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの量（重量部）は、重曹の量よりもｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの量を多くするのが好ましい。重曹の量よりもｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの量を多くすることによって、ｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの分解ガスである窒素ガスを重曹の分解ガスである炭酸ガスよりも多くすることが可能となる。発泡成形後には、炭酸ガスだけでなく、拡散係数が低い窒素ガスで保持されているため、発泡成形後の急激な収縮、変形を抑制することができる。より好ましくは、ｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの量（重量部）／重曹の量（重量部）＝５．５／４．５～７７／２３である。 As the blowing agent, baking soda (sodium hydrogen carbonate) and p,p'-oxybisbenzenesulfonyl hydrazide (OBSH) are used in combination. Baking soda alone tends to cause shrinkage of the crosslinked polyolefin foam after foaming, while p,p'-oxybisbenzenesulfonyl hydrazide alone tends to cause insufficient foaming. By using baking soda and p,p'-oxybisbenzenesulfonyl hydrazide in combination, shrinkage after foaming and insufficient foaming can be prevented. Regarding the amount of baking soda (parts by weight) and the amount of p,p'-oxybisbenzenesulfonyl hydrazide (parts by weight), it is preferable that the amount of p,p'-oxybisbenzenesulfonyl hydrazide is greater than the amount of baking soda. By making the amount of p,p'-oxybisbenzenesulfonyl hydrazide larger than the amount of baking soda, nitrogen gas, which is the decomposition gas of p,p'-oxybisbenzenesulfonyl hydrazide, is more concentrated than carbon dioxide gas, which is the decomposition gas of baking soda. It is also possible to increase the number of After foam molding, the material is held not only by carbon dioxide gas but also by nitrogen gas, which has a low diffusion coefficient, so that rapid shrinkage and deformation after foam molding can be suppressed. More preferably, the amount of p,p'-oxybisbenzenesulfonyl hydrazide (parts by weight)/the amount of sodium bicarbonate (parts by weight) = 5.5/4.5 to 77/23.
重曹及びｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドは、ポリオレフィン系架橋発泡体の製造時における加熱によって、それぞれ熱分解してガスを発生し、ポリオレフィン系樹脂を発泡させる。重曹は、１４０℃～１７０℃で熱分解により炭酸ガスを発生し、分解残渣として炭酸ナトリウムを生じる。一方、ｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドは、１５５℃～１６５℃で熱分解により窒素ガスを発生し、分解残渣としてポリジチオフェニルエーテル、ポリチオフェニルベンゼンスルホニルエーテルを生じる。重曹及びｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの何れも分解残渣としてアンモニアを生じないため、ポリオレフィン架橋発泡体のアンモニア濃度を減らすことができる。
また、重曹とｐ，ｐ’－オキシビスベンゼンスルホニルヒドラジドの両者の熱分解温度の範囲の差が±１５℃以内と近く、１５５℃～１６５℃の範囲で、ともに熱分解可能であるため、発泡バランスがよく、混合する発泡剤として好ましい。
Baking soda and p,p'-oxybisbenzenesulfonyl hydrazide are each thermally decomposed by heating during production of the polyolefin crosslinked foam to generate gas and foam the polyolefin resin. Baking soda generates carbon dioxide gas through thermal decomposition at 140°C to 170°C, and produces sodium carbonate as a decomposition residue. On the other hand, p,p'-oxybisbenzenesulfonyl hydrazide generates nitrogen gas by thermal decomposition at 155° C. to 165° C., producing polydithophenyl ether and polythiophenylbenzenesulfonyl ether as decomposition residues. Since neither baking soda nor p,p'-oxybisbenzenesulfonyl hydrazide produces ammonia as a decomposition residue, the ammonia concentration in the polyolefin crosslinked foam can be reduced.
In addition, the difference in the thermal decomposition temperature ranges of both baking soda and p,p'-oxybisbenzenesulfonyl hydrazide is close, within ±15°C, and both can be thermally decomposed in the range of 155°C to 165°C. It is well-balanced and is preferred as a foaming agent to be mixed.
