JP5633274B2 - Method for producing foam molded article - Google Patents
Method for producing foam molded article Download PDFInfo
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- JP5633274B2 JP5633274B2 JP2010215531A JP2010215531A JP5633274B2 JP 5633274 B2 JP5633274 B2 JP 5633274B2 JP 2010215531 A JP2010215531 A JP 2010215531A JP 2010215531 A JP2010215531 A JP 2010215531A JP 5633274 B2 JP5633274 B2 JP 5633274B2
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- citric acid
- baking soda
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- molded article
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- 239000006260 foam Substances 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 22
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 18
- 238000005187 foaming Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 8
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000036316 preload Effects 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920005679 linear ultra low density polyethylene Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
本発明は、化学発泡剤を用いた発泡成形体の製造方法に関するものである。 The present invention relates to a method for producing a foamed molded article using a chemical foaming agent.
従来、発泡成形体を得る方法として重曹とクエン酸（又はクエン酸塩）とを使用した無機系化学発泡剤を用いる方法が知られている（特許文献１参照）。この化学発泡剤は、酸（クエン酸）と塩基（重曹）との化学反応により炭酸ガスを発生させ、そのガスにより熱可塑性樹脂を発泡させるというものである。重曹、クエン酸は、それぞれ粉末状態で使用することもできるが、取り扱い性の観点から、重曹とクエン酸とを１つのマスターバッチとして、当該マスターバッチを基材樹脂と混練して成形するのが一般的である。 Conventionally, a method using an inorganic chemical foaming agent using sodium bicarbonate and citric acid (or citrate) is known as a method for obtaining a foamed molded product (see Patent Document 1). This chemical foaming agent generates carbon dioxide gas by a chemical reaction between an acid (citric acid) and a base (bicarbonate), and foams a thermoplastic resin with the gas. Baking soda and citric acid can be used in powder form, but from the viewpoint of handleability, baking soda and citric acid are used as one master batch, and the master batch is kneaded with the base resin and molded. It is common.
しかし、従来の化学発泡剤マスターバッチを用いた場合、重曹とクエン酸との酸塩基反応が、マスターバッチを作製してから保管するまでの段階で起こる。そのため、発泡成形をする際には発生する炭酸ガスの量が低下する。 However, when a conventional chemical blowing agent masterbatch is used, an acid-base reaction between baking soda and citric acid occurs at a stage from preparation of the masterbatch to storage. For this reason, the amount of carbon dioxide generated during foam molding is reduced.
本発明は、上記のような問題を解決するためになされたものであり、化学発泡剤を用いて見掛け密度の小さい発泡成形体を製造できる発泡成形体の製造方法を提供する。 The present invention has been made to solve the above-described problems, and provides a method for producing a foamed molded product that can produce a foamed molded product having a small apparent density using a chemical foaming agent.
本発明は、重曹マスターバッチと、当該重曹マスターバッチとは別に形成されたクエン酸マスターバッチと、基材樹脂と、をそれぞれ押出機に投入し混練してなる混合樹脂を、前記押出機から押し出して発泡成形体を成形することを特徴とする。 The present invention is to extrude a mixed resin obtained by charging a sodium bicarbonate master batch, a citric acid master batch formed separately from the sodium bicarbonate master batch, and a base resin into an extruder and kneading them from the extruder. Forming a foamed molded product.
本発明によれば、化学発泡剤を用いて見掛け密度の小さい発泡成形体を製造できる。 According to the present invention, it is possible to produce a foamed molded article having a small apparent density using a chemical foaming agent.
以下、添付図面を参照しながら、本実施形態の発泡成形体の製造方法について説明する。 Hereinafter, the manufacturing method of the foaming molding of this embodiment is demonstrated, referring an accompanying drawing.
