JP2000109621A - Liquid additive-impregnated powdery ethylene/vinyl acetate copolymer composition, resin composition using this, and molded article made of these compositions - Google Patents
Liquid additive-impregnated powdery ethylene/vinyl acetate copolymer composition, resin composition using this, and molded article made of these compositionsInfo
- Publication number
- JP2000109621A JP2000109621A JP10286217A JP28621798A JP2000109621A JP 2000109621 A JP2000109621 A JP 2000109621A JP 10286217 A JP10286217 A JP 10286217A JP 28621798 A JP28621798 A JP 28621798A JP 2000109621 A JP2000109621 A JP 2000109621A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- ethylene
- acetate copolymer
- liquid additive
- impregnated
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液体添加剤含浸粉
末エチレン−酢酸ビニル共重合体組成物、及びこれを用
いた樹脂組成物、並びにこれら組成物からなる成形物に
関し、さらに詳しくは、従来のエチレン−酢酸ビニル共
重合体に液体添加剤を混練した組成物に較べて、混練が
容易で、しかも品質良く製造することができ、かつ液体
添加剤の樹脂マスターバッチとしても好適な液体添加剤
含浸粉末エチレン−酢酸ビニル共重合体組成物、及びこ
れを熱可塑性樹脂又は合成ゴムに配合した樹脂組成物、
並びにこれら組成物を成形した成形物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid additive-impregnated powdery ethylene-vinyl acetate copolymer composition, a resin composition using the same, and a molded product comprising these compositions. A liquid additive that is easier to knead, can be produced with high quality, and is also suitable as a resin masterbatch of a liquid additive, as compared with a composition obtained by kneading a liquid additive with an ethylene-vinyl acetate copolymer of Impregnated powder ethylene-vinyl acetate copolymer composition, and a resin composition blended with a thermoplastic resin or synthetic rubber,
And a molded product obtained by molding these compositions.
【０００２】[0002]
【従来の技術】エチレン−酢酸ビニル共重合体は、一般
に、柔軟性に富み、強靭で、かつ耐寒性に優れ、ヒート
シールが良好であることから、農業用フィルム、ストレ
ッチフィルム、ラップフィルム、保護フィルム、粘着性
フィルム等に使用されるだけでなく、押出し、ドライ、
ノンソルベントの各ラミネーション用フィルム材料とし
ても好適であるため、味噌、コンニャク、液体スープ等
の水物食品包材、粉薬、削り節、コーヒー、お茶の葉等
の乾燥医薬食品用包材、乾燥材包剤、カイロ包材等のシ
ール材フィルム等に広く使用されている。しかし、エチ
レン−酢酸ビニル共重合体を上記各種用途に使用する
際、場合によっては、エチレン−酢酸ビニル共重合体に
液体添加剤を配合する必要がある。エチレン−酢酸ビニ
ル共重合体に固体の添加剤を練り込む場合は、通常のミ
キサーや押出機で混練すれば、容易に分散し、良好な混
練品が得られるが、液体の添加剤の場合は、混練中に樹
脂がうまく混練できずに滑ってしまったり、混練中に液
体添加剤がミキサーや押出機等から漏れてしまったりす
る問題点があった。そのため、エチレン−酢酸ビニル共
重合体に液体添加剤を混練する際に生じる上記問題点を
解消し、分散性良くかつ多量の液体添加剤でも混練する
ことが可能な方策について、これまで数多くの試みがな
されてきたが、いずれも十分に満足の行くものではなか
った。2. Description of the Related Art Ethylene-vinyl acetate copolymers are generally excellent in flexibility, toughness, excellent cold resistance and good heat sealing. Not only used for film, adhesive film, etc., but also for extrusion, dry,
Since it is also suitable as a non-solvent film material for lamination, it can be used as a packaging material for aquatic foods such as miso, konjac, liquid soup, a powdered medicine, a sharpener, coffee, tea leaves, etc. It is widely used as a sealant for adhesives and body warming materials. However, when the ethylene-vinyl acetate copolymer is used for the above-mentioned various uses, it may be necessary in some cases to blend a liquid additive into the ethylene-vinyl acetate copolymer. When kneading a solid additive into the ethylene-vinyl acetate copolymer, if kneaded with a usual mixer or extruder, it can be easily dispersed and a good kneaded product can be obtained, but in the case of a liquid additive, However, during kneading, there was a problem that the resin did not knead well and slipped, or the liquid additive leaked from a mixer, an extruder, or the like during kneading. For this reason, many attempts have been made to solve the above-mentioned problems that occur when kneading a liquid additive into an ethylene-vinyl acetate copolymer and to knead even a large amount of liquid additive with good dispersibility. Have been done, but none have been fully satisfactory.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、エチ
レン−酢酸ビニル共重合体に液体添加剤を混練した際
に、分散性良くかつ多量の液体添加剤でも混練すること
ができるエチレン−酢酸ビニル共重合体組成物を提供
し、さらには、これをマスターバッチとして配合した樹
脂組成物又はこれら組成物を用いて成形した品質の良好
な成形物を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide an ethylene-acetic acid copolymer which has good dispersibility and can be kneaded with a large amount of a liquid additive when the liquid additive is kneaded with the ethylene-vinyl acetate copolymer. Another object of the present invention is to provide a vinyl copolymer composition, and further provide a resin composition blended as a masterbatch or a molded article of good quality molded using these compositions.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意研究を重ねた結果、液体添加剤を特
定の物性と粒度を有する粉末状のエチレン−酢酸ビニル
共重合体に含浸させることにより、上記課題が解決でき
ることを見出した。本発明は、これらの知見に基づいて
完成に至ったものである。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a liquid additive can be converted into a powdery ethylene-vinyl acetate copolymer having specific physical properties and particle size. It has been found that the above problem can be solved by impregnation. The present invention has been completed based on these findings.
