JP2004256740A - Ethylene copolymer pellet - Google Patents

Ethylene copolymer pellet Download PDF

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Publication number
JP2004256740A
JP2004256740A JP2003050893A JP2003050893A JP2004256740A JP 2004256740 A JP2004256740 A JP 2004256740A JP 2003050893 A JP2003050893 A JP 2003050893A JP 2003050893 A JP2003050893 A JP 2003050893A JP 2004256740 A JP2004256740 A JP 2004256740A
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Prior art keywords
ethylene
copolymer
weight
fatty acid
pellet
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JP2003050893A
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JP4192628B2 (en
Inventor
Hirohide Sakano
博英 坂野
Satoshi Yukioka
聡 雪岡
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Tosoh Corp
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Tosoh Corp
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Priority to JP2003050893A priority Critical patent/JP4192628B2/en
Priority to TW093103297A priority patent/TWI251609B/en
Priority to KR1020040011734A priority patent/KR100679546B1/en
Priority to CNB2004100072059A priority patent/CN1300237C/en
Publication of JP2004256740A publication Critical patent/JP2004256740A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
    • B07B4/00—Separating solids from solids by subjecting their mixture to gas currents
    • B07B4/02—Separating solids from solids by subjecting their mixture to gas currents while the mixtures fall
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
    • B07B13/00—Grading or sorting solid materials by dry methods, not otherwise provided for; Sorting articles otherwise than by indirectly controlled devices
    • B07B13/08—Grading or sorting solid materials by dry methods, not otherwise provided for; Sorting articles otherwise than by indirectly controlled devices according to weight
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
    • B07B13/00—Grading or sorting solid materials by dry methods, not otherwise provided for; Sorting articles otherwise than by indirectly controlled devices
    • B07B13/14—Details or accessories
    • B07B13/16—Feed or discharge arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
    • B07B9/00—Combinations of apparatus for screening or sifting or for separating solids from solids using gas currents; General arrangement of plant, e.g. flow sheets
