JPH0120653B2 - - Google Patents
Info
- Publication number
- JPH0120653B2 JPH0120653B2 JP58009428A JP942883A JPH0120653B2 JP H0120653 B2 JPH0120653 B2 JP H0120653B2 JP 58009428 A JP58009428 A JP 58009428A JP 942883 A JP942883 A JP 942883A JP H0120653 B2 JPH0120653 B2 JP H0120653B2
- Authority
- JP
- Japan
- Prior art keywords
- odor
- polyethylene
- molding
- temperature
- pressure polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 polyethylene Polymers 0.000 claims description 22
- 239000004698 Polyethylene Substances 0.000 claims description 21
- 229920000573 polyethylene Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000003475 lamination Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 description 12
- 230000009965 odorless effect Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000005026 oriented polypropylene Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Description
【発明の詳細な説明】
本発明は、高圧法ポリエチレンの改良方法に関
し、更に詳しくは高圧法ポリエチレンに特定の化
合物を添加して、無臭化する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for improving high-pressure polyethylene, and more particularly to a method for adding a specific compound to high-pressure polyethylene to make it odorless.
従来、高圧法ポリエチレンを高温で押出し、ア
ルミ箔、OPP、ナイロンやポリエステルのフイ
ルム等にラミネートする場合、独特のポリエチレ
ン臭を発生し、ラミネート製品が例えば食品包装
に使われたときに内容物の食品に異質の臭いを感
じさせていた。本発明者の観察によると、成形温
度230℃までは臭いの増加は殆んど認められない
が、それ以上の温度では温度上昇とともに臭いが
強くなり、300℃を越えると激しいコゲ臭が発生
した。 Conventionally, when high-pressure polyethylene is extruded at high temperatures and laminated onto aluminum foil, OPP, nylon or polyester film, etc., a distinctive polyethylene odor is generated, and when the laminated product is used for food packaging, for example, the food content It gave off a foreign odor. According to the inventor's observation, almost no increase in odor was observed up to a molding temperature of 230°C, but at temperatures higher than that, the odor became stronger as the temperature increased, and when it exceeded 300°C, a strong burnt odor occurred. .
高圧法ポリエチレンを改良して無臭化する方法
として、ポリエチレンの分子構造を改良する方法
が知られている。即ちポリエチレン分子内に不飽
和結合や３級炭素数を減らして空気酸化の作用を
受けにくい構造にする方法、ポリエチレン中の低
分子量ポリマー含量を減らして高温成形時に揮発
しにくい構造にする方法、及びポリエチレンにオ
クタデシル ３−（３，５−ジタ−シヤルブチル
−４−ヒドロキシフエニル）プロピオネートやペ
ンタエリスチル テトラキス〔３−（３，５−ジ
タ−シヤルブチル−４−ヒドロキシフエニル）プ
ロピオネート〕等の耐熱性の良い抗酸化剤を添加
する方法等である。 As a method of improving high-pressure polyethylene to make it odorless, a method of improving the molecular structure of polyethylene is known. Specifically, there are methods to create a structure that is less susceptible to air oxidation by reducing the number of unsaturated bonds and tertiary carbons in the polyethylene molecule, methods to reduce the low molecular weight polymer content in polyethylene to create a structure that is less likely to volatilize during high temperature molding, and Polyethylene has heat resistance properties such as octadecyl 3-(3,5-diter-sialbutyl-4-hydroxyphenyl) propionate and pentaerythyl tetrakis [3-(3,5-diter-sial butyl-4-hydroxyphenyl) propionate]. For example, adding a good antioxidant.
これらの方法を用いれば確かに比較的低温での
成形による臭い強度を低下させることができる
が、成形温度が230℃以上では徐々に臭いが強く
なり無臭とは云い難いものとなる。又、空気酸化
されにくい分子構造にしたものや抗酸化剤を添加
したものは、ラミネート成形時の溶融膜表面の酸
化が不十分となり、Al箔、OPP、ナイロン、ポ
リエステル等との接着が悪化し、デラミを起し易
いという別の欠点を生じる。 By using these methods, it is certainly possible to reduce the odor intensity caused by molding at a relatively low temperature, but when the molding temperature is 230°C or higher, the odor gradually becomes stronger and it is difficult to say that it is odorless. In addition, if the molecular structure is resistant to air oxidation or if antioxidants are added, the surface of the molten film during lamination molding will not be sufficiently oxidized, resulting in poor adhesion to Al foil, OPP, nylon, polyester, etc. Another drawback is that delamination is likely to occur.