【０００５】すなわち、本発明によれば、メルトフロー
レートが０．１〜１００ｇ／１０分、酢酸ビニル含有量
が３〜３５重量％、平均粒径が０．０１〜１．５ｍｍの
粉末状エチレン−酢酸ビニル共重合体１００重量部に、
液体添加剤を０．０１〜２００重量部含浸させてなる液
体添加剤含浸粉末エチレン−酢酸ビニル共重合体組成物
が提供される。さらに、本発明によれば、液体添加剤
は、防曇剤、滑剤、酸化防止剤、光安定剤、紫外線吸収
剤、及び粘着付与剤からなる群から選択される少なくと
も１種の添加剤であることを特徴とする上記の液体添加
剤含浸粉末エチレン−酢酸ビニル共重合体組成物が提供
される。That is, according to the present invention, powdered ethylene having a melt flow rate of 0.1 to 100 g / 10 min, a vinyl acetate content of 3 to 35% by weight, and an average particle size of 0.01 to 1.5 mm is used. -100 parts by weight of vinyl acetate copolymer,
Provided is a liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition obtained by impregnating a liquid additive with 0.01 to 200 parts by weight. Further, according to the present invention, the liquid additive is at least one additive selected from the group consisting of anti-fogging agents, lubricants, antioxidants, light stabilizers, ultraviolet absorbers, and tackifiers. A liquid ethylene-vinyl acetate copolymer composition impregnated with the liquid additive as described above is provided.
【０００６】また、本発明によれば、上記いずれかの液
体添加剤含浸粉末エチレン−酢酸ビニル共重合体組成物
１〜９９重量％に、熱可塑性樹脂又は合成ゴム９９〜１
重量％を混合又は混練してなる樹脂組成物が提供され
る。Further, according to the present invention, any one of the liquid additive-impregnated powdery ethylene-vinyl acetate copolymer compositions of 1 to 99% by weight is added to a thermoplastic resin or a synthetic rubber of 99 to 1% by weight.
Provided is a resin composition obtained by mixing or kneading by weight.
【０００７】さらにまた、本発明によれば、上記いずれ
かの液体添加剤含浸粉末エチレン−酢酸ビニル共重合体
組成物又は樹脂組成物を、押出成形、射出成形、回転成
形又は圧縮成形してなる成形物が提供される。Furthermore, according to the present invention, any one of the above-mentioned liquid additive-impregnated powdery ethylene-vinyl acetate copolymer composition or resin composition is formed by extrusion molding, injection molding, rotational molding or compression molding. A molded article is provided.
【０００８】[0008]
【発明の実施の形態】以下、本発明について詳細に説明
する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【０００９】１．エチレン−酢酸ビニル共重合体 本発明に使用されるエチレン−酢酸ビニル共重合体は、
高圧ラジカル重合法と呼ばれる重合方法によって製造さ
れる。この重合方法は、例えば、モノマーであるエチレ
ンと酢酸ビニルとを高圧ポンプを使用して反応器に圧送
し、反応温度１５０〜３５０℃、反応圧力１００〜３０
０ＭＰａの条件下で有機過酸化物等のラジカル発生触媒
を用いて行われる。本発明では、エチレン−酢酸ビニル
共重合体は、特定の物性、すなわち、特定のメルトフロ
ーレートと酢酸ビニル含有量を有し、しかも、特定の粒
度（平均粒径）をもつことが重要である。エチレン−酢
酸ビニル共重合体のメルトフローレートは、０．１〜１
００ｇ／１０分、好ましくは、０．５〜３０ｇ／１０
分、さらに好ましくは、１〜５ｇ／１０分である。メル
トフローレートは、ＪＩＳ Ｋ７２１０に準拠して設定
されるが、０．１ｇ／１０分未満であると、加工性が悪
化し、一方、１００ｇ／１０分を越えると、耐熱性及び
機械的強度が悪化するので望ましくない。また、エチレ
ン−酢酸ビニル共重合体の酢酸ビニル含有量は、３〜３
５重量％、好ましくは、１０〜２５重量％である。酢酸
ビニル含有量は、ＪＩＳ Ｋ６７３０に準拠して設定さ
れるが、３重量％未満であると、柔軟性、透明性、及び
粘着性が劣り、一方、３５重量％を越えると、機械的強
度及び耐熱性が悪化するので望ましくない。さらに、粉
末状のエチレン−酢酸ビニル共重合体の平均粒径は、
０．０１〜１．５ｍｍ、好ましくは、０．０５〜０．５
ｍｍである。これが０．０１ｍｍ未満であると、飛散し
やすく取扱が困難になり、一方、１．５ｍｍを越える
と、液体添加剤が含浸しにくくなるので望ましくない。1. Ethylene-vinyl acetate copolymer Ethylene-vinyl acetate copolymer used in the present invention,
It is produced by a polymerization method called a high-pressure radical polymerization method. In this polymerization method, for example, the monomers ethylene and vinyl acetate are pumped into a reactor using a high-pressure pump, and the reaction temperature is 150 to 350 ° C., and the reaction pressure is 100 to 30.
The reaction is performed using a radical generating catalyst such as an organic peroxide under the condition of 0 MPa. In the present invention, it is important that the ethylene-vinyl acetate copolymer has specific physical properties, that is, has a specific melt flow rate and vinyl acetate content, and has a specific particle size (average particle size). . The melt flow rate of the ethylene-vinyl acetate copolymer is 0.1 to 1
00 g / 10 min, preferably 0.5 to 30 g / 10
Min, more preferably 1 to 5 g / 10 min. The melt flow rate is set in accordance with JIS K7210. If the melt flow rate is less than 0.1 g / 10 minutes, the processability deteriorates. On the other hand, if it exceeds 100 g / 10 minutes, the heat resistance and the mechanical strength are reduced. It is not desirable because it worsens. The vinyl acetate content of the ethylene-vinyl acetate copolymer is 3 to 3
It is 5% by weight, preferably 10 to 25% by weight. The vinyl acetate content is set in accordance with JIS K6730. If it is less than 3% by weight, flexibility, transparency, and tackiness are poor. On the other hand, if it exceeds 35% by weight, mechanical strength and It is not desirable because heat resistance deteriorates. Further, the average particle size of the powdery ethylene-vinyl acetate copolymer is
0.01 to 1.5 mm, preferably 0.05 to 0.5
mm. If it is less than 0.01 mm, it is easily scattered and handling becomes difficult. On the other hand, if it exceeds 1.5 mm, it becomes difficult to impregnate the liquid additive, which is not desirable.
