JPH05222235A - Production of polyolefinic foam - Google Patents
Production of polyolefinic foamInfo
- Publication number
- JPH05222235A JPH05222235A JP4056775A JP5677592A JPH05222235A JP H05222235 A JPH05222235 A JP H05222235A JP 4056775 A JP4056775 A JP 4056775A JP 5677592 A JP5677592 A JP 5677592A JP H05222235 A JPH05222235 A JP H05222235A
- Authority
- JP
- Japan
- Prior art keywords
- foam
- producing
- foaming agent
- fluorinated hydrocarbon
- polyolefin
- 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.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリオレフィン発泡
体、例えばポリエチレン、ポリプロピレンなどの発泡体
の製造方法に関し、詳しくは、特定の発泡剤を用いたポ
リオレフィン発泡体の新規な製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyolefin foam, for example, a foam made of polyethylene, polypropylene or the like, and more particularly to a novel method for producing a polyolefin foam using a specific foaming agent.
【０００２】[0002]
【従来の技術】ポリオレフィンの発泡には、毒性が少な
く、不燃性で、化学的に安定なトリクロロフルオロメタ
ン(R11) 、ジクロロジフルオロメタン(R12) 、1,2-ジク
ロロテトラフルオロエタン(R114)、モノクロロペンタフ
ルオロエタン(R115)等のクロロフルオロ炭化水素( 以
下、ＣＦＣフロンという) が用いられてきた。2. Description of the Related Art Polyolefin foam is less toxic, non-flammable and chemically stable trichlorofluoromethane (R11), dichlorodifluoromethane (R12), 1,2-dichlorotetrafluoroethane (R114), Chlorofluorohydrocarbons such as monochloropentafluoroethane (R115) (hereinafter referred to as CFC freon) have been used.
【０００３】[0003]
【発明が解決しようとする課題】塩素原子を含むＣＦＣ
フロンは、対流圏内での寿命が長く、拡散して成層圏に
達し、ここで太陽光線により分解して発生する塩素ラジ
カルがオゾンと連鎖反応を起こし、オゾン層を破壊する
とのことから、その使用規制が実施されることとなっ
た。このため、これら従来のＣＦＣフロンに代わり、オ
ゾン層を破壊しにくいヒドロクロロフルオロ炭化水素
（ＨＣＦＣ）や、塩素原子を含まないのでオゾン層を破
壊しないヒドロフルオロ炭化水素（ＨＦＣ）などの代替
フロンの探索が活発に行われている。CFC containing chlorine atom
Freon has a long life in the troposphere, diffuses and reaches the stratosphere, where the chlorine radicals that are decomposed by sunlight cause a chain reaction with ozone, which destroys the ozone layer. Will be implemented. Therefore, in place of these conventional CFC freons, hydrochlorofluorohydrocarbons (HCFCs) that are less likely to destroy the ozone layer, and alternative fluorocarbons (HFCs) that do not destroy the ozone layer because they do not contain chlorine atoms are used. The search is active.
【０００４】本発明は、従来のＣＦＣフロンが有してい
る優れた特性を満足しながら代替フロンとして使用でき
る、オゾン層を破壊しない特定のフッ素化炭化水素を必
須成分として含む発泡剤を用いたポリオレフィン発泡体
の製造方法を提供することを目的とする。The present invention uses a blowing agent containing a specific fluorinated hydrocarbon which does not destroy the ozone layer and which can be used as an alternative CFC while satisfying the excellent characteristics of conventional CFC CFCs. An object is to provide a method for producing a polyolefin foam.
【０００５】[0005]
【課題を解決するための手段】本発明は、ポリオレフィ
ンと発泡剤を高温高圧下で混合し低圧帯域に押し出し、
ポリオレフィン発泡体を製造する方法において、発泡剤
として水素原子の一部または全部をフッ素原子で置換し
た炭素数３のフッ素化炭化水素を必須成分として用いる
ことを特徴とするポリオレフィン発泡体の製造方法を提
供する。According to the present invention, a polyolefin and a foaming agent are mixed under high temperature and high pressure and extruded into a low pressure zone,
A method for producing a polyolefin foam, which comprises using, as an essential component, a fluorinated hydrocarbon having 3 carbon atoms in which some or all of hydrogen atoms are replaced by fluorine atoms, as a blowing agent. provide.
