JP4904526B2 - Polyolefin-based resin laminate foam having deodorizing function, and cylindrical body or molded body comprising the same - Google Patents
Polyolefin-based resin laminate foam having deodorizing function, and cylindrical body or molded body comprising the same Download PDFInfo
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- JP4904526B2 JP4904526B2 JP2006242400A JP2006242400A JP4904526B2 JP 4904526 B2 JP4904526 B2 JP 4904526B2 JP 2006242400 A JP2006242400 A JP 2006242400A JP 2006242400 A JP2006242400 A JP 2006242400A JP 4904526 B2 JP4904526 B2 JP 4904526B2
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- Prior art keywords
- foam
- polyolefin resin
- polyolefin
- deodorizing function
- gas
- Prior art date
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- 229920005672 polyolefin resin Polymers 0.000 title claims description 89
- 239000006260 foam Substances 0.000 title claims description 78
- 230000001877 deodorizing effect Effects 0.000 title claims description 36
- 239000002781 deodorant agent Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 description 50
- 239000007789 gas Substances 0.000 description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 39
- 238000009413 insulation Methods 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000004088 foaming agent Substances 0.000 description 16
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- -1 silver ions Chemical class 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
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- 238000005187 foaming Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 235000019645 odor Nutrition 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- 238000004332 deodorization Methods 0.000 description 6
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
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- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229930007845 β-thujaplicin Natural products 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
本発明はポリオレフィン系樹脂架橋発泡体に消臭機能を有したポリオレフィン系樹脂層を設けたポリオレフィン系樹脂積層発泡体に関するものである。 The present invention relates to a polyolefin resin laminate foam in which a polyolefin resin layer having a deodorizing function is provided on a polyolefin resin crosslinked foam.
ポリオレフィン系樹脂発泡体は冷暖房機器の配管用断熱材、水道管凍結防止用断熱材、金属屋根断熱材など保温、保冷、断熱の分野や台所マット、風呂マット、自動車内装材などの緩衝材の分野で広く使用されている。 Polyolefin-based resin foams are used for heat insulation, cold insulation, heat insulation such as pipe insulation for air conditioning equipment, water pipe freeze prevention, metal roof insulation, etc., and cushioning materials such as kitchen mats, bath mats, automobile interior materials, etc. Widely used in.
発泡体の気泡形状を細微にコントロールできるアゾ系の熱分解型化学発泡剤を用いて電離性放射線により架橋を施したポリオレフィン系発泡体は特に熱伝導率が小さく、保温、保冷、断熱の分野では好適に使用される。しかしながらアゾ系の熱分解型化学発泡剤はその分解過程でアンモニア類の生成があり、密閉空間に該ポリオレフィン系発泡体を設置した場合、アンモニア臭気を呈する場合があった。また、屋内外に配置された配管断熱材周囲に雨水、台所や風呂、洗濯場で使用する水等の影響で高湿状態となり臭気を発生する場合があった。 Polyolefin foam that has been crosslinked by ionizing radiation using an azo-based pyrolytic chemical foaming agent that can finely control the foam shape of the foam has particularly low thermal conductivity, and in the fields of heat insulation, cold insulation and heat insulation. Preferably used. However, the azo-based thermally decomposable chemical foaming agent generates ammonia during the decomposition process, and when the polyolefin-based foam is installed in a sealed space, it sometimes exhibits an ammonia odor. In addition, there is a case where the surroundings of the pipe heat insulating material arranged indoors and outdoors are in a high humidity state due to the influence of rain water, water used in the kitchen, bath, laundry, etc. and generate odor.
本発明は、かかる従来技術の背景に鑑み、アゾ系熱分解型化学発泡剤を使用したポリオレフィン系樹脂発泡体の臭気や、該発泡体を使用する環境下で周辺を含めた臭気を抑制することができるポリオレフィン系樹脂積層発泡体を提供することにある。 In view of the background of such conventional technology, the present invention suppresses the odor of polyolefin resin foam using an azo-based pyrolytic chemical foaming agent and the odor including the surroundings in the environment where the foam is used. An object of the present invention is to provide a polyolefin-based resin laminate foam that can be used.
本発明はかかる課題を解決するために、次の手段を採用するものである。すなわち、ポリオレフィン系樹脂発泡体の少なくとも片面の表層面に、少なくとも消臭剤を含むポリオレフィン系樹脂層が設けられ、前記消臭剤が、ポリオレフィン系樹脂層のポリオレフィン系樹脂100重量部に対し1〜30重量部であることを特徴とする消臭機能を有するポリオレフィン系樹脂積層発泡体である。
The present invention employs the following means in order to solve such problems. That is, a polyolefin resin layer containing at least a deodorant is provided on at least one surface of the polyolefin resin foam, and the deodorizer is 1 to 100 parts by weight of the polyolefin resin of the polyolefin resin layer. a polyolefin-based resin laminate foam having a deodorizing function, wherein 30 parts by weight der Rukoto.
本発明の発泡体を用いることで、保温性、保冷性、断熱性、緩衝性、耐衝撃性等のポリオレフィン系樹脂発泡体が有する機能を活用する用途で、ポリオレフィン系樹脂発泡体を使用する環境において、その環境の雰囲気中に臭気を有する場合、その臭気を軽減することが可能であり、特にポリオレフィン系樹脂中に消臭剤が含まれることにより長期的な効果を付与することが可能となる。 By using the foam of the present invention, the environment in which the polyolefin resin foam is used in applications that utilize the functions of the polyolefin resin foam such as heat retention, cold insulation, heat insulation, buffering, and impact resistance. In the case of having an odor in the atmosphere of the environment, the odor can be reduced, and in particular, a long-term effect can be imparted by including a deodorant in the polyolefin resin. .
本発明の消臭機能を有するポリオレフィン系樹脂積層発泡体とはポリオレフィン系樹脂発泡体に効率的かつ長期に臭気を軽減する機能を付与するため、発泡体の少なくとも片方の表面に消臭剤を付与したポリオレフィン系樹脂層を設けることが必要である。かかる消臭剤は、酸化や還元等の反応機構や酸・アルカリの中和機構等の化学的反応により悪臭の物質的変化をもたらし除去効果を有するものや、抗菌作用により菌の繁殖を抑制し、菌の繁殖による臭気を軽減するものである。ここで示す悪臭とは塩基性、酸性、アルデヒド系、硫黄系のガスに大別され、それぞれ具体的には塩基性ガスはアンモニア、ピリジン、トリメチルアミン等が例示され、酸性ガスは酢酸、イソ吉草酸、酪酸等が例示され、アルデヒド系ガスはアセトアルデヒド、ホルムアルデヒド、2−ノナール等が例示され、硫黄系ガスは硫化水素、メチルメルカプタン等が例示される。 The polyolefin-based resin laminate foam having a deodorizing function of the present invention provides a deodorizing agent to at least one surface of the foam in order to give the polyolefin-based resin foam a function to reduce odor efficiently and in the long term. It is necessary to provide a polyolefin-based resin layer. Such a deodorant has a removal effect due to a chemical reaction such as a reaction mechanism such as oxidation or reduction, or a neutralization mechanism of acid / alkali, and has a removal effect. , To reduce the odor caused by the growth of bacteria. The bad odors shown here are roughly classified into basic, acidic, aldehyde-based, and sulfur-based gases. Specific examples of basic gases include ammonia, pyridine, trimethylamine, and the like, and acidic gases include acetic acid and isovaleric acid. Butyric acid and the like are exemplified, acetaldehyde, formaldehyde, 2-nonal and the like are exemplified as the aldehyde-based gas, and hydrogen sulfide, methyl mercaptan and the like are exemplified as the sulfur-based gas.