本実施形態の発泡成形体の製造方法は、重曹マスターバッチと、当該重曹マスターバッチとは別に形成されたクエン酸マスターバッチと、基材樹脂と、をそれぞれ押出機に投入し混練してなる混合樹脂を、押出機から押し出して発泡成形体を成形する。なお、マスターバッチとして使用する重曹、クエン酸の粉末粒子径は特に限定しないが、100μｍ以下であることが望ましい。 The method for producing a foamed molded product of the present embodiment is a mixing method in which a baking soda master batch, a citric acid master batch formed separately from the baking soda master batch, and a base resin are put into an extruder and kneaded. Resin is extruded from an extruder to form a foamed molded article. The powder particle size of baking soda and citric acid used as a master batch is not particularly limited, but is preferably 100 μm or less.
また、重曹とクエン酸の添加重量比率は、図１に示す通り、クエン酸が重曹よりも多量になると見掛け密度が下がりにくくなる為、重曹：クエン酸＝3以上：1であることが望ましい。即ち、重曹とクエン酸の添加重量比率が、重曹：クエン酸＝3以上：1となるように、重曹マスターバッチと、クエン酸マスターバッチと、を原料樹脂に配合することが望ましい。 Further, as shown in FIG. 1, the added weight ratio of baking soda and citric acid is preferably baking soda: citric acid = 3 or more: 1 because the apparent density is hardly lowered when citric acid becomes larger than baking soda. That is, it is desirable to add the baking soda master batch and the citric acid master batch to the raw material resin so that the added weight ratio of baking soda and citric acid is baking soda: citric acid = 3 or more: 1.
発泡剤の添加量（重曹の重量とクエン酸の重量との和）は、基材となる樹脂やブロー成形温度、所望の見掛け密度によっても異なるが0.2〜3.0wt%の範囲内で添加するのが望ましく、0.8〜1.2wt%の範囲内であるのがより好ましい。 The amount of foaming agent added (the sum of the weight of baking soda and citric acid) depends on the base resin, blow molding temperature, and the desired apparent density, but it should be added within the range of 0.2 to 3.0 wt%. Is desirable, and it is more preferably within the range of 0.8 to 1.2 wt%.
原料樹脂は、200℃におけるメルトテンション（MT）が7gf以上かつ200℃におけるMTとメルトフローレイト（MFR）の積が15g2/10min以上有することが好ましい。MTが7gfより小さい樹脂は、溶融樹脂表面から気泡の破裂（破泡）が発生し、パリソンを十分に発泡させることが困難である。又、MTとMFRの積が小さい樹脂は、流動性の悪さが発泡性に悪影響を及ぼす傾向がある他、型内で賦形する際、形状を転写することが困難になる虞がある。 Raw material resin preferably has a product of melt tension at 200 ℃ (MT) MT and the melt flow rate at that 7gf more and 200 ° C. (MFR) is 15 g 2 / 10min or more. Resins with MT smaller than 7 gf cause bubble burst (bubble breakage) from the surface of the molten resin, and it is difficult to sufficiently foam the parison. In addition, a resin having a small product of MT and MFR tends to have an adverse effect on foamability due to poor fluidity, and it may be difficult to transfer the shape when forming in a mold.
原料樹脂は、単独で用いるのみならず、2種類以上を混合して用いても良い。例えば、主原料の特性が損なわれない範囲で、ポリプロピレン系樹脂、高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン等のエチレン系樹脂、ブテン系樹脂、スチレン系樹脂等の他の樹脂成分を必要に応じて混合しても良い。 The raw material resins may be used alone or in combination of two or more. For example, other resin components such as polypropylene resins, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and other ethylene-based resins, butene-based resins, and styrene-based resins, as long as the characteristics of the main raw material are not impaired. May be mixed as necessary.