【０００６】本発明においては発泡剤として水素原子の
一部または全部をフッ素原子で置換した炭素数３のフッ
素化炭化水素（以下、特定フッ素化炭化水素という）を
用いることが重要である。特定フッ素化炭化水素として
は、C3H7F 、C3H6F2、C3H5F3、C3H4F4、C3H3F5、C3H
2F6、C3HF7 、C3F8、シクロ-C3F6 から選ばれる少なく
とも一種のフッ素化炭化水素が好ましい。In the present invention, it is important to use a fluorinated hydrocarbon having 3 or less carbon atoms (hereinafter referred to as a specific fluorinated hydrocarbon) in which some or all of hydrogen atoms are substituted with fluorine atoms as the blowing agent. Specific fluorinated hydrocarbons include C 3 H 7 F, C 3 H 6 F 2 , C 3 H 5 F 3 , C 3 H 4 F 4 , C 3 H 3 F 5 , C 3 H
At least one fluorinated hydrocarbon selected from 2 F 6 , C 3 HF 7 , C 3 F 8 and cyclo-C 3 F 6 is preferable.
【０００７】本発明のポリオレフィン発泡体の製造方法
において用いる発泡剤は、オゾン層を破壊せず、従来の
ＣＦＣフロンと同等の特性を有し、同じ使い方ができ、
従来技術の大幅な変更を要しないなどの利点がある。The foaming agent used in the method for producing a polyolefin foam of the present invention does not destroy the ozone layer, has the same characteristics as conventional CFC freon, and can be used in the same manner.
There are advantages such as not requiring significant changes to the conventional technology.
【０００８】本発明における発泡剤の量は、特に限定さ
れることはないが、ポリオレフィンの 100重量部に対し
て、 0.1重量部〜50重量部使用することが好ましい。The amount of the foaming agent in the present invention is not particularly limited, but it is preferable to use 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyolefin.
【０００９】本発明の発泡剤には、必要に応じてその他
の成分を更に添加混合することができる。例えば、プロ
パン、ブタン、ペンタン、イソペンタン、ヘキサン、イ
ソヘキサン、ネオヘキサン、ヘプタン、イソヘプタン、
2,3-ジメチルブタン、シクロペンタンなどの炭化水素
類、クロロメタン、ジクロロメタンなどのハロゲン化炭
化水素類、イソプロピルエーテルなどのエーテル類等の
添加成分を一種以上適宜添加することができる。If necessary, other components can be further added to and mixed with the foaming agent of the present invention. For example, propane, butane, pentane, isopentane, hexane, isohexane, neohexane, heptane, isoheptane,
One or more additive components such as hydrocarbons such as 2,3-dimethylbutane and cyclopentane, halogenated hydrocarbons such as chloromethane and dichloromethane, and ethers such as isopropyl ether can be appropriately added.
【００１０】また、トリクロロフルオロメタン(R11) 、
ジクロロジフルオロメタン(R12) 、1,1,2-トリクロロ-
1,2,2- トリフルオロエタン(R113)、1,2-ジクロロテト
ラフルオロエタン(R114)、モノクロロペンタフルオロエ
タン(R115)の如きＣＦＣフロン、あるいは2,2-ジクロロ
-1,1,1- トリフルオロエタン(R123)、1,2-ジクロロ-1,
1,2- トリフルオロエタン(R123a) 、1,1-ジクロロ-1-
フルオロエタン(R141b) 、3,3-ジクロロ-1,1,1,2,2- ペ
ンタフルオロプロパン(R225ca)、1,3-ジクロロ-1,1,2,
2,3- ペンタフルオロプロパン(R225cb)、3-クロロ-1,1,
2,2- テトラフルオロプロパン(R244ca)、1-クロロ-1,2,
2,3- テトラフルオロプロパン(R244cb)、3-クロロ -1,
1,2,2,3-ペンタフルオロプロパン(R235ca)、1,1-ジクロ
ロ-1,2,2- トリフルオロプロパン(R243cc)の如きＨＣＦ
Ｃフロン等の一種以上を、単独であるいは上記添加成分
と共に本発明の特定フッ素化炭化水素と併用できる。Further, trichlorofluoromethane (R11),
Dichlorodifluoromethane (R12), 1,1,2-trichloro-
CFC Freon such as 1,2,2-trifluoroethane (R113), 1,2-dichlorotetrafluoroethane (R114), monochloropentafluoroethane (R115), or 2,2-dichloro
-1,1,1-trifluoroethane (R123), 1,2-dichloro-1,
1,2-trifluoroethane (R123a), 1,1-dichloro-1-
Fluoroethane (R141b), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (R225ca), 1,3-dichloro-1,1,2,
2,3-Pentafluoropropane (R225cb), 3-chloro-1,1,
2,2-tetrafluoropropane (R244ca), 1-chloro-1,2,
2,3-Tetrafluoropropane (R244cb), 3-chloro-1,
HCF such as 1,2,2,3-pentafluoropropane (R235ca) and 1,1-dichloro-1,2,2-trifluoropropane (R243cc)
One or more of C-Freon and the like can be used alone or in combination with the above-mentioned additional components with the specific fluorinated hydrocarbon of the present invention.