本発明に用いる消臭剤は無機系化合物と有機系化合物があり、無機系化合では銀イオンや亜鉛イオンを有する珪酸塩化合物、銀イオンや亜鉛イオンを有する燐酸塩化合物、銀イオンや亜鉛イオンを有する燐酸カルシウム化合物、粒子径が50nm以下の酸化亜鉛等が例示され、有機系化合物では分子内に複数のベンゼン環やナフタレン環等の芳香環に結合したヒドロキシ基を有する化合物等が例示され、具体的には2,4,4´−トリクロロ−2´−ヒドロキシジフェニルエーテル、4,4´−ジクロロ−2ヒドロキシフェニルエーテル、4−イソプロピルトロポロン、ポリフェノール類等が例示される。ここで示すポリフェノール類はフラボノール、イソフラボン、タンニン、ケンチン、カテキン、プロアントシアニジン等が例示される。上記消臭剤は単独で用いても2種類以上を併用してもよい。また単独または2種類以上併用した消臭剤の総添加量はポリオレフィン系樹脂100重量部に対し1〜30重量部が好ましく、更に2〜20重量部が好ましい。添加量が1重量部未満であれば消臭性能が劣る場合や均一分散が困難となる場合があり、一方30重量部を超えると熱溶融加工時の分散不良、混練不良、加工機器の各所ロールへの付着による工程不安定といった不具合が発生する場合がある。 Deodorants used in the present invention include inorganic compounds and organic compounds. In inorganic compounds, silicate compounds having silver ions and zinc ions, phosphate compounds having silver ions and zinc ions, silver ions and zinc ions are used. Examples include calcium phosphate compounds having a particle diameter of 50 nm or less, and organic compounds include compounds having a hydroxy group bonded to an aromatic ring such as a plurality of benzene rings or naphthalene rings in the molecule. Specifically, 2,4,4′-trichloro-2′-hydroxydiphenyl ether, 4,4′-dichloro-2hydroxyphenyl ether, 4-isopropyltropolone, polyphenols and the like are exemplified. Examples of the polyphenols shown here include flavonol, isoflavone, tannin, kentin, catechin, proanthocyanidin and the like. The above deodorants may be used alone or in combination of two or more. The total amount of the deodorant used alone or in combination of two or more is preferably from 1 to 30 parts by weight, more preferably from 2 to 20 parts by weight, based on 100 parts by weight of the polyolefin resin. If the amount added is less than 1 part by weight, the deodorizing performance may be inferior or uniform dispersion may be difficult. On the other hand, if the amount added exceeds 30 parts by weight, poor dispersion during kneading, kneading failure, and various rolls of processing equipment Problems such as process instability due to adhesion to the surface may occur.
かかる消臭剤はポリオレフィン系樹脂への分散性や固着性を向上させるため消臭剤の表面に公知の処理を施すことが好ましく、例えばシランカップリング剤等の有機官能基を有する表面処理剤、ワックスエマルジョン等のコート剤、共重合系ポリマーやエステル等の分散剤等を用いても良い。 Such a deodorant is preferably subjected to a known treatment on the surface of the deodorant in order to improve dispersibility and adhesion to the polyolefin resin, for example, a surface treatment agent having an organic functional group such as a silane coupling agent, A coating agent such as a wax emulsion, a dispersing agent such as a copolymer polymer or an ester may be used.
本発明に用いるポリオレフィン系樹脂とは、オレフィン系炭化水素の重合体または共重合体である。ポリオレフィン系樹脂としては特に限定されないが、例えばエチレン−酢酸ビニル共重合体、エチレン−エチルアクリレート共重合体、エチレン−ジエン共重合体、エチレン−プロピレン−ジエン3元共重合体、エチレン−オクテン共重合体、低密度ポリエチレン、エチレンと炭素数が4〜12のα−オレフィンとを共重合した直鎖状のポリエチレン、高密度ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、オレフィン系熱可塑性エラストマー等が例示され、それぞれ単独あるいは2種類以上を組み合わせて使用することができる。エチレンに共重合させるα−オレフィンについては特に限定されないが、たとえばプロピレン、1−ブテン、1−ペンテン、3,3−ジメチル−1−ブテン、4−メチル−1−ペンテン、4,4−ジメチル−1−ペンテン、1−デセン、1−ドデセン、1−テトラデセン、1−オクタデセン等が好ましい。 The polyolefin resin used in the present invention is a polymer or copolymer of an olefin hydrocarbon. The polyolefin resin is not particularly limited. For example, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-diene copolymer, ethylene-propylene-diene terpolymer, ethylene-octene copolymer Examples include coalescence, low density polyethylene, linear polyethylene copolymerized with ethylene and α-olefin having 4 to 12 carbon atoms, high density polyethylene, polypropylene, ethylene-propylene copolymer, olefin-based thermoplastic elastomer, etc. Each can be used alone or in combination of two or more. The α-olefin copolymerized with ethylene is not particularly limited. For example, propylene, 1-butene, 1-pentene, 3,3-dimethyl-1-butene, 4-methyl-1-pentene, 4,4-dimethyl- 1-pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene and the like are preferable.
かかるポリオレフィン系樹脂の融点は80℃〜150℃が望ましく、更に90℃〜140℃が好ましい。融点が80℃未満であれば、一般的な使用環境温度で寸法等の著しい変化が生じる場合や加熱を伴う成型加工等で早期に溶融するため表面不良や成型不良といった不良が発生する場合がある。一方融点が150℃を超えると例えば消臭剤を溶融混練等の加熱を伴う混練加工をする際、加工温度による消臭剤の分解等が発生する場合や加熱を伴う成型加工等で消臭剤が一部分解し消臭機能が低下する場合がある。 The melting point of the polyolefin resin is desirably 80 ° C. to 150 ° C., and more preferably 90 ° C. to 140 ° C. If the melting point is less than 80 ° C., a significant change in dimensions or the like may occur at a general use environment temperature, or a defect such as a surface defect or a molding defect may occur due to melting at an early stage in a molding process involving heating. . On the other hand, when the melting point exceeds 150 ° C., for example, when the deodorant is kneaded with heating such as melting and kneading, the deodorant is decomposed due to the processing temperature, or the molding process with heating is performed. May be partially decomposed and the deodorizing function may be reduced.
