JPH09176359A - Production of polyolefin resin foamed material - Google Patents
Production of polyolefin resin foamed materialInfo
- Publication number
- JPH09176359A JPH09176359A JP34009395A JP34009395A JPH09176359A JP H09176359 A JPH09176359 A JP H09176359A JP 34009395 A JP34009395 A JP 34009395A JP 34009395 A JP34009395 A JP 34009395A JP H09176359 A JPH09176359 A JP H09176359A
- Authority
- JP
- Japan
- Prior art keywords
- agent
- vinyl acetate
- foaming agent
- foam
- weight
- 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.)
- Pending
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリオレフィン系
樹脂発泡体の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a polyolefin resin foam.
【０００２】[0002]
【従来の技術】ポリオレフィン系樹脂発泡体は、柔軟
性、機械的強度、風合、焼却時の耐環境性等に優れてお
り、パイプ等の断熱材、緩衝材等の用途に広く利用され
ている。なかでも、フロン発泡剤を用いたポリエチレン
樹脂発泡体は、水道水、温水、エアコン等の冷媒用パイ
プ等の断熱材として広範囲で用いられている。しかし、
発泡剤であるフロンは、オゾン破壊等の環境問題から、
全廃規制が進行している。このため、オゾン破壊係数の
少ないフロンや、窒素、炭酸ガス、空気等の発泡剤によ
る検討が最近特に盛んに行われているが、これらの発泡
剤とポリエチレン等のポリオレフィン樹脂との相溶性が
不十分なため、高発泡倍率の発泡体が得られないといっ
た問題がある。2. Description of the Related Art Polyolefin resin foams are excellent in flexibility, mechanical strength, feeling, environment resistance at the time of incineration, and are widely used for heat insulating materials such as pipes and cushioning materials. There is. Among them, a polyethylene resin foam using a CFC foaming agent is widely used as a heat insulating material for pipes for refrigerants such as tap water, hot water and air conditioners. But,
Freon, which is a foaming agent, is
Abolition regulations are in progress. For this reason, studies have recently been particularly actively conducted using chlorofluorocarbons having a low ozone depletion potential and blowing agents such as nitrogen, carbon dioxide, and air, but the compatibility of these blowing agents with polyolefin resins such as polyethylene is unsatisfactory. Since it is sufficient, there is a problem that a foam having a high expansion ratio cannot be obtained.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、かかる状況
に鑑みなされたもので、外観特性に優れ、高発泡倍率を
有するポリオレフィン系樹脂発泡体の製造法を提供する
ことにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a polyolefin resin foam having excellent appearance characteristics and a high expansion ratio.
【０００４】[0004]
【課題を解決するための手段】かくして、本発明によれ
ば、ポリオレフィン系樹脂、核形成剤、収縮防止剤等か
らなるポリオレフィン系樹脂組成物を加熱して軟化、ま
たは熔融させた後、揮発性発泡剤を供給し混合して得ら
れる組成物を、低圧域に開放することにより発泡させる
発泡体の製造方法において、エチレン−酢酸ビニル共重
合体エチレン−酢酸ビニル共重合体を主成分とするポリ
オレフィン系樹脂を用いることにより、高発泡倍率を有
し外観特性に優れるポリオレフィン系樹脂発泡体が提供
される。Thus, according to the present invention, a polyolefin resin composition comprising a polyolefin resin, a nucleating agent, a shrinkage inhibitor, etc. is heated and softened or melted, and then volatile. A method for producing a foam, in which a composition obtained by supplying and mixing a foaming agent is opened in a low pressure range, in a method for producing a foam, an ethylene-vinyl acetate copolymer, a polyolefin containing an ethylene-vinyl acetate copolymer as a main component. By using the resin, a polyolefin resin foam having a high expansion ratio and excellent appearance characteristics is provided.