【００１０】２．液体添加剤 本発明に使用される液体添加剤は、常温で液体である樹
脂用添加剤の他に、常温では固体であるがエチレン−酢
酸ビニル共重合体の融点では溶融して液体となる（すな
わち、エチレン−酢酸ビニル共重合体の融点未満の融点
を有する）樹脂用添加剤をも包含する。これらの液体添
加剤としては、防曇剤、滑剤、酸化防止剤、光安定剤、
紫外線吸収剤、粘着付与剤等がある。防曇剤としては、
ジグリセリンモノラウレート、ジグリセリンモノミリス
テート、ジグリセリンモノパルミテート、ジグリセリン
モノステアリレート、ジグリセリンモノベヘネート、ジ
グリセリンモノオレート等のジグリセリン脂肪酸エステ
ル；グリセリンモノラウレート、グリセリンモノミリス
テート、グリセリンモノパルミテート、グリセリンモノ
ステアレート、グリセリンモノベヘネート、グリセリン
モノオレート等のグリセリン脂肪酸エステル；ラウリル
アルコール、ミリスチルアルコール、パルミチルアルコ
ール、ステアリルアルコール、ベヘニルアルコール、オ
レイルアルコール等の高級脂肪族アルコール等を例示で
きる。滑剤としては、パラフィンワックス、流動パラフ
ィン等のワックス；ジメチルポリシロキサン、メチルフ
ェニルポリシロキサン等のシリコーンオイル；オレフィ
ン酸アマイド、エルカ酸アマイド等の脂肪酸アマイド等
を例示できる。酸化防止剤としては、オクタデシル−３
−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニ
ル）プロピオート、ジステアリルペンタエルスリトール
ジフォスファイト、トリス（ノニルフェニル）フォスフ
ァイト、ジラウリル−３，３’−チオジプロピオネー
ト、ジステアリル−３，３’−チオジプロピオネート、
ジミリスチル−３，３’−チオジプロピオネート、２，
５，７，８−テトラメチル−２（４’，８’，１２’−
トリメチルトリデシル）クロマン６−オール等を例示で
きる。光安定剤としては、ビス（１−オクチロキシ−
２，２，６，６−テトラメチル−４−ピペジル）セバケ
ート、ビス（１，２，２，６，６−ペンタメチル−４−
ピペリジル）セバケート等を例示できる。紫外線吸収剤
としては、フェニル・サリシレート、ｐ−ｔ−ブチルフ
ェニル・サリシレート、２−ヒドロキシ−４−メトキシ
・ベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキ
シ・ベンゾフェノン、４−ドデシロキシ−２−ヒドロキ
シ・ベンゾフェノン、ヒドロキシフェニル・ベンゾトリ
アゾール誘導体等を例示できる。粘着付与剤としては、
ポリブテン、クロマンインデンオイル、液体テレピン系
粘着付与剤等を例示できる。これらの液体添加剤の内
で、防曇剤や粘着付与剤は、樹脂に対する添加量が多い
ので、利用価値が高く、特に好ましい。エチレン−酢酸
ビニル共重合体に対する液体添加剤の添加量は、粉末状
エチレン−酢酸ビニル共重合体１００重量部に対して、
通常は、０．０１〜２００重量部、好ましくは、５〜１
００重量部である。添加量が０．０１重量部未満である
と、液体添加剤の添加効果がなく、一方、２００重量部
を越えると、液体添加剤がエチレン−酢酸ビニル共重合
体に十分含浸しないので望ましくない。[0010] 2. Liquid Additive In addition to the resin additive that is liquid at room temperature, the liquid additive used in the present invention is solid at room temperature but melts and becomes liquid at the melting point of the ethylene-vinyl acetate copolymer ( That is, a resin additive having a melting point lower than the melting point of the ethylene-vinyl acetate copolymer) is also included. These liquid additives include anti-fogging agents, lubricants, antioxidants, light stabilizers,
There are ultraviolet absorbers and tackifiers. As anti-fog agent,
Diglycerin fatty acid esters such as diglycerin monolaurate, diglycerin monomyristate, diglycerin monopalmitate, diglycerin monostearate, diglycerin monobehenate, diglycerin monooleate; glycerin monolaurate, glycerin monomyristate Glycerin fatty acid esters such as glycerin monopalmitate, glycerin monostearate, glycerin monobehenate and glycerin monooleate; higher aliphatic alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol and oleyl alcohol. Can be illustrated. Examples of the lubricant include waxes such as paraffin wax and liquid paraffin; silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane; and fatty acid amides such as olefin acid amide and erucic acid amide. As an antioxidant, octadecyl-3
-(3,5-di-t-butyl-4-hydroxyphenyl) propioate, distearylpentaerthritol diphosphite, tris (nonylphenyl) phosphite, dilauryl-3,3'-thiodipropionate, Stearyl-3,3'-thiodipropionate,
Dimyristyl-3,3'-thiodipropionate, 2,
5,7,8-tetramethyl-2 (4 ′, 8 ′, 12′-
Trimethyltridecyl) chroman 6-ol and the like. As a light stabilizer, bis (1-octyloxy-
2,2,6,6-tetramethyl-4-pipedyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-)
Piperidyl) sebacate and the like. Examples of the ultraviolet absorber include phenyl salicylate, pt-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 4-dodecyloxy-2-hydroxybenzophenone. And hydroxyphenyl benzotriazole derivatives. As a tackifier,
Examples thereof include polybutene, chromanindene oil, and liquid turpentine tackifier. Among these liquid additives, the antifogging agent and the tackifier are particularly preferred because of their high added value to the resin because of their large amounts added to the resin. The amount of the liquid additive added to the ethylene-vinyl acetate copolymer is based on 100 parts by weight of the powdery ethylene-vinyl acetate copolymer.
Usually, 0.01 to 200 parts by weight, preferably 5 to 1 parts by weight.
00 parts by weight. If the amount is less than 0.01 part by weight, the effect of adding the liquid additive is not obtained, while if it exceeds 200 parts by weight, the liquid additive does not sufficiently impregnate the ethylene-vinyl acetate copolymer, which is not desirable.