尚、必要に応じて気泡調整剤を用いて気泡径を調整することができる。代表的なものとしては、タルク、シリカ、ゼオライト、モレキュラーシーブ、酸化亜鉛、炭酸カルシウム等の無機系気泡調整剤がある。これらの無機系気泡調整剤は気泡生成時の核となり、気泡をより微細にすることができる。その他の気泡調整剤としては発泡助剤として使用する有機酸の有機酸塩を気泡調整剤として用いる方法がある。これらは緩衝作用により、酸・塩基反応を穏やかにし、気泡の過度の成長を抑えることができる。 In addition, a bubble diameter can be adjusted using a bubble regulator as needed. Typical examples include inorganic bubble regulators such as talc, silica, zeolite, molecular sieve, zinc oxide, and calcium carbonate. These inorganic bubble regulators serve as nuclei at the time of bubble generation and can make the bubbles finer. As another bubble regulator, there is a method of using an organic acid salt of an organic acid used as a foaming aid as a bubble regulator. These can moderate acid / base reaction and suppress excessive growth of bubbles by buffering action.
（MTの測定方法）
原料樹脂のMTは、例えば、株式会社東洋精機製作所製のメルトテンションテスターII型等によって測定することができる。具体的にはオリフィス径2.095mm、長さ8mmのオリフィスを有するメルトテンションテスターを用い、上記オリフィスから樹脂温度200℃、押出のピストン速度10mm/minの条件で樹脂を紐状に押出して、この紐状物を直径45mmの張力検出用プーリーに掛けたあと、直径50mmの巻取りローラーで巻取り速度4 rpmで巻き取る。
(MT measurement method)
The MT of the raw material resin can be measured by, for example, a melt tension tester type II manufactured by Toyo Seiki Seisakusho Co., Ltd. Specifically, using a melt tension tester having an orifice with an orifice diameter of 2.095 mm and a length of 8 mm, the resin is extruded into a string from the orifice under the conditions of a resin temperature of 200 ° C. and an extrusion piston speed of 10 mm / min. The product is hung on a tension detection pulley having a diameter of 45 mm, and then wound with a winding roller having a diameter of 50 mm at a winding speed of 4 rpm.
MTを求めるには、ピストン内に原料を入れ、ピストン内の温度が200±0.2℃になったあと予備荷重をかけ、4分間保持する（このとき考えられる原料の種類としては、バージン原料樹脂、予め溶融混練を行なった樹脂の細断物、成形体から切り出し細断した樹脂の3種類が考えられる）。予備荷重はMFRによって異なり、表１の通りである。その後、巻取り速度5rpmにおいて、巻取りを行い、張力検出用プーリーと連結する検出機により検出される紐状物のMTを経時的に測定し、縦軸にMT（gf）を、横軸に時間（秒）を取り、チャートに示すと図２のように振幅をもったグラフが得られる。図２においてMTは、振幅の安定した部分の振幅の中央値（X）をとる。尚、希に発生する特異的な振幅は無視するものとする。 To obtain the MT, put the raw material in the piston, apply the preload after the temperature in the piston reaches 200 ± 0.2 ° C, and hold it for 4 minutes (conceivable types of raw materials include virgin raw resin, Three types are possible: a resin shredded product that has been melt-kneaded in advance, and a resin that has been cut from a molded product and shredded. The preload varies according to the MFR and is shown in Table 1. Thereafter, winding is performed at a winding speed of 5 rpm, and the MT of the string-like material detected by a detector connected to the tension detection pulley is measured over time. MT (gf) is plotted on the vertical axis and MT (gf) is plotted on the horizontal axis. When time (seconds) is taken and shown in the chart, a graph having amplitude as shown in FIG. 2 is obtained. In FIG. 2, MT takes the median value (X) of the amplitude where the amplitude is stable. It should be noted that a specific amplitude that occurs rarely is ignored.
（MFRの測定方法）
MFRはJIS K7210に記載されている200℃、荷重2.16kgfで測定した値を採用するものとする。
(Measurement method of MFR)
The value measured at 200 ° C and a load of 2.16kgf described in JIS K7210 shall be used for MFR.