【０００５】[0005]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明で用いるポリオレフィン系樹脂は、エチレン−酢
酸ビニル共重合体を成分として含むことを特徴としてお
り、該共重合体単独、もしくは、他のポリオレフィン系
樹脂、例えばポリエチレン、ポリプロピレン、エチレン
とαオレフィンとの共重合体やエチレンと他のモノマ
ー、例えばエチルアクリレート等との共重合体も用いる
ことができる。また、プロピレンとαオレフィンとの共
重合体、例えばプロピレン−スチレン共重合体等も用い
ることができる。エチレン−酢酸ビニル共重合体と他の
ポリオレフィン系樹脂との割合は用いるエチレン−酢酸
ビニル共重合体の酢酸ビニル含有量にもよるが、一般的
には重量比で１００／０〜２５／７５である。２５／７
５より少ないとＨＦＣ系発泡剤との相溶性が劣り結果と
して発泡倍率が不十分となる。本発明におけるエチレン
−酢酸ビニル共重合体の酢酸ビニル含有量は、５〜４１
重量％で、好ましくは５〜２５重量％である。５重量％
以下であると、発泡剤の相溶性が不十分となり、４１重
量％以上では、融解温度が低下し、得られる発泡体の耐
熱性が不十分となる。また、該エチレン−酢酸ビニル共
重合体のメルトインデックス（ＭＩ：ＪＩＳ Ｋ ６７
３０）は、０．５〜１５０ｇ／１０分、好ましくは１〜
６０ｇ／１０分である。メルトインデックスは、発泡剤
含有時には、さらに高流動化することから、下限につい
ては０．５ｇ／１０分程度で発泡が良好に行われ、上限
については、１５０ｇ／１０分以上の場合、気泡膜の強
度が不十分となって、発泡が良好に行われなくなる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyolefin-based resin used in the present invention is characterized by containing an ethylene-vinyl acetate copolymer as a component, and the copolymer alone or other polyolefin-based resin such as polyethylene, polypropylene, ethylene and α-olefin. A copolymer of ethylene and a copolymer of ethylene and another monomer such as ethyl acrylate can also be used. Further, a copolymer of propylene and α-olefin, such as a propylene-styrene copolymer, can be used. Although the ratio of the ethylene-vinyl acetate copolymer to the other polyolefin-based resin depends on the vinyl acetate content of the ethylene-vinyl acetate copolymer used, it is generally 100/0 to 25/75 by weight. is there. 25/7
When it is less than 5, the compatibility with the HFC-based foaming agent is poor and, as a result, the expansion ratio becomes insufficient. The vinyl acetate content of the ethylene-vinyl acetate copolymer in the present invention is 5 to 41.
%, Preferably 5 to 25% by weight. 5% by weight
When it is below, the compatibility of the foaming agent becomes insufficient, and when it is 41% by weight or more, the melting temperature is lowered and the heat resistance of the obtained foam becomes insufficient. Further, the melt index (MI: JIS K 67) of the ethylene-vinyl acetate copolymer
30) is 0.5 to 150 g / 10 minutes, preferably 1 to
It is 60 g / 10 minutes. When the melt index contains a foaming agent, the fluidity is further increased, so that the lower limit is about 0.5 g / 10 minutes for good foaming, and the upper limit is 150 g / 10 minutes or more, the foam film is The strength becomes insufficient and the foaming is not performed well.
【０００６】本発明で用いる発泡剤は、不燃性で、オゾ
ン破壊係数が実質的にゼロに近いフロンであれば特に限
定しないが、ハイドロフルオロカーボン（ＨＦＣ）系の
一部のフロンが一例として挙げられる。具体例として
は、１，１，１，２−テトラフルオロエタン（ＨＦＣ−
１３４ａ）単独系や、該化合物との混合系発泡剤等を挙
げることができる。本発明で用いる発泡剤の添加量は、
目的とする発泡体の発泡倍率により異なるが、一般的に
は樹脂に対して３〜３０重量部、好ましくは５〜２５重
量部程度用いられる。The foaming agent used in the present invention is not particularly limited as long as it is a non-flammable CFC having an ozone depletion potential of substantially zero, and a part of hydrofluorocarbon (HFC) CFCs can be mentioned as an example. . As a specific example, 1,1,1,2-tetrafluoroethane (HFC-
Examples of 134a) include a single-type foaming agent and a mixed-type foaming agent with the compound. The amount of the foaming agent used in the present invention is
The amount is generally 3 to 30 parts by weight, preferably 5 to 25 parts by weight, based on the resin, although it depends on the expansion ratio of the desired foam.