【００１１】３．液体添加剤含浸粉末エチレン−酢酸ビ
ニル共重合体組成物 本発明の液体添加剤含浸粉末エチレン−酢酸ビニル共重
合体組成物は、前述した特定の物性と粒度を有する粉末
状のエチレン−酢酸ビニル共重合体に所定量の液体添加
剤を含浸させることにより調製される。液体添加剤を含
浸させる方法は、特に限定するものではないが、例え
ば、常温または加熱した液体添加剤を規定量計量して規
定量の粉末状エチレン−酢酸ビニル共重合体に加え、ヘ
ンシェルミキサーやリボンブレンダー等の混合機で混合
することにより行われる。また、粉末状エチレン−酢酸
ビニル共重合体に液体添加剤をさらに十分含浸させたい
場合には、上記混合した後、常温または加熱した状態で
５分〜２４時間静置する方法により行い得る。本発明の
液体添加剤含浸粉末エチレン−酢酸ビニル共重合体組成
物には、本発明の特性を損なわない範囲で少量の他の粉
末状樹脂を配合してもよい。その際、配合の仕方として
は、原料として使用する粉末状エチレン−酢酸ビニル共
重合体の中に他の粉末状樹脂を配合するか、或いは調製
された液体添加剤含浸粉末エチレン−酢酸ビニル共重合
体組成物の中に他の粉末状樹脂を配合するかのいずれの
方法であってもよい。このような他の粉末状樹脂として
は、高圧法低密度ポリエチレン、エチレン−アクリル酸
エチル共重合体、直鎖状低密度エチレン−α−オレフィ
ン共重合体、超低密度エチレン−α−オレフィン共重合
体、高密度ポリエチレン、ポリプロピレン、アイオノマ
ー、スチレン系エラストマー等が挙げられる。3. Liquid additive-impregnated powder ethylene-vinyl acetate copolymer composition The liquid additive-impregnated powder ethylene-vinyl acetate copolymer composition of the present invention is a powdery ethylene-vinyl acetate copolymer having the specific physical properties and particle size described above. It is prepared by impregnating a polymer with a predetermined amount of a liquid additive. The method of impregnating the liquid additive is not particularly limited.For example, a normal amount or a heated liquid additive is weighed in a specified amount and added to a specified amount of the powdery ethylene-vinyl acetate copolymer, and a Henschel mixer or the like is used. This is performed by mixing with a mixer such as a ribbon blender. When it is desired to further impregnate the powdery ethylene-vinyl acetate copolymer with the liquid additive, the mixing can be carried out by a method of allowing the mixture to stand at room temperature or in a heated state for 5 minutes to 24 hours. The liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition of the present invention may contain a small amount of another powdery resin as long as the properties of the present invention are not impaired. At this time, the compounding method is to mix another powdery resin in the powdery ethylene-vinyl acetate copolymer used as a raw material, or to prepare a liquid additive-impregnated powdered ethylene-vinyl acetate copolymer. Any method of blending another powdery resin into the united composition may be used. Such other powdery resins include high-pressure low-density polyethylene, ethylene-ethyl acrylate copolymer, linear low-density ethylene-α-olefin copolymer, and ultra-low-density ethylene-α-olefin copolymer. Coalesce, high-density polyethylene, polypropylene, ionomer, styrene-based elastomer and the like.
【００１２】４．樹脂組成物 本発明の樹脂組成物は、前述した液体添加剤含浸粉末エ
チレン−酢酸ビニル共重合体組成物を液体添加剤の樹脂
マスターバッチとして用いて、これに熱可塑性樹脂又は
合成ゴムを配合することにより調製される。本発明に使
用される熱可塑性樹脂又は合成ゴムとしては、液体添加
剤含浸粉末エチレン−酢酸ビニル共重合体組成物と相溶
性のあるポリオレフィン系樹脂が好ましいが、ポリオレ
フィン系樹脂以外の熱可塑性樹脂や合成ゴムも使用でき
る。その際、配合する熱可塑性樹脂又は合成ゴムは、必
ずしも１種のものに限られるものではなく、２種以上の
ものを同時に併用することもできる。そして配合する熱
可塑性樹脂又は合成ゴムの形態は、粉末状、ペレット
状、フレーク状、ブロック状等のいかなる形態であって
もよい。ポリオレフィン系樹脂としては、エチレン−酢
酸ビニル共重合体、エチレン−アクリル酸エチル共重合
体、高圧法低密度ポリエチレン、直鎖状低密度エチレン
−α−オレフィン共重合体、超低密度エチレン−α−オ
レフィン共重合体、高密度ポリエチレン、ポリプロピレ
ン、アイオノマー等を例示できるが、この中では、エチ
レン−酢酸ビニル共重合体が最も好ましく使用される。
ポリオレフィン系樹脂以外の熱可塑性樹脂又は合成ゴム
としては、ポリスチレン、ポリアクリレート、ポリメタ
クリレート、ポリ塩化ビニル、ポリ塩化ビニリデン、ポ
リアクリロニトリル、ポリビニルエーテル、ポリビニル
ケトン、ポリエーテル、ポリカーボンエート、ポリエス
テル、ポリアミド、ポリサルホン、ポリエーテルサルホ
ン、ポリフェニレンサルファイド、ポリアリレート、ポ
リエーテルイミド、ポリアミドイミド、ポリエーテルエ
ーテルケトン、アクリルゴム、アクリロニトリルブタジ
エンゴム、イソプレンゴム、ウレタンゴム、エチレンプ
ロピレンゴム、クロロスルホン化ポリエチレン、クロロ
プレンゴム、シリコーンゴム、スチレンブタジエンゴ
ム、ブタジエンゴム、ブチルゴム、フッ素ゴム等を例示
できる。液体添加剤含浸粉末エチレン−酢酸ビニル共重
合体組成物と熱可塑性樹脂又は合成ゴムとの配合割合
は、前者が１〜９９重量％に対して後者が９９〜１重量
％の割合である。4. Resin composition The resin composition of the present invention uses the liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition described above as a resin masterbatch of a liquid additive, and blends a thermoplastic resin or a synthetic rubber with this. It is prepared by As the thermoplastic resin or the synthetic rubber used in the present invention, a polyolefin resin compatible with the liquid additive-impregnated powder ethylene-vinyl acetate copolymer composition is preferable, but a thermoplastic resin other than the polyolefin resin or Synthetic rubber can also be used. At that time, the thermoplastic resin or synthetic rubber to be compounded is not necessarily limited to one kind, and two or more kinds can be used simultaneously. The form of the thermoplastic resin or the synthetic rubber to be compounded may be any form such as powder, pellet, flake, block and the like. Examples of the polyolefin resin include ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, high-pressure low-density polyethylene, linear low-density ethylene-α-olefin copolymer, and ultra-low-density ethylene-α- Olefin copolymers, high-density polyethylenes, polypropylenes, ionomers and the like can be exemplified. Among them, ethylene-vinyl acetate copolymers are most preferably used.