【００１１】本発明におけるポリオレフィンとしては、
エチレンホモポリマー、例えば低密度または高密度ポリ
エチレン、エチレンコポリマー、例えばエチレン−酢酸
ビニルコポリマー、エチレン−プロピレンコポリマー、
エチレン−1-ブテンコポリマー、エチレン−塩化ビニル
コポリマー、エチレン−メチルメタクリレートコポリマ
ー、エチレン−アクリロニトリルコポリマー、あるいは
ポリプロピレンなどを挙げることができる。As the polyolefin in the present invention,
Ethylene homopolymers such as low or high density polyethylene, ethylene copolymers such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers,
Examples thereof include ethylene-1-butene copolymer, ethylene-vinyl chloride copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylonitrile copolymer, and polypropylene.
【００１２】さらに、本発明においては、シリカ、タル
ク、ケイ酸カルシウム、ワラストナイト、カオリン、ク
レイ、マイカ、酸化亜鉛、酸化チタン、脂肪酸金属塩
類、例えばステアリン酸バリウム、ステアリン酸亜鉛、
ステアリン酸アルミニウム、ステアリン酸カルシウムな
どの各種添加剤を用いることもできる。Further, in the present invention, silica, talc, calcium silicate, wollastonite, kaolin, clay, mica, zinc oxide, titanium oxide, fatty acid metal salts such as barium stearate, zinc stearate,
Various additives such as aluminum stearate and calcium stearate can also be used.
【００１３】[0013]
【実施例】以下の実施例及び比較例においては、30mm直
径を有する単軸スクリュー型押出機を用いて発泡体をつ
くった。この押出機のスクリューは、フィード領域、圧
縮・溶融領域、計量領域及び混合領域から成っている。
計量領域と混合領域の間の押出機バーレルには、発泡剤
用の注入口が備えられている。この注入口には、発泡剤
を注入するために、高圧定容量ポンプが接続されてい
る。押出機の放出端は、口径５mmの丸い孔を有する口金
を備えている。EXAMPLES In the following examples and comparative examples, foams were made using a single screw extruder having a diameter of 30 mm. The screw of this extruder consists of a feed zone, a compression / melt zone, a metering zone and a mixing zone.
The extruder barrel between the metering zone and the mixing zone is equipped with an inlet for blowing agent. A high-pressure constant-volume pump is connected to this inlet for injecting a foaming agent. The discharge end of the extruder is equipped with a die having a round hole with a diameter of 5 mm.
【００１４】実施例１〜18及び比較例１〜２ メルトインデックス2.0g/10minのポリエチレン（旭ダウ
製「Ｆ−1920Ｒ」：商品名）の 100重量部に対し、添加
剤としてのステアリン酸カルシウム 0.1重量部及びケイ
酸カルシウム 0.4重量部を、Ｖミキサーにて混合し、上
記押出機のホッパーより供給した。一方、表１に示す各
種発泡剤を上記高圧定容量ポンプを用いて、押出機バー
レルの注入口より一定量注入し、押出機内の高圧・高温
下において、樹脂と発泡剤を混合し、口金より押し出し
発泡せしめた。Examples 1 to 18 and Comparative Examples 1 to 2 0.1 part by weight of calcium stearate as an additive to 100 parts by weight of polyethylene (“F-1920R” manufactured by Asahi Dow, trade name) having a melt index of 2.0 g / 10 min. Parts and 0.4 parts by weight of calcium silicate were mixed in a V mixer and fed from the hopper of the extruder. On the other hand, various foaming agents shown in Table 1 were injected from the injection port of the extruder barrel using the above-mentioned high-pressure constant-volume pump, and the resin and the foaming agent were mixed under high pressure and high temperature in the extruder, and then from the die. It was extruded and foamed.
【００１５】実施例19〜36及び比較例３〜４ メルトインデックス2.0g/10minのポリエチレンに代えて
ポリプロピレン樹脂の100重量部を用い、ケイ酸カルシ
ウムを 0.4重量部に代えて 0.5重量部とし、表２に示す
各種発泡剤を用いたほかは実施例１と同様にして、ポリ
プロピレン発泡体をつくった。Examples 19 to 36 and Comparative Examples 3 to 4 100 parts by weight of polypropylene resin was used in place of polyethylene having a melt index of 2.0 g / 10 min, and 0.5 parts by weight was used instead of 0.4 parts by weight of calcium silicate. A polypropylene foam was produced in the same manner as in Example 1 except that various foaming agents shown in 2 were used.