ポリオレフィン系樹脂には例えばエチレンを主鎖とするポリエチレン系樹脂あるいはその共重合体などとプロピレンを主鎖とするポリプロピレン系樹脂あるいはその共重合体などがあり、メルトフローレート(MFR)の測定温度は主に主鎖を形成する成分や融点に関連している。ポリオレフィン系樹脂に使用する融点が100〜140℃の範囲であるエチレンを主鎖とするポリエチレン系樹脂あるいはその共重合体などは190℃で測定したMFRにおいて0.1〜50g/10分であることが好ましく、更に、1〜30g/10分であることが好ましい。MFRが0.1g/10分未満であると押出機等でフィルム状のポリオレフィン系樹脂層を製造する際、混錬圧力過剰による生産性低下や消臭剤の分解や分散不良あるいは吐出変動による幅方向、長手方向の厚み不良等の不具合が生じる場合があり、一方50g/10分を越えると混錬圧力不足による幅方向の厚み調整不良や消臭剤の分散不良となる場合がある。 Polyolefin resins include, for example, polyethylene resins having ethylene as the main chain or copolymers thereof, polypropylene resins having propylene as the main chain or copolymers thereof, and the measurement temperature of the melt flow rate (MFR) is It is mainly related to the components that form the main chain and the melting point. Polyethylene resin having ethylene as the main chain or a copolymer thereof having a melting point of 100 to 140 ° C. used for polyolefin resin is 0.1 to 50 g / 10 min in MFR measured at 190 ° C. Is preferable, and it is more preferable that it is 1-30 g / 10min. When the MFR is less than 0.1 g / 10 min, when producing a film-like polyolefin resin layer with an extruder or the like, the productivity decreases due to excessive kneading pressure, the deodorant decomposes or disperses poorly, or the width due to discharge fluctuation In some cases, defects such as a thickness failure in the direction and the longitudinal direction may occur. On the other hand, if it exceeds 50 g / 10 minutes, a thickness adjustment failure in the width direction due to insufficient kneading pressure and a dispersion of the deodorant may occur.
また、ポリオレフィン系樹脂に使用する融点が130℃〜160℃の範囲であるプロピレンを主鎖とするポリプロピレン系樹脂あるいはその共重合体などは230℃で測定したMFRにおいて0.1〜50g/10分であることが好ましく、更に、0.3〜30g/10分であることが好ましい。MFRが0.1g/10分未満であると押出機等でフィルム状のポリオレフィン系樹脂層を製造する際、混錬圧力過剰による生産性低下や消臭剤の分解や分散不良あるいは吐出変動による幅方向、長手方向の厚み不良等の不具合が生じる場合があり、一方50g/10分を越えると混錬圧力不足による幅方向の厚み調整不良や消臭剤の分散不良となる場合がある。ここで示すMFRとは2001年版JIS K 6922−2及びJIS K 6921−2に準じた測定方法で測定したものである。また、ここで示す融点とは、示差走査熱量分析で測定したDSC曲線から得られるものであり、測定方法は次に示すとおりである。 In addition, a polypropylene resin having a main chain of propylene having a melting point of 130 ° C. to 160 ° C. or a copolymer thereof used in a polyolefin resin is 0.1 to 50 g / 10 min in MFR measured at 230 ° C. It is preferable that it is 0.3-30 g / 10min. When the MFR is less than 0.1 g / 10 min, when producing a film-like polyolefin resin layer with an extruder or the like, the productivity decreases due to excessive kneading pressure, the deodorant decomposes or disperses poorly, or the width due to discharge fluctuation In some cases, defects such as a thickness failure in the direction and the longitudinal direction may occur. On the other hand, if it exceeds 50 g / 10 minutes, a thickness adjustment failure in the width direction due to insufficient kneading pressure and a dispersion of the deodorant may occur. The MFR shown here is measured by a measuring method according to JIS K 6922-2 and JIS K 6921-2. The melting point shown here is obtained from a DSC curve measured by differential scanning calorimetry, and the measuring method is as follows.
示差走査熱量分析装置を用い、−50℃から200℃の間で10℃/分の速度で昇温し、200℃で5分間保持した後、200℃から−50℃の間で10℃/分の速度で降温し、更に−50℃で5分間保持した後、−50℃から200℃の間で10℃/分の速度で昇温した2度目の昇温で得られたDSC曲線の結晶融解ピーク温度を融点とする。 Using a differential scanning calorimeter, the temperature was raised between −50 ° C. and 200 ° C. at a rate of 10 ° C./minute, held at 200 ° C. for 5 minutes, and then between 200 ° C. and −50 ° C. at 10 ° C./minute. The DSC curve was melted at the second temperature increase after the temperature was decreased at a rate of 5 ° C. and held at −50 ° C. for 5 minutes and then increased at a rate of 10 ° C./min between −50 ° C. and 200 ° C. The peak temperature is taken as the melting point.
本発明に用いるポリオレフィン系樹脂発泡体とは、ポリオレフィン系樹脂とガスの混合体であり、その製造方法は特に限定されないが、押出機内でガスあるいは気化する溶剤を溶融させ高圧下で押出ながら発泡する押出発泡法、ガスあるいは気化する溶剤を含有した樹脂粒子を予備発泡し更に金型内で発泡融着するビーズ発泡法、高圧容器内でポリオレフィン系樹脂にガスを溶解し常圧で加熱し発泡するガス含浸法といった溶剤気散法やポリオレフィン系樹脂と熱分解型化学発泡剤を溶融混錬し常圧加熱にて発泡する常圧発泡法、押出機内で熱分解型化学発泡剤を加熱分解し高圧下で押出ながら発泡する押出発泡法、プレス金型内で熱分解型化学発泡剤を加熱分解し減圧しながら発泡するプレス発泡法といった発泡剤分解法等が例示される。 The polyolefin resin foam used in the present invention is a mixture of a polyolefin resin and a gas, and its production method is not particularly limited, but foams while melting a gas or a solvent to be vaporized in an extruder and extruding under high pressure. Extrusion foaming method, bead foaming method in which resin particles containing gas or vaporizing solvent are pre-foamed and then foamed and fused in a mold, gas is dissolved in polyolefin resin in a high-pressure vessel, and heated at normal pressure to foam Solvent diffusion method such as gas impregnation method, normal pressure foaming method by melting and kneading polyolefin resin and thermal decomposition type chemical foaming agent and foaming by normal pressure heating, thermal decomposition of thermal decomposition type chemical foaming agent in the extruder and high pressure Examples thereof include an extrusion foaming method in which foaming is performed while extruding under pressure, and a foaming agent decomposing method in which a thermally decomposable chemical foaming agent is thermally decomposed in a press mold and foamed while being decompressed.
ここで示す溶剤気散法に用いるガスあるいは気化する溶剤は特に限定するものではなく、例えば有機、無機系の各種があり、有機系物理発泡剤としてはプロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、ノルマルヘキサン、イソヘキサン、シクロヘキサン等の脂肪族炭化水素、シクロプロパン、シクロブタン、シクロペンタン等の環式脂肪族炭化水素、シクロロフルオロメタン、ジクロロジフルオロメタン、ジクロロテトラフルオロエタン、トリクロロフルオロメタン、テトラフルオロエタン等のハロゲン化炭化水素が例示され、無機系物理発泡剤としては炭酸ガス、窒素、ヘリウム等が例示され、それぞれ単独あるいは2種類以上を組み合わせて使用することができる。 The gas used in the solvent diffusing method or the solvent to be vaporized is not particularly limited. For example, there are various organic and inorganic types, and examples of the organic physical foaming agent include propane, normal butane, isobutane, normal pentane, and isopentane. Aliphatic hydrocarbons such as normal hexane, isohexane, cyclohexane, cycloaliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, trichlorofluoromethane, tetrafluoro Halogenated hydrocarbons such as ethane are exemplified, and examples of the inorganic physical foaming agent include carbon dioxide, nitrogen, helium and the like, and each can be used alone or in combination of two or more.