As thermoplastic resins or synthetic rubbers other than polyolefin resins, polystyrene, polyacrylate, polymethacrylate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl ether, polyvinyl ketone, polyether, polycarbonate, polyester, polyamide, Polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, polyetherimide, polyamideimide, polyetheretherketone, acrylic rubber, acrylonitrile butadiene rubber, isoprene rubber, urethane rubber, ethylene propylene rubber, chlorosulfonated polyethylene, chloroprene rubber, Examples include silicone rubber, styrene butadiene rubber, butadiene rubber, butyl rubber, and fluoro rubber. The mixing ratio of the liquid additive impregnated powder ethylene-vinyl acetate copolymer composition and the thermoplastic resin or synthetic rubber is 1 to 99% by weight of the former and 99 to 1% by weight of the latter.
【００１３】５．成形物 本発明の液体添加剤含浸粉末エチレン−酢酸ビニル共重
合体組成物は、これをそのまま成形して成形物とするこ
ともできるが、前述したように、マスターバッチとして
も使用することができる。マスターバッチとして使用す
る場合は、熱可塑性樹脂又は合成ゴム１〜９９重量％と
液体添加剤含浸粉末エチレン−酢酸ビニル共重合体組成
物９９〜１重量％とを混合または混練し、前述の樹脂組
成物とした後、これを成形して成形物とすることができ
る。ここで、混合とは、各種ブレンダー等の混合機等を
用いて混合することを意味し、混練とは、バンバリーミ
キサーや押出機等を用いて混練することを意味する。成
形手段は、特に限定するものではないが、例えば、押出
成形、射出成形、回転成形、圧縮成形等を例示できる。
これらの中でも、フィルム、シート等を成形する押出成
形が特に好ましい。5. Molded product The liquid additive-impregnated powder ethylene-vinyl acetate copolymer composition of the present invention can be molded as it is, but as described above, it can also be used as a master batch. . When used as a masterbatch, 1 to 99% by weight of a thermoplastic resin or synthetic rubber and 99 to 1% by weight of a liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition are mixed or kneaded, and the above resin composition is mixed. After forming the product, it can be formed into a formed product. Here, mixing means mixing using a mixer such as various blenders and the like, and kneading means kneading using a Banbury mixer or an extruder. The molding means is not particularly limited, and examples thereof include extrusion molding, injection molding, rotational molding, and compression molding.
Among these, extrusion molding for forming a film, a sheet or the like is particularly preferable.
【００１４】[0014]
【実施例】以下に、本発明について実施例及び比較例を
挙げてさらに詳細に説明するが、本発明は、これらの実
施例に特に限定されるものではない。The present invention will be described below in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００１５】実施例１ メルトフローレートが３ｇ／１０分、酢酸ビニル含有量
が１８重量％、平均粒径が０．８ｍｍの粉末状エチレン
−酢酸ビニル共重合体１００重量部と、液体防曇剤であ
るジグリセリン脂肪酸エステル２５重量部とを、ヘンシ
ェルミキサーで常温にて混合し、液体防曇剤含浸粉末エ
チレン−酢酸ビニル共重合体組成物を得た。この液体防
曇剤含浸粉末エチレン−酢酸ビニル共重合体組成物は、
粉末表面に液体防曇剤の滲み出しもなく、さらさらして
おり、取扱いやすかった。Example 1 100 parts by weight of a powdery ethylene-vinyl acetate copolymer having a melt flow rate of 3 g / 10 min, a vinyl acetate content of 18% by weight and an average particle size of 0.8 mm, and a liquid antifog agent Was mixed at room temperature with a Henschel mixer to obtain a powdered ethylene-vinyl acetate copolymer composition impregnated with a liquid anti-fogging agent. This liquid anti-fog agent impregnated powder ethylene-vinyl acetate copolymer composition,
There was no bleeding of the liquid anti-fogging agent on the powder surface, and the powder was smooth and easy to handle.
【００１６】比較例１ 実施例１の含浸方法に代えて、混練方法で実施した。す
なわち、実施例１と同一の組成であるメルトフローレー
トが３ｇ／１０分、酢酸ビニル含有量が１８重量％、平
均粒径が０．８ｍｍの粉末状エチレン−酢酸ビニル共重
合体１００重量部と、液体防曇剤であるジグリセリン脂
肪酸エステル２５重量部とを、混練温度１２０℃でバン
バリーミキサーで混練したが、樹脂が滑ってしまい混練
することができなかった。Comparative Example 1 A kneading method was used in place of the impregnation method of Example 1. That is, 100 parts by weight of a powdery ethylene-vinyl acetate copolymer having the same composition as in Example 1 having a melt flow rate of 3 g / 10 min, a vinyl acetate content of 18% by weight, and an average particle size of 0.8 mm. And 25 parts by weight of diglycerin fatty acid ester as a liquid antifog agent were kneaded with a Banbury mixer at a kneading temperature of 120 ° C., but the resin slipped and could not be kneaded.
