JP4688272B2 - Polyester resin composition and sheet manufacturing method - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、カレンダー成形、押出成形時に、充分な溶融加工性を持つポリエステル系樹脂組成物に関し、詳しくは、カレンダーロールからの剥離性、透明性、エンボス耐熱性および耐溶剤性にも優れたポリエステル系樹脂組成物に関するものである。
【０００２】
【従来の技術】
家具や什器、扉、棚板等の表面材あるいは木口材や冷蔵庫、テレビキャビネット等の弱電製品の表面化粧に使われる化粧シートや事務用のケース類、食品や医薬品等の包装材用としてポリエステエル系樹脂シートの用途が拡大しつつある。
これらポリエステル系樹脂シートは、従来、樹脂ペレットを溶融し押出加工によりシート成形するのが一般的である。ところが、上記の押出加工による成形法では、Ｔダイより所定の厚さのシートを押出し、これをガラス転移点以下に制御されたキャストロールでシート化されるが、シートの成形速度が遅く、生産性が良好とは言えない。
【０００３】
このポリエステル系樹脂をカレンダー加工によりシートを製造したり、製造されたシートを熱ラミネートや熱エンボス加工などの２次加工時に使用する熱ロールに強く粘着する欠点があり、特開平１１−３４３３５３号公報には、カレンダー加工でシートを成形する際、脂肪酸エステル系滑剤を使用することにより粘着を抑えて、カレンダー成形を可能にすることが記載されている。
しかしながら、脂肪酸エステル系滑剤を使用しても溶融粘度があまり高くないので、０．０５〜０．２ｍｍという比較的薄肉のシートを製造することや高温エンボス等での２次加工が困難であるという欠点がある。
【０００４】
【発明が解決しようとする課題】
本発明は、特定の非晶質・低晶質ポリエステル系樹脂を主成分としたポリエステル系樹脂組成物において、特定の樹脂や化合物を配合することによって、カレンダーロールからの剥離性や、エンボス耐熱性および耐溶剤性を付与することのできるポリエステル系樹脂組成物を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明は、主成分がテレフタル酸からなるジカルボン酸成分と、１５〜８０モル％の１，４−シクロヘキサンジメタノールと２０〜８５モル％のエチレングリコールからなるジオール成分とから構成された非晶質・低晶質ポリエステル樹脂６０〜９５重量％と、ポリブチレンテレフタレート樹脂、ポリエチレンテレスタレート樹脂から選ばれた少なくとも１種の高晶質ポリエステル樹脂５〜４０重量％とのポリエステル樹脂成分１００重量部に対して、滑剤として有機リン酸トリエステル化合物を０．１〜３重量部配合してなることを特徴とするポリエステル系樹脂組成物であって、該有機リン酸トリエステル化合物が、次式によって示される化合物であることを特徴とするポリエステル系樹脂組成物を提供するものである。
〔ＲＯ（ＣＨ２ＣＨ２Ｏ）ｍ〕３ＰＯ
（式中、Ｒは、同一或いは異なる炭素数１０〜２２のアルキル基またはアルキルアリール基、ｍは１〜１０の整数を表す）
上記のポリエステル樹脂成分１００重量部に対して、該有機リン酸トリエステル化合物は０．１〜３重量部、好ましくは０．３〜２．５重量部を配合する。この配合量が０．１重量部未満であると、カレンダー加工性や高温エンボスでの加工性が低下し、また、３重量部を超えると透明性が悪化したり、シート表面への吹き出しが多くなり印刷性が損なわれるので好ましくない。
【０００６】
透明性が必要でない場合、上記ポリエステル樹脂成分１００重量部に対して、さらにゴム成分のコア部分に、ビニル単量体がグラフト重合されてシェル部分を構成したたコアシェル型改質剤１〜２０重量部を配合してなることを特徴とする請求項１記載のポリエステル系樹脂組成物である。
【０００７】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明における非晶質・低晶質ポリエステル樹脂は、主成分がテレフタル酸からなるジカルボン酸成分と、１５〜８０モル％の１，４−シクロヘキサンジメタノールと２０〜８５モル％のエチレングリコールからなるジオール成分とから構成されたものであり、具体的には、１，４−シクロヘキサンジメタノールが３０モル％前後の非晶質ポリエステル樹脂：イーストマンケミカル社製の商品名「ＰＥＴＧ ６７６３」「Ｐｒｏｖｉｓｔａ」、また、１，４−シクロヘキサンジメタノール成分が７０モル％前後の低晶質ポリエステル樹脂：イーストマンケミカル社製の商品名「ＰＣＴＧ」「ＰＣＴＡ」を挙げることができる。
【０００８】
本発明では、上記の非晶質・低晶質ポリエステル樹脂の他に、高晶質ポリエステル系樹脂を配合する。具体的には、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂などを挙げることができる。
上記の非晶質・低晶質ポリエステル樹脂と高晶質ポリエステル樹脂とから構成されたポリエステル樹脂成分に対して、高晶質ポリエステル樹脂の配合割合は、５〜４０重量％の範囲で用いることができる。
上記の高晶質ポリエステル樹脂の配合割合が、５重量％未満であると耐溶剤性の改良が不十分であり、４０重量％を超えるとシートの再加熱による結晶化が生じて透明性が損なわれたり、溶融粘度が低下し、高温エンボス性が悪化するので好ましくない。
【００１０】
必要に応じて配合されるコアシェル型改質剤としては、ゴム成分のコア部に、ビニル単量体がグラフト重合されてシェル部を構成したコアシェル型改質剤で上記のポリエステル樹脂成分１００重量部に対して１〜２０重量部を配合することができる。
このコアシェル型改質剤のコア部分としては、アクリル系ゴム、オレフィン系ゴム、ジエン系ゴム、アクリル−シロキサン系複合ゴムなどが挙げられ、例えば、アクリル系ゴムのコアシェル型改質剤は、代表的なものとして、ブチルアクリレートのようなアクリル酸エステルと少量の架橋モノマーとを重合させたアクリル系ゴムからなるコア部に、メチルメタクリレート、アクリロニトリル、スチレンなどのビニル単量体がグラフト重合されシェル部が構成された改質剤で、呉羽化学社製の「ＨＩＡ−８０」、ローム・アンド・ハース社製の「アクリロイドＫＭ−３３０」、三菱レイヨン社製の「メタブレンＷ−３００」、「メタブレンＷ−５３０」などとして市販されている樹脂が好適に用いられる。
また、アクリル−シロキサン系複合ゴムのコアシェル型改質剤は、アクリル系ポリマーとポリオルガノシロキサンとからなる複合ゴムからなるコア部に、上記のビニル単量体がグラフト重合されてなるもので、三菱レイヨン社製の「メタブレンＳ２００１」、「メタブレンＳＸ００６」として市販されている。
これらのコアシェル型改質剤は、樹脂組成物に滑性を付与し、又、溶融粘度を上げることができるので、加熱ゲル化状態での組成物の移送を容易にし、カレンダーロールへの定量供給精度が高まり、シートの厚み精度を改善し、平滑性に優れたシートを製造できるという効果がある。
【００１１】
必要に応じて、上記の有機リン酸トリエステル化合物以外の滑剤やアクリル系加工助剤を本発明の性能を損なわない範囲で配合することができる。
例えば、アクリル系加工助剤としては、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎブチル、アクリル酸イソブチル、アクリル酸−２−エチルヘキシルなどのアクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎブチル、メタクリル酸イソブチル、メタクリル酸−２−エチルヘキシルなどのメタクリル酸エステルを主成分とした重量平均分子量が１００万〜５００万の共重合体が好ましく、三菱レイヨン社製の「メタブレンＰ−５５１」、「メタブレンＰ−５３０Ａ」、鐘淵化学工業社製の「カネエースＰＡ−３０」、「カネエースＰＡ−１００」などを挙げることができる。
【００１２】
これらのアクリル系加工助剤の配合割合は、ポリエステル系樹脂組成物１００重量部に対して、１０重量部以下、好ましくは０．５〜８重量部、更に好ましくは１〜６重量部の範囲とすることができる。配合することにより、滑性の付与や溶融粘度を高め、薄く均一な表面性を付与できるという効果がある。
【００１３】
さらに、本発明においては、従来より配合されている各種の添加剤、例えば、顔料、ヒンダードアミン系光安定剤、紫外線吸収剤、酸化防止剤、帯電防止剤、無機および有機充填剤や相溶性のある樹脂などを配合することができる。
【００１４】
本発明のポリエステル樹脂組成物は、前記の樹脂成分、有機リン酸トリエステル化合物、及び必要に応じて上記のような各種の添加剤を、それぞれ所用量配合し、溶融混練して原料を調整した後、通常のカレンダー加工法によりシート化して製造される。カレンダーのロール温度は、通常１６５〜１９０℃、好ましくは１７５〜１８５℃とすることができる。
【００１５】
【実施例】
以下、実施例及び比較例を挙げてさらに具体的に本発明を説明するが、本発明はこれに限定されるものではない。なお、各評価項目およびその評価は次に示す条件でおこなった。
【００１６】
（１）耐溶剤性：
カレンダーで製造した厚さ０．３ｍｍのシートを、幅５０ｍｍ、長さ１５０ｍｍの大きさに切断し、表１に示す各溶剤１ｃｃを含ませた脱脂綿（約３０ｍｍ角、１７０ｍｇ）で、このシートの表面を２０往復擦りつけ、２０分間放置した後、シート状態を観察して、次の評価基準で評価した。
○：シートの外観変形なし。
△：若干の外観変化あり。
×：溶剤に侵され、外観変化が大きい。
【００１７】
（２）高温エンボス性：
シートを凹凸の深度が２０μｍ、表面温度が１１０℃〜１５０℃のエンボスロールでエンボスを転写成形した時、シートの表面に深度が８０％以上を保持できる場合のエンボスロールの表面温度の最高値を測定した。
◎：１５０℃以上
○：１３０℃以上、１５０℃未満
△：１１０℃以上、１３０℃未満
×：１１０℃未満
【００１８】
（３）透明性（ヘーズ値）：
カレンダーで製造した厚さ０．３ｍｍのシートをＪＩＳ−Ｋ７１０５に準拠して、ヘーズ値を測定した。
○：ヘーズ値が５．０％未満
△：ヘーズ値が５．０％以上、１０．０％未満
×：ヘーズ値が１０．０％以上
【００１９】
実施例１
非晶質ポリエステル樹脂（イーストマンケミカル社製、商品名「ＰＥＴＧ６７６３」）９０重量％、高晶質ポリエステル樹脂としてポリブチレンテレフタレート樹脂（ポリプラスチック社製、商品名「６００ＦＰ」）１０重量％からなるポリエステル樹脂成分１００重量部に対して、滑剤として有機リン酸トリエステル化合物（川研ファインケミカル社製、商品名「ＬＴＰ−２」、（ポリオキシエチレンラウリルエーテル）リン酸トリエステル）１重量部およびフェノール系酸化防止剤１重量部を配合し、通常のカレンダー加工法により、厚さ０．３ｍｍの透明ポリエステル系樹脂シートを製造した。厚み精度およびカレンダー加工性は良好であった。
耐溶剤性、高温エンボス性および透明性の評価を表１に示す。
【００２０】
実施例２
非晶質ポリエステル樹脂（イーストマンケミカル社製、商品名「ＰＥＴＧ６７６３」）４０重量％、低晶質ポリエステル樹脂（イーストマンケミカル社製、商品名「ＰＣＴＧ」）４０重量％、高晶質ポリエステル樹脂としてポリブチレンテレフタレート樹脂（ポリプラスチック社製、商品名「６００ＦＰ」）２０重量％からなるポリエステル樹脂成分１００重量部に対して、滑剤として有機リン酸トリエステル化合物（川研ファインケミカル社製、商品名「ＬＴＰ−２」）１重量部およびフェノール系酸化防止剤１重量部を配合し、通常のカレンダー加工法により、厚さ０．３ｍｍの透明ポリエステル系樹脂シートを製造した。厚み精度およびカレンダー加工性は良好であった。
耐溶剤性、高温エンボス性および透明性の評価を表１に示す。
【００２１】
実施例３
非晶質ポリエステル樹脂（イーストマンケミカル社製、商品名「ＰＥＴＧ６７６３」）４０重量％、低晶質ポリエステル樹脂（イーストマンケミカル社製、商品名「ＰＣＴＧ」）３０重量％、高晶質ポリエステル樹脂としてポリブチレンテレフタレート樹脂（ポリプラスチック社製、商品名「６００ＦＰ」）３０重量％からなるポリエステル樹脂成分１００重量部に対して、滑剤として有機リン酸トリエステル化合物（川研ファインケミカル社製、商品名「ＬＴＰ−２」）１重量部およびフェノール系酸化防止剤１重量部を配合し、通常のカレンダー加工法により、厚さ０．３ｍｍの透明ポリエステル系樹脂シートを製造した。厚み精度およびカレンダー加工性は良好であった。
耐溶剤性、高温エンボス性および透明性の評価を表１に示す。
【００２２】
実施例４
非晶質ポリエステル樹脂（イーストマンケミカル社製、商品名「ＰＥＴＧ６７６３」）５０重量％、低晶質ポリエステル樹脂（イーストマンケミカル社製、商品名「ＰＣＴＡ」）２０重量％、高晶質ポリエステル樹脂としてポリエチレンテレフタレート樹脂（三菱レイヨン社製、商品名「ＭＡ５２１Ｈ」）３０重量％からなるポリエステル樹脂成分１００重量部に対して、滑剤として有機リン酸トリエステル化合物（川研ファインケミカル社製、商品名「ＬＴＰ−２」）１重量部およびフェノール系酸化防止剤１重量部を配合し、通常のカレンダー加工法により、厚さ０．３ｍｍの透明ポリエステル系樹脂シートを製造した。厚み精度およびカレンダー加工性は良好であった。
耐溶剤性、高温エンボス性および透明性の評価を表１に示す。
【００２３】
比較例１
非晶質ポリエステル樹脂（イーストマンケミカル社製、商品名「ＰＥＴＧ６７６３」）１００重量部に対して、滑剤として有機リン酸トリエステル化合物（川研ファインケミカル社製、商品名「ＬＴＰ−２」）１重量部およびフェノール系酸化防止剤１重量部を配合し、通常のカレンダー加工法により、厚さ０．３ｍｍの透明ポリエステル系樹脂シートを製造した。厚み精度およびカレンダー加工性は良好であった。
耐溶剤性、高温エンボス性および透明性の評価を表１に示す。
【００２４】
比較例２