また、発泡剤分解法に用いる熱分解型化学発泡剤とは、熱を加えることで分解しガスを放出する化学発泡剤であれば特に限定するものではなく、例えば有機、無機系の各種があり、有機系にはアゾジカルボンアミド、N,N´−ジニトロソペンタメチレンテトラミン、P.P´−オキシベンゼンスルフォニルヒドラジドなど、無機系には重炭酸ナトリウム、炭酸アンモニウム、重炭酸アンモニウム、カルシウムアジドなどが例示され、それぞれ単独あるいは2種類以上を組み合わせて使用することができ、必要に応じて熱分解型発泡剤の分解性を改善する尿素、脂肪酸の金属塩、亜鉛華等の発泡助剤を添加しても良い。 The pyrolytic chemical foaming agent used in the foaming agent decomposing method is not particularly limited as long as it is a chemical foaming agent that decomposes and releases gas when heat is applied. For example, there are various organic and inorganic types. Organic systems include azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, P.I. Examples of inorganic systems such as P′-oxybenzenesulfonyl hydrazide include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, calcium azide, etc., which can be used singly or in combination of two or more, as necessary. You may add foaming adjuvants, such as urea which improves the decomposability | degradability of a thermal decomposition type foaming agent, the metal salt of a fatty acid, and zinc white.
ポリオレフィン系樹脂発泡体は、電離性放射線を照射し架橋させる電子線架橋法、ジクミルパ−オキサイド、ターシャリーブチルパ−ベンゾエ−ト、ジタ−シャリ−ブチルパ−オキサイド等の有機過酸化物を混練し発泡時に該有機過酸化物を分解し架橋させる化学架橋法、シラン基を持つポリオレフィン系樹脂を混合し加熱水分と接触することで架橋させるシラン架橋法などの方法を用いポリオレフィン系樹脂架橋発泡体としても良く、必要に応じて架橋特性を改善するジビニルベンゼン、トリメチロールプロパントリメタクリレート等の架橋助剤を用いても良い。 Polyolefin resin foam is foamed by kneading organic peroxides such as electron beam cross-linking method, dicumyl peroxide, tertiary butyl perbenzoate, di-tert-butyl peroxide, etc. A polyolefin resin cross-linked foam using a method such as a chemical cross-linking method in which the organic peroxide is sometimes decomposed and cross-linked, or a silane cross-linking method in which a polyolefin resin having a silane group is mixed and brought into contact with heated moisture is used. It is also possible to use a crosslinking aid such as divinylbenzene or trimethylolpropane trimethacrylate that improves the crosslinking properties as necessary.
本発明に用いるポリオレフィン系樹脂発泡体の厚みは0.5〜500mmが好ましく、更には3〜100mmが好ましい。厚みが0.5mm未満であれば保温性、保冷性、断熱性や緩衝性、クッション性といった性能が著しく低下し、必要とする保温、保冷、断熱の温度特性を満たさない場合や緩衝性、クッション性等の耐衝撃性を満たさない場合があり、一方、厚みが500mmを越えると断熱性能や耐衝撃性は満たされるが、加工特性や生産性の低下、価格の高騰等といった問題が生じる場合がある。ここで示す厚みとは、JIS K−7222に準じた測定方法で測定した数値を示す。 The polyolefin resin foam used in the present invention preferably has a thickness of 0.5 to 500 mm, more preferably 3 to 100 mm. If the thickness is less than 0.5 mm, performance such as heat retention, cold insulation, heat insulation, cushioning, and cushioning properties will be remarkably lowered. However, if the thickness exceeds 500 mm, the thermal insulation performance and impact resistance are satisfied, but problems such as reduced processing characteristics and productivity, and increased prices may occur. is there. The thickness shown here indicates a numerical value measured by a measurement method according to JIS K-7222.
本発明に用いるポリオレフィン系樹脂発泡体の見掛け密度は20〜200kg/m3が好ましく、更には25〜50kg/m3が好ましい。見掛け密度が20kg/m3より小さい場合、圧縮特性や強伸度等の機械的特性が低下し断熱性能や加工特性が不備が生じる場合があり、一方見かけ密度が200kg/m3を超える場合、断熱性能が著しく低下し、必要とする保温や保冷の温度特性を満たさない場合がある。ここで示す厚み、見掛け密度とは、2001年版JIS K−7222に準じた測定方法で測定した数値を示す。 The apparent density of the polyolefin resin foam used in the present invention is preferably 20 to 200 kg / m 3, more preferably 25 to 50 kg / m 3 . When the apparent density is less than 20 kg / m 3 , mechanical properties such as compression characteristics and high elongation may be deteriorated, resulting in insufficiency in heat insulation performance and processing characteristics, while when the apparent density exceeds 200 kg / m 3 , Insulation performance may be significantly reduced, and the required thermal insulation and cold insulation temperature characteristics may not be satisfied. The thickness and the apparent density shown here indicate numerical values measured by a measuring method according to the 2001 edition JIS K-7222.
本発明の消臭機能を有したポリオレフィン系樹脂積層発泡体において消臭剤を添加したポリオレフィン系樹脂層とポリオレフィン系樹脂発泡体を積層する方法は特に限定されず、公知の方法を用いて積層しても良い。具体的積層方法としては、予めTダイを用いた単軸押出機や二軸押出機等の公知の押出機やカレンダーロール等で未延伸のフィルム状に成形した消臭機能を有したポリオレフィン系樹脂層を溶媒系、水系等の液状、ゲル状、固形状の公知の接着剤や公知の粘着テープを介してポリオレフィン系樹脂発泡体と積層する方法や熱風、ヒータ等の公知の熱源による加熱、火炎処理等でポリオレフィン系樹脂発泡体の表面を溶融後、予め未延伸フィルム状に成型した該樹脂層と圧着により溶着する方法、あるいはTダイを用いた公知の押出機等を用いフィルム状に押し出した該樹脂層を同時にポリオレフィン系樹脂発泡体と冷却圧着し積層する方法が例示される。 In the polyolefin resin laminated foam having a deodorizing function of the present invention, the method of laminating the polyolefin resin layer to which the deodorant is added and the polyolefin resin foam is not particularly limited, and it is laminated using a known method. May be. As a specific lamination method, a polyolefin-based resin having a deodorizing function, which has been formed into an unstretched film by a known extruder such as a single-screw extruder or a twin-screw extruder using a T-die or a calender roll in advance. A method of laminating a layer with a polyolefin resin foam via a known liquid, gel or solid adhesive such as a solvent or water, or a known adhesive tape, heating with a known heat source such as hot air or a heater, flame After melting the surface of the polyolefin resin foam by treatment, etc., it was extruded into a film using a method of welding with the resin layer previously molded into an unstretched film, or a known extruder using a T-die. A method of laminating the resin layer with a polyolefin resin foam at the same time by cooling and pressing is exemplified.