【００１７】実施例２ メルトフローレートが３ｇ／１０分、酢酸ビニル含有量
が１８重量％、平均粒径が０．８ｍｍの粉末状エチレン
−酢酸ビニル共重合体１００重量部と、液体粘着付与剤
であるポリブテン２５重量部とを、ヘンシェルミキサー
で常温にて混合し、液体粘着付与剤含浸粉末エチレン−
酢酸ビニル共重合体組成物を得た。この液体粘着付与剤
含浸粉末エチレン−酢酸ビニル共重合体組成物は、粉末
表面に液体粘着付与剤の滲み出しもなく、さらさらして
おり、取扱いやすかった。Example 2 100 parts by weight of a powdery ethylene-vinyl acetate copolymer having a melt flow rate of 3 g / 10 min, a vinyl acetate content of 18% by weight and an average particle size of 0.8 mm, and a liquid tackifier And 25 parts by weight of polybutene at room temperature with a Henschel mixer to obtain a liquid tackifier impregnated powder ethylene-
A vinyl acetate copolymer composition was obtained. The liquid tackifier-impregnated powder ethylene-vinyl acetate copolymer composition was free from bleeding of the liquid tackifier on the powder surface, and was easy to handle.
【００１８】比較例２ 実施例２の含浸方法に代えて、混練方法で実施した。す
なわち、実施例２と同一の組成であるメルトフローレー
トが３ｇ／１０分、酢酸ビニル含有量が１８重量％、平
均粒径が０．８ｍｍの粉末状エチレン−酢酸ビニル共重
合体１００重量部と、液体粘着付与剤であるポリブテン
２５重量部とを、混練温度１２０℃でバンバリーミキサ
ーで混練したが、樹脂が滑ってしまい混練することがで
きなかった。Comparative Example 2 A kneading method was used in place of the impregnation method of Example 2. That is, a melt flow rate having the same composition as in Example 2 was 3 g / 10 min, a vinyl acetate content was 18% by weight, and an average particle size was 100 parts by weight of a powdery ethylene-vinyl acetate copolymer having a diameter of 0.8 mm. Then, 25 parts by weight of polybutene as a liquid tackifier was kneaded at a kneading temperature of 120 ° C. with a Banbury mixer, but the resin slipped and could not be kneaded.
【００１９】実施例３ メルトフローレートが２ｇ／１０分、酢酸ビニル含有量
が１５重量％のペレット状エチレン−酢酸ビニル共重合
体９０重量％と、実施例１で得た液体防曇剤含浸粉末エ
チレン−酢酸ビニル共重合体組成物１０重量％とを混合
した後、その混合物を４０ｍｍφインフレーションフィ
ルム押出機に投入し、押出温度１６０℃、ブロー比２、
吐出量１５ｋｇ／ｈｒで押出し、厚さ３０μｍのフィル
ムを成膜した。加工する際の押出加工性、フィルムの曇
り度、光沢、防曇性および外観を評価した。評価方法は
次の通りであって、評価結果は表１に示したが、すべて
の評価結果は良好であった。 押出加工性：押出加工中に、吐出変動が無く、フィルム
厚みの変動が無く、安定加工できるものを合格とする。 曇り度：ＪＩＳ Ｋ−７１０５に準拠した。 光沢：ＪＩＳ Ｋ−７１０５に準拠した。角度は、６０
°で行った。 防曇性：５００ｃｃのビーカーに水を１５０ｃｃ加え、
上面の入口全面にフィルムを張り付けて密閉し、この密
閉したビーカーを温度６０℃の恒温水槽に入れ、３日後
にビーカー入口に張ったフィルムに付着した水滴の付着
面積を肉眼で観察し、水滴付着面積の割合で判定した。
水滴付着面積の割合が２０％未満のものを合格とする。 外観：フィルムを肉眼で観察し、フィルムにフィッシュ
アイ、ダラ、ムラ等がないものを合格とする。Example 3 90% by weight of a pelletized ethylene-vinyl acetate copolymer having a melt flow rate of 2 g / 10 minutes and a vinyl acetate content of 15% by weight, and the liquid antifogging agent impregnated powder obtained in Example 1 After mixing 10% by weight of the ethylene-vinyl acetate copolymer composition, the mixture was put into a 40 mmφ blown film extruder, and the extrusion temperature was 160 ° C., the blow ratio was 2, and
The film was extruded at a discharge rate of 15 kg / hr to form a film having a thickness of 30 μm. The extrudability during processing, the haze, gloss, antifogging property and appearance of the film were evaluated. The evaluation method was as follows, and the evaluation results are shown in Table 1. All the evaluation results were good. Extrusion processability: Passable if there is no fluctuation in discharge and no fluctuation in film thickness during extrusion processing and stable processing is possible. Cloudiness: Based on JIS K-7105. Gloss: Based on JIS K-7105. The angle is 60
° C. Anti-fog property: Add 150 cc of water to a 500 cc beaker,
A film is attached to the entire upper surface of the inlet and sealed, and the sealed beaker is placed in a constant temperature water bath at a temperature of 60 ° C., and after 3 days, the area of water droplets adhering to the film stretched at the inlet of the beaker is visually observed. Judgment was made based on the area ratio.
Those having a water droplet adhesion area ratio of less than 20% are regarded as acceptable. Appearance: Observe the film with the naked eye, and if the film has no fish-eye, dara, unevenness, etc., pass the film.
【００２０】[0020]
【表１】 [Table 1]
【００２１】比較例３ 液体防曇剤含浸用に使用した平均粒径が０．８ｍｍの粉
末状エチレン−酢酸ビニル共重合体に代えて、平均粒径
が１．８ｍｍの粉末状エチレン−酢酸ビニル共重合体を
使用した以外は、実施例１を実施し、液体防曇剤含浸粉
末エチレン−酢酸ビニル共重合体組成物を得た。次いで
これを実施例３で使用した液体防曇剤含浸粉末エチレン
−酢酸ビニル共重合体組成物に代えた以外は、実施例３
を実施し、実施例３と同じく厚さ３０μｍのフィルムを
得た。このフィルムを実施例３と同様に評価したとこ
ろ、防曇性は、不合格であった。Comparative Example 3 Powdered ethylene-vinyl acetate having an average particle size of 1.8 mm was used in place of the powdery ethylene-vinyl acetate copolymer having an average particle size of 0.8 mm used for impregnating the liquid antifogging agent. Example 1 was repeated, except that the copolymer was used, to obtain a powdered ethylene-vinyl acetate copolymer composition impregnated with a liquid antifogging agent. Example 3 was repeated except that this was replaced with the liquid anti-fog agent impregnated powder ethylene-vinyl acetate copolymer composition used in Example 3.