（見掛け密度の測定方法）
発泡成形体の見掛け密度は、発泡成形体の一部を切り出したものを試験片とし、この試験片の重量（g）を該試験片の体積（cm3）で割って求める。
尚、発泡成形体がブロー成形品の場合は、試験片としてはブロー圧が作用している面を使用する（コンプレッション部は使用しない）。
(Apparent density measurement method)
The apparent density of the foam molded article is obtained by dividing a part of the foam molded article as a test piece and dividing the weight (g) of the test piece by the volume (cm 3 ) of the test piece.
In addition, when a foaming molding is a blow molded product, the surface on which blow pressure acts is used as a test piece (the compression portion is not used).
（発泡剤マスターバッチ／発泡助剤マスターバッチの作製）
発泡剤MBは、低密度ポリエチレン（融点106℃、MFR 14g/10min）に重曹（平均粒子径50〜200μｍ程度のもの）をドライブレンドし、二軸押出機にて混練したものとした。尚、重曹は、発泡剤MB全体の40wt%を占めるように混合した。
発泡助剤MBは、低密度ポリエチレン（融点106℃、MFR 14g/10min）にクエン酸（平均粒子径50〜100μm程度のもの）をドライブレンドし、二軸押出機にて混練したものとした。尚、クエン酸は、発泡剤MB全体の40wt%を占めるように混合した。
重量比が、発泡剤MB：発泡助剤MB＝6：1となるように、発泡剤MBと発泡助剤MBとをドライブレンドしたものを化学発泡剤として使用した。
(Production of foaming agent masterbatch / foaming aid masterbatch)
The foaming agent MB was obtained by dry blending sodium bicarbonate (having an average particle size of about 50 to 200 μm) into low density polyethylene (melting point: 106 ° C., MFR: 14 g / 10 min) and kneading with a twin screw extruder. Baking soda was mixed so as to occupy 40 wt% of the entire foaming agent MB.
Foaming aid MB was obtained by dry blending citric acid (having an average particle size of about 50 to 100 μm) into low density polyethylene (melting point: 106 ° C., MFR: 14 g / 10 min) and kneading with a twin screw extruder. Citric acid was mixed so as to occupy 40 wt% of the entire foaming agent MB.
A dry blend of foaming agent MB and foaming aid MB was used as the chemical foaming agent so that the weight ratio was foaming agent MB: foaming aid MB = 6: 1.
（ブロー成形体の作製１）
表２に示す配合の基材樹脂100重量部に対して化学発泡剤を3重量部添加したものをシリンダ径75mm押出機に供給し、アキュームレ−ターヘッドを介して発泡パリソンを形成した。アキュームレ−ターで溶融樹脂を溜める際は、アキュームレ−ター内で溶融樹脂が発泡しない程度に加圧することが望ましい。次いで、得られた発泡パリソンを金型で挟み、吹き込み針にて金型内に0.05MPaの圧縮空気を送り込み、ダクト形状の中空発泡成形体を賦形した。中空発泡成形体の印字部やブロー比が高くなる部分はスリットベント等の真空ベントを設けることが好ましい。成形体は肉厚1.5〜2.0mmとなるように重量調整を行なった。
(Preparation of blow molded product 1)
What added 3 weight part of chemical foaming agents with respect to 100 weight part of base resin of the mixing | blending shown in Table 2 was supplied to the cylinder diameter 75mm extruder, and the foaming parison was formed through the accumulator head. When accumulating molten resin with an accumulator, it is desirable to apply pressure to the extent that the molten resin does not foam in the accumulator. Next, the obtained foamed parison was sandwiched between molds, and compressed air of 0.05 MPa was fed into the mold with a blow needle to shape a duct-shaped hollow foamed molded product. It is preferable to provide a vacuum vent such as a slit vent in the printed part of the hollow foamed molded product or a part where the blow ratio becomes high. The weight of the molded body was adjusted so that the thickness was 1.5 to 2.0 mm.