発泡剤の量はポリオレフィン系樹脂１００重量部に対して３．０～３５重量部が好ましい。発泡剤の量が少なすぎると、発泡が不良になったり、密度が高くなったりする。一方、発泡剤の量が多すぎると、発泡型を開放した際に発泡体が破裂したり、密度が低くなりすぎたりする。 The amount of the blowing agent is preferably 3.0 to 35 parts by weight per 100 parts by weight of the polyolefin resin. If the amount of foaming agent is too small, foaming will be poor or the density will be high. On the other hand, if the amount of foaming agent is too large, the foam may burst when the foaming mold is opened, or the density may become too low.
発泡性樹脂組成物には、発泡剤と共に架橋剤が含まれる。架橋剤としては、ジクミルパーオキサイド、２，５－ジメチル－２，５－ビス－ターシャリーブチルパーオキシヘキサン、１，３－ビス－ターシャリーパーオキシ－イソプロピルベンゼンなどの有機過酸化物等を挙げることができる。架橋剤の量は、ポリオレフィン系樹脂１００重量部に対して１．０～５．０重量部が好ましい。 The foamable resin composition contains a crosslinking agent together with a foaming agent. Examples of the crosslinking agent include organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis-tert-butylperoxyhexane, and 1,3-bis-tert-peroxy-isopropylbenzene. be able to. The amount of the crosslinking agent is preferably 1.0 to 5.0 parts by weight per 100 parts by weight of the polyolefin resin.
また、発泡性樹脂組成物には、適宜助剤が含まれる。助剤としては、発泡助剤、造核剤、その他の無機フィラー、着色剤などが挙げられる。発泡助剤としては、酸化亜鉛、酸化鉛等の金属酸化物、低級又は高級脂肪酸あるいはそれらの金属塩等を挙げることができる。造核剤としては、重炭酸カルシウムなどを挙げることができる。その他の無機フィラーとしては、導電性カーボンブラックなどを挙げることができる。 Further, the foamable resin composition contains an auxiliary agent as appropriate. Examples of the auxiliary agent include a foaming auxiliary agent, a nucleating agent, other inorganic fillers, and a coloring agent. Examples of the foaming aid include metal oxides such as zinc oxide and lead oxide, lower or higher fatty acids, or metal salts thereof. Examples of the nucleating agent include calcium bicarbonate. Other inorganic fillers include conductive carbon black and the like.
一段発泡の場合の加熱及び加圧は、発泡倍率によって異なるが、例として加熱温度１３０～１７０℃、加熱時間３０～６０分、圧力５～３５Ｐａ程度を挙げる。
二段発泡の場合の加熱及び加圧は、発泡倍率によって異なるが、例として一次発泡時の加熱温度１００～１５０℃、加熱時間３０～６０分、圧力５～３５Ｐａ程度、二次発泡時の加熱温度１４０～１７０℃、加熱時間２５～１８０分程度を挙げる。発泡倍率は、一段発泡及び二段発泡の何れの場合でも６～４０倍が好ましい。発泡倍率は、未発泡樹脂を１０００ｋｇ/ｍ３とし、以下式１で算出される値である。
１０００ｋｇ/ｍ３（未発泡） ÷ 発泡体密度実測値（ｋｇ/ｍ３） （式１）
発泡体密度実測値は、ＪＩＳ Ｋ ６７６７に準拠して測定した値である。
発泡倍率が低すぎると発泡体が柔軟化されすぎて形状が保持できず緩衝材として好ましくない結果となり、逆に高すぎると発泡体は硬くなって柔軟性にかけ緩衝材として好ましくない結果となる。また、一段発泡及び二段発泡時における発泡倍率の調整は、発泡剤によって６～４０倍となるようにする。
Heating and pressurization in the case of one-stage foaming vary depending on the expansion ratio, but examples include heating temperature of 130 to 170°C, heating time of 30 to 60 minutes, and pressure of about 5 to 35 Pa.
Heating and pressurization in the case of two-stage foaming vary depending on the expansion ratio, but examples include heating temperature of 100 to 150°C during primary foaming, heating time of 30 to 60 minutes, pressure of about 5 to 35 Pa, and heating during secondary foaming. The temperature is 140 to 170°C and the heating time is about 25 to 180 minutes. The expansion ratio is preferably 6 to 40 times in both one-stage foaming and two-stage foaming. The expansion ratio is a value calculated using the following formula 1, assuming that the unfoamed resin is 1000 kg/m 3 .