    • B07B9/02—Combinations of similar or different apparatus for separating solids from solids using gas currents

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  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene copolymer pellet that has the improvement in blocking of the pellet. <P>SOLUTION: As the ethylene copolymer pellet is used an ethylene copolymer pellet which is produced by blending, based on 100 pts.wt. ethylene copolymer, (a) 0.01-0.5 pt.wt. unsaturated fatty acid bisamide having a melting point of 100°C-180°C and (b) 0.01-0.5 pt.wt. lubricant having a melting point of 60-90°C and depressing the melting point of the component (a) by 20°C or more by using the component (b) in combination with the component (a). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【０００１】
【発明の属する技術分野】
本発明はペレットの融着（以下、ペレットのブロッキングと称する）を改良したエチレン系共重合体ペレットに関するものである。
【０００２】
【従来の技術】
エチレン系共重合体、例えばエチレン−酢酸ビニル共重合体（以下、ＥＶＡと略す）のペレットは、その高い粘着性のために、ペレット製造工程、その後の貯蔵、輸送等によりペレット同士が強固なブロッキングを起こし、また、その流動性が極めて乏しいために、ペレットの生産時、包装作業時において多大な労力を要するといった問題を抱え、長時間にわたる貯蔵、輸送等も困難であった。これらの問題を解決する方法として、従来よりペレットに対する種々の処理方法が提案されている。
【０００３】
ペレットのブロッキング防止方法としては、例えばタルク、シリカ等の無機物質、ポリオレフィン微粉末、ポリエチレンワックス及びその分散液をペレット表面にコーティングする方法や高級脂肪酸又はその塩、Ｎ，Ｎ’−エチレンビスオレアミド、Ｎ，Ｎ’−エチレンビスエルクアミド、Ｎ，Ｎ’−ジオレイルジプイミド、Ｎ，Ｎ’−ジエルシルアジプイミドを混合する方法がある。しかしながら、上記の各種方法には多くの問題が存在している。
【０００４】
例えば、ＥＶＡに無機物質であるタルク、シリカ等を混合付着させ添加した場合は、ペレットの流動性を得るため多量の添加が必要となるが、ＥＶＡとの相溶性が乏しいため末端製品の機能を著しく損なう問題がある。
【０００５】
ポリオレフィン微粉末の水系スラリーによる重合体ペレットへのコーティング方法では、微粉末ポリオレフィンの水系への分散が極めて乏しいと共に、ペレットへの付着性が弱いために、現実に粘着性を防止し、良好な流動性を確保する域までに達することができない問題がある（例えば、特許文献１参照）。
【０００６】
また、ポリエチレンワックス又はポリエチレンワックスを主成分とする分散液等でＥＶＡペレットにコーティングを実施した場合には、耐粘着性についてはある程度の効果は見られるものの、実用的な流動性を得るには至らず、またそのコーティングペレットを融解させた場合、乳濁状を呈する問題があるため、用途面から制約を受ける（例えば、特許文献２参照）。
【０００７】
さらに、高粘着性エチレン系ポリマーペレットに低粘着性ＥＶＡ分散液でコーティングを実施した場合には、コーティング剤として用いるＥＶＡの融点が低いと共に、該物質中の酢酸ビニル含有率いかんによっては、現実的に粘着性を防止し、良好な流動性を有する該コーティングペレットを得るに至らない等の問題がある（例えば、特許文献３参照）。
【０００８】
高級脂肪酸又はその塩を混合する方法（例えば、特許文献４参照）や、Ｎ，Ｎ’−エチレンビスオレアミド、Ｎ，Ｎ’−エチレンビスエルクアミド、Ｎ，Ｎ’−ジオレイルジプイミド、Ｎ，Ｎ’−ジエルシルアジプイミドの群から選ばれた添加剤を含有させる方法が提案されている（例えば、特許文献５参照）が、該ペレットは添加剤のブリード速度が充分でないため、初期のペレットのプロッキング防止効果が劣る。
【０００９】
【特許文献１】米国特許第３５２８８４１号公報
【特許文献２】特開昭５６−６７２０９号公報
【特許文献３】特開昭４８−３２９３９号公報
【特許文献４】特開昭５６−１３６３４７号公報
【特許文献５】特開昭５７−２００４３４号公報
【発明が解決しようとする課題】
本発明の目的は、ペレットのブロッキングを改良したエチレン系共重合体ペレットを提供することにある。
【００１０】
【課題を解決する手段】
本発明はかかる点を考慮し鋭意検討した結果、エチレン系共重合体に特定の滑剤を添加することにより、エチレン系共重合体のペレットのブロッキングを改良できることを見出し本発明を完成するに至った。
【００１１】