特に消臭効果を効率よく付与するには、接着剤等を用いない方法が好ましく、公知の押出機等でポリオレフィン系樹脂と消臭剤を溶融混錬し、Tダイでフィルム状に押し出した樹脂層を同時にポリオレフィン系樹脂発泡体と冷却圧着し積層する方法が好ましい。更にポリオレフィン系樹脂層とポリオレフィン系樹脂発泡体の主要樹脂を同一とすることで強固な融着が可能となり安定的に積層できることから好ましい。ここで主要樹脂とは複数種類のポリオレフィン系樹脂を混合した場合50%を超える樹脂成分を示す。 In particular, in order to efficiently impart a deodorizing effect, a method that does not use an adhesive or the like is preferable. A resin obtained by melt-kneading a polyolefin-based resin and a deodorant with a known extruder or the like, and extruding it into a film with a T-die A method in which the layers are simultaneously laminated with a polyolefin resin foam by cooling and pressing is preferred. Further, it is preferable that the polyolefin resin layer and the main resin of the polyolefin resin foam are made the same so that strong fusion is possible and stable lamination is possible. Here, the main resin indicates a resin component exceeding 50% when plural kinds of polyolefin-based resins are mixed.
また、かかる発泡体は物品との接触面積を小さくし傷を軽減する効果や手作業時の滑り止め効果、あるいは湾曲加工した時の表面皺を目立たなくする意匠性向上効果といった施工時の作業効率を向上するため、少なくとも片面のポリオレフィン系樹脂層側に規則的凹凸形状を設けることが望ましい。規則的凹凸形状を設ける方法は特に限定されないが、上記方法で作成した消臭機能を有するポリオレフィン系樹脂積層発泡体のポリオレフィン系樹脂層側を熱風、ヒータ等の公知の熱源により加熱した後、該樹脂層側に配置したロール表面を規則的凹凸形状に刻印した金属ロールで加圧し、該ロールの規則的凹凸形状を該樹脂層に転写する方法、押出機等を用い溶融状態とした該樹脂層をポリオレフィン系樹脂発泡体と冷却圧着する際、該樹脂層側に配置したロール表面を規則的凹凸形状に刻印した金属ロールで加圧し該ロールの規則的凹凸形状を該樹脂層に転写する方法が例示される。 In addition, such foam has a work efficiency during construction such as an effect of reducing scratches by reducing the contact area with the article, an anti-slip effect during manual work, or a design improvement effect that makes surface wrinkles less noticeable when curved. In order to improve this, it is desirable to provide a regular uneven shape on at least one side of the polyolefin resin layer. The method of providing the regular uneven shape is not particularly limited, but after heating the polyolefin resin layer side of the polyolefin resin laminated foam having the deodorizing function prepared by the above method with a known heat source such as hot air or a heater, The method of transferring the regular uneven shape of the roll to the resin layer by pressing a roll surface arranged on the resin layer side with a metal roll engraved in a regular uneven shape, and the resin layer in a molten state using an extruder or the like Is a method of transferring the regular concavo-convex shape of the roll to the resin layer by pressurizing the roll surface arranged on the resin layer side with a metal roll engraved with a regular concavo-convex shape when cooling and pressing with a polyolefin resin foam Illustrated.
本発明の消臭機能を有したポリオレフィン系樹脂層の厚みは0.01〜2mmが好ましく、更に、0.05〜1mmが好ましい。厚みが0.01mm未満であれば取り扱いによっては傷、破れの発生頻度が高くなり作業性が低下する場合があり、一方2mmを越えると軽量性、柔軟性、緩衝性などの発泡体特性を著しく低下させる場合や高い剛性により加工性が低下する場合がある。かかるポリオレフィン系樹脂層は、ポリオレフィン系樹脂発泡体と積層した後加熱し所定形状に成型できるように未延伸であることが好ましい。 The thickness of the polyolefin resin layer having a deodorizing function of the present invention is preferably 0.01 to 2 mm, and more preferably 0.05 to 1 mm. If the thickness is less than 0.01 mm, the frequency of occurrence of scratches and tears may increase depending on handling, and workability may be reduced. On the other hand, if the thickness exceeds 2 mm, the foam properties such as lightness, flexibility, and cushioning are remarkably increased. In some cases, the workability may be lowered due to the reduction or high rigidity. Such a polyolefin resin layer is preferably unstretched so that it can be heated and molded into a predetermined shape after being laminated with a polyolefin resin foam.
本発明の消臭機能を有したポリオレフィン系樹脂積層発泡体は、必要に応じて例えば難燃剤、難燃助剤、分散剤、顔料、離型剤、造核剤、紫外線吸収剤、光安定剤など公知の各種添加剤をポリオレフィン系樹脂層及び/又はポリオレフィン系樹脂発泡体に添加しても良い。上記添加剤のうち有機系の添加剤は熱分解等により消臭機能を低下させる場合があるためポリオレフィン系樹脂100重量部に対し5重量部未満の添加が好ましい。また、無機系の添加剤は引張強度、引裂強度等の機械的特性を低下させる場合があるためポリオレフィン系樹脂100重量部に対し30重量部未満の添加が好ましい。 The polyolefin resin laminated foam having a deodorizing function according to the present invention is, for example, a flame retardant, a flame retardant aid, a dispersant, a pigment, a mold release agent, a nucleating agent, an ultraviolet absorber, and a light stabilizer. Various known additives such as those may be added to the polyolefin resin layer and / or the polyolefin resin foam. Of the above-mentioned additives, organic additives may reduce the deodorizing function by thermal decomposition or the like, so addition of less than 5 parts by weight with respect to 100 parts by weight of the polyolefin-based resin is preferable. In addition, since inorganic additives may reduce mechanical properties such as tensile strength and tear strength, addition of less than 30 parts by weight with respect to 100 parts by weight of polyolefin resin is preferable.
本発明の消臭機能を有したポリオレフィン系樹脂積層発泡体は配管内を流れる気体や液体等の流動性を有する物体の保温、保冷、結露防止を効率的に行うため、配管形状に則した被覆とする円筒体とすることが望ましい。かかる発泡体を円筒体とする方法は特に限定されないが、例えば上記方法で積層した該発泡体を円筒の直径に応じた幅に切断し、熱風や赤外線ヒータ等の公知の熱源で該発泡体を加熱しながら円錐形状の口金を通す方法、あるいはポリオレフィン系樹脂発泡体を円筒の直径に応じた幅に切断し、熱風や赤外線ヒータ等の公知の熱源で該発泡体を加熱しながら円錐形状の口金を通し円筒体とした後、適度な幅に切断した未延伸のフィルム状に成形した消臭機能を有したポリオレフィン系樹脂層を溶媒系、水系等の液状、ゲル状、固形状の公知の接着剤や公知の粘着テープで接着する方法が例示される。 The polyolefin-based resin laminated foam having a deodorizing function of the present invention is a coating that conforms to the shape of the pipe in order to efficiently keep warm, cool, and prevent dew condensation of a fluid object such as gas or liquid flowing in the pipe. It is desirable to use a cylindrical body. The method of making the foam into a cylindrical body is not particularly limited. For example, the foam laminated by the above-described method is cut into a width corresponding to the diameter of the cylinder, and the foam is removed with a known heat source such as hot air or an infrared heater. A method of passing a cone-shaped base while heating, or cutting a polyolefin resin foam into a width corresponding to the diameter of the cylinder, and heating the foam with a known heat source such as hot air or an infrared heater while heating the foam A polyolefin resin layer having a deodorizing function formed into an unstretched film cut into an appropriate width after being made into a cylindrical body through a solvent, a water-based liquid, gel, or solid known adhesive The method of adhering with an agent or a well-known adhesive tape is illustrated.