1000kg/m 3 (unfoamed) ÷ Actual foam density (kg/m 3 ) (Formula 1)
The foam density actual value is a value measured in accordance with JIS K 6767.
If the expansion ratio is too low, the foam becomes too flexible and cannot hold its shape, resulting in an undesirable result as a cushioning material.On the other hand, if the expansion ratio is too high, the foam becomes hard, resulting in poor flexibility, resulting in an undesirable result as a cushioning material. Further, the expansion ratio during one-stage foaming and two-stage foaming is adjusted to 6 to 40 times depending on the foaming agent.
ポリオレフィンとして低密度ポリエチレン（ＬＤＰＥ）：ＭＦＲ２、密度０．９２４ｋｇ／ｍ３、品番ＵＢＥポリエチレンＦ２２４Ｃ、宇部丸善ポリエチレン株式会社製を用い、重曹：三協化成株式会社製セルマイク２６６、ｐ，ｐ'－オキシビスベンゼンスルホニルヒドラジド（ＯＢＳＨ）：永和化成工業社製ネオセルボンＮ＃５０００、アゾジカルボンアミド（ＡＤＣＡ）：永和化成工業社製パンスレンＨ７３１０を、図１の配合とした。さらに架橋剤（図１に示さず）として化薬アクゾ株式会社製カヤクミルＤ－４０ＣをＬＤＰＥ１００重量部に対して２．７重量部配合した混合物をニーダーにて混練し、その後ロールにて混練し、実施例１～７及び比較例１～６の発泡性樹脂組成物を得た。混練は、１Ｌニーダーを用いて９０℃の温度で２０分間行った。 Low-density polyethylene (LDPE): MFR2, density 0.924 kg/m 3 , product number UBE polyethylene F224C, manufactured by Ube Maruzen Polyethylene Co., Ltd., was used as the polyolefin, baking soda: Cellmic 266, manufactured by Sankyo Kasei Co., Ltd., p, p'-oxy Bisbenzenesulfonyl hydrazide (OBSH): Neocellvon N#5000 manufactured by Eiwa Kasei Kogyo Co., Ltd., and azodicarbonamide (ADCA): Pansuren H7310 manufactured by Eiwa Kasei Kogyo Co., Ltd. were used in the formulation shown in FIG. Furthermore, a mixture containing 2.7 parts by weight of Kayakumil D-40C manufactured by Kayaku Akzo Co., Ltd. as a crosslinking agent (not shown in FIG. 1) per 100 parts by weight of LDPE was kneaded in a kneader, and then kneaded in a roll. Foamable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 6 were obtained. Kneading was performed at a temperature of 90° C. for 20 minutes using a 1 L kneader.
前記発泡性樹脂組成物を用い、実施例１～４については一段発泡により製造し、実施例５、６及び比較例１～６については二段発泡より製造した。
実施例１～４は、混練後の発泡性樹脂組成物を、発泡型に充填して加圧下加熱し、除圧して発泡させ、発泡型からポリオレフィン系架橋発泡体を取り出した。発泡型の成形空間は、縦１６０ｍｍ、横１６０ｍｍ、深さ３３ｍｍ、容積０.８５Ｌである。発泡性樹脂組成物の充填量は、何れも９００ｇ、加圧は７Ｐａ、加熱は１３５℃で５０分間である。
Using the foamable resin composition, Examples 1 to 4 were produced by one-stage foaming, and Examples 5 and 6 and Comparative Examples 1 to 6 were produced by two-stage foaming.
In Examples 1 to 4, the foamable resin composition after kneading was filled into a foaming mold, heated under pressure, and foamed by removing the pressure, and the polyolefin crosslinked foam was taken out from the foaming mold. The molding space of the foam mold has a length of 160 mm, a width of 160 mm, a depth of 33 mm, and a volume of 0.85 L. The filling amount of the foamable resin composition was 900 g, the pressure was 7 Pa, and the heating was 135° C. for 50 minutes.