ここで、中空発泡成形体の肉厚は、以下のように算出する。
中空発泡成形体の表面積S（cm2）及び重量W（g）を測定し、前記見掛け密度より下記（１）式より算出する。
中空発泡成形体の厚み（mm）＝W／（S×ρ×10）・・・・（１）式
W：中空発泡成形体の重量（g）
S：中空発泡成形体の表面積（cm2）
ρ：中空発泡成形体の見掛け密度（g/cm3）
Here, the thickness of the hollow foamed molded product is calculated as follows.
The surface area S (cm 2 ) and weight W (g) of the hollow foamed molded article are measured, and calculated from the following equation (1) from the apparent density.
Hollow foam molded product thickness (mm) = W / (S x ρ x 10) ··· (1)
W: Weight of hollow foam molding (g)
S: Surface area of the hollow foamed molded product (cm 2 )
ρ: Apparent density of hollow foamed molded product (g / cm 3 )
表２に見掛け密度と外観の評価結果を示す。尚、表２の2MB方式とは、発泡剤MBと発泡助剤MBをそれぞれ別個のMBにして使用した方式であり、1MB方式とは発泡剤と発泡助剤が同一のMBを使用した方式である。また、基材樹脂の原料として用いた樹脂は以下の通りである。
PP1：プロピレン単独重合体（ボレアリス社製、商品名：Daploy WB130）、MT=40cN（190℃）、MFR=2.1g/10min（230℃）、密度＝900kg/m3。
PP2：結晶性エチレン−プロピレンブロック共重合体（日本ポリプロ株式会社製、商品名：ニューフォーマー FB3312）、MT=7cN（190℃）、MFR=3g/10min（230℃）、密度＝900kg/m3。
LLDPE:メタロセン系触媒により重合された直鎖状超低密度ポリエチレンであるエチレン−ヘキセン−１共重合体（住友化学株式会社製、エクセレン CX2001）、MFR=2g/10min（230℃）、密度＝898kg/m3。
LDPE:低密度ポリエチレン（住友化学株式会社製、スミカセン F108）、MFR=0.42g/10min（230℃）、密度＝920kg/m3。
Table 2 shows the evaluation results of the apparent density and the appearance. The 2MB system in Table 2 is a system that uses the foaming agent MB and the foaming aid MB as separate MBs. The 1MB system uses the same MB for the foaming agent and the foaming aid. is there. Moreover, the resin used as a raw material of base resin is as follows.
PP1: Propylene homopolymer (manufactured by Borealis, trade name: Daploy WB130), MT = 40 cN (190 ° C.), MFR = 2.1 g / 10 min (230 ° C.), density = 900 kg / m 3 .
PP2: crystalline ethylene-propylene block copolymer (manufactured by Nippon Polypro Co., Ltd., trade name: New Former FB3312), MT = 7cN (190 ° C), MFR = 3g / 10min (230 ° C), density = 900kg / m 3 .
LLDPE: An ethylene-hexene-1 copolymer (Sumitomo Chemical Co., Ltd., Exelen CX2001), a linear ultra-low density polyethylene polymerized with a metallocene catalyst, MFR = 2g / 10min (230 ° C), density = 898kg / m 3 .
LDPE: Low density polyethylene (Sumitomo Chemical Co., Sumikasen F108), MFR = 0.42 g / 10 min (230 ° C.), density = 920 kg / m 3 .
実施例１は、2MB方式であるため、1MB方式の比較例１に比べて、見掛け密度が小さく（発泡倍率が高く）なっている。
また、実施例１は、200℃におけるメルトテンション（MT）が7gf以上で、200℃におけるメルトフローレイト（MFR）とMTの積が15g2/10min以上であるため、実施例２、実施例３、実施例４に比べて見掛け密度が小さく成形できている。また、外観も、実施例２、実施例３に比べて優れている。
実施例２はMT、MT×MFRともに低すぎた為に、実施例１に比べ見掛け密度は大きくなり、又、成形品表面も劣る結果となった。
実施例３はMTが低すぎたことによる破泡が見られ、実施例１に比べ見掛け密度は大きくなった。また、表面が破泡した状態で固化した為に表面が鮫肌状になり、外観も劣る結果となった。
実施例４はMTが高かった為に、破泡は見られなかったが、MT×MFRが低かったことにより、溶融樹脂の流動性が見掛け密度にも悪影響を及ぼす結果となった。又、金型の転写性が実施例１、実施例３よりも若干劣っていた。
比較例１は重曹とクエン酸の酸塩基相互作用が発泡に悪影響を及ぼし、十分な見掛け密度を得ることができなかった。
Since Example 1 is a 2 MB system, the apparent density is smaller (the foaming ratio is higher) than Comparative Example 1 of the 1 MB system.