即ち本発明は、エチレン系共重合体１００重量部に対し、（ａ）融点が１００℃〜１８０℃の不飽和脂肪酸ビスアミド０．０１〜０．５重量部、（ｂ）６０〜９０℃の融点を有し、（ａ）と併用することにより（ａ）の融点が２０℃以上降下する滑剤０．０１〜０．５重量部を配合してなることを特徴とするエチレン系共重合体ペレットに関するものである。
【００１２】
以下、本発明について詳細に説明する。
【００１３】
本発明のエチレン系共重合体としては、特に制限がなく、エチレン系共重合体と称されるエチレン−α、β−不飽和カルボン酸エステル共重合体、エチレン−ビニルエステル共重合体、エチレン−ビニルエステル−α、β−不飽和カルボン酸三元共重合体、エチレン−α−オレフィン共重合体等が含まれる。具体的にはエチレン−酢酸ビニル共重合体、エチレン−エチルアクリレート共重合体、エチレン−メチルメタクリレート共重合体、エチレン−メチルメタクリレート共重合体、エチレン−１−ブテン共重合体、エチレン−１−ヘキセン共重合体、エチレン−１−オクテン共重合体、エチレン−４−メチル−１−ペンテン共重合体、エチレン−プロピレン共重合体ゴム、エチレン−プロピレンジエン共重合体ゴム、エチレン−ブテン共重合体ゴム等がある。この中でも軟化点が低いエチレン−酢酸ビニル共重合体が好ましい。
【００１４】
特にペレットのプロッキングが問題になるＪＩＳ Ｋ６９２４−１（１９９７）に準拠した酢酸ビニル含有率（ＶＡｃ）２７〜５０ｗｔ％を含有し、ＪＩＳ Ｋ６９２４−１（１９９７）に準拠したメルトマスフローレイト（ＭＦＲ）が、
ＭＦＲ＞４３１．９８×（ＶＡｃ）−０．７７３１
を満たすエチレン−酢酸ビニル共重合体がさらに好ましい。
【００１５】
本発明において使用される（ａ）不飽和脂肪酸ビスアミドは、融点が１００〜１８０℃であり、具体的には、エチレンビスステアリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスエルカ酸アミド、エチレンビスラウリン酸アミド等が挙げられ、その中でもエチレン共重合体との相溶性やブリード性の面からエチレンビスオレイン酸アミドが好ましい。
【００１６】
本発明における（ａ）不飽和脂肪酸ビスアミドの配合量は、エチレン系共重合体１００重量部に対し０．０１〜０．５重量部、好ましくは０．０５〜０．２重量部である。０．０１重量部より少ない場合はブロッキング防止効果が低く、０．５重量部を超えると経時で滑剤が多量に表面にブリードして接着性の低下等の問題が発生する。
【００１７】
本発明において使用される（ｂ）滑剤は、（ａ）不飽和脂肪酸ビスアミドとの併用により（ａ）不飽和脂肪酸ビスアミドの融点が２０℃以上降下する融点が６０〜９０℃の滑剤であれば特に制限はなく、脂肪酸、脂肪酸アミド等が含まれる。融点が６０℃未満ではブロッキング防止効果が小さく、９０℃を超える場合は初期のブロッキング防止効果が劣る。具体的には、ステアリン酸、パルミチン酸、ベヘニン酸等の飽和脂肪酸、エルカ酸アミド、オレイン酸アミド等の不飽和脂肪酸アミド等が挙げられ、単独又は混合物として用いられる。滑剤の中でも表面移行性が速く、ブロッキング防止性能の優れる不飽和脂肪酸アミド等が好ましい。不飽和脂肪酸アミドの中でも不飽和脂肪酸ビスアミドのブリード性が向上するエルカ酸アミドがさらに好ましい。
【００１８】
本発明における（ｂ）滑剤の配合量は、エチレン系共重合体１００重量部に対し０．０１〜０．５重量部、好ましくは０．０５〜０．２重量部である。０．０１重量部より少ない場合はブロッキング防止効果が低く、０．５重量部を超えると経時で滑剤が多量に表面にブリードして接着性の低下等の問題が発生する。
【００１９】
本発明における（ａ）不飽和脂肪酸ビスアミドと（ｂ）滑剤との配合（ｗｔ％）比（ａ）／（ｂ）は、不飽和脂肪酸ビスアミドのブリードの面から７０／３０〜３０／７０が好ましい。
【００２０】
本発明における滑剤の添加方法は特に限定されず、任意の方法によって得られる。具体例としては、押出機、バンバリーミキサー、ニーダー等で溶融混練する方法、分散液等でペレット表面にコーティングする方法、ペレットとドライブレンドする方法等がある。中でも溶融混練法により得られたペレットはブロッキング防止性能に優れており好ましい。
【００２１】
本発明のエチレン系共重合体のペレットは、ブロッキング防止効果、流動性等を考慮すると、ＪＩＳ Ｂ０６０１（１９９４）に準拠した表面粗さＲａ値は、１．０〜２．５μｍであることが好ましい。表面粗さを粗くする具体例としては、アンダーウォーターカット、ストランドカット、ホットカット等の方式でカッティングしたペレットを格子上の凹凸がついた移送用配管（ナーリング）、リング状に凹凸のついた移送用配管（エコー）を通すこと等で表面を粗すことができる。
【００２２】
本発明でいう表面粗さＲａ値は、具体的にカラーレーザ顕微鏡ＶＫ−８５００（キーエンス製）を使用して求める。
【００２３】
本発明のエチレン系共重合体ペレットには必要に応じ、顔料、染料、酸化防止剤、滑剤、耐候剤、ブロッキング防止剤、各種安定剤、無機充填剤を配合することができる。
【００２４】
【実施例】
次に本発明を実施例及び比較例によって説明するが、本発明はこれらの実施例に限定されるものではない。
【００２５】
なお、以下の実施例及び比較例においての試験方法は次の方法によって測定し性能を評価した。
（１）ペレットのプロッキング試験
溶融混練により得られたエチレン系共重合体ペレット１００ｇを内径６０×６０×６０ｍｍの試験片作製箱に入れ６８．６Ｎの仕込み荷重を載せ、３０℃で４８時間放置いた後、２３℃で２４時間放置する。得られた試験片を速度１０ｍｍ／ｍｉｎで圧縮し、破壊に要した最大荷重を測定する。また溶融混練後１ケ月間２３℃の雰囲気下に放置したエチレン系共重合体ペレットについても同様の試験を行う。ブロッキング強度が４９０Ｎ未満を○、４９０Ｎ以上のものを×とした。なお、これらの結果を表１に示した。
