JP2019131702A - Polyolefin crosslinked foam, and manufacturing method therefor - Google Patents
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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 crosslinked polyolefin 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 cross-linked foam is durable and excellent in chemical resistance and weather resistance, so it is widely used in shock buffering applications such as residential flooring and wall materials, building joint materials, automobile interior materials, and packaging materials. It is used.
Foaming of a polyolefin cross-linked foam is mainly carried out by pyrolysis foaming using a pyrolytic foaming agent that allows easy control of cost and thickness of the foam. As the pyrolytic foaming agent, an azodicarbonamide (ADCA) foaming agent having 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, since azodicarbonamide-based foaming agents generate ammonia as a decomposition residue, when used as cushioning members for packaging, polyolefin-based crosslinked foams for electronic devices, medical parts, automotive interior materials, headlamps, etc. There is a problem of contamination and corrosion by residual ammonia. For example, a headlamp has a problem of being clouded by ammonia. Furthermore, azodicarbonamide (ADCA) has a decomposition temperature as high as 200 to 210 ° C., and it was necessary to increase the mold temperature during the production of the foam.
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-based crosslinked foam, an olefin-based crosslinked foam containing an ammonia adsorbent and reducing 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-based crosslinked foam having an ammonia concentration reduced to 200 ppm to 1000 ppm is insufficient for solving the problems of contamination and corrosion due to 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。 This invention is made | formed in view of the said point, Comprising: It aims at provision of the polyolefin-type crosslinked foam which can prevent the contamination and corrosion by ammonia, and its manufacturing method.
請求項１の発明は、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 invention of claim 1 relates to a polyolefin-based crosslinked foam having a density of 20 to 160 kg / m 3 , an ammonia concentration of 0 ppm to 100 ppm, and a glass strength of 5% or less.
請求項２の発明は、請求項１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 invention of claim 2 is characterized in that, in claim 1, the foaming agent is a combined use of baking soda and p, p'-oxybisbenzenesulfonylhydrazide.
請求項３の発明は、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。 The invention of claim 3 is a method for producing a polyolefin-based crosslinked foam having a density of 20 to 160 kg / m 3 , an ammonia concentration of 0 ppm to 100 ppm, and a glass consistency of 5% or less. , P′-oxybisbenzenesulfonyl hydrazide is used in combination with a larger amount of p, p′-oxybisbenzenesulfonyl hydrazide than the amount of baking soda, and foaming 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-based crosslinked foam.
請求項４の発明は、請求項３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。 The invention of claim 4 is characterized in that, in claim 3, the blowing agent is an amount of p, p′-oxybisbenzenesulfonylhydrazide / amount of baking soda = 5.5 / 4.5 to 77/23. And
請求項５の発明は、請求項３または４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。
The invention of
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-based crosslinked foam capable of preventing contamination and corrosion by residual ammonia is obtained.
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-based crosslinked foam of the present invention is suitable for impact buffering applications such as residential flooring and wall materials, building joint materials, automobile interior materials, and packaging materials, and has a density (conforming to JIS K 6767). 20 to 160 kg / m 3 , the ammonia concentration is 0 ppm to 100 ppm, and the glass consistency (ISO 6452 compliant) is 5% or less. The ammonia concentration was measured by using an ammonia detector tube (manufactured by Gastec) after putting 0.1 g of the sample into a 500 cc round bottom flask and leaving it in an oven at 80 ° C. for 2 hours, taking it out and allowing it to cool.
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 the polyolefin-based crosslinked foam is used as, for example, a cushioning member for packing, if the density of the polyolefin-based crosslinked foam is too low, the foam is too soft and the shape cannot be maintained, resulting in an unfavorable result as a cushioning material. . On the other hand, if the density is too high, the foam becomes hard and is subjected to flexibility, resulting in an undesirable result as a cushioning material. For this reason, the density is preferably 20 to 160 kg / m 3 .
Moreover, since the problem of the contamination and corrosion with respect to the packaged product will become large when the ammonia concentration of polyolefin type cross-linked foam is too high, the ammonia concentration is preferably 0 ppm to 100 ppm.
If the polyolefin-based crosslinked foam has an excessively high glass strength, the packaged headlamp is likely to be fogged. Therefore, the glass strength 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 that form polyolefin-based crosslinked foams include polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-, such as low density, medium density, high density, and linear low density. Vinyl acetate copolymer, copolymer of ethylene and each acrylic acid ester of methyl, ethyl, propyl or butyl (the content of this ester; within 45 mol%), or chlorine up to 60% by weight of each of these. And the like. 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。 The polyolefin-based crosslinked resin foam is produced by one-stage foaming or two-stage foaming. In one-stage foaming, a foamable resin composition containing a polyolefin resin and a foaming agent is filled in a foaming mold, heated and pressurized to decompose the foaming agent, and then the foaming mold is opened to foam the desired polyolefin. A cross-linked resin foam is obtained. In two-stage foaming, a foamable resin composition containing a polyolefin-based resin and a foaming agent is filled into a primary foaming mold and primary foamed by heating and pressurizing to form a primary foam, and then the outer shape of the primary foam The primary foam is accommodated in a secondary foaming mold having a larger inner surface shape, and subjected to secondary foaming by heating under normal pressure to obtain a desired polyolefin-based crosslinked foam. In the two-stage foaming, a foam having a higher foaming ratio than that in the first-stage foaming is obtained.