【００１６】発泡性を評価するために、従来のＣＦＣフ
ロンを用いて発泡体を製造（比較例１〜４）し、これと
の比較を行った。表１及び表２における発泡体表面と
は、発泡体の表面シワ、凹凸などを比較し、従来品と遜
色ないものを〇印とした。また、発泡体形状とは、発泡
体断面を拡大鏡により肉眼で観察し、気泡の独立性、気
泡の大きさの均一性等が、従来品と遜色ないものを〇印
とした。In order to evaluate the foamability, foams were produced using conventional CFC freon (Comparative Examples 1 to 4) and compared with them. The surface of the foam in Tables 1 and 2 was compared with the surface of the foam for wrinkles, unevenness, etc., and those that were comparable to the conventional product were marked with a circle. In addition, the foam shape is indicated by ◯ when the foam cross-section is visually observed with a magnifying glass and the independence of cells and the uniformity of cell size are comparable to those of conventional products.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】[0019]
【発明の効果】本発明のポリオレフィン発泡体の製造方
法において用いる特定のフッ素化炭化水素からなる発泡
剤は、オゾン層を破壊せず、従来のＣＦＣフロンが有し
ている優れた特性を満足し、従来のＣＦＣフロンと同じ
使い方ができ、従来技術の大幅な変更を要しない等の利
点がある。EFFECTS OF THE INVENTION The blowing agent composed of a specific fluorinated hydrocarbon used in the method for producing a polyolefin foam of the present invention does not destroy the ozone layer and satisfies the excellent properties of conventional CFC freon. The advantage is that it can be used in the same way as the conventional CFC Freon and does not require a significant modification of the conventional technology.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 23:00 (72)発明者 青柳 美奈子 神奈川県川崎市幸区塚越３丁目474番２号 旭硝子株式会社玉川分室内 (72)発明者 北村 健郎 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical indication C08L 23:00 (72) Inventor Minako Aoyagi 3-474-2 Tsukagoshi, Saiwai-ku, Kawasaki-shi, Kanagawa Asahi Glass Tamagawa Branch Chamber Co., Ltd. (72) Inventor Kenro Kitamura 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory
Claims (2)
合し、低圧帯域に押し出し、ポリオレフィン発泡体を製
造する方法において、発泡剤として水素原子の一部また
は全部をフッ素原子で置き換えた炭素数３のフッ素化炭
化水素を使用することを特徴とするポリオレフィン発泡
体の製造方法。1. A method for producing a polyolefin foam by mixing a polyolefin and a foaming agent under high temperature and high pressure and extruding into a low-pressure zone, wherein the foaming agent has 3 or less carbon atoms in which some or all of hydrogen atoms are replaced by fluorine atoms. 1. A method for producing a polyolefin foam, which comprises using the fluorinated hydrocarbon as described above.
C3H6F2、C3H5F3、C3H4F4、C3H3F5、C3H2F6、C3HF7 、C3
F8、シクロ-C3F6 から選ばれる少なくとも一種である請
求項１の製造方法。2. A fluorinated hydrocarbon having 3 carbon atoms is C 3 H 7 F,
C 3 H 6 F 2 , C 3 H 5 F 3 , C 3 H 4 F 4 , C 3 H 3 F 5 , C 3 H 2 F 6 , C 3 HF 7 , C 3
The method according to claim 1, wherein the method is at least one selected from F 8 and cyclo-C 3 F 6 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4056775A JPH05222235A (en) | 1992-02-07 | 1992-02-07 | Production of polyolefinic foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4056775A JPH05222235A (en) | 1992-02-07 | 1992-02-07 | Production of polyolefinic foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05222235A true JPH05222235A (en) | 1993-08-31 |
Family
ID=13036833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4056775A Withdrawn JPH05222235A (en) | 1992-02-07 | 1992-02-07 | Production of polyolefinic foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05222235A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0664038A (en) * | 1992-06-19 | 1994-03-08 | New Japan Chem Co Ltd | Stretched beta-crystalline polypropylene film and manufacture thereof |
| US5433880A (en) * | 1993-01-15 | 1995-07-18 | E. I. Du Pont De Nemours And Company | Refrigerant compositions which include a sulfur compound |
| US5484546A (en) * | 1993-05-19 | 1996-01-16 | E. I. Du Pont De Nemours And Company | Refrigerant compositions including an acylic fluoroether |