（２）融点降下温度測定
（ａ）不飽和脂肪酸ビスアミドのＤＳＣを測定し、その最も高融点側のピークトップＴｍ１、（ａ）不飽和脂肪酸ビスアミドと（ｂ）滑剤との溶融混練物のＤＳＣを測定し、その最も高融点側のピークトップをＴｍ２とした。Ｔｍ１とＴｍ２の差を融点降下温度とした。なお、これらの結果を表１に示した。
【００２６】
実施例１
表１に示した配合に従い、ＭＦＲ４００ｇ／１０ｍｉｎ、ＶＡｃ３３ｗｔ％を含有するエチレン−酢酸ビニル共重合体（ウルトラセン０Ｂ５４Ｂ、東ソー（株）製）１００重量部、エチレンビスオレイン酸アミド０．１重量部、エルカ酸アミド０．１重量部を溶融混練後、アンダーウォーターカットでカッティング後、ペレット表面を粗し、表面粗さＲａ値が１．６μｍのペレットを得た。得られたペレットのブロッキング強度を評価した。エチレンビスオレイン酸アミドの融点Ｔｍ１は１２０℃、エルカ酸アミドの融点は８２℃、エチレンビスオレイン酸アミドとエルカ酸アミド５０／５０（ｗｔ％）の混合物の融点Ｔｍ２は７５℃となった。融点降下の結果及びブロッキング強度の結果を表２に示した。
【００２７】
【表１】

Figure 2004256740
【表２】
Figure 2004256740
実施例２
ＭＦＲ４００ｇ／１０ｍｉｎ、ＶＡｃ３３ｗｔ％を含有するエチレン−酢酸ビニル共重合体（ウルトラセン０Ｂ５４Ｂ、東ソー（株）製）１００重量部、エチレンビスオレイン酸アミド０．５重量部、エルカ酸アミド０．５重量部を溶融混練後、アンダーウォーターカットでカッティング後、ペレット表面を粗し、表面粗さＲａ値が１．６μｍのペレットを得た。得られたペレットのブロッキング強度を評価し、その結果を表２に示した。
【００２８】
実施例３
ＭＦＲ４００ｇ／１０ｍｉｎ、ＶＡｃ３３ｗｔ％を含有するエチレン−酢酸ビニル共重合体（ウルトラセン０Ｂ５４Ｂ、東ソー（株）製）１００重量部、エチレンビスオレイン酸アミド０．０５重量部、エルカ酸アミド０．０５重量部を溶融混練後、アンダーウォーターカットでカッティング後、ペレット表面を粗し、表面粗さＲａ値が１．６μｍのペレットを得た。得られたペレットのブロッキング強度を評価し、その結果を表２に示した。
【００２９】
実施例４
ＭＦＲ４００ｇ／１０ｍｉｎ、ＶＡｃ３３ｗｔ％を含有するエチレン−酢酸ビニル共重合体（ウルトラセン０Ｂ５４Ｂ、東ソー（株）製）１００重量部、エチレンビスオレイン酸アミド０．０５重量部、オレイン酸アミド０．０５重量部を溶融混練後、アンダーウォーターカットでカッティング後、ペレット表面を粗し、表面粗さＲａ値が１．６μｍのペレットを得た。得られたペレットのブロッキング強度を評価した。エチレンビスオレイン酸アミドとオレイン酸アミド０．１重量部ずつの混合物の融点降下の結果及びブロッキング強度の結果を表２に示した。
【００３０】
比較例１
ＭＦＲ４００ｇ／１０ｍｉｎ、ＶＡｃ３３ｗｔ％を含有するエチレン−酢酸ビニル共重合体（ウルトラセン０Ｂ５４Ｂ、東ソー（株）製）のペレット表面を粗し、表面粗さＲａ値が１．６μｍのペレットを得た。得られたペレットのブロッキング強度を評価し、その結果を表２に示した。このペレットはブロッキング強度が高く実用的ではない。
【００３１】
比較例２
ＭＦＲ４００ｇ／１０ｍｉｎ、ＶＡｃ３３ｗｔ％を含有するエチレン−酢酸ビニル共重合体（ウルトラセン０Ｂ５４Ｂ、東ソー（株）製）１００重量部、エチレンビスオレイン酸アミド０．２重量部を溶融混練後、アンダーウォーターカットでカッティング後、ペレット表面を粗し、表面粗さＲａ値が１．６μｍのペレットを得た。得られたペレットのブロッキング強度を評価し、その結果を表２に示した。このペレットは生産直後のブロッキング強度が高く実用的ではない。
【００３２】
比較例３
ＭＦＲ４００ｇ／１０ｍｉｎ、ＶＡｃ３３ｗｔ％を含有するエチレン−酢酸ビニル共重合体（ウルトラセン０Ｂ５４Ｂ、東ソー（株）製）１００重量部、エルカ酸アミド０．２重量部を溶融混練後、アンダーウォーターカットでカッティング後、ペレット表面を粗し、表面粗さＲａ値が１．６μｍのペレットを得た。得られたペレットのブロッキング強度を評価し、その結果を表２に示した。このペレットはブロッキング強度が高く実用的ではない。
【００３３】
比較例４
ＭＦＲ４００ｇ／１０ｍｉｎ、ＶＡｃ３３ｗｔ％を含有するエチレン−酢酸ビニル共重合体（ウルトラセン０Ｂ５４Ｂ、東ソー（株）製）１００重量部、エチレンビスオレイン酸アミド０．１５重量部、エルカ酸アミド０．０５重量部を溶融混練後、アンダーウォーターカットでカッティング後、ペレット表面を粗し、表面粗さＲａ値が１．６μｍのペレットを得た。得られたペレットのブロッキング強度を評価した。エチレンビスオレイン酸アミド０．１５重量部とエルカ酸アミド０．０５重量部の混合物の融点降下の結果及びブロッキング強度の結果を表２に示した。このペレットは生産直後のブロッキング強度が高く実用的ではない。
【００３４】
【発明の効果】
以上のように、本発明におけるエチレン系共重合体は耐ペレットのプロッキング性を向上させることが可能である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an ethylene copolymer pellet having improved fusion of pellets (hereinafter, referred to as pellet blocking).