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 foaming agent, sodium bicarbonate (sodium bicarbonate) and p, p'-oxybisbenzenesulfonyl hydrazide (OBSH) are used in combination. Sodium bicarbonate alone tends to cause shrinkage after foaming of the polyolefin-based crosslinked foam, while p, p'-oxybisbenzenesulfonyl hydrazide alone tends to cause insufficient foaming. By using sodium bicarbonate and p, p'-oxybisbenzenesulfonylhydrazide in combination, shrinkage after foaming and insufficient foaming can be made difficult to occur. The amount of sodium bicarbonate (parts by weight) and the amount of p, p'-oxybisbenzenesulfonyl hydrazide (parts by weight) are preferably greater than the amount of sodium bicarbonate. By increasing the amount of p, p′-oxybisbenzenesulfonyl hydrazide over the amount of sodium bicarbonate, nitrogen gas, which is a decomposition gas of p, p′-oxybisbenzenesulfonyl hydrazide, is changed from carbon dioxide, which is a decomposition gas of sodium bicarbonate. Can be increased. After foam molding, since not only carbon dioxide gas but also nitrogen gas having a low diffusion coefficient is held, rapid shrinkage and deformation after foam molding can be suppressed. More preferably, the amount of p, p′-oxybisbenzenesulfonylhydrazide (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′-oxybisbenzenesulfonylhydrazide are thermally decomposed by heating during the production of the polyolefin-based crosslinked foam to generate gas, thereby foaming the polyolefin-based resin. Sodium bicarbonate generates carbon dioxide by thermal decomposition at 140 ° C. to 170 ° C., and sodium carbonate is generated as a decomposition residue. On the other hand, p, p′-oxybisbenzenesulfonyl hydrazide generates nitrogen gas by thermal decomposition at 155 ° C. to 165 ° C., and produces polydithiophenyl ether and polythiophenylbenzenesulfonyl ether as decomposition residues. Neither baking soda nor p, p′-oxybisbenzenesulfonyl hydrazide produces ammonia as a decomposition residue, so the ammonia concentration in the polyolefin crosslinked foam can be reduced.
In addition, the difference in thermal decomposition temperature range between sodium bicarbonate and p, p'-oxybisbenzenesulfonyl hydrazide is close to within ± 15 ° C, and both can be thermally decomposed in the range of 155 ° C to 165 ° C. Good balance and preferable 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 foaming agent is preferably 3.0 to 35 parts by weight with respect to 100 parts by weight of the polyolefin resin. If the amount of the foaming agent is too small, foaming becomes poor or the density becomes high. On the other hand, when the amount of the foaming agent is too large, the foam bursts or the density becomes too low when the foaming mold is opened.
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。 A foaming 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-tertiary butyl peroxyhexane, 1,3-bis-tertiary peroxy-isopropylbenzene, and the like. be able to. The amount of the crosslinking agent is preferably 1.0 to 5.0 parts by weight with respect to 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。 Moreover, an auxiliary agent is suitably contained in the foamable resin composition. Examples of auxiliary agents include foaming auxiliary agents, nucleating agents, other inorganic fillers, and coloring agents. Examples of the foaming aid include metal oxides such as zinc oxide and lead oxide, lower or higher fatty acids, and metal salts thereof. Examples of the nucleating agent include calcium bicarbonate. Examples of other inorganic fillers include conductive carbon black.
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。
Although heating and pressurization in the case of one-stage foaming vary depending on the foaming ratio, examples include a heating temperature of 130 to 170 ° C., a heating time of 30 to 60 minutes, and a pressure of about 5 to 35 Pa.
Heating and pressurization in the case of two-stage foaming vary depending on the foaming ratio. For example, the heating temperature during primary foaming is 100 to 150 ° C., the heating time is 30 to 60 minutes, the pressure is about 5 to 35 Pa, and the heating during secondary foaming. The temperature is about 140 to 170 ° C., and the heating time is about 25 to 180 minutes. The expansion ratio is preferably 6 to 40 times in either case of single-stage foaming or two-stage foaming. The expansion ratio is a value calculated by Equation 1 below, assuming that the unfoamed resin is 1000 kg / m 3 .