【０００７】本発明では熱分解型発泡剤も併用してもよ
いが、これらの化合物としては、ポリオレフィン系樹脂
の溶融温度以上の温度で加熱時に分解して気体を発生す
る化合物であれば特に限定しないが、アゾジカルボンア
ミド、ベンゼンスルホニルヒドラジド、ジニトロソペン
タメチレンテトラミン、トルエンスルホニルヒドラジド
等を代表例として挙げることができる。該熱分解型発泡
剤の添加量は、所望の発泡倍率に応じて適宜定めること
ができるが、樹脂成分の合計量１００重量部に対して、
３〜５０重量部、好ましくは５〜４０重量部の範囲内で
使用される。In the present invention, a thermal decomposition type foaming agent may be used in combination, but these compounds are not particularly limited as long as they are compounds which decompose to generate gas when heated at a temperature higher than the melting temperature of the polyolefin resin. However, azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, toluenesulfonyl hydrazide and the like can be mentioned as typical examples. The addition amount of the thermal decomposition type foaming agent can be appropriately determined according to the desired expansion ratio, but with respect to the total amount of the resin components of 100 parts by weight,
It is used in the range of 3 to 50 parts by weight, preferably 5 to 40 parts by weight.
【０００８】本発明で使用する核形成剤としては、炭酸
カルシウム、クレー、タルク、二酸化珪素、炭酸ソー
ダ、クエン酸、酸化マグネシウム等の化合物を挙げるこ
とができるが、これらに限定されるものではない。該核
剤の添加量は、樹脂１００重量部に対して、０．０５〜
５重量部、好ましくは０．１〜３重量部混合される。Examples of the nucleating agent used in the present invention include, but are not limited to, compounds such as calcium carbonate, clay, talc, silicon dioxide, sodium carbonate, citric acid and magnesium oxide. . The amount of the nucleating agent added is 0.05 to 100 parts by weight of the resin.
5 parts by weight, preferably 0.1 to 3 parts by weight are mixed.
【０００９】本発明で使用する収縮防止剤としては、ス
テアリン酸モノグリセライド等の多価アルコール脂肪酸
エステルを用いることもできる。該収縮防止剤の添加量
は、樹脂１００重量部に対して、０．０５〜５重量部、
好ましくは０．１〜３重量部混合される。As the shrinkage-preventing agent used in the present invention, polyhydric alcohol fatty acid ester such as stearic acid monoglyceride can also be used. The amount of the shrinkage inhibitor added is 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin,
Preferably 0.1 to 3 parts by weight are mixed.
【００１０】本発明においては、必要に応じて各種添加
剤、例えば、酸化防止剤、紫外線吸水剤、製泡剤、帯電
防止剤、顔料、充填材等を加えることができる。In the present invention, various additives such as an antioxidant, an ultraviolet ray absorbing agent, a foaming agent, an antistatic agent, a pigment and a filler can be added if necessary.
【００１１】以上の材料を用いた発泡方法は、特に限定
するものではないが、従来実施されている押出発泡法や
圧力容器を用いる方法等を用いることができる。例え
ば、押出発泡法では以下の方法で行われる。すなわち、
ポリオレフィン系樹脂、核剤、収縮防止剤等からなるポ
リオレフィン系樹脂組成物を押出機（単軸、多軸）等を
用いて混練し、樹脂の溶融域以降のシリンダー部から発
泡剤を供給した後、溶融樹脂組成物の温度を発泡時の適
切な溶融粘度となるように調整し、ダイスから低圧域に
押し出すことにより行われる。The foaming method using the above materials is not particularly limited, but a conventionally practiced extrusion foaming method or a method using a pressure vessel can be used. For example, in the extrusion foaming method, the following method is used. That is,
After kneading a polyolefin resin composition consisting of a polyolefin resin, a nucleating agent, a shrinkage inhibitor, etc. using an extruder (single screw, multi screw), etc., and supplying a foaming agent from the cylinder part after the melting region of the resin. The temperature of the molten resin composition is adjusted so as to have an appropriate melt viscosity at the time of foaming, and the molten resin composition is extruded from a die into a low pressure range.