本発明者は、種々の検討を行なつた結果、230
℃以上の高温成形で発生する臭い成分の大部分が
酢酸、プロピオン酸、吉草酸などのカルボン酸で
あることをつきとめ、次のような化合物を高圧法
ポリエチレンに添加することによつて高温成形時
に発生する臭いを無くすることができ、ひいては
成形品の臭いも無くなることを見出した。 As a result of various studies, the inventor found that 230
It was discovered that most of the odor components generated during high-temperature molding at temperatures above ℃ are carboxylic acids such as acetic acid, propionic acid, and valeric acid, and by adding the following compounds to high-pressure polyethylene, it is possible to reduce the odor during high-temperature molding. It has been found that the odor generated can be eliminated, and that the odor of molded products can also be eliminated.
即ち、無臭化に有用な化合物としては、酸化マ
グネシウム、酸化カルシウム、水酸化カルシウム
が有用である。 That is, as compounds useful for deodorization, magnesium oxide, calcium oxide, and calcium hydroxide are useful.
添加量は、高圧法ポリエチレンの加工温度によ
つても異なるが成形時に発生する遊離カルボン酸
をカルボン酸塩にするに十分な量でよく、通常は
ポリエチレンに対して0.005〜0.2重量％、好しく
は0.03〜0.1重量％で有効である。 The amount added varies depending on the processing temperature of the high-pressure polyethylene, but it may be sufficient to convert free carboxylic acid generated during molding into a carboxylic acid salt, and is usually 0.005 to 0.2% by weight based on the polyethylene, preferably is effective at 0.03-0.1% by weight.
添加する方法は、通常使用される押出機、ニー
ダー、バンバリーミキサー等の混練機で練り込む
方法でよく、又は、ポリエチレンペレツトにドラ
イブレンドしてそのまま加工成形押出機に供給す
ることもできる。もちろんマスターバツチ法でも
よい。 The addition method may be a method of kneading with a commonly used kneading machine such as an extruder, kneader, or Banbury mixer, or it may be dry blended with polyethylene pellets and supplied as it is to a processing and molding extruder. Of course, the master batch method may also be used.
なお本発明において高圧法ポリエチレンとは、
重合圧力500Kg／cm2以上の高圧で、温度100〜300
℃の条件下にて重合されるポリエチレンをいう。 In addition, in the present invention, high-pressure polyethylene refers to
Polymerization pressure 500Kg/ cm2 or higher, temperature 100-300
Refers to polyethylene that is polymerized under conditions of ℃.
比較例 １〜３
溶融指数４ｇ／10min、密度0.923ｇ／cm3の高
圧法ポリエチレンを口径40mm、Ｌ／Ｄ＝22の押出
機を備えたＴダイを使用して押出量12Kg／hrの下
で押出樹脂温度160℃、230℃および300℃で成形
したフイルムの臭い指数（１…全然臭いを感じな
い、２…若干感じる、３…感じる、４…やゝ強く
感じる、５…強く感じる；とする。以下同じ）
は、それぞれ２、２乃至３、５であつた。Comparative Examples 1 to 3 High-pressure polyethylene with a melt index of 4 g/10 min and a density of 0.923 g/cm 3 was extruded at an extrusion rate of 12 Kg/hr using a T-die equipped with an extruder with a diameter of 40 mm and L/D = 22. Odor index of films molded at extrusion resin temperatures of 160°C, 230°C, and 300°C (1...not smelling at all, 2...slightly smelling, 3...feeling, 4...feeling rather strong, 5...feeling strongly; .same as below)
were 2,2 to 3,5, respectively.