また、保温、保冷、結露防止を必要とする配管の湾曲部位、継手部位、バルブ等の流量調節部位等配管形状が円筒体と異なる部位や緩衝性、クッション性を必要とする所定形状の部位には、該部位と同等形状の所定形状に成型し被覆することが望ましい。かかる発泡体を所定形状の成型体とする方法は特に限定されないが、例えば上記方法で積層した該発泡体を循環式熱風オーブンや赤外線ヒータ等の公知の熱源で加熱した後、微細孔を有する金属製や木製等の所定型の上に置き、微細孔より空気を抜き取り該発泡体と所定型を密着する方法が例示される。 In addition, pipes that require heat insulation, cold insulation, anti-condensation, joints, flow control parts such as valves, etc. Is preferably molded and coated into a predetermined shape equivalent to the portion. There is no particular limitation on the method for forming the foam into a molded body having a predetermined shape. For example, the foam laminated by the above method is heated with a known heat source such as a circulating hot air oven or an infrared heater, and then a metal having fine holes. An example is a method in which the foam is placed on a predetermined mold such as made or wooden, the air is extracted from the fine holes, and the foam and the predetermined mold are in close contact with each other.
以下、本発明を以下の実施例を用いて更により詳細に説明するが、以下の実施例は一例であり特に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are merely examples and are not particularly limited.
本発明における消臭評価基準は次の通りである。 The deodorant evaluation criteria in the present invention are as follows.
アンモニアガス消臭試験方法
100mm角に裁断した試験体をテドラーバッグに入れヒートシールにより密封したものと、試験体を入れない以外は同様に調整したものを用意し、それぞれに予め作成したアンモニアガス3リットルを封入した後、室温で3時間放置した。放置後、それぞれの濃度をガス検知管(株式会社ガステック社製、検知管は3Laを使用)により測定した。
ここで用いたアンモニアガスの調整方法は、テドラーバックに28%アンモニア水特級試薬(ナカライテクス株式会社製)2gと空気5リットルを封入し、室温で3時間放置したものを使用した。
Ammonia gas deodorization test method Prepare a test piece cut into a 100 mm square and put it in a tedlar bag and seal it by heat sealing. Was allowed to stand at room temperature for 3 hours. After being allowed to stand, each concentration was measured with a gas detector tube (manufactured by Gastec Co., Ltd., 3La detector tube was used).
As the method for adjusting the ammonia gas used here, 2 g of 28% ammonia water special grade reagent (manufactured by Nacalai Tex Co., Ltd.) and 5 liters of air were enclosed in a Tedlar bag and left at room temperature for 3 hours.
酢酸ガス消臭試験方法
100mm角に裁断した試験体をテドラーバッグに入れヒートシールにより密封したものと、試験体を入れない以外は同様に調整したものを用意し、それぞれに予め作成した酢酸ガス3リットルを封入した後、室温で3時間放置した。放置後、それぞれの濃度をガス検知管(株式会社ガステック社製、検知管は81を使用)により測定した。
ここで用いた酢酸ガスの調整方法は、テドラーバックに酢酸特級試薬(ナカライテクス株式会社製)0.5gと空気5リットルを封入し、室温で3時間放置したものを使用した。
Acetic acid gas deodorization test method Prepare a specimen cut into a 100mm square in a Tedlar bag and sealed by heat sealing, and a similar adjustment except that the specimen is not put. Was allowed to stand at room temperature for 3 hours. After being allowed to stand, each concentration was measured with a gas detector tube (manufactured by Gastec Co., Ltd., using 81 detector tube).
As a method for adjusting the acetic acid gas used here, 0.5 g of acetic acid special grade reagent (manufactured by Nacalai Tex Co., Ltd.) and 5 liters of air were enclosed in a Tedlar bag and left at room temperature for 3 hours.
判定方法
試験体を入れたもののガス濃度か試験体を入れていないもののガス濃度で除した数値の百分率(以下ガス残存率と称する)が、アンモニアガス消臭試験法と酢酸ガス消臭試験法のどちらも95%以下を合格(◎)と判定し、どちらか一方の試験で95%以下であれば合格(○)と判定し、両試験とも95%を超える場合は不合格(×)と判定した。
Judgment method The percentage of the numerical value divided by the gas concentration of the specimen with or without the specimen (hereinafter referred to as the residual gas ratio) is the value of the ammonia gas deodorization test method and the acetic acid gas deodorization test method. In both cases, 95% or less is judged as pass (◎), and if either test is 95% or less, it is judged as pass (○), and if both tests exceed 95%, it is judged as fail (x). did.
[実施例1]
MFRが3.6g/10分、密度が0.922g/cm3の高圧法低密度ポリエチレン(東ソー株式会社製ペトロセン310)50重量部とMFRが3.0g/10分、密度が0.935g/cm3の直鎖状低密度ポリエチレン(東ソー株式会社製ニポロン−L M50)50重量部をそれぞれ粉砕機を用い2mm以下に粉砕した後、熱分解型化学発泡剤アゾジカルボンアミド(永和化成工業株式会社製ビニホールAC#1)10.5重量部、酸化防止剤ペンタエリスリト−ルテトラキス[3-(3,5-ジ−tert-ブチル−4−ヒドロキシフェニル)プロピオネート](チバ・スペシャリティ・ケミカルズ株式会社製IRGANOX1010)0.3重量部をスーパーミキサーで混合し、140〜160℃に加熱した90mmφの単軸押出機でTダイを用いて厚さ1.8mmの長尺シート状に成形した後、70kGyの電子線を加速電圧800kVで照射し、架橋せしめた後、240℃に加熱した縦型熱風発泡装置で2〜3分加熱し厚さ4.3mm、見掛け密度31kg/m3の長尺発泡体を得た。
[Example 1]
50 parts by weight of high pressure method low density polyethylene (Petrocene 310 manufactured by Tosoh Corporation) having an MFR of 3.6 g / 10 min and a density of 0.922 g / cm 3, an MFR of 3.0 g / 10 min, and a density of 0.935 g / 50 parts by weight of cm 3 linear low-density polyethylene (Nipolon-LM50 manufactured by Tosoh Corporation) was pulverized to 2 mm or less using a pulverizer, respectively, and then pyrolyzed chemical foaming agent azodicarbonamide (Yewa Kasei Kogyo Co., Ltd.). Binihol AC # 1) 10.5 parts by weight, antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals) IRGANOX1010) 90mmφ single screw extrusion mixed 0.3 parts by weight with a super mixer and heated to 140-160 ° C After forming into a long sheet with a thickness of 1.8 mm using a T-die, 70 kGy electron beam was irradiated at an acceleration voltage of 800 kV, crosslinked, and then heated with a vertical hot air foaming device heated to 240 ° C. After heating for 3 minutes, a long foam having a thickness of 4.3 mm and an apparent density of 31 kg / m 3 was obtained.
