JP2015077728A - 熱可塑性樹脂シート及び成形体 - Google Patents
熱可塑性樹脂シート及び成形体 Download PDFInfo
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- JP2015077728A JP2015077728A JP2013216168A JP2013216168A JP2015077728A JP 2015077728 A JP2015077728 A JP 2015077728A JP 2013216168 A JP2013216168 A JP 2013216168A JP 2013216168 A JP2013216168 A JP 2013216168A JP 2015077728 A JP2015077728 A JP 2015077728A
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- thermoplastic resin
- antistatic
- skin layer
- sheet
- resin sheet
- Prior art date
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- Granted
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
【解決手段】
2種2層以上の多層構成において、熱可塑性樹脂と、タルクおよび白顔料から成るメイン層と、反対側に少なくとも一種の熱可塑性樹脂と帯電防止剤を含む帯電防止性樹脂組成物をスキン層とした積層シートを調製する。前記樹脂組成物で構成されたシートを熱成形することにより、コンタミネーションやスープ粉末付着防止に効果がある帯電防止性に優れかつ撥水性を有する成形品が得られる。高分子型帯電防止剤としては脂肪酸エステルスルホン酸塩を主成分とするもので、表面抵抗率は1013Ω/□以下であることが好ましく、水滴接触角が90°以上である。該積層シートは、共押出法で製造することが好ましい。
【選択図】なし
Description
ポリプロピレン系樹脂自身もホモ・ランダムコポリマー・ゴム成分添加による結晶化の違いにより、自由電子のトラップ数が異なるため、コブロックポリマーが使用されるが(例えば、特許文献6参照)、成形体の剛性不足が懸念されるという問題がある。
本発明における熱可塑性樹脂としては、例えばポリオレフィン系重合体が用いられる。このポリオレフィン系重合体のうち、特にポリプロピレン系重合体が、剛性や耐熱性の点で望ましい。
前記熱可塑性樹脂と帯電防止剤とを組み合わせると、帯電防止性に優れた樹脂組成物が得られる。帯電防止剤としては、例えば、ノニオン性帯電防止剤、アニオン性帯電防止剤、カチオン性帯電防止剤、両性帯電防止剤等の帯電防止剤が挙げられる。
本発明の熱可塑性樹脂には、帯電防止効果を調整する目的で、高分子量の帯電防止剤、金属酸化物、カーボンブラック、導電性付与剤、高級アルコール等を加えてもよい。さらに、必要に応じて、目ヤニ防止剤、着色剤、分散剤、離型剤、安定化剤(酸化防止剤、紫外線吸収剤、熱安定化剤等)、難燃剤、滑剤、アンチブロッキング剤、充填剤等を添加してもよい。
無機物添加剤としては、樹脂量の使用率低減からのコストダウン、防火性、剛性・耐衝撃性等の機械物性の観点から、タルク、マイカ、カーボンブラック、シリカ、ドロマイト粉、ケイ酸塩、石英粉、珪藻土、アルミナ、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム等が挙げられる。化学式としては、Mg3Si4O10(OH)2を主成分とするものが良い。平均粒子径は、20μm以下、好ましくは1.0〜18μm、さらには2.5〜15μm 程度がよく、バルク表面に撥水性の凹凸を形成し、撥水性を向上させ得る等の点でより好ましい。
白色顔料としては、亜鉛華、鉛白、リトポン、酸化チタン、沈降性硫酸バリウムおよびバライト粉などがある。しかし、食品用途では、食品添加物に限定される。食品衛生法適合の食品添加物である白色顔料の酸化チタンとしては、99%以上の高純度酸化チタンがある。酸化チタンの白色顔料は、衛生上、衛生管理上、及び食品の印象上から食品用途では最適である。化学式としては、TiO2を主成分とするものが良い。平均粒子径は、1μm以下、好ましくは0.01〜0.8μm以下、さらには0.05〜0.3μm程度がよく、バルクの光遮蔽性能を向上させ得る等の点でより好ましい。遮蔽性は添加量がある程度多くなるとあまり高くならないため、コストとの兼ね合いで決めるのが良い。
本発明の熱可塑性樹脂シートは、複数の層で構成された積層シートである。熱可塑性樹脂シート全体の厚みは、0.1〜3.0mm、好ましくは0.2〜2.0mm、さらに好ましくは0.5〜1.2mm程度である。