実施例 １〜２
比較例と同じポリエチレンに酸化マグネシウム
を0.05重量％添加し、押出樹脂温度300℃で成形
したフイルムの臭い指数は２であり、臭いの改良
効果が著しかつた。Examples 1-2 A film produced by adding 0.05% by weight of magnesium oxide to the same polyethylene as in the comparative example and molding the film at an extrusion resin temperature of 300°C had an odor index of 2, indicating a remarkable odor improvement effect.
酸化マグネシウムの代りに酸化カルシウムを使
用しても同様の結果が得られた。 Similar results were obtained using calcium oxide instead of magnesium oxide.
実施例 ３
比較例と同じポリエチレンに水酸化カルシウム
を0.03重量％添加し、押出樹脂温度300℃で成形
したフイルムの臭い指数は３であつた。Example 3 A film made by adding 0.03% by weight of calcium hydroxide to the same polyethylene as in the comparative example and molding the film at an extrusion resin temperature of 300°C had an odor index of 3.
本発明によれば、容易にかつ安価に入手できる
化合物を使用し、これを単に添加するだけで高圧
法ポリエチレンを改良してその成形品を無臭化す
ることができると共に、従来法のようなラミネー
ト成形におけるデラミの欠点を生じることもな
い。 According to the present invention, by simply adding a compound that is easily and inexpensively available, it is possible to improve high-pressure polyethylene and make the molded product odorless, and it is also possible to make the molded product odorless, as well as to eliminate the need for lamination unlike conventional methods. There is no problem of delamination during molding.
Claims (1)
出ラミネーシヨンする方法に於て、該高圧法ポリ
エチレンが酸化マグネシウム、酸化カルシウムな
らびに水酸化カルシウムからなる群から選ばれた
１種または２種以上の化合物を0.005〜0.2重量％
含有することを特徴とする押出ラミネーシヨン
法。1. In a method of extrusion lamination of high-pressure polyethylene at a temperature of 300°C or higher, the high-pressure polyethylene contains one or more compounds selected from the group consisting of magnesium oxide, calcium oxide, and calcium hydroxide. 0.005-0.2% by weight
An extrusion lamination method characterized by containing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP942883A JPS59136340A (en) | 1983-01-25 | 1983-01-25 | Method for improving high-pressure polyethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP942883A JPS59136340A (en) | 1983-01-25 | 1983-01-25 | Method for improving high-pressure polyethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59136340A JPS59136340A (en) | 1984-08-04 |
| JPH0120653B2 true JPH0120653B2 (en) | 1989-04-18 |
Family
ID=11720059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP942883A Granted JPS59136340A (en) | 1983-01-25 | 1983-01-25 | Method for improving high-pressure polyethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59136340A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01272647A (en) * | 1988-04-25 | 1989-10-31 | Chisso Corp | Polyethylene resin composition |
| JP5991506B2 (en) * | 2011-11-16 | 2016-09-14 | 学校法人関東学院 | Film deterioration prevention material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4927537A (en) * | 1972-07-07 | 1974-03-12 | ||
| JPS5110264A (en) * | 1974-07-15 | 1976-01-27 | Kataoka Kikai Seisakusho Kk | Makikaekino makitorichoryokuseigyosochi |
| JPS51116883A (en) * | 1975-04-07 | 1976-10-14 | Nippon Petrochem Co Ltd | A process for manufacturing a multi-layer thermoplastic film |
| JPS5689515A (en) * | 1979-12-21 | 1981-07-20 | Du Pont Mitsui Polychem Co Ltd | Production of laminate and extrusion die used therefor |
-
1983
- 1983-01-25 JP JP942883A patent/JPS59136340A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4927537A (en) * | 1972-07-07 | 1974-03-12 | ||
| JPS5110264A (en) * | 1974-07-15 | 1976-01-27 | Kataoka Kikai Seisakusho Kk | Makikaekino makitorichoryokuseigyosochi |
| JPS51116883A (en) * | 1975-04-07 | 1976-10-14 | Nippon Petrochem Co Ltd | A process for manufacturing a multi-layer thermoplastic film |
| JPS5689515A (en) * | 1979-12-21 | 1981-07-20 | Du Pont Mitsui Polychem Co Ltd | Production of laminate and extrusion die used therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59136340A (en) | 1984-08-04 |
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