[0002]
[Prior art]
Pellets of an ethylene-based copolymer, for example, an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA), are strongly blocked due to their high adhesiveness due to the pellet production step, subsequent storage, transportation, and the like. In addition, due to the extremely poor fluidity, there is a problem that a large amount of labor is required in the production of the pellets and in the packaging operation, and it has been difficult to store and transport for a long time. As a method for solving these problems, various treatment methods for pellets have been conventionally proposed.
[0003]
Examples of the method for preventing blocking of the pellet include a method of coating the surface of the pellet with an inorganic substance such as talc or silica, a fine powder of polyolefin, polyethylene wax or a dispersion thereof, a higher fatty acid or a salt thereof, N, N'-ethylenebisoleamide. , N, N'-ethylenebiserquamide, N, N'-dioleyldipimide, and N, N'-dielsyladipimide. However, there are many problems with the various methods described above.
[0004]
For example, in the case where talc, silica, or the like, which is an inorganic substance, is mixed and added to EVA, a large amount of addition is required to obtain the fluidity of the pellets. However, since the compatibility with EVA is poor, the function of the end product is reduced. There is a significant impairment problem.
[0005]
In the method of coating polymer pellets with an aqueous slurry of polyolefin fine powder, the dispersion of the fine polyolefin powder in the aqueous system is extremely poor, and the adhesion to the pellets is weak. There is a problem that it is not possible to reach the region where the performance is ensured (for example, see Patent Document 1).
[0006]
Further, when coating EVA pellets with polyethylene wax or a dispersion containing polyethylene wax as a main component, a certain degree of effect can be seen on the anti-adhesion property, but practical fluidity cannot be obtained. In addition, when the coating pellets are melted, there is a problem that the pellets are emulsified, and thus there is a limitation in terms of application (for example, see Patent Document 2).
[0007]
Further, when coating is performed on a high-adhesion ethylene-based polymer pellet with a low-adhesion EVA dispersion, the melting point of EVA used as a coating agent is low, and depending on the vinyl acetate content in the substance, a realistic value is required. In addition, there is a problem that the adhesion of the coating pellets is prevented and the coating pellets having good fluidity cannot be obtained (for example, see Patent Document 3).
[0008]
A method of mixing a higher fatty acid or a salt thereof (for example, see Patent Document 4), N, N'-ethylenebisoleamide, N, N'-ethylenebiserquamide, N, N'-dioleyldipimide, N , N'-dielsyladipimide, has been proposed (for example, see Patent Document 5). Is inferior in the effect of preventing blocking of pellets.
[0009]
[Patent Document 1] U.S. Pat. No. 3,588,841 [Patent Document 2] JP-A-56-67209 [Patent Document 3] JP-A-48-32939 [Patent Document 4] JP-A-56-136347 [Patent Document 5] JP-A-57-200444 [Problems to be Solved by the Invention]
An object of the present invention is to provide an ethylene-based copolymer pellet having improved pellet blocking.
[0010]
[Means to solve the problem]
As a result of intensive studies in consideration of such points, the present invention has found that by adding a specific lubricant to the ethylene copolymer, it is possible to improve the blocking of the pellets of the ethylene copolymer, thereby completing the present invention. .
[0011]
That is, the present invention relates to (a) 0.01 to 0.5 parts by weight of an unsaturated fatty acid bisamide having a melting point of 100 to 180 ° C, and (b) a melting point of 60 to 90 ° C with respect to 100 parts by weight of an ethylene copolymer. Characterized by comprising 0.01 to 0.5 parts by weight of a lubricant whose melting point of (a) falls by 20 ° C. or more when used in combination with (a). Things.
[0012]
Hereinafter, the present invention will be described in detail.
[0013]
The ethylene-based copolymer of the present invention is not particularly limited, and ethylene-α, β-unsaturated carboxylic acid ester copolymer, ethylene-vinyl ester copolymer, ethylene- Vinyl ester-α, β-unsaturated carboxylic acid terpolymers, ethylene-α-olefin copolymers and the like are included. Specifically, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-1-butene copolymer, ethylene-1-hexene Copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-propylene copolymer rubber, ethylene-propylene diene copolymer rubber, ethylene-butene copolymer rubber Etc. Among them, an ethylene-vinyl acetate copolymer having a low softening point is preferable.
[0014]
In particular, a vinyl acetate content (VAc) of 27 to 50 wt% in accordance with JIS K6924-1 (1997), in which pellet blocking becomes a problem, and a melt mass flow rate (MFR) in accordance with JIS K6924-1 (1997) But,
MFR> 431.98 * (VAc) -0.7731
An ethylene-vinyl acetate copolymer that satisfies the following condition is more preferable.