Was carried out to obtain a film having a thickness of 30 μm as in Example 3. When this film was evaluated in the same manner as in Example 3, the antifogging property was rejected.
【００２２】実施例４ メルトフローレートが１．５ｇ／１０分、酢酸ビニル含
有量が１８重量％のペレット状エチレン−酢酸ビニル共
重合体８５重量％と、実施例２で得た液体粘着付与剤含
浸粉末エチレン−酢酸ビニル共重合体組成物１５重量％
とを混合した後、その混合物を４０ｍｍφインフレーシ
ョンフィルム押出機に投入し、押出温度１６０℃、ブロ
ー比１．５、吐出量３０ｋｇ／ｈｒで押出し、厚さ２０
０μｍのフィルムを成膜した。加工する際の押出加工
性、フィルムの曇り度、光沢、粘着性および外観を評価
した。評価方法は、粘着性以外は全て前記の通りであっ
た。粘着性は、次の通りであり、評価結果は表２に示し
たが、すべての評価結果は良好であった。 粘着性：ＡＳＴＭ Ｄ３３５４に準拠して行い、測定値
が５００ｇ／１００ｃｍ２以上のものを合格とする。た
だし、粘着加速条件は、温度５０℃のオーブン中に荷重
４ｋｇ／１００ｃｍ２の重りを乗せ、経過時間２４時間
である。Example 4 85% by weight of a pelletized ethylene-vinyl acetate copolymer having a melt flow rate of 1.5 g / 10 minutes and a vinyl acetate content of 18% by weight, and the liquid tackifier obtained in Example 2 Impregnated powder ethylene-vinyl acetate copolymer composition 15% by weight
And then the mixture is introduced into a 40 mmφ blown film extruder, extruded at an extrusion temperature of 160 ° C., a blow ratio of 1.5 and a discharge rate of 30 kg / hr, and has a thickness of 20 mm.
A 0 μm film was formed. The extrudability during processing, the haze, gloss, tackiness and appearance of the film were evaluated. The evaluation method was as described above except for the adhesiveness. The tackiness was as follows, and the evaluation results are shown in Table 2. All the evaluation results were good. Adhesion: Performed according to ASTM D3354, and those with a measured value of 500 g / 100 cm 2 or more are accepted. However, the condition for accelerating the adhesion is that a weight of 4 kg / 100 cm 2 is placed in an oven at a temperature of 50 ° C. and the elapsed time is 24 hours.
【００２３】[0023]
【表２】 [Table 2]
【００２４】比較例４ 液体粘着付与剤含浸用に使用した平均粒径が０．８ｍｍ
の粉末状エチレン−酢酸ビニル共重合体に代えて、平均
粒径が１．８ｍｍの粉末状エチレン−酢酸ビニル共重合
体を使用した以外は、実施例２を実施し、液体粘着付与
剤含浸粉末エチレン−酢酸ビニル共重合体組成物を得
た。次いでこれを実施例４で使用した液体粘着付与剤含
浸粉末エチレン−酢酸ビニル共重合体組成物に代えた以
外は、実施例４を実施し、実施例４と同じく厚さ２００
μｍのフィルムを得た。このフィルムを実施例４と同様
に評価したところ、粘着性は不合格であった。Comparative Example 4 The average particle size used for impregnation of the liquid tackifier was 0.8 mm.
Example 2 was repeated except that a powdery ethylene-vinyl acetate copolymer having an average particle size of 1.8 mm was used in place of the powdery ethylene-vinyl acetate copolymer of Example 1. An ethylene-vinyl acetate copolymer composition was obtained. Next, Example 4 was carried out except that this was replaced with the liquid tackifier-impregnated powder ethylene-vinyl acetate copolymer composition used in Example 4, and the same thickness as in Example 4 was applied.
A μm film was obtained. When this film was evaluated in the same manner as in Example 4, the adhesiveness was rejected.
【００２５】[0025]
【発明の効果】本発明の液体添加剤含浸粉末エチレン−
酢酸ビニル共重合体組成物は、エチレン−酢酸ビニル共
重合体に液体添加剤を混練した従来の組成物に較べて、
製造が容易であり、しかも液体添加剤を均一に規定量配
合できるばかりでなく、多量の液体添加剤であっても配
合することができる。そのため、この液体添加剤含浸粉
末エチレン−酢酸ビニル共重合体組成物は、特に液体添
加剤用のマスターバッチとしての利用価値が高く、この
マスターバッチを使用した樹脂組成物からは、良好な物
性を示す成形物が容易に得られるという顕著な効果があ
る。The liquid additive-impregnated powder of the present invention, ethylene-
The vinyl acetate copolymer composition is compared with a conventional composition in which a liquid additive is kneaded with an ethylene-vinyl acetate copolymer,
It is easy to manufacture, and not only can a liquid additive be uniformly blended in a prescribed amount, but also a large amount of liquid additive can be blended. Therefore, the liquid additive-impregnated powder ethylene-vinyl acetate copolymer composition has high utility value especially as a masterbatch for liquid additives, and has good physical properties from a resin composition using this masterbatch. There is a remarkable effect that the molded product shown can be easily obtained.
フロントページの続き Ｆターム(参考） 4J002 AA01X AC00X AC03X AC06X AC07X AC08X AC09X AE034 AE044 AE05Y BB03X BB05X BB06W BB06X BB10X BB12X BB15X BB17Y BB18X BB23X BB27X BC03X BD04X BD10X BD12X BE02X BE05X BG04X BG05X BG10X BK00Y CF00X CF16X CG00X CH00X CH09X CK02X CL00X CM04X CN01X CN03X CP03X CP034 EC066 EE039 EH056 EJ028 EJ069 EL098 EP017 EU079 EU179 EV068 EW068 EW118 FD049 FD059 FD078 FD174 FD177 FD206 FD34Y FD346 GA01 GG02 Front page of the continued F-term (reference) 4J002 AA01X AC00X AC03X AC06X AC07X AC08X AC09X AE034 AE044 AE05Y BB03X BB05X BB06W BB06X BB10X BB12X BB15X BB17Y BB18X BB23X BB27X BC03X BD04X BD10X BD12X BE02X BE05X BG04X BG05X BG10X BK00Y CF00X CF16X CG00X CH00X CH09X CK02X CL00X CM04X CN01X CN03X CP03X CP034 EC066 EE039 EH056 EJ028 EJ069 EL098 EP017 EU079 EU179 EV068 EW068 EW118 FD049 FD059 FD078 FD174 FD177 FD206 FD34Y FD346 GA01 GG02
Claims (4)
／１０分、酢酸ビニル含有量が３〜３５重量％、平均粒
径が０．０１〜１．５ｍｍの粉末状エチレン−酢酸ビニ
ル共重合体１００重量部に、液体添加剤を０．０１〜２
００重量部含浸させてなる液体添加剤含浸粉末エチレン
−酢酸ビニル共重合体組成物。1. The melt flow rate is from 0.1 to 100 g.