実施例５、６及び比較例１～６は、混練後の発泡性樹脂組成物を一次発泡型に充填して加圧下加熱し、除圧して発泡させ、その後に一次発泡型から一次発泡体を取り出す一次発泡工程を行い、得られた一次発泡体を二次発泡型に収容し、常圧下二次加熱による二次発泡を行って、二次発泡型からポリオレフィン系架橋発泡体を取り出した。 In Examples 5 and 6 and Comparative Examples 1 to 6, the foamable resin composition after kneading was filled into a primary foaming mold, heated under pressure, and foamed by removing the pressure, and then the primary foam was removed from the primary foaming mold. A primary foaming process for taking out was carried out, the obtained primary foam was placed in a secondary foaming mold, secondary foaming was performed by secondary heating under normal pressure, and the polyolefin crosslinked foam was taken out from the secondary foaming mold.
一次発泡型の成形空間は、縦１６０ｍｍ、横１６０ｍｍ、深さ３３ｍｍ、容積０．８５Ｌである。発泡性樹脂組成物の充填量は、何れも９００ｇ、加圧は７Ｐａ、加熱は１３０℃で５０分間である。
二次発泡型の成形空間は、縦３００ｍｍ、横３００ｍｍ、深さ５５ｍｍ、容積１．５Ｌである。加熱は１５０℃で５０分間である。
The molding space of the primary foam mold has a length of 160 mm, a width of 160 mm, a depth of 33 mm, and a volume of 0.85 L. The filling amount of the foamable resin composition was 900 g, the pressure was 7 Pa, and the heating was at 130° C. for 50 minutes.
The molding space of the secondary foam mold has a length of 300 mm, a width of 300 mm, a depth of 55 mm, and a volume of 1.5 L. Heating is at 150°C for 50 minutes.
各実施例及び各比較例における密度（ＪＩＳ Ｋ ６７６７準拠）、発泡倍率、アンモニア濃度、ガラス霞度（ＩＳＯ６４５２準拠）、収縮を測定した。測定結果は図１に示す。 The density (based on JIS K 6767), expansion ratio, ammonia concentration, glass haze (based on ISO 6452), and shrinkage in each example and each comparative example were measured. The measurement results are shown in Figure 1.
発泡倍率は、上記式１により算出した。
アンモニア濃度は、丸底フラスコに０．１ｇのサンプルを投入し、８０℃のオーブンで２時間加熱し、その後冷えないうちに１０～１０００ｐｐｍを測定できるガステック製検知管（品番：３Ｍ）で粗々の値を測定した後、１００ｐｐｍ未満を測定できる、精度の良いガステック検知管（品番：３Ｌ）にてアンモニア濃度を測定した。
ガラス霞度（フォギング）は、サンプルをガラス板で遮蔽した状態で８０℃×２０時間加熱し、ガラス板に付着した曇り度を日本電色工業株式会社製（品番：ＮＤＨ－２０Ｈ）により測定した。
収縮は、発泡型から取り出した直後の発泡体の厚み寸法と、発泡型から取り出してから２４時間後の厚み寸法との差分を測定し、その差分を発泡型から取り出した直後の発泡体の厚み寸法に対する比率で表した。収縮が５．０％以下の場合に「〇」とし、５．０％を超える場合は「×」とした。
総合判定は、アンモニア濃度が０ｐｐｍ～１００ｐｐｍ、ガラス霞度が５％以下、収縮が５．０％以下の条件を全て満たす場合に「〇」とし、一つでも外れる場合に「×」とした。
The foaming ratio was calculated using the above formula 1.
Ammonia concentration was determined by placing 0.1 g of sample in a round bottom flask, heating it in an oven at 80°C for 2 hours, and then using a Gastech detector tube (product number: 3M) that can measure 10 to 1000 ppm before cooling. After measuring each value, the ammonia concentration was measured using a highly accurate Gastech detection tube (product number: 3L) that can measure less than 100 ppm.
Glass haze (fogging) was measured by heating the sample at 80°C for 20 hours while shielding it with a glass plate, and measuring the degree of fogging attached to the glass plate using Nippon Denshoku Industries Co., Ltd. (product number: NDH-20H). .
Shrinkage is measured by measuring the difference between the thickness of the foam immediately after taking it out of the foaming mold and the thickness dimension 24 hours after taking it out from the foaming mold, and calculating the difference as the thickness of the foam immediately after taking it out from the foaming mold. Expressed as a ratio to the dimensions. When the shrinkage was 5.0% or less, it was marked as "○", and when it exceeded 5.0%, it was marked as "x".