【００１２】本発明によれば、ポリオレフィン系樹脂組
成物を加熱して軟化、または熔融させた後、揮発性発泡
剤を供給し混合して得られた組成物を低圧域に開放する
ことにより発泡させる方法において、エチレン−酢酸ビ
ニル共重合体を用いることにより、ＨＦＣ系発泡剤との
相溶性が改善され、該発泡剤をより多く添加することが
できる。この結果、より大きな発泡倍率を有し、外観特
性に優れた発泡体を得ることができる。According to the present invention, a polyolefin resin composition is heated to soften or melt it, and then a volatile foaming agent is supplied and mixed to release the composition, which is then expanded to a low pressure range. In the method described above, by using the ethylene-vinyl acetate copolymer, the compatibility with the HFC-based foaming agent is improved, and the foaming agent can be added in a larger amount. As a result, it is possible to obtain a foam having a larger expansion ratio and excellent appearance characteristics.
【００１３】[0013]
【実施例】以下、本発明について、実施例及び比較例を
挙げて説明するが、本発明はこれらの実施例に限定され
るものではない。EXAMPLES Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
【００１４】実施例１ 酢酸ビニル含有量が２０重量％、ＭＦＲが２０（ｇ／１
０分、１９０℃）で密度が０．９４ｇ／ｃｍ3 のエチレ
ン−酢酸ビニル共重合体１００重量部に対して、タルク
を０．６重量部、ステアリン酸モノグリセライドを０．
５重量部をタンブラー中で混合した後、スクリュー系４
０ｍｍの単軸押出機２台からなるタンデム押出機の第一
段押出機に供給し加熱溶融させ、溶融ゾーン直後に設け
た発泡剤圧入孔から１，１，１，２−テトラフルオロエ
タン（ＨＦＣ−１３４ａ）発泡剤を、１２重量部の割合
で高圧定量ポンプを介して押出機に供給し、第二押出機
の先端に設けたストランドダイ（直径約２ｍｍ）を介し
てロッド状発泡体を得た。ちなみに、発泡倍率は約２６
倍で外観が良好な発泡体であった。 押出条件 第一押出機 スクリュー 圧縮比：３（フルフライトタイプ） 回転数：１０ｒｐｍ シリンダー温度（C1/C2/C3/C4)：150/190/160/160 ℃ 第二押出機 スクリュー 圧縮比：３（フルフライトタイプ） 回転数：１０ｒｐｍ シリンダー温度（C5/C6/C7/C8)：130/120/110/100 ℃ アダプター温度：１００℃ ダイス温度 ：１００℃Example 1 Vinyl acetate content 20% by weight, MFR 20 (g / 1
0 minutes, 190 ° C) with a density of 0.94 g / cm 3 0.6 parts by weight of talc and 0.1 part of stearic acid monoglyceride per 100 parts by weight of the ethylene-vinyl acetate copolymer.
After mixing 5 parts by weight in a tumbler, screw system 4
It is fed to a first-stage extruder of a tandem extruder consisting of two 0 mm single-screw extruders, heated and melted, and 1,1,1,2-tetrafluoroethane (HFC) is introduced through a foaming agent injection hole provided immediately after the melting zone. -134a) The blowing agent was supplied to the extruder through a high-pressure metering pump at a ratio of 12 parts by weight, and a rod-shaped foam was obtained through a strand die (diameter of about 2 mm) provided at the tip of the second extruder. It was By the way, the expansion ratio is about 26.