/ 10 min, 100 parts by weight of a powdery ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 35% by weight and an average particle size of 0.01 to 1.5 mm, and adding a liquid additive of 0.01 to 2 parts by weight.
A liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition impregnated with 00 parts by weight.
剤、光安定剤、紫外線吸収剤、及び粘着付与剤からなる
群から選択される少なくとも１種の添加剤であることを
特徴とする請求項１に記載の液体添加剤含浸粉末エチレ
ン−酢酸ビニル共重合体組成物。2. The liquid additive is at least one additive selected from the group consisting of an antifogging agent, a lubricant, an antioxidant, a light stabilizer, an ultraviolet absorber, and a tackifier. The ethylene-vinyl acetate copolymer composition impregnated with a liquid additive according to claim 1.
粉末エチレン−酢酸ビニル共重合体組成物１〜９９重量
％に、熱可塑性樹脂又は合成ゴム９９〜１重量％を混合
又は混練してなる樹脂組成物。3. A thermoplastic resin or synthetic rubber is mixed or kneaded with 1 to 99% by weight of the liquid additive-impregnated powdery ethylene-vinyl acetate copolymer composition according to claim 1 or 2 or kneaded. A resin composition comprising:
添加剤含浸粉末エチレン−酢酸ビニル共重合体組成物又
は樹脂組成物を、押出成形、射出成形、回転成形又は圧
縮成形してなる成形物。4. The liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition or resin composition according to claim 1, obtained by extrusion molding, injection molding, rotational molding or compression molding. Moldings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28621798A JP3544870B2 (en) | 1998-10-08 | 1998-10-08 | Liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition, resin composition using the same, and molded article composed of these compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28621798A JP3544870B2 (en) | 1998-10-08 | 1998-10-08 | Liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition, resin composition using the same, and molded article composed of these compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000109621A true JP2000109621A (en) | 2000-04-18 |
| JP3544870B2 JP3544870B2 (en) | 2004-07-21 |
Family
ID=17701498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28621798A Expired - Fee Related JP3544870B2 (en) | 1998-10-08 | 1998-10-08 | Liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition, resin composition using the same, and molded article composed of these compositions |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3544870B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091858A (en) * | 2005-09-28 | 2007-04-12 | Kitagawa Ind Co Ltd | Urethane-based resin material and heat conductive material |
| WO2023085082A1 (en) * | 2021-11-10 | 2023-05-19 | 株式会社Adeka | Resin additive masterbatch, synthetic resin composition, and molded object |
-
1998
- 1998-10-08 JP JP28621798A patent/JP3544870B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091858A (en) * | 2005-09-28 | 2007-04-12 | Kitagawa Ind Co Ltd | Urethane-based resin material and heat conductive material |
| WO2023085082A1 (en) * | 2021-11-10 | 2023-05-19 | 株式会社Adeka | Resin additive masterbatch, synthetic resin composition, and molded object |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3544870B2 (en) | 2004-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0172650B1 (en) | Polyolefin blends containing reactive agents | |
| US3231636A (en) | High shear strength blends of high and low density polyethylene | |
| US10738188B2 (en) | Maleic anhydride grafted LLDPE having high melt index | |
| JP6226864B2 (en) | Improved resin composition for extrusion coating | |
| JPS621737A (en) | Blend of polyolefin and reactive additive-containing polymer | |
| JPH075750B2 (en) | Extrusion method of low density polyethylene | |
| EP0254236B1 (en) | Film-forming compositions and fog resistant film produced therefrom | |
| JP2003510438A (en) | Block chlorinated polyolefins used as impact modifier tougheners for PVC or CPVC | |
| JPS5980444A (en) | Low density independent foam type foamed product from ethylene copolymer/vinyl or vinylidene halide polymer blend | |
| KR20010072370A (en) | High clarity polyethylene compositions | |
| JP2001081250A (en) | Polyolefin resin composition | |
| RU2219201C2 (en) | Polyethylene-based composition for pipes and pipe joins | |
| JP3544870B2 (en) | Liquid additive-impregnated powdered ethylene-vinyl acetate copolymer composition, resin composition using the same, and molded article composed of these compositions | |
| CN110791030A (en) | Zinc-free halogenated butyl rubber/polypropylene thermoplastic elastomer and preparation method thereof | |
| JP3396153B2 (en) | Thermoforming resin composition and sheet | |
| US5922812A (en) | 4-methyl-1-pentene polymer composition | |
| JPH0329820B2 (en) | ||
| JP3544872B2 (en) | Liquid additive-impregnated granular ethylene-α-olefin copolymer composition, resin composition using the same, and molded article composed of these compositions | |
| CN114957842B (en) | Medical low-odor composition, medical low-odor film material and preparation method thereof | |
| JP4034473B2 (en) | Polyolefin resin material for extrusion lamination | |
| JPS636038A (en) | Polyethylene resin composition | |
| EP3676327B1 (en) | Polypropylene composition | |
| JPH06256594A (en) | Filler-containing resin composition | |
| JP6759657B2 (en) | Low temperature easy processable resin composition | |
| JPH0564650B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20031202 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040129 |
|
| TRDD | Decision of grant or rejection written | ||
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20040130 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040316 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040406 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090416 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090416 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100416 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100416 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110416 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110416 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120416 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130416 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140416 Year of fee payment: 10 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |