JP5271589B2 - Method for producing polyolefin foam hot-press molded product - Google Patents
Method for producing polyolefin foam hot-press molded product Download PDFInfo
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- JP5271589B2 JP5271589B2 JP2008106431A JP2008106431A JP5271589B2 JP 5271589 B2 JP5271589 B2 JP 5271589B2 JP 2008106431 A JP2008106431 A JP 2008106431A JP 2008106431 A JP2008106431 A JP 2008106431A JP 5271589 B2 JP5271589 B2 JP 5271589B2
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Description
本発明は、発泡体の熱圧成形品の製造方法に関するものである。 The present invention relates to a method for producing a hot-press molded product of a foam.
従来から知られた発泡体の熱圧成形品は、加熱した金型の中に発泡体を入れて加圧加熱し、金型内部形状と同じ形に成形している（特開２００７−２４５６０１号公報）。 A conventionally known hot-press molded product of foam is formed in the same shape as the inner shape of the mold by placing the foam in a heated mold and heating it under pressure (Japanese Patent Application Laid-Open No. 2007-245601). Publication).
また、金型内で発泡粒子を発泡させて成形品を得る方法（特開平８−９２４０７号公報）、（特開２００３−２２６７７５号公報）が知られている。
しかしながら、
本発明者らは、従来の成形品の製造方法の欠点を解消し、バリの発生が無く、外観のきれいな成形品の製造方法を開発した。 The inventors of the present invention have developed a method for producing a molded article that eliminates the drawbacks of the conventional method for producing a molded article and has no appearance of burrs and has a beautiful appearance.
ポリオレフィン樹脂に発泡剤、架橋剤を添加混練し、得られた架橋性発泡性組成物を密閉金型Ａに充填し、加圧下に加熱、整形して取り出し、次いで密閉金型Ｂに入れ加圧下に加熱して発泡剤、架橋剤を分解した後冷却して成形品よりも小さい発泡体を得、得られた発泡体を金型Ｃに入れ加圧下に加熱して成形する発泡体熱圧成形品の製造方法である。
本発明において、金型Ａの体積が金型Ｂの体積の１〜５％小さいことが好ましく、且つ、金型Ｃの寸法が金型Ｂの寸法縦横厚みの各１．５〜２．５倍であるこが好ましい。金型Ａの体積が金型Ｂの体積の５％より大きい場合は、金型Ｂの中で仕込み不足が生じ、１％未満の小さい場合は、金型Ｂでバリ漏れが生じる。金型Ｃの寸法が金型Ｂの寸法の１．５倍未満の場合、成形品にバリが発生し、２．５場合を超える場合は、硬さや強度に劣る成形品しか得られない。
A foaming agent and a crosslinking agent are added and kneaded to the polyolefin resin, and the resulting crosslinkable foamable composition is filled into a closed mold A, heated under pressure, shaped and taken out, and then put into a closed mold B under pressure. After heating, the foaming agent and the crosslinking agent are decomposed and cooled to obtain a foam smaller than the molded product, and the foam obtained is put into a mold C and heated to form under pressure. Product manufacturing method.
In the present invention, the volume of the mold A is preferably 1 to 5% smaller than the volume of the mold B, and the dimension of the mold C is 1.5 to 2.5 times the dimension length and width of the mold B. It is preferable that When the volume of the mold A is larger than 5% of the volume of the mold B, charging is insufficient in the mold B, and when the volume is smaller than 1%, the burrs leak in the mold B. When the dimension of the mold C is less than 1.5 times the dimension of the mold B, burrs are generated in the molded product, and when it exceeds 2.5, only a molded product inferior in hardness and strength can be obtained.
本発明の方法によれば、金型より大きい発泡体を金型に入れて成形しないため、金型の合わせ面にバリが発生することが無い。 According to the method of the present invention, since a foam larger than the mold is not put into the mold and molded, no burr is generated on the mating surface of the mold.
しかも、発泡粒子を金型に入れて発泡させないため、外観のきれいな成形品を得ることが出来る。 In addition, since the foamed particles are not put into a mold and foamed, a molded product having a clean appearance can be obtained.
本発明において使用できる樹脂は熱可塑性樹脂、例えば、低、中、高、直鎖状ポリエチレン、エチレン−酢酸ビニル共重合体、ポリプロピレン等のポリオレフィン系樹脂、塩化ビニル樹脂、ポリスチレン、エラストマー等、また、エチレンプロピレンジエン共重合体ゴム（ＥＰＤＭ）等のゴムを挙げることができる。 Resins that can be used in the present invention are thermoplastic resins, for example, low, medium, high, linear polyethylene, ethylene-vinyl acetate copolymers, polyolefin resins such as polypropylene, vinyl chloride resins, polystyrene, elastomers, etc. Mention may be made of rubbers such as ethylene propylene diene copolymer rubber (EPDM).