| US5538659A (en) * | 1993-03-29 | 1996-07-23 | E. I. Du Pont De Nemours And Company | Refrigerant compositions including hexafluoropropane and a hydrofluorocarbon |
| US5558810A (en) * | 1994-11-16 | 1996-09-24 | E. I. Du Pont De Nemours And Company | Pentafluoropropane compositions |
| US5562855A (en) * | 1994-09-29 | 1996-10-08 | E. I. Du Pont De Nemours And Company | Octafluorobutane compositions |
| US5626790A (en) * | 1992-11-19 | 1997-05-06 | E. I. Du Pont De Nemours And Company | Refrigerant compositions including 1,1,2-trifluoroethane and hexafluoropropane |
| US5672293A (en) * | 1994-03-11 | 1997-09-30 | E. I. Du Pont De Nemours And Company | Hydrofluorocarbon compositions |
| US5688431A (en) * | 1994-09-29 | 1997-11-18 | E. I. Du Pont De Nemours And Company | Octafluorobutane compositions |
| WO1998036020A1 (en) * | 1997-02-17 | 1998-08-20 | Daikin Industries, Ltd. | Process for the production of polyolefin resin foams |
| US6531441B1 (en) | 1994-03-11 | 2003-03-11 | E. I. Du Pont De Nemours And Company | Hydrofluorocarbon compositions |
| EP1040158B1 (en) * | 1997-12-19 | 2005-03-02 | Trexel, Inc. | Microcellular foam extrusion/blow molding process and article made thereby |
-
1992
- 1992-02-07 JP JP4056775A patent/JPH05222235A/en not_active Withdrawn
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0664038A (en) * | 1992-06-19 | 1994-03-08 | New Japan Chem Co Ltd | Stretched beta-crystalline polypropylene film and manufacture thereof |
| US5626790A (en) * | 1992-11-19 | 1997-05-06 | E. I. Du Pont De Nemours And Company | Refrigerant compositions including 1,1,2-trifluoroethane and hexafluoropropane |
| US5433880A (en) * | 1993-01-15 | 1995-07-18 | E. I. Du Pont De Nemours And Company | Refrigerant compositions which include a sulfur compound |
| US5616275A (en) * | 1993-03-29 | 1997-04-01 | E. I. Du Pont De Nemours And Company | Azeotrope(like) mixtures of two hexafluoropropane stereoisomers |
| US5538659A (en) * | 1993-03-29 | 1996-07-23 | E. I. Du Pont De Nemours And Company | Refrigerant compositions including hexafluoropropane and a hydrofluorocarbon |
| US5484546A (en) * | 1993-05-19 | 1996-01-16 | E. I. Du Pont De Nemours And Company | Refrigerant compositions including an acylic fluoroether |
| US5607616A (en) * | 1993-05-19 | 1997-03-04 | E. I. Du Pont De Nemours And Company | Azeotrope(like) compositions with fluoromethyl trifluoromethyl ether and dimethyl ether |
| US5785883A (en) * | 1994-03-11 | 1998-07-28 | E. I. Du Pont De Nemours And Company | Hydrofluorocarbon compositions with tetrafluoroethane and cyclopropane |
| US5672293A (en) * | 1994-03-11 | 1997-09-30 | E. I. Du Pont De Nemours And Company | Hydrofluorocarbon compositions |
| US6531441B1 (en) | 1994-03-11 | 2003-03-11 | E. I. Du Pont De Nemours And Company | Hydrofluorocarbon compositions |
| US6846792B2 (en) | 1994-03-11 | 2005-01-25 | E. I. Du Pont De Nemours And Company | Hydrofluorocarbon compositions |
| US5562855A (en) * | 1994-09-29 | 1996-10-08 | E. I. Du Pont De Nemours And Company | Octafluorobutane compositions |
| US5654264A (en) * | 1994-09-29 | 1997-08-05 | E. I. Du Pont De Nemours And Company | Octafluorobutane compositions |
| US5688431A (en) * | 1994-09-29 | 1997-11-18 | E. I. Du Pont De Nemours And Company | Octafluorobutane compositions |
| US5558810A (en) * | 1994-11-16 | 1996-09-24 | E. I. Du Pont De Nemours And Company | Pentafluoropropane compositions |
| WO1998036020A1 (en) * | 1997-02-17 | 1998-08-20 | Daikin Industries, Ltd. | Process for the production of polyolefin resin foams |
| EP1040158B1 (en) * | 1997-12-19 | 2005-03-02 | Trexel, Inc. | Microcellular foam extrusion/blow molding process and article made thereby |
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