[0015]
The (a) unsaturated fatty acid bisamide used in the present invention has a melting point of 100 to 180 ° C., specifically, ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene bis erucic acid amide, ethylene bis laurine Acid amides and the like, among which ethylene bisoleic acid amide is preferred from the viewpoint of compatibility with the ethylene copolymer and bleeding properties.
[0016]
The amount of the unsaturated fatty acid bisamide (a) in the present invention is 0.01 to 0.5 part by weight, preferably 0.05 to 0.2 part by weight, per 100 parts by weight of the ethylene copolymer. When the amount is less than 0.01 part by weight, the anti-blocking effect is low. When the amount exceeds 0.5 part by weight, a large amount of the lubricant bleeds on the surface over time to cause problems such as a decrease in adhesiveness.
[0017]
The lubricant (b) used in the present invention is preferably (a) a lubricant having a melting point of 60 to 90 ° C. in which the melting point of the unsaturated fatty acid bisamide drops by 20 ° C. or more when used in combination with the unsaturated fatty acid bisamide. There is no limitation, and fatty acids and fatty acid amides are included. If the melting point is lower than 60 ° C., the anti-blocking effect is small, and if it exceeds 90 ° C., the initial anti-blocking effect is poor. Specific examples include saturated fatty acids such as stearic acid, palmitic acid, and behenic acid, and unsaturated fatty acid amides such as erucamide and oleic acid amide, and used alone or as a mixture. Among the lubricants, unsaturated fatty acid amides and the like, which have a high surface transferability and are excellent in antiblocking performance, are preferred. Among the unsaturated fatty acid amides, erucic acid amide which improves the bleeding property of the unsaturated fatty acid bisamide is more preferable.
[0018]
The blending amount of the lubricant (b) in the present invention is 0.01 to 0.5 part by weight, preferably 0.05 to 0.2 part by weight, based on 100 parts by weight of the ethylene copolymer. When the amount is less than 0.01 part by weight, the anti-blocking effect is low. When the amount exceeds 0.5 part by weight, a large amount of the lubricant bleeds on the surface over time to cause problems such as a decrease in adhesiveness.
[0019]
In the present invention, the mixing ratio (a) / (b) of (a) the unsaturated fatty acid bisamide and (b) the lubricant is preferably 70/30 to 30/70 from the viewpoint of the bleeding of the unsaturated fatty acid bisamide. .
[0020]
The method for adding the lubricant in the present invention is not particularly limited, and can be obtained by any method. Specific examples include a method of melt-kneading with an extruder, a Banbury mixer, a kneader or the like, a method of coating the pellet surface with a dispersion or the like, and a method of dry blending with the pellet. Among them, pellets obtained by the melt-kneading method are preferable because they have excellent antiblocking performance.
[0021]
The pellets of the ethylene copolymer of the present invention preferably have a surface roughness Ra value of 1.0 to 2.5 μm in accordance with JIS B0601 (1994) in consideration of the anti-blocking effect, fluidity, and the like. . Specific examples of roughening the surface roughness include a transfer pipe (knurling) having irregularities on a grid for pellets cut by a method such as underwater cut, strand cut, or hot cut, or a transfer having irregularities in a ring shape. The surface can be roughened by passing through a pipe (echo) for use.
[0022]
The surface roughness Ra value referred to in the present invention is specifically determined using a color laser microscope VK-8500 (manufactured by Keyence).
[0023]
If necessary, pigments, dyes, antioxidants, lubricants, weathering agents, antiblocking agents, various stabilizers, and inorganic fillers can be added to the ethylene copolymer pellets of the present invention.
[0024]
【Example】
Next, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
[0025]
The test methods in the following Examples and Comparative Examples were measured by the following methods to evaluate the performance.
(1) Procking test of pellets 100 g of ethylene copolymer pellets obtained by melt-kneading were placed in a test piece preparation box having an inner diameter of 60 × 60 × 60 mm, a loading load of 68.6 N was placed thereon, and left at 30 ° C. for 48 hours. And leave at 23 ° C. for 24 hours. The obtained test piece is compressed at a speed of 10 mm / min, and the maximum load required for breaking is measured. The same test is also performed on the ethylene copolymer pellets left for one month in an atmosphere at 23 ° C. after melt kneading. When the blocking strength was less than 490 N, it was evaluated as ○. Table 1 shows these results.
(2) Measurement of melting point drop temperature (a) DSC of unsaturated fatty acid bisamide was measured, and the DSC of the melt-kneaded product of (a) unsaturated fatty acid bisamide and (b) lubricant was measured. Measurement was performed, and the peak top on the highest melting point side was defined as Tm2. The difference between Tm1 and Tm2 was defined as the melting point drop temperature. Table 1 shows these results.