本発明でいう発泡剤とは、使用する樹脂の溶融温度以上の分解温度を有する化学発泡剤であり、例えばアゾ系化合物のアゾジカルボンアミド、バリウムアゾジカルボキシレート等；ニトロソ系化合物のジニトロソペンタメチレンテトラミン、トリニトロトリメチルトリアミン等；ヒドラジッド系化合物のｐ，ｐ‘−オキシビスベンゼンスルホニルヒドラジッド等；スルホニルセミカルバジッド系化合物のｐ，ｐ‘−オキシビスベンゼンスルホニルセミカルバジッド、トルエンスルホニルセミカルバジッド等がある。 The foaming agent referred to in the present invention is a chemical foaming agent having a decomposition temperature equal to or higher than the melting temperature of the resin used. For example, azo compounds such as azodicarbonamide and barium azodicarboxylate; nitroso compounds such as dinitrosopenta Methylenetetramine, trinitrotrimethyltriamine, etc .; p, p′-oxybisbenzenesulfonyl hydrazide, etc. of hydrazide compounds; p, p′-oxybisbenzenesulfonyl semicarbazide, toluenesulfonyl semicarbazide of sulfonyl semicarbazide compounds, etc. There are Jid etc.
本発明でいう架橋剤とは、使用する樹脂中において少なくとも樹脂の流動開始温度以上の分解温度を有するものであって、加熱により分解され、遊離ラジカルを発生してその分子間もしくは分子内に架橋結合を生じせしめるラジカル発生剤であるところの有機過酸化物、例えばジクミルパーオキサイド、１，１−ジターシャリーブチルパーオキサイド、１，１−ジターシャリーブチルパーオキシー３，３，５−トリメチルシクロヘキサン、２，５−ジメチルー２，５−ジターシャリーブチルパーオキシヘキサン、２，５−ジメチルー２，５−ジターシャリーブチルパーオキシヘキシン、α、α―ジターシャリーブチルパーオキシイソプロピルベンゼン、ターシャリーブチルパーオキシケトン、ターシャリーブチルパーオキシベンゾエートなどがあるが、その時に使用される樹脂によって最適な有機過酸化物を選択しなければならない。 The cross-linking agent as used in the present invention has a decomposition temperature that is at least equal to or higher than the resin flow start temperature in the resin to be used, decomposes by heating, generates free radicals, and crosslinks between or within the molecules. Organic peroxides that are radical generators that form bonds, such as dicumyl peroxide, 1,1-ditertiary butyl peroxide, 1,1-ditertiary butyl peroxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-ditertiary butyl peroxyhexane, 2,5-dimethyl-2,5-ditertiary butyl peroxyhexyne, α, α-ditertiary butyl peroxyisopropylbenzene, tertiary butyl peroxy Such as ketones and tertiary butyl peroxybenzoate However, the optimum organic peroxide must be selected depending on the resin used at that time.
本発明において、発泡助剤を発泡剤の種類に応じて添加することができる。発泡助剤としては尿素を主成分とした化合物、酸化亜鉛、酸化鉛等の金属酸化物、サリチル酸、ステアリン酸等を主成分とする化合物、即ち高級脂肪酸あるいは高級脂肪酸の金属化合物などがある。 In the present invention, a foaming aid can be added depending on the type of foaming agent. Examples of the foaming aid include compounds mainly composed of urea, metal oxides such as zinc oxide and lead oxide, compounds mainly composed of salicylic acid and stearic acid, that is, higher fatty acids or higher fatty acid metal compounds.
本発明においては、使用する組成物の物性の改良或いは価格の低下を目的として、架橋結合に著しい悪影響を与えない配合剤（充填剤）、例えば酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化ケイ素等の金属酸化物、炭酸マグネシウム、炭酸カルシウム等の炭酸塩、あるいはパルプ等の繊維物質、又は各種染料、顔料並びに蛍光物質、その他常用のゴム配合剤等を必要に応じて添加することができる。 In the present invention, for the purpose of improving the physical properties of the composition to be used or reducing the price, a compounding agent (filler) that does not significantly adversely affect the cross-linking, such as zinc oxide, titanium oxide, calcium oxide, magnesium oxide, oxidation Metal oxides such as silicon, carbonates such as magnesium carbonate and calcium carbonate, fiber materials such as pulp, various dyes, pigments, fluorescent materials, and other conventional rubber compounding agents can be added as necessary. .