1000 kg / m 3 (not foamed) ÷ foam density measured value (kg / m 3 ) (Formula 1)
The measured value of foam density is a value measured according to JIS K 6767.
If the expansion ratio is too low, the foam is too soft and cannot retain its shape, which is not preferable as a cushioning material. Conversely, if the foaming ratio is too high, the foam becomes hard and is not flexible as a cushioning material. Moreover, adjustment of the expansion ratio at the time of one-stage foaming and two-stage foaming is made to be 6 to 40 times with a 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., baking soda: Sankyo Kasei Co., Ltd. Cellmic 266, p, p′-oxy Bisbenzenesulfonyl hydrazide (OBSH): Neocerbon N # 5000 manufactured by Eiwa Kasei Kogyo Co., Ltd., and Azodicarbonamide (ADCA): Panthrene H7310 manufactured by Eiwa Kasei Kogyo Co., Ltd. were used as the formulation shown in FIG. Furthermore, as a cross-linking agent (not shown in FIG. 1), a mixture in which 2.7 parts by weight of Kayaku Mill D-40C manufactured by Kayaku Akzo Co., Ltd. with respect to 100 parts by weight of LDPE was kneaded with a kneader, and then kneaded with a roll, The 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 single-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 in a foaming mold, heated under pressure, decompressed and foamed, and a polyolefin-based crosslinked foam was taken out from the foaming mold. The molding space for the foaming mold is 160 mm long, 160 mm wide, 33 mm deep, and 0.85 L in volume. The filling amount of the foamable resin composition is 900 g for all, the pressure is 7 Pa, and the heating is 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, decompressed and foamed, and then the primary foam was removed from the primary foaming mold. The primary foaming process to take out was performed, the obtained primary foam was accommodated in the secondary foaming mold, the secondary foaming was performed by secondary heating under normal pressure, and the polyolefin-based 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 foaming mold is 160 mm long, 160 mm wide, 33 mm deep, and 0.85 L in volume. The filling amount of the foamable resin composition is 900 g for all, the pressure is 7 Pa, and the heating is 130 ° C. for 50 minutes.
The molding space of the secondary foaming mold is 300 mm long, 300 mm wide, 55 mm deep, and 1.5 L in volume. 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 (conforming to JIS K 6767), expansion ratio, ammonia concentration, glass strength (conforming to ISO6452), and shrinkage in each example and each comparative example were measured. The measurement results are shown in FIG.
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 expansion ratio was calculated by the above formula 1.
Ammonia concentration was roughly measured with a GASTEC detector tube (part number: 3M), in which a 0.1 g sample was put into a round bottom flask, heated in an oven at 80 ° C. for 2 hours, and then measured at 10 to 1000 ppm before cooling. After measuring various values, the ammonia concentration was measured with an accurate GASTEC detector tube (product number: 3 L) capable of measuring less than 100 ppm.
The glass haze (fogging) was heated at 80 ° C. for 20 hours while the sample was shielded with a glass plate, and the haze attached to the glass plate was measured by Nippon Denshoku Industries Co., Ltd. (product number: NDH-20H). .
Shrinkage is measured by measuring the difference between the thickness dimension of the foam immediately after removal from the foaming mold and the thickness dimension 24 hours after removal from the foaming mold, and the thickness of the foam immediately after removal from the foaming mold. Expressed as a ratio to dimensions. When the shrinkage was 5.0% or less, “◯” was indicated, and when the shrinkage exceeded 5.0%, “X” was indicated.
The overall judgment was “◯” when all the conditions of
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 the foaming agent is 3.0 parts by weight and the weight ratio of OBSH / sodium bicarbonate is 6/4. Example 1 has an ammonia concentration of 15 ppm, a glass glass strength of 0.7%, a density of 150 kg / m 3 , a foaming ratio of 6.7 times, and a shrinkage of 2.1%, and the overall evaluation is “◯”.
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 the foaming agent is 3.0 parts by weight and the weight ratio of OBSH / sodium bicarbonate is 2/1. In Example 2, the ammonia concentration was 25 ppm, the glass purity was 2.3%, the density was 140 kg / m 3 , the foaming ratio was 7.0 times, and the shrinkage was 2.1%, and the overall evaluation was “◯”.
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 the foaming agent is 7.0 parts by weight and the weight ratio of OBSH / sodium bicarbonate is 6/4. In Example 3, the ammonia concentration was 5 ppm, the glass purity was 0.3%, the density was 80 kg / m 3 , the foaming ratio was 12.5 times, and the shrinkage was 2.3%, and the overall evaluation was “◯”.
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 the foaming agent is 7.0 parts by weight and the weight ratio of OBSH / sodium bicarbonate is 76/24. In Example 4, the ammonia concentration was 40 ppm, the glass strength was 2.1%, the density was 75 kg / m 3 , the foaming ratio was 13.3 times, the shrinkage was 2.6%, and the overall evaluation was “◯”.