In Example 1, since a melt tension at 200 ° C. (MT) is at least 7 gf, is melt flow rate (MFR) and the product of MT is 15 g 2 / 10min or more at 200 ° C., Example 2, Example 3 Compared to Example 4, the apparent density is small. In addition, the external appearance is also superior to that of Example 2 and Example 3.
In Example 2, since both MT and MT × MFR were too low, the apparent density was larger than that in Example 1, and the surface of the molded product was inferior.
In Example 3, bubbles were broken due to MT being too low, and the apparent density was higher than that in Example 1. Moreover, since the surface solidified in the state where the foam was broken, the surface became a skin-like shape, resulting in poor appearance.
In Example 4, since the MT was high, no bubble breakage was observed, but due to the low MT × MFR, the fluidity of the molten resin had an adverse effect on the apparent density. Also, the transferability of the mold was slightly inferior to those of Examples 1 and 3.
In Comparative Example 1, the acid-base interaction between sodium bicarbonate and citric acid had an adverse effect on foaming, and a sufficient apparent density could not be obtained.
（ブロー成形体の作製２）
原料系樹脂は表３に示すものとし、原料樹脂100重量部に対して化学発泡剤を１〜３重量部添加したものを、上述した（ブロー成形体の作製１）と同様の方法でダクト形状の中空発泡成形体を作製した。尚、表２の2MB方式とは、発泡剤MBと発泡助剤MBをそれぞれ別個のMBにして使用した方式であり、1MB方式とは発泡剤と発泡助剤が同一のMBを使用した方式である。また、基材樹脂の原料として用いた樹脂は、上述したPP1、PP2の他、以下の通りである。
PE:エチレン重合体（東ソー株式会社製、08S55A）、MT=4.19cN、MFR=4g/10min（230℃）、密度＝952kg/cm3。
(Production of blow molded product 2)
The raw material resin is as shown in Table 3, and 1 to 3 parts by weight of a chemical foaming agent is added to 100 parts by weight of the raw material resin in the same manner as described above (Preparation of blow molded body 1). A hollow foamed molded article was prepared. The 2MB system in Table 2 is a system that uses the foaming agent MB and the foaming aid MB as separate MBs. The 1MB system uses the same MB for the foaming agent and the foaming aid. is there. In addition to the PP1 and PP2 described above, the resin used as the raw material for the base resin is as follows.
PE: ethylene polymer (manufactured by Tosoh Corporation, 08S55A), MT = 4.19 cN, MFR = 4 g / 10 min (230 ° C.), density = 952 kg / cm 3 .
実施例５〜８と比較例２〜５を比較すると、発泡剤の添加量が違ういずれの場合においても2MB方式である実施例２〜５の方が、見掛け密度が下がり易いことがわかった。 When Examples 5 to 8 and Comparative Examples 2 to 5 were compared, it was found that in any case where the amount of addition of the foaming agent was different, the apparent density was more likely to decrease in Examples 2 to 5 using the 2MB system.
以上、本発明の実施形態及び実施例について説明したが、上記実施形態及び実施例のみに本発明の範囲を限定するものではなく、本発明の要旨を逸脱しない範囲において種々の変更を施した形態での実施が可能である。 Although the embodiments and examples of the present invention have been described above, the scope of the present invention is not limited to the above-described embodiments and examples, and various modifications are made without departing from the scope of the present invention. Implementation is possible.
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