[0026]
Example 1
According to the composition shown in Table 1, 100 parts by weight of an ethylene-vinyl acetate copolymer (Ultracene 0B54B, manufactured by Tosoh Corporation) containing 400 g / 10 min of MFR and 33 wt% of Vac, 0.1 part by weight of ethylene bisoleic acid amide, After melting and kneading 0.1 part by weight of erucamide, the pellet surface was roughened after cutting by underwater cutting to obtain a pellet having a surface roughness Ra value of 1.6 μm. The blocking strength of the obtained pellet was evaluated. The melting point Tm1 of ethylenebisoleamide was 120 ° C., the melting point of erucamide was 82 ° C., and the melting point Tm2 of a mixture of ethylenebisoleamide and erucamide 50/50 (wt%) was 75 ° C. Table 2 shows the results of the melting point drop and the blocking strength results.
[0027]
[Table 1]
Figure 2004256740
[Table 2]
Figure 2004256740
Example 2
MFR 400 g / 10 min, 100 parts by weight of ethylene-vinyl acetate copolymer (Ultracene 0B54B, manufactured by Tosoh Corporation) containing 33 wt% of VAc, 0.5 parts by weight of ethylene bisoleic acid amide, 0.5 parts by weight of erucamide After melt-kneading, the pellet surface was roughened after cutting by underwater cutting to obtain a pellet having a surface roughness Ra value of 1.6 μm. The blocking strength of the obtained pellets was evaluated, and the results are shown in Table 2.
[0028]
Example 3
MFR 400 g / 10 min, 100 parts by weight of ethylene-vinyl acetate copolymer (Ultracene 0B54B, manufactured by Tosoh Corporation) containing 33 wt% of VAc, 0.05 parts by weight of ethylene bisoleic amide, 0.05 parts by weight of erucamide After melt-kneading, the pellet surface was roughened after cutting by underwater cutting to obtain a pellet having a surface roughness Ra value of 1.6 μm. The blocking strength of the obtained pellets was evaluated, and the results are shown in Table 2.
[0029]
Example 4
MFR 400 g / 10 min, 100 parts by weight of ethylene-vinyl acetate copolymer (Ultracene 0B54B, manufactured by Tosoh Corporation) containing 33 wt% of VAc, 0.05 parts by weight of ethylene bisoleic acid amide, 0.05 parts by weight of oleic acid amide After melt-kneading, the pellet surface was roughened after cutting by underwater cutting to obtain a pellet having a surface roughness Ra value of 1.6 μm. The blocking strength of the obtained pellet was evaluated. Table 2 shows the results of the melting point drop and the blocking strength of the mixture of ethylene bisoleic acid amide and 0.1 part by weight of oleic acid amide.
[0030]
Comparative Example 1
The pellet surface of an ethylene-vinyl acetate copolymer (Ultracene 0B54B, manufactured by Tosoh Corporation) containing 400 g / 10 min of MFR and 33 wt% of VAc was roughened to obtain a pellet having a surface roughness Ra value of 1.6 μm. The blocking strength of the obtained pellets was evaluated, and the results are shown in Table 2. These pellets have high blocking strength and are not practical.
[0031]
Comparative Example 2
100 parts by weight of an ethylene-vinyl acetate copolymer (Ultracene 0B54B, manufactured by Tosoh Corporation) containing 400 g / 10 min of MFR and 33 wt% of VAc, and 0.2 parts by weight of ethylenebisoleic acid amide are melt-kneaded and then underwater cut. After cutting, the pellet surface was roughened to obtain a pellet having a surface roughness Ra value of 1.6 μm. The blocking strength of the obtained pellets was evaluated, and the results are shown in Table 2. These pellets have high blocking strength immediately after production and are not practical.
[0032]
Comparative Example 3
100 parts by weight of an ethylene-vinyl acetate copolymer (Ultracene 0B54B, manufactured by Tosoh Corporation) containing 400 g / 10 min of MFR and 33 wt% of VAc, and 0.2 parts by weight of erucamide are melt-kneaded and then cut by underwater cutting. The surface of the pellet was roughened to obtain a pellet having a surface roughness Ra value of 1.6 μm. The blocking strength of the obtained pellets was evaluated, and the results are shown in Table 2. These pellets have high blocking strength and are not practical.
[0033]
Comparative Example 4
100 parts by weight of ethylene-vinyl acetate copolymer (Ultracene 0B54B, manufactured by Tosoh Corporation) containing 400 g / 10 min of MFR and 33 wt% of VAc, 0.15 parts by weight of ethylenebisoleic amide, 0.05 parts by weight of erucamide After melt-kneading, the pellet surface was roughened after cutting by underwater cutting to obtain a pellet having a surface roughness Ra value of 1.6 μm. The blocking strength of the obtained pellet was evaluated. Table 2 shows the results of the melting point drop and the blocking strength of a mixture of 0.15 parts by weight of ethylenebisoleic amide and 0.05 part by weight of erucamide. These pellets have high blocking strength immediately after production and are not practical.