It was a foam that doubled in appearance. Extrusion conditions 1st extruder Screw compression ratio: 3 (full flight type) Rotation speed: 10 rpm Cylinder temperature (C1 / C2 / C3 / C4): 150/190/160/160 ℃ 2nd extruder screw compression ratio: 3 ( Full flight type) Rotation speed: 10 rpm Cylinder temperature (C5 / C6 / C7 / C8): 130/120/110/100 ℃ Adapter temperature: 100 ℃ Die temperature: 100 ℃
【００１５】実施例２ １，１，１，２−テトラフルオロエタン（ＨＦＣ−１３
４ａ）９２重量部と、１，１，−ジフルオロエタン（Ｈ
ＦＣ−１５２ａ）８重量部の混合系発泡剤を用いた以外
実施例１と同様にしてポリオレフィン発泡体を成形し、
発泡倍率が約２８倍で外観が良好な発泡体を得た。Example 2 1,1,1,2-tetrafluoroethane (HFC-13
4a) 92 parts by weight and 1,1, -difluoroethane (H
FC-152a) A polyolefin foam was molded in the same manner as in Example 1 except that 8 parts by weight of the mixed foaming agent was used,
A foam having an expansion ratio of about 28 and a good appearance was obtained.
【００１６】実施例３ 酢酸ビニル含有量が１０重量％、ＭＦＲが１０（ｇ／１
０分、１９０℃）で密度が０．９３ｇ／ｃｍ3 のエチレ
ン−酢酸ビニル共重合体を用いた以外実施例１と同様に
してポリオレフィン発泡体を成形し、発泡倍率が約２５
倍で外観が良好な発泡体を得た。Example 3 Vinyl acetate content 10% by weight, MFR 10 (g / 1
0 minutes, 190 ° C) with a density of 0.93 g / cm 3 A polyolefin foam was molded in the same manner as in Example 1 except that the ethylene-vinyl acetate copolymer of Example 1 was used, and the expansion ratio was about 25.
Doubled to obtain a foam having a good appearance.
【００１７】実施例４ 酢酸ビニル含有量が５重量％、ＭＦＲが２（ｇ／１０
分、１９０℃）で密度が０．９２ｇ／ｃｍ3 のエチレン
−酢酸ビニル共重合体を用いた以外実施例１と同様にし
てポリオレフィン発泡体を成形し、発泡倍率が約２３倍
で外観が良好な発泡体を得た。ただし、ダイス温度は１
０２℃とした。Example 4 Vinyl acetate content 5% by weight, MFR 2 (g / 10
Min, 190 ° C) with a density of 0.92 g / cm 3 A polyolefin foam was molded in the same manner as in Example 1 except that the ethylene-vinyl acetate copolymer was used to obtain a foam having an expansion ratio of about 23 and a good appearance. However, the die temperature is 1
It was set to 02 ° C.
【００１８】実施例５ 樹脂として、酢酸ビニル含有量が２８重量％、ＭＦＲが
２０（ｇ／１０分、１９０℃）で密度が０．９５ｇ／ｃ
ｍ3 のエチレン−酢酸ビニル共重合体４０重量部と、Ｍ
ＦＲが２０（ｇ／１０分、１９０℃）で密度が０．９１
６ｇ／ｃｍ3 のポリエチレン６０重量部を用い、発泡剤
を１５重量％を用いた以外実施例１と同様にしてポリオ
レフィン発泡体を成形し、発泡倍率が約２９倍で外観が
良好な発泡体を得た。ただし、ダイス温度は９５℃とし
た。Example 5 As a resin, the vinyl acetate content is 28% by weight, the MFR is 20 (g / 10 minutes, 190 ° C.) and the density is 0.95 g / c.
m 3 40 parts by weight of ethylene-vinyl acetate copolymer
FR is 20 (g / 10min, 190 ° C) and density is 0.91
6 g / cm 3 A polyolefin foam was molded in the same manner as in Example 1 except that 60 parts by weight of polyethylene was used and a blowing agent was used in an amount of 15% by weight, and a foam having a foaming ratio of about 29 times and a good appearance was obtained. However, the die temperature was 95 ° C.