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 the foaming agent is 25.0 parts by weight and the weight ratio of OBSH / sodium bicarbonate is 6/4. Example 5 has an ammonia concentration of 20 ppm, a glass haze of 0.4%, a density of 33 kg / m 3 , an expansion ratio of 30.0 times, and a shrinkage of 3.6%, and the overall evaluation is “◯”.
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 the foaming agent is 35.0 parts by weight and the weight ratio of OBSH / bicarbonate is 6/4. In Example 6, the ammonia concentration was 15 ppm, the glass strength was 0.5%, the density was 25 kg / m 3 , the foaming ratio was 40.0 times, and the shrinkage was 3.4%, and the overall evaluation was “◯”.
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 the foaming agent is 7.0 parts by weight, and the weight ratio of OBSH / sodium bicarbonate is 0/7, and does not contain OBSH. Comparative Example 1 has an ammonia concentration of 0 ppm, a glass strength of 0.1%, a density of 200 kg / m 3 , a foaming ratio of 5 times, and a shrinkage of 7.2%, and the overall evaluation is “x”. In Comparative Example 1, the ammonia concentration and the glass vigor were small, but since the blowing agent was baking soda alone, the 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 the foaming agent is 7.0 parts by weight and the weight ratio of OBSH / sodium bicarbonate is 5/5, and the amounts of OBSH and sodium bicarbonate are equal. Comparative Example 2 has an ammonia concentration of 30 ppm, a glass purity of 2.4%, a density of 100 kg / m 3 , a foaming ratio of 10 times, and a shrinkage of 5.8%, and is an overall evaluation “x”. In Comparative Example 2, the ammonia concentration and the glass haze were small, but the density was high and the shrinkage was large.
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 the foaming agent is 7.0 parts by weight and the weight ratio of OBSH / sodium bicarbonate is 8/2. Comparative Example 3 has an ammonia concentration of 60 ppm, a glass purity 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 an overall evaluation “x”. In Comparative Example 3, the density was high and foaming was insufficient.
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 the foaming agent is 7.0 parts by weight and the weight ratio of OBSH / sodium bicarbonate is 7/0, and does not include sodium bicarbonate. Comparative Example 4 has an ammonia concentration of 65 ppm, a glass purity of 3.6%, a density of 230 kg / m 3 , an expansion ratio of 4.3 times, and a shrinkage of 1.7%, and is an overall evaluation “x”. In Comparative Example 4, since the foaming agent was OBSH alone, crosslinking was performed in advance, foaming was not sufficiently performed, the density was high, and foaming was insufficient.
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 the foaming agent is 2.0 parts by weight and the weight ratio of OBSH / sodium bicarbonate is 6/4, and the amount of the foaming agent is small. Since Comparative Example 5 does not foam, the ammonia concentration, the glass strength, and the shrinkage cannot be measured, and the overall evaluation is “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 using 5.0 parts by weight of ADCA alone as a foaming agent. Comparative Example 6 has an ammonia concentration of 900 ppm, a glass strength of 22%, a density of 65 kg / m 3 , an expansion ratio of 15 times, and a shrinkage of 1.8%, and is an overall evaluation “x”. Since the comparative example 6 uses ADCA as a foaming 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, in the present invention, a polyolefin-based crosslinked foam having a low residual ammonia concentration and capable of preventing contamination and corrosion by ammonia is obtained.
Claims (5)
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。 A method for producing a polyolefin-based crosslinked foam having a density of 20 to 160 kg / m 3 , an ammonia concentration of 0 ppm to 100 ppm, and a glass strength of 5% or less,
Baking soda and p, p'-oxybisbenzenesulfonyl hydrazide as a blowing agent are used in combination with a larger amount of p, p'-oxybisbenzenesulfonyl hydrazide than the amount of baking soda. A method for producing a polyolefin-based crosslinked foam, wherein foaming is performed 6 to 40 times.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021201056A1 (en) * | 2020-03-31 | 2021-10-07 | 積水化学工業株式会社 | Polyolefin resin foam sheet and vehicle interior member |
| KR20220145469A (en) * | 2021-04-21 | 2022-10-31 | 한국신발피혁연구원 | Foam composition applied for inorganic chemical blowing agent with improved foaming efficiency |
| KR102565837B1 (en) * | 2021-04-21 | 2023-08-11 | 한국신발피혁연구원 | Foam composition applied for inorganic chemical blowing agent with improved foaming efficiency |
| CN115850832A (en) * | 2022-09-06 | 2023-03-28 | 东莞市盈圆合创新材料有限公司 | Environment-friendly antibacterial electron radiation cross-linked polyolefin foam and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7431871B2 (en) | 2024-02-15 |
| JP7027183B2 (en) | 2022-03-01 |
| JP2022063318A (en) | 2022-04-21 |
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