本発明において使用する金型の材質は、鉄、アルミ等の金属を用いることができる。ただし、金型Ｂはかなり高いプレス圧がかかるため、鉄製の金型を用いる方がよい。 As the material of the mold used in the present invention, a metal such as iron or aluminum can be used. However, since a very high press pressure is applied to the mold B, it is better to use an iron mold.
次に、本発明の熱圧成形品の製造方法について説明する。 Next, the manufacturing method of the hot-press molded product of this invention is demonstrated.
本発明の発泡体熱圧成形品の製造方法は、用いた発泡剤や有機過酸化物などによる発泡温度や架橋開始温度などにより、従来公知の方法及び適宜の条件で発泡及び成形を行うことができる。特に好ましい方法及び条件を下記に記述する。 The method for producing a foam hot-press molded product of the present invention can be foamed and molded by a conventionally known method and appropriate conditions depending on the foaming temperature, crosslinking initiation temperature, etc. with the used foaming agent or organic peroxide. it can. Particularly preferred methods and conditions are described below.
樹脂成分１００重量部に周知の発泡剤、発泡助剤及び有機過酸化物を添加し、これをミキシングロール、加圧式ニーダー、押出機等によって練和する。次いで、得られた発泡性樹脂組成物をプレス中の金型Ａに入れ、一定時間２０ｋｇ／ｃｍ２以上の圧力にて９０〜１１０℃で加熱する。次いで、該組成物を金型Ｂに入れ、一定時間１３０ｋｇ／ｃｍ２以上の圧力にて１４０〜１７０℃で加熱して発泡剤、架橋剤を分解した後、冷却して発泡体を取り出す。取り出した発泡体を金型Ｃに入れ、一定時間２０ｋｇ／ｃｍ２以上の圧力にて１１０〜１２０℃で加熱すると、発泡体は金型Ｃ内部いっぱいに膨らみ充填する。充填後冷却して成形品を取り出す。 A well-known foaming agent, foaming assistant, and organic peroxide are added to 100 parts by weight of the resin component, and this is kneaded by a mixing roll, a pressure kneader, an extruder, or the like. Next, the obtained expandable resin composition is put into a mold A during pressing and heated at 90 to 110 ° C. at a pressure of 20 kg / cm 2 or more for a certain time. Next, the composition is put in a mold B, heated at 140 to 170 ° C. at a pressure of 130 kg / cm 2 or more for a predetermined time to decompose the foaming agent and the crosslinking agent, and then cooled to take out the foam. When the taken-out foam is put into the mold C and heated at 110 to 120 ° C. at a pressure of 20 kg / cm 2 or more for a predetermined time, the foam swells and fills the inside of the mold C. Cool after filling and remove the molded product.
直鎖状低密度ポリエチレン（商品名：アフィニティーＥＧ８２００、密度０．８７０ｇ／ｃｍ３、メルトインデックス５．０ｇ／１０ｍｉｎ、ダウ・ケミカル日本製）１００重量部、アゾジカルボンアミド４．５重量部、ジクミルパーオキサイド０．８重量部、炭酸カルシウム３０重量部からなる組成物を金型Ａに入れ４０ｋｇ／ｃｍ２、１００℃で１０分間加圧加熱した後取り出した。取り出したコンパウンドを金型Ｂに入れ、１５０ｋｇ／ｃｍ２、１６０℃で６０分間加圧加熱した後、冷却し発泡体を得た。
次いで、発泡体を金型Ｃに入れ、４０ｋｇ／ｃｍ２、１２０℃で２０分加圧加熱した後冷却して熱圧成形品を得た。
Linear low-density polyethylene (trade name: affinity EG8200, density 0.870 g / cm 3 , melt index 5.0 g / 10 min, manufactured by Dow Chemical Japan), 100 parts by weight, azodicarbonamide 4.5 parts by weight, dicumyl A composition comprising 0.8 parts by weight of peroxide and 30 parts by weight of calcium carbonate was placed in a mold A, heated at 40 kg / cm 2 at 100 ° C. for 10 minutes, and then taken out. The taken-out compound was put into the metal mold B, heated under pressure at 150 kg / cm 2 and 160 ° C. for 60 minutes, and then cooled to obtain a foam.
Next, the foam was put into a mold C, heated under pressure at 40 kg / cm 2 and 120 ° C. for 20 minutes, and then cooled to obtain a hot-pressure molded product.
金型Ａは金型Ｂの体積より２％小さく、金型Ｃは金型Ｂの寸法縦横厚みの２倍のものを使用した。 The mold A was 2% smaller than the volume of the mold B, and the mold C was twice as long as the dimension B of the mold B.