MFRが3.0g/10分、密度が0.935g/cm3の直鎖状低密度ポリエチレン(東ソー株式会社製ニポロン−L M50)100重量部に消臭剤として銀イオンや亜鉛イオンを有する珪酸塩化合物(株式会社シナネンゼオミック社製ゼオミック)20重量部を130〜150℃に加熱した40mmφの二軸押出機で溶融混練し、ノズルから押出すことにより直径2mmの棒状のストランドを作り、水冷後長さ3mmにカッティングし消臭性樹脂組成物を得た。該消臭性樹脂組成物を140〜160℃に加熱した65mmφの単軸押出機に投入しTダイを介してシート状に押し出した直後、上記長尺発泡体と共に間隙を発泡体厚みの半数に調整した2本のロールに通し消臭機能を有するポリオレフィン系樹脂積層発泡体を得た。この時の樹脂層の厚みを幅方向に5点ノギスで測定した平均値は0.15mmであった。 Silicic acid having silver ions and zinc ions as a deodorant in 100 parts by weight of linear low density polyethylene (Nipolon-LM50 manufactured by Tosoh Corporation) having an MFR of 3.0 g / 10 min and a density of 0.935 g / cm 3 After melt-kneading 20 parts by weight of a salt compound (Zeomic manufactured by Sinanen Zeomic Co., Ltd.) with a 40 mmφ twin-screw extruder heated to 130 to 150 ° C., a rod-like strand having a diameter of 2 mm is formed by extruding from a nozzle, and after water cooling Cutting to a length of 3 mm gave a deodorant resin composition. Immediately after the deodorant resin composition is put into a 65 mmφ single screw extruder heated to 140 to 160 ° C. and extruded into a sheet through a T-die, the gap with the long foam is reduced to half of the foam thickness. The polyolefin-based resin laminated foam having a deodorizing function was obtained through the two adjusted rolls. The average value of the thickness of the resin layer measured at this time with a 5-point caliper in the width direction was 0.15 mm.
表1に示すとおり、上記方法で得た消臭機能を有するポリオレフィン系樹脂積層発泡体のアンモニアガスのガス残存率は89%、酢酸ガスのガス残存率は82%であり合格(◎)判定であった。 As shown in Table 1, the polyolefin resin laminated foam having the deodorizing function obtained by the above method has a residual gas rate of 89% for ammonia gas and a residual gas rate for acetic acid gas of 82%. there were.
[実施例2]
MFRが3.6g/10分、密度が0.922g/cm3の高圧法低密度ポリエチレン(東ソー株式会社製ペトロセン310)100重量部を粉砕機を用い2mm以下に粉砕した後、熱分解型化学発泡剤アゾジカルボンアミド(永和化成工業株式会社製ビニホールAC#1)3.5重量部、酸化防止剤ペンタエリスリト−ルテトラキス[3-(3,5-ジ−tert-ブチル−4−ヒドロキシフェニル)プロピオネート](チバ・スペシャリティ・ケミカルズ株式会社製IRGANOX1010)0.3重量部をスーパーミキサーで混合し、140〜160℃に加熱した90mmφの単軸押出機でTダイを用いて厚さ1.8mmの長尺シート状に成形した後、70kGyの電子線を加速電圧800kVで照射し、架橋せしめた後、240℃に加熱した縦型熱風発泡装置で2〜3分加熱し厚さ2.7mm、見掛け密度105kg/m3の長尺発泡体としたほかは実施例1と同様に消臭機能を有するポリオレフィン系樹脂積層発泡体を得た。この時の樹脂層の厚みを幅方向に5点ノギスで測定した平均値は0.08mmであった。
表1に示すとおり、上記方法で得た消臭機能を有するポリオレフィン系樹脂積層発泡体のアンモニアガスのガス残存率は92%、酢酸ガスのガス残存率は86%であり合格(◎)判定であった。
[Example 2]
After pulverizing 100 parts by weight of high pressure method low density polyethylene (Petrocene 310 manufactured by Tosoh Corporation) having an MFR of 3.6 g / 10 min and a density of 0.922 g / cm 3 to 2 mm or less, pyrolysis-type chemistry Foaming agent azodicarbonamide (Vinole AC # 1 manufactured by Eiwa Chemical Industries Ltd.) 3.5 parts by weight, antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] (IRGANOX1010 manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.3 parts by weight was mixed with a super mixer and heated to 140 to 160 ° C. with a 90 mmφ single screw extruder using a T die and a thickness of 1.8 mm. After forming into a long sheet shape, 70 kGy electron beam is irradiated at an acceleration voltage of 800 kV to crosslink, and then heated to 240 ° C. A polyolefin-based resin laminated foam having a deodorizing function in the same manner as in Example 1 except that it was heated in a vertical hot air foaming apparatus for 2 to 3 minutes to obtain a long foam having a thickness of 2.7 mm and an apparent density of 105 kg / m 3. Got the body. The average value of the thickness of the resin layer measured at this time with a 5-point caliper in the width direction was 0.08 mm.
As shown in Table 1, the polyolefin resin laminated foam having the deodorizing function obtained by the above method has a residual gas rate of 92% for ammonia gas and a residual gas rate for acetic acid gas of 86%. there were.
[実施例3]
MFRが8.0g/10分、密度が0.925g/cm3の高圧法低密度ポリエチレン(東ソー株式会社製ペトロセン207)100重量部を粉砕機を用い2mm以下に粉砕した後、熱分解型化学発泡剤アゾジカルボンアミド(永和化成工業株式会社製ビニホールAC#1)15.5重量部、酸化防止剤ペンタエリスリト−ルテトラキス[3-(3,5-ジ−tert-ブチル−4−ヒドロキシフェニル)プロピオネート](チバ・スペシャリティ・ケミカルズ株式会社製IRGANOX1010)0.3重量部をスーパーミキサーで混合し、140〜160℃に加熱した90mmφの単軸押出機でTダイを用いて厚さ1.8mmの長尺シート状に成形した後、60kGyの電子線を加速電圧800kVで照射し、架橋せしめた後、240℃に加熱した縦型熱風発泡装置で2〜3分加熱し厚さ5.2mm、見掛け密度21kg/m3の長尺発泡体としたほかは実施例1と同様に消臭機能を有するポリオレフィン系樹脂積層発泡体を得た。この時の樹脂層の厚みを幅方向に5点ノギスで測定した平均値は0.18mmであった。
表1に示すとおり、上記方法で得た消臭機能を有するポリオレフィン系樹脂積層発泡体のアンモニアガスのガス残存率は96%、酢酸ガスのガス残存率は92%であり合格(○)判定であった。
[Example 3]
After pulverizing 100 parts by weight of high-pressure low-density polyethylene (Petrocene 207 manufactured by Tosoh Corporation) having an MFR of 8.0 g / 10 min and a density of 0.925 g / cm 3 to 2 mm or less using a pulverizer, 15.5 parts by weight of a foaming agent azodicarbonamide (Vinole AC # 1 manufactured by Eiwa Chemical Industries Ltd.), antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] (IRGANOX1010 manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.3 parts by weight was mixed with a super mixer and heated to 140 to 160 ° C. with a 90 mmφ single screw extruder using a T die and a thickness of 1.8 mm. After forming into a long sheet shape, it is irradiated with an electron beam of 60 kGy at an acceleration voltage of 800 kV, crosslinked, and then heated to 240 ° C. A polyolefin-based resin laminated foam having a deodorizing function in the same manner as in Example 1 except that it was heated for 2-3 minutes in the vertical hot-air foaming apparatus and made into a long foam having a thickness of 5.2 mm and an apparent density of 21 kg / m 3. Got the body. The average value of the thickness of the resin layer measured at this time with a 5-point caliper in the width direction was 0.18 mm.