[0034]
【The invention's effect】
As described above, the ethylene copolymer of the present invention can improve the blocking resistance of pellets.

Claims (9)

エチレン系共重合体１００重量部に対し、（ａ）融点が１００℃〜１８０℃の不飽和脂肪酸ビスアミド０．０１〜０．５重量部、（ｂ）６０〜９０℃の融点を有し、（ａ）と併用することにより（ａ）の融点が２０℃以上降下する滑剤０．０１〜０．５重量部を配合してなることを特徴とするエチレン系共重合体ペレット。(A) 0.01 to 0.5 parts by weight of an unsaturated fatty acid bisamide having a melting point of 100 ° C to 180 ° C, and (b) a melting point of 60 to 90 ° C with respect to 100 parts by weight of the ethylene-based copolymer, Ethylene-based copolymer pellets characterized by comprising 0.01 to 0.5 parts by weight of a lubricant which reduces the melting point of (a) by 20 ° C. or more when used in combination with (a). エチレン系共重合体ペレットが、溶融混練物であることを特徴とする請求項１に記載のエチレン系共重合体ペレット。The ethylene-based copolymer pellet according to claim 1, wherein the ethylene-based copolymer pellet is a melt-kneaded product. エチレン系共重合体が、エチレン−酢酸ビニル共重合体であることを特徴とする請求項１又は請求項２に記載のエチレン系共重合体ペレット。The ethylene copolymer pellet according to claim 1 or 2, wherein the ethylene copolymer is an ethylene-vinyl acetate copolymer. エチレン系共重合体が、ＪＩＳ Ｋ６９２４−１（１９９７）に準拠した酢酸ビニル（以下、ＶＡｃと略す）含有率２７〜５０ｗｔ％を含有し、ＪＩＳ Ｋ６９２４−１（１９９７）に準拠したメルトマスフローレイト（以下、ＭＦＲと略す）が次式を満たすエチレン−酢酸ビニル共重合体であることを特徴とする請求項１〜請求項３のいずれかに記載のエチレン系共重合体ペレット。
ＭＦＲ＞４３１．９８×（ＶＡｃ）−０．７７３１ The ethylene-based copolymer contains vinyl acetate (hereinafter abbreviated as VAc) content of 27 to 50% by weight based on JIS K6924-1 (1997), and melt mass flow rate based on JIS K6924-1 (1997). The ethylene-based copolymer pellet according to any one of claims 1 to 3, wherein MFR is an ethylene-vinyl acetate copolymer satisfying the following formula.
MFR> 431.98 * (VAc) -0.7731 （ａ）不飽和脂肪酸ビスアミドと（ｂ）滑剤との配合比（ｗｔ％）が、７０／３０〜３０／７０であることを特徴とする請求項１〜請求項４のいずれかに記載のエチレン系共重合体ペレット。The ethylene according to any one of claims 1 to 4, wherein the blending ratio (wt%) of (a) the unsaturated fatty acid bisamide and (b) the lubricant is 70/30 to 30/70. -Based copolymer pellets. （ａ）不飽和脂肪酸ビスアミドが、エチレンビスオレイン酸アミドであることを特徴とする請求項１〜請求項５のいずれかに記載のエチレン系共重合体ペレット。The ethylene copolymer pellet according to any one of claims 1 to 5, wherein (a) the unsaturated fatty acid bisamide is ethylene bisoleic acid amide. （ｂ）滑剤が、不飽和脂肪酸アミドであることを特徴とする請求項１〜請求項６のいずれかに記載のエチレン系共重合体ペレット。(B) The ethylene copolymer pellet according to any one of claims 1 to 6, wherein the lubricant is an unsaturated fatty acid amide. 不飽和脂肪酸アミドが、エルカ酸アミドであることを特徴とする請求項１〜請求項７のいずれかに記載のエチレン系共重合体ペレット。The ethylene copolymer pellet according to any one of claims 1 to 7, wherein the unsaturated fatty acid amide is erucic acid amide. ＪＩＳ Ｂ０６０１（１９９４）に準拠した表面粗さＲａ値が、１．０〜２．５μｍであることを特徴とする請求項１〜請求項８のいずれかに記載のエチレン系共重合体ペレット。The ethylene-based copolymer pellet according to any one of claims 1 to 8, wherein the surface roughness Ra value according to JIS B0601 (1994) is 1.0 to 2.5 µm.
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CN115477801B (en) * 2021-06-16 2023-12-05 长春石油化学股份有限公司 Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure comprising the same

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