本発明のポリオレフィン系樹脂シートは、自由吹込成形、真空成形、折り曲げ加工、圧空成形、マッチモールド成形、熱板成形等の慣用の熱成形などで二次成形することができる。二次成形品としては、例えば、包装用材料、食品用容器、薬品用容器、トレー、エンボステープ又はキャリアテープ等が挙げられる。
本発明の樹脂組成物及びシートでは、金型に対する非接触面のみならず、延伸や配向が生じる熱成形域での帯電防止性も大きく向上できる。より具体的には、収容凹部を熱成形すると、熱影響のある収容凹部の底壁および内外面の帯電防止剤が少なからずブリードするため、帯電防止性を早期に発現でき、しかも持続できる。
メルトインデックスMIは、JISK7210に規定された方法に従い、測定した。測定温度は230℃であり、試験荷重は21.18Nとする。
プロピレン−エチレンブロック共重合体において、プロピレン−エチレンランダム共重合体部分の全ブロック共重合体に対する重量比率X(重量%)は、プロピレン単独重合体部分と全ブロック共重合体の各々の結晶融解熱量を測定することによって、次式から算出した。
X=1−(ΔHf)T/(ΔHf)P
(ΔHf)T:ブロック共重合体全体の融解熱量(cal/g)
(ΔHf)P:プロピレンホモポリマー部分の融解熱量(cal/g)
事前に、粒子を混合前に粉の状態でレーザー回折散乱方式粒度分布計を用いて測定を行う。測定装置としては、例えば、堀場製作所社製LA−920型が測定精度において優れているので好ましい。
シート断面をフェザー刃で削り、株式会社NIKON社製AZ100M 光学顕微鏡にて、粒子の有無層によりスキン・メイン各層の厚みを計測した。
押出シート成形品を温度20℃、湿度50%RHで2〜7日間養生させ、JISK6911に準拠して測定した表面固有抵抗値を測定した。
押出シート成形品を1日後にスタチックオネストメーター(宍戸静電気株式会社製) にかけて10kv、2分間荷電し、荷電を停止した後の半減期を測定した。帯電圧減衰半減期の数値は秒(SEC)で示す。この値(SEC)が小さいほど帯電量が多い場合の帯電防止性が優れている。
サンプルシートと純水の水滴接触角に関しては、JIS−R3257(1999年)に準じて、協和界面科学(株)製DropMaster500を用いて、10回測定を行い、その平均値をもって水滴接触角とし、数値は角度(°)で示す。なお、測定に際しては20±2℃、65±5%RHの雰囲気下、試料フィルムの測定面に水滴を滴下後、1分後に水滴のなす角度を読み取った。水滴接触角が低いほど親水性が高く、水滴接触角が高いほど撥水が高い。
成形した樹脂シートを3〜30日後内に真空圧空成形した直方体容器(フランジ部シール巾5mm)に、板紙シート(80 g/m2)とポリエチレン樹脂(30μm)をラミネートした被着体を温度210(℃)、圧力1000(N)、圧力保持時間0.7(SEC)の条件で成形容器フランジ部を両側からアルミ型で挟み込み、容器と被着体をシールさせ、常温まで冷却する。その後、40℃75%RHにて1週間アニールし、常温まで冷却1時間後、引張試験機を用いて直方体角部から90度方向に300mm/分の引張速度で剥離した最大強度の値ニュートン(N)を示す。シール接着強度は、容器と蓋との密封性の指標であり、初期強度は20N程度、低くても15N程度が望ましく、経時で低下が著しいものは、輸送時のシールはがれの原因となるため、実使用上好ましくない。
成形した樹脂シートを3〜14日後内に直方体カップ状に真空圧空成形を行い、味の素製 ほんだし5gをカップに秤量後、内部充填しシールを行った。プラスチック板上を20cm巾20往復の容器内撹拌を行う。撹拌終了後、PPカップを上下反転させ、内部充填物を落下させ、秤量する。
◎:0.01g以下であり、非常に良好。
○:0.05g以下0.01g以上であり、概ね良好。
×:0.05g以上であり、好ましくない。
各測定項目のトータルの評価として、以下の分類を行った。
◎:問題なし。測定項目において十分な性能を有する。
○:実使用上問題なし
△:使用上問題あり
×:使用不可
・熱可塑性樹脂シートの製造:PP(A−1)、PP(A−2)、PP(A−3)
表1に示すプロピレン単独重合体及びエチレン・プロピレンブロック共重合体を用いた。プロピレン単独重合体からなる重量平均分子量380,000のプロピレン・エチレン共重合体から構成され、ブロック共重合体は、チーグラー系触媒を用い気相重合法によって製造したものをペレット化し、シート製造時に添加する方法で使用した。
帯電防止剤主成分は、スルホン酸ナトリウム塩を用い、PP(A−2)に上記帯電防止剤18重量%+ブロッキング防止剤 球状シリカ3重量%をブレンダーにて混合後、押出混練を行いペレット化した。帯電防止成分を高濃度に濃縮したマスターバッチを作り、シート製造時に添加する方法で使用した。