As shown in Table 1, in the polyolefin resin laminated foam having the deodorizing function obtained by the above method, the residual gas rate of ammonia gas is 96%, the residual gas rate of acetic acid gas is 92%, there were.
[実施例4]
消臭剤添加量を2重量部としたほかは実施例1と同様に消臭機能を有するポリオレフィン系樹脂積層発泡体を得た。この時の樹脂層の厚みを幅方向に5点ノギスで測定した平均値は0.13mmであった。
[Example 4]
A polyolefin-based resin laminate foam having a deodorizing function was obtained in the same manner as in Example 1 except that the amount of deodorant added was 2 parts by weight. The average value of the thickness of the resin layer measured at this time with a 5-point caliper in the width direction was 0.13 mm.
表1に示すとおり、上記方法で得た消臭機能を有するポリオレフィン系樹脂積層発泡体のアンモニアガスのガス残存率は97%、酢酸ガスのガス残存率は93%であり合格(○)判定であった。 As shown in Table 1, in the polyolefin resin laminated foam having the deodorizing function obtained by the above method, the residual gas rate of ammonia gas was 97%, and the residual gas rate of acetic acid gas was 93%. there were.
[実施例5]
MFRが24g/10分、密度が0.918g/cm3の高圧法低密度ポリエチレン(東ソー株式会社製ペトロセン202)100重量部に消臭剤としてタンニン(松尾薬品産業株式会社製パンシル)10重量部を120〜140℃に加熱した40mmφの二軸押出機で溶融混練し、ノズルから押出すことにより直径2mmの棒状のストランドを作り、水冷後長さ3mmにカッティングし消臭性樹脂組成物を得たほかは実施例1と同様に消臭機能を有するポリオレフィン系樹脂積層発泡体を得た。この時の樹脂層の厚みを幅方向に5点ノギスで測定した平均値は0.10mmであった。
表1に示すとおり、上記方法で得た消臭機能を有するポリオレフィン系樹脂積層発泡体のアンモニアガスのガス残存率は91%、酢酸ガスのガス残存率は92%であり合格(◎)判定であった。
[Example 5]
10 parts by weight of tannin (Matsuo Pharmaceutical Co., Ltd. Pancil) as a deodorant in 100 parts by weight of high-pressure low-density polyethylene (Tosoh Corporation Petrocene 202) having an MFR of 24 g / 10 min and a density of 0.918 g / cm 3 Is melt-kneaded with a 40 mmφ twin-screw extruder heated to 120 to 140 ° C., extruded from a nozzle to form a rod-like strand having a diameter of 2 mm, cut into a length of 3 mm after water cooling, and a deodorant resin composition is obtained. In the same manner as in Example 1, a polyolefin resin laminated foam having a deodorizing function was obtained. The average value of the thickness of the resin layer measured at this time with a 5-point caliper in the width direction was 0.10 mm.
As shown in Table 1, the polyolefin resin laminated foam having the deodorizing function obtained by the above method has a residual gas ratio of ammonia gas of 91% and a residual gas ratio of acetic acid gas of 92%. there were.
[実施例6]
実施例1の消臭機能を有するポリオレフィン系樹脂積層発泡体を100mm幅に裁断し、最小直径が34mmの円錐状口金中に180℃の熱風を吹付けながら円筒状に成型した。ガス消臭試験のサンプルは長さ100mmに裁断した円筒を試験体とした。
[Example 6]
The polyolefin-based resin laminate foam having a deodorizing function of Example 1 was cut into a width of 100 mm, and molded into a cylindrical shape while blowing hot air at 180 ° C. into a conical base having a minimum diameter of 34 mm. The sample for the gas deodorization test was a cylinder cut to a length of 100 mm.
表1に示すとおり、上記方法で得た消臭機能を有するポリオレフィン系樹脂積層発泡体のアンモニアガスのガス残存率は91%、酢酸ガスのガス残存率は92%であり合格(◎)判定であった。 As shown in Table 1, the polyolefin resin laminated foam having the deodorizing function obtained by the above method has a residual gas ratio of ammonia gas of 91% and a residual gas ratio of acetic acid gas of 92%. there were.
[実施例7]
実施例1の消臭機能を有するポリオレフィン系樹脂積層発泡体を150℃の熱風オーブン中で3分間加熱し、直径180mm、深さ50mmの円柱状メス型金型で真空成型した。ガス消臭試験のサンプルは円柱底面より100mm角を裁断し試験体とした。
[Example 7]
The polyolefin-based resin laminated foam having a deodorizing function of Example 1 was heated in a hot air oven at 150 ° C. for 3 minutes, and vacuum molded with a cylindrical female mold having a diameter of 180 mm and a depth of 50 mm. A sample for the gas deodorization test was cut into a 100 mm square from the bottom of the cylinder to obtain a test specimen.
表1に示すとおり、上記方法で得た消臭機能を有するポリオレフィン系樹脂積層発泡体のアンモニアガスのガス残存率は88%、酢酸ガスのガス残存率は93%であり合格(◎)判定であった。 As shown in Table 1, in the polyolefin resin laminated foam having the deodorizing function obtained by the above method, the residual gas rate of ammonia gas was 88%, and the residual gas rate of acetic acid gas was 93%. there were.
[比較例1]
消臭剤を用いない以外は実施例1と同様に消臭機能を有するポリオレフィン系樹脂積層発泡体を得た。この時の樹脂層の厚みを幅方向に5点ノギスで測定した平均値は0.11mmであった。
表1に示すとおり、上記方法で得た消臭機能を有するポリオレフィン系樹脂積層発泡体のアンモニアガスのガス残存率は100%、酢酸ガスのガス残存率は100%であり不合格(×)判定であった。
[Comparative Example 1]
A polyolefin resin laminated foam having a deodorizing function was obtained in the same manner as in Example 1 except that no deodorant was used. The average value of the thickness of the resin layer measured at this time with a 5-point caliper in the width direction was 0.11 mm.
As shown in Table 1, the polyolefin resin laminated foam having a deodorizing function obtained by the above method has a gas residual rate of 100% and a gas residual rate of acetic acid gas of 100%, which is rejected (x). Met.
以上述べたように、実施例に示した本発明による消臭機能を有するポリオレフィン系樹脂積層発泡体はポリオレフィン系樹脂発泡体の少なくとも片面の表層面に、ポリオレフィン系樹脂100重量部に対し少なくとも消臭剤1〜30重量部含むポリオレフィン系樹脂層を設けることけることで得ることができる。 As described above, the polyolefin resin laminated foam having a deodorizing function according to the present invention shown in the examples is at least deodorized with respect to 100 parts by weight of the polyolefin resin on the surface of at least one surface of the polyolefin resin foam. It can be obtained by providing a polyolefin resin layer containing 1 to 30 parts by weight of the agent.
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