【００１９】実施例６ １，１，１，２−テトラフルオロエタン（ＨＦＣ−１３
４ａ）９７重量部と、プロパン３重量部の混合系発泡剤
を用いた以外実施例１と同様にしてポリオレフィン発泡
体を成形し、発泡倍率が約２７倍で外観が良好な発泡体
を得た。Example 6 1,1,1,2-Tetrafluoroethane (HFC-13
4a) A polyolefin foam was molded in the same manner as in Example 1 except that a mixed foaming agent of 97 parts by weight and 3 parts by weight of propane was used to obtain a foam having an expansion ratio of about 27 and a good appearance. .
【００２０】比較例１ ＭＦＲが２０（ｇ／１０分、１９０℃）で密度が０．９
１６ｇ／ｃｍ3 のポリエチレン１００重量部を用いた以
外実施例１と同様にしてポリオレフィン発泡体を成形し
た。該得られた発泡体は外観が良好であったが、発泡倍
率は約１４倍であった。Comparative Example 1 MFR of 20 (g / 10 minutes, 190 ° C.) and density of 0.9
16 g / cm 3 A polyolefin foam was molded in the same manner as in Example 1 except that 100 parts by weight of polyethylene was used. The obtained foam had a good appearance, but the expansion ratio was about 14 times.
【００２１】[0021]
【発明の効果】本発明によれば、ポリオレフィン系樹脂
が、酢酸ビニル含有量を含むために、発泡剤と樹脂の相
溶性が改善され、結果として発泡剤の添加量を多くでき
るようになったために、高発泡倍率で外観特性の優れた
発泡体を、オゾン破壊係数がゼロでかつ不燃性の発泡剤
を用いて作製できるようになり、工業的メリットは極め
て大である。According to the present invention, since the polyolefin resin contains a vinyl acetate content, the compatibility between the foaming agent and the resin is improved, and as a result, the amount of the foaming agent added can be increased. Moreover, it becomes possible to produce a foam having a high expansion ratio and excellent appearance characteristics by using a non-flammable foaming agent having an ozone depletion potential of 0, which is extremely industrially advantageous.
Claims (3)
止剤等からなるポリオレフィン系樹脂組成物を加熱して
軟化、または熔融させた後、揮発性発泡剤を供給し混合
して得られる該組成物を低圧域に開放することにより、
発泡させることからなる発泡体の製造方法において、エ
チレン−酢酸ビニル共重合体を成分とするポリオレフィ
ン系樹脂を用いることを特徴とするポリオレフィン系樹
脂発泡体の製造方法。1. A composition obtained by heating and softening or melting a polyolefin-based resin composition comprising a polyolefin-based resin, a nucleating agent, a shrinkage-preventing agent, etc., and then supplying and mixing a volatile foaming agent. By opening things in the low pressure range,
A method for producing a foam, which comprises foaming, wherein a polyolefin resin containing an ethylene-vinyl acetate copolymer as a component is used.
ル含有量が、５〜４１重量％であることを特徴とする請
求項１のポリオレフィン系樹脂発泡体の製造方法。2. The method for producing a polyolefin resin foam according to claim 1, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 5 to 41% by weight.
オゾン破壊係数がゼロで、かつ不燃性であることを特徴
とする請求項１または２記載のポリオレフィン系樹脂発
泡体の製造方法。3. The volatile blowing agent is an HFC-based blowing agent,
The method for producing a polyolefin resin foam according to claim 1 or 2, wherein the ozone depletion coefficient is zero and it is nonflammable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34009395A JPH09176359A (en) | 1995-12-27 | 1995-12-27 | Production of polyolefin resin foamed material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34009395A JPH09176359A (en) | 1995-12-27 | 1995-12-27 | Production of polyolefin resin foamed material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09176359A true JPH09176359A (en) | 1997-07-08 |
Family
ID=18333654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34009395A Pending JPH09176359A (en) | 1995-12-27 | 1995-12-27 | Production of polyolefin resin foamed material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09176359A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7619027B2 (en) * | 2002-08-12 | 2009-11-17 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
-
1995
- 1995-12-27 JP JP34009395A patent/JPH09176359A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7619027B2 (en) * | 2002-08-12 | 2009-11-17 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
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