無機添加剤の主成分はタルクであり、化学式Mg3Si4O10(OH)2で表される。堀場製作所社製LA−920型で測定し、平粒径15.0μmのものを使用した。直鎖状低密度ポリエチレン[エボリュー(登録商標SP3010)三井化学(株)製、密度(JIS K 7112)=0.925g/cc3、MI=0.9/10分]に60重量%をブレンダーにて混合後、押出混練を行いペレット化した。タルク成分を高濃度に濃縮したマスターバッチを作り、これを無機添加剤としてシート製造時に添加する方法で使用した。
白色顔料主成分は酸化チタンであり、化学式TiO2で表され、堀場製作所社製LA−920型で測定し、平粒径15.0μmのものを使用。直鎖状低密度ポリエチレン[エボリュー(登録商標SP3010) 三井化学(株)製、密度(JIS K 7112)=0.925g/cc3、MI=0.9/10分]に60重量%をブレンダーにて混合後、押出混練を行いペレット化した。白色顔料成分を高濃度に濃縮したマスターバッチを作り、これを白色顔料としてシート製造時に添加する方法で使用した。
表2に示すシート構成配合比率および構成厚さであり、「PP」はポリプロピレンを意味する。「PP」および「帯電防止剤」をヘンシェルミキサーであらかじめ混合後、スキン層側にフィードされる押出機に投入した。「無機添加剤」は80℃で3時間程度乾燥し、「PP」および「白色顔料」をヘンシェルミキサーであらかじめ混合後、メイン層側にフィードされる押出機に投入した。押出機は、スキン層側はスクリュー径135mm、スクリュー長4500mm単軸押出機、メイン層側はスクリュー径50mm、スクリュー長2835mm単軸押出機を用いた。押出機シリンダー温度240℃で溶融混練した後、マルチフィードブロック積層Tダイの外層にスキン層原料を供給し、積層ダイの内層(冷却ロール反対面)にはメイン層原料を供給し、スキン層/メイン層の構成からなる2種2層の積層シート共押出を行った。ダイ温度230℃で35℃の冷却ロールにメイン層が接するようキャストして急冷固化しながらシート状を形成した。スキン/メイン層の構成厚さ比率は押出量比率で制御し、ダイ圧はギアポンプで一定圧となるよう制御を行い、調整した。TD方向の厚さフレはヒートボルト方式で制御を行い、中心厚さ±8%以内に収まるように調整した。このシート状物を、冷却ロールによって冷却して、幅650mm×厚み0.9mmのシートを製造した。エアギャップは1.1mm とし、引き取り速度は12.0m/分とし、引き取りシート総厚が0.9mmとなるように調整した。シーティング後、恒温恒湿状態(温度23±2℃、湿度50±5%)で24時間以上調整し、得られたシートの帯電防止性能を測定した。測定結果の詳細は表3に示す通りである。
上記に示した方法に従って作製したシートを株式会社脇坂エンジニアリング社製真空圧空成形機FVS-500を用いて成形体に加工した。具体的には、上記に得られたシートを650mm×650mm程度の正方形ステンレス枠に固定後、遠赤ヒ−タ−(温度設定:550℃)で時間20秒加熱し、メス型金型にオス型プラグを挿入と同時にロータリーポンプにて真空引きを行い、カップサンプル(寸法:外長辺130mm×内短辺120mm×高さ95mm、内長辺115mm×短辺105mm,フランジ巾片側7mm、壁面厚さ:0.2〜0.3mm、長方形容器)を成形した。成形したカップサンプルを、恒温恒湿状態(温度23±2℃、湿度50±5%)で24時間以上調整し、その一部を切り出し、撥水性、帯電防止性およびシール測定をした。測定結果の詳細は表3に示す通りである。
Claims (7)
- スキン層及びメイン層を含む2層以上の多層からなり、
前記スキン層は、熱可塑性樹脂と帯電防止剤とを含み、
前記メイン層は、熱可塑性樹脂と無機物添加剤とを含み、
前記スキン層の厚みが所定長以下であり、
延伸されると前記スキン層における撥水性が増加する熱可塑性樹脂シート。
- 前記スキン層の厚みが10μm以上50μm以下であり、
延伸されると前記スキン層における水滴接触角が90°以上となる請求項1記載の熱可塑性樹脂シート。
- 前記スキン層の表面抵抗率が9×1013Ω以下である請求項1または請求項2記載の熱可塑性樹脂シート。
- 前記スキン層及び前記メイン層に含まれる前記熱可塑性樹脂は、ポリオレフィン系重合体である請求項1乃至請求項3いずれか一項記載の熱可塑性樹脂シート。
- 前記帯電防止剤は、スルホン酸塩を実質的成分とする請求項1乃至請求項4いずれか一項記載の熱可塑性樹脂シート。
- 前記無機物添加剤の平均粒子径は20μm以下である請求項1乃至請求項5いずれか一項記載の熱可塑性樹脂シート。
- 請求項1記載の熱可塑性樹脂シートを熱成形した成形体。
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