得られた熱圧成型品は、バリのカットが必要ない外観のきれいな成型品であった。
比較例１
The obtained hot-pressed molded product was a molded product with a beautiful appearance that did not require burr cutting.
Comparative Example 1
実施例１と同様の配合で、金型Ａに入れる工程を省略し、金型Ｂ，Ｃの工程のみを行い熱圧成型品を得た。 With the same composition as in Example 1, the process of putting in the mold A was omitted, and only the processes of the molds B and C were performed to obtain a hot-press molded product.
得られた熱圧成型品は、金型の合わせ面に亀裂が生じた成形品であった。
比較例２
The obtained hot-press molded product was a molded product in which a crack occurred on the mating surface of the mold.
Comparative Example 2
実施例１と同様の配合で、金型Ａ，Ｂの行程を行い、冷却せずに取り出して金型Ｃに入れるようとしたが、製品が急激に発泡するため割れてしまい、金型Ｃに仕込めなかった。
比較例３
In the same composition as in Example 1, the processes of molds A and B were performed, and the molds C and B were taken out without being cooled and put in the mold C. I could not prepare.
Comparative Example 3
金型Ａの体積が金型Ｂの体積より０．５％小さいこと以外は、実施例１と同様の行程を行い熱圧成形品を得た。 Except that the volume of the mold A was 0.5% smaller than the volume of the mold B, the same process as in Example 1 was performed to obtain a hot-press molded product.
得られた熱圧成形品は、金型の合わせ面にバリが発生した成形品であった。
比較例４
The obtained hot-press molded product was a molded product in which burrs occurred on the mating surface of the mold.
Comparative Example 4
金型Ａの体積が金型Ｂの体積より６％小さいこと以外は、実施例１と同様の行程を行ったが、金型Ｃに充填せず、きれいな熱圧成形品が得られなかった。
比較例５
Except that the volume of the mold A was 6% smaller than the volume of the mold B, the same process as in Example 1 was performed, but the mold C was not filled and a clean hot-press molded product was not obtained.
Comparative Example 5
金型Ｃの寸法が金型Ｂの寸法縦横厚みの１．３倍であること以外は、実施例１と同様の行程を行い熱圧成形品を得た。 Except that the dimension of the mold C was 1.3 times the vertical and horizontal thicknesses of the mold B, the same process as in Example 1 was performed to obtain a hot-press molded product.
得られた熱圧成形品は、金型の合わせ面にバリが発生した成形品であった。
比較例６
The obtained hot-press molded product was a molded product in which burrs occurred on the mating surface of the mold.
Comparative Example 6
金型Ｃの寸法が金型Ｂの寸法縦横厚みの２．８倍であること以外は、実施例１と同様の行程を行ったが、硬さや強度に劣った熱圧成形品しか得られなかった。 Except that the dimension of the mold C is 2.8 times the vertical and horizontal thicknesses of the mold B, the same process as in Example 1 was performed, but only a hot-press molded product with poor hardness and strength was obtained. It was.
以上のように、本発明の方法によれば、バリの発生が無く、外観のきれいな熱圧成形品を得ることが出来る。本発明の方法によって製造された熱圧成形品は、雑貨、福祉関係をはじめ、柔軟性及び弾力性を求められる成形品の用途に適用できる。
As described above, according to the method of the present invention, a hot-press molded product having no appearance of burrs and having a beautiful appearance can be obtained. The hot-press molded product produced by the method of the present invention can be applied to uses of molded products that require flexibility and elasticity, as well as general merchandise and welfare relationships.
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| JP2008106431A JP5271589B2 (en) | 2008-04-16 | 2008-04-16 | Method for producing polyolefin foam hot-press molded product |
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| JP2008106431A JP5271589B2 (en) | 2008-04-16 | 2008-04-16 | Method for producing polyolefin foam hot-press molded product |
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| JP5271589B2 true JP5271589B2 (en) | 2013-08-21 |
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| JPS6221525A (en) * | 1985-07-22 | 1987-01-29 | Sanwa Kako Kk | Manufacture of polyolefin foam |
| JPS63125325A (en) * | 1986-11-14 | 1988-05-28 | Sekisui Plastics Co Ltd | Manufacture of crosslinked polyolefin foam |
| JP3272779B2 (en) * | 1992-07-27 | 2002-04-08 | 株式会社イノアックコーポレーション | Method for producing polyolefin plate-like foam |
| JP2004035744A (en) * | 2002-07-04 | 2004-02-05 | Sanwa Kako Co Ltd | Luminous polyolefin open-cell foam and its manufacturing process |
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