The overall evaluation was evaluated as "○" if all of the following conditions were satisfied: ammonia concentration of 0 ppm to 100 ppm, glass haze of 5% or less, and shrinkage of 5.0% or less, and "x" if any of the conditions were met.
実施例１は、発泡剤の量が３．０重量部、ＯＢＳＨ／重曹の重量比が６／４の例である。実施例１は、アンモニア濃度１５ｐｐｍ、ガラス霞度０．７％、密度１５０ｋｇ／ｍ３、発泡倍率６．７倍、収縮２．１％であり、総合評価「〇」である。 Example 1 is an example in which the amount of blowing agent was 3.0 parts by weight and the weight ratio of OBSH/baking soda was 6/4. Example 1 has an ammonia concentration of 15 ppm, a glass haze of 0.7%, a density of 150 kg/m 3 , a foaming ratio of 6.7 times, and a shrinkage of 2.1%, and is given an overall evaluation of "Good".
実施例２は、発泡剤の量が３．０重量部、ＯＢＳＨ／重曹の重量比が２／１の例である。実施例２は、アンモニア濃度２５ｐｐｍ、ガラス霞度２．３％、密度１４０ｋｇ／ｍ３、発泡倍率７．０倍、収縮２．１％であり、総合評価「〇」である。 Example 2 is an example in which the amount of blowing agent is 3.0 parts by weight and the weight ratio of OBSH/baking soda is 2/1. Example 2 has an ammonia concentration of 25 ppm, a glass haze of 2.3%, a density of 140 kg/m 3 , a foaming ratio of 7.0 times, and a shrinkage of 2.1%, and is given an overall rating of "Good".
実施例３は、発泡剤の量が７．０重量部、ＯＢＳＨ／重曹の重量比が６／４の例である。実施例３は、アンモニア濃度５ｐｐｍ、ガラス霞度０．３％、密度８０ｋｇ／ｍ３、発泡倍率１２．５倍、収縮２．３％であり、総合評価「〇」である。 Example 3 is an example in which the amount of blowing agent is 7.0 parts by weight and the weight ratio of OBSH/baking soda is 6/4. Example 3 has an ammonia concentration of 5 ppm, a glass haze of 0.3%, a density of 80 kg/m 3 , a foaming ratio of 12.5 times, and a shrinkage of 2.3%, and is given an overall rating of "Good".
実施例４は、発泡剤の量が７．０重量部、ＯＢＳＨ／重曹の重量比が７６／２４の例である。実施例４は、アンモニア濃度４０ｐｐｍ、ガラス霞度２．１％、密度７５ｋｇ／ｍ３、発泡倍率１３．３倍、収縮２．６％であり、総合評価「〇」である。 Example 4 is an example in which the amount of blowing agent was 7.0 parts by weight and the weight ratio of OBSH/baking soda was 76/24. Example 4 has an ammonia concentration of 40 ppm, a glass haze of 2.1%, a density of 75 kg/m 3 , a foaming ratio of 13.3 times, and a shrinkage of 2.6%, and is given an overall evaluation of "Good".
実施例５は、発泡剤の量が２５．０重量部、ＯＢＳＨ／重曹の重量比が６／４の例である。実施例５は、アンモニア濃度２０ｐｐｍ、ガラス霞度０．４％、密度３３ｋｇ／ｍ３、発泡倍率３０．０倍、収縮３．６％であり、総合評価「〇」である。 Example 5 is an example in which the amount of blowing agent was 25.0 parts by weight and the weight ratio of OBSH/baking soda was 6/4. Example 5 has an ammonia concentration of 20 ppm, a glass haze of 0.4%, a density of 33 kg/m 3 , a foaming ratio of 30.0 times, and a shrinkage of 3.6%, and is given an overall evaluation of "Good".
実施例６は、発泡剤の量が３５．０重量部、ＯＢＳＨ／重曹の重量比が６／４の例である。実施例６は、アンモニア濃度１５ｐｐｍ、ガラス霞度０．５％、密度２５ｋｇ／ｍ３、発泡倍率４０．０倍、収縮３．４％であり、総合評価「〇」である。 Example 6 is an example in which the amount of blowing agent was 35.0 parts by weight and the weight ratio of OBSH/baking soda was 6/4. Example 6 has an ammonia concentration of 15 ppm, a glass haze of 0.5%, a density of 25 kg/m 3 , a foaming ratio of 40.0 times, and a shrinkage of 3.4%, and is given an overall evaluation of "Good".
比較例１は、発泡剤の量が７．０重量部、ＯＢＳＨ／重曹の重量比が０／７の例であり、ＯＢＳＨが含まれていない。比較例１は、アンモニア濃度０ｐｐｍ、ガラス霞度０．１％、密度２００ｋｇ／ｍ３、発泡倍率５倍、収縮７．２％であり、総合評価「×」である。比較例１は、アンモニア濃度及びガラス霞度が小さかったが、発泡剤が重曹単独のため、成形後に炭酸ガスが急激に抜けることで、密度が高く、収縮も大きかった。 Comparative Example 1 is an example in which the amount of blowing agent is 7.0 parts by weight, the weight ratio of OBSH/baking soda is 0/7, and OBSH is not included. Comparative Example 1 has an ammonia concentration of 0 ppm, a glass haze of 0.1%, a density of 200 kg/m 3 , a foaming ratio of 5 times, and a shrinkage of 7.2%, and is given an overall evaluation of "x". Comparative Example 1 had low ammonia concentration and glass haze, but because the foaming agent was baking soda alone, carbon dioxide gas rapidly escaped after molding, resulting in high density and large shrinkage.
比較例２は、発泡剤の量が７．０重量部、ＯＢＳＨ／重曹の重量比が５／５の例であり、ＯＢＳＨと重曹の量が等しい。比較例２は、アンモニア濃度３０ｐｐｍ、ガラス霞度２．４％、密度１００ｋｇ／ｍ３、発泡倍率１０倍、収縮５．８％であり、総合評価「×」である。比較例２は、アンモニア濃度及びガラス霞度については小さかったが、密度が高く、収縮が大きかった。 Comparative Example 2 is an example in which the amount of blowing agent is 7.0 parts by weight, the weight ratio of OBSH/baking soda is 5/5, and the amounts of OBSH and baking soda are equal. Comparative Example 2 has an ammonia concentration of 30 ppm, a glass haze of 2.4%, a density of 100 kg/m 3 , a foaming ratio of 10 times, and a shrinkage of 5.8%, and is given an overall evaluation of "x". Comparative Example 2 had low ammonia concentration and glass haze, but high density and large shrinkage.
比較例３は、発泡剤の量が７．０重量部、ＯＢＳＨ／重曹の重量比が８／２の例である。比較例３は、アンモニア濃度６０ｐｐｍ、ガラス霞度３．１％、密度１８０ｋｇ／ｍ３、発泡倍率５．５倍、収縮１．８％であり、総合評価「×」である。比較例３は、密度が高く、発泡不足であった。 Comparative Example 3 is an example in which the amount of blowing agent was 7.0 parts by weight and the weight ratio of OBSH/baking soda was 8/2. Comparative Example 3 has an ammonia concentration of 60 ppm, a glass haze of 3.1%, a density of 180 kg/m 3 , a foaming ratio of 5.5 times, and a shrinkage of 1.8%, and is given an overall evaluation of "x". Comparative Example 3 had high density and insufficient foaming.
比較例４は、発泡剤の量が７．０重量部、ＯＢＳＨ／重曹の重量比が７／０の例であり、重曹を含まない。比較例４は、アンモニア濃度６５ｐｐｍ、ガラス霞度３．６％、密度２３０ｋｇ／ｍ３、発泡倍率４．３倍、収縮１．７％であり、総合評価「×」である。比較例４は、発泡剤がＯＢＳＨ単独のため、架橋が先行して行われ、発泡が十分になされず、密度が高く、発泡不足であった。 Comparative Example 4 is an example in which the amount of blowing agent is 7.0 parts by weight, the weight ratio of OBSH/baking soda is 7/0, and baking soda is not included. Comparative Example 4 has an ammonia concentration of 65 ppm, a glass haze of 3.6%, a density of 230 kg/m 3 , a foaming ratio of 4.3 times, and a shrinkage of 1.7%, and is given an overall evaluation of "x". In Comparative Example 4, since the foaming agent was OBSH alone, crosslinking was performed in advance, and foaming was not performed sufficiently, resulting in high density and insufficient foaming.
比較例５は、発泡剤の量が２．０重量部、ＯＢＳＨ／重曹の重量比が６／４の例であり、発泡剤の量が少ない。比較例５は、発泡しないため、アンモニア濃度、ガラス霞度、収縮を測定できず、総合評価「×」である。比較例５は、発泡しないため密度が９００ｋｇ／ｍ３と高かった。発泡倍率は１．１倍であった。 Comparative Example 5 is an example in which the amount of blowing agent is 2.0 parts by weight and the weight ratio of OBSH/baking soda is 6/4, and the amount of blowing agent is small. In Comparative Example 5, since no foaming occurred, ammonia concentration, glass haze, and shrinkage could not be measured, and the overall evaluation was "x". Comparative Example 5 had a high density of 900 kg/m 3 because it did not foam. The expansion ratio was 1.1 times.
比較例６は、発泡剤としてＡＤＣＡを単独で５．０重量部使用した例である。比較例６は、アンモニア濃度９００ｐｐｍ、ガラス霞度２２％、密度６５ｋｇ／ｍ３、発泡倍率１５倍、収縮１．８％であり、総合評価「×」である。比較例６は、発泡剤としてＡＤＣＡを使用するため、アンモニア濃度及びガラス霞度が何れも高かった。 Comparative Example 6 is an example in which 5.0 parts by weight of ADCA was used alone as a blowing agent. Comparative Example 6 has an ammonia concentration of 900 ppm, a glass haze of 22%, a density of 65 kg/m 3 , a foaming ratio of 15 times, and a shrinkage of 1.8%, and is given an overall evaluation of "x". In Comparative Example 6, since ADCA was used as a blowing agent, both the ammonia concentration and the glass haze were high.
このように、本発明では、残留するアンモニア濃度が低く、アンモニアによる汚染、腐食を防ぐことができるポリオレフィン系架橋発泡体が得られる。 As described above, the present invention provides a polyolefin crosslinked foam that has a low residual ammonia concentration and can prevent contamination and corrosion caused by ammonia.
Claims (2)
A polyolefin crosslinked foam having a density of 20 to 33 kg/m 3 and an ammonia concentration of 5 ppm to 20 ppm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003292661A (en) | 2002-03-29 | 2003-10-15 | Tosoh Corp | Polyolefin resin composition for foaming and foam composed of the same |
| JP2012097285A (en) | 2012-02-20 | 2012-05-24 | Inoac Corp | Method for manufacturing polyolefin resin foam |
| JP2012224751A (en) | 2011-04-20 | 2012-11-15 | Sanwa Kako Co Ltd | Method for producing crosslinked polyolefin resin foam |
| JP2013142146A (en) | 2012-01-12 | 2013-07-22 | Tosoh Corp | Foaming agent master batch, and foamed body using the same |
| JP2015145503A (en) | 2015-03-31 | 2015-08-13 | 東レペフ加工品株式会社 | Resin foam, cylindrical body and molded body |
| JP2017145367A (en) | 2016-02-19 | 2017-08-24 | 東レ株式会社 | Flame-retardant polyolefin resin crosslinked foam |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003292661A (en) | 2002-03-29 | 2003-10-15 | Tosoh Corp | Polyolefin resin composition for foaming and foam composed of the same |
| JP2012224751A (en) | 2011-04-20 | 2012-11-15 | Sanwa Kako Co Ltd | Method for producing crosslinked polyolefin resin foam |
| JP2013142146A (en) | 2012-01-12 | 2013-07-22 | Tosoh Corp | Foaming agent master batch, and foamed body using the same |
| JP2012097285A (en) | 2012-02-20 | 2012-05-24 | Inoac Corp | Method for manufacturing polyolefin resin foam |
| JP2015145503A (en) | 2015-03-31 | 2015-08-13 | 東レペフ加工品株式会社 | Resin foam, cylindrical body and molded body |
| JP2017145367A (en) | 2016-02-19 | 2017-08-24 | 東レ株式会社 | Flame-retardant polyolefin resin crosslinked foam |
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