上記の比較例１において、滑剤を有機リン酸ジエステル化合物（昭島化学工業社製、（ポリオキシエチレントリデシルエーテル）リン酸ジエステル）１重量部に置き換えたこと以外は、比較例１と同様にして通常のカレンダー加工法により、透明ポリエステル系樹脂シートを製造した。厚み精度およびカレンダー加工性は良好であった。
耐溶剤性、高温エンボス性および透明性の評価を表１に示す。
【００２５】
比較例３
上記の実施例１において、滑剤をモンタン酸ワックス（クラリアントジャパン社製）１重量部に置き換えたこと以外は、実施例１と同様にして通常のカレンダー加工法により、ポリエステル系樹脂シートを製造した。厚み精度およびカレンダー加工性は良好であった。
耐溶剤性、高温エンボス性および透明性の評価を表１に示す。
【００２６】
比較例４
非晶質ポリエステル樹脂（イーストマンケミカル社製、商品名「ＰＥＴＧ６７６３」）５０重量％、高晶質ポリエステル樹脂としてポリブチレンテレフタレート樹脂（ポリプラスチック社製、商品名「６００ＦＰ」）５０重量％からなるポリエステル樹脂成分１００重量部に対して、滑剤として有機リン酸トリエステル化合物（川研ファインケミカル社製、商品名「ＬＴＰ−２」）１重量部およびフェノール系酸化防止剤１重量部を配合し、通常のカレンダー加工法により、厚さ０．３ｍｍの透明ポリエステル系樹脂シートを製造した。厚み精度およびカレンダー加工性は良好であった。
耐溶剤性、高温エンボス性および透明性の評価を表１に示す。
【００２７】
【表１】
【発明の効果】
本発明のポリエステル系樹脂組成物は、カレンダーロールからの剥離性や、高温エンボスおよび耐溶剤性が良好であるので、カレンダー成形性に優れ、化粧シートや包装材などの用途に使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester-based resin composition having sufficient melt processability at the time of calender molding and extrusion molding, and more specifically, polyester excellent in peelability from a calender roll, transparency, embossing heat resistance and solvent resistance. The present invention relates to a resin composition.
[0002]
[Prior art]
Polyester as a surface material for furniture, furniture, doors, shelves, etc., or as a cosmetic sheet or office case used for the surface makeup of low-end electrical appliances such as a mouthpiece, a refrigerator, or a TV cabinet, or as a packaging material for food or pharmaceutical products. Applications of resin-based resin sheets are expanding.
Conventionally, these polyester resin sheets are generally formed by melting resin pellets and forming the sheet by extrusion. However, in the molding method by the above-described extrusion process, a sheet having a predetermined thickness is extruded from a T-die, and this is formed into a sheet by a cast roll controlled below the glass transition point. It cannot be said that the property is good.
[0003]
There is a defect that a sheet is produced from this polyester resin by calendering, and the produced sheet strongly adheres to a heat roll used during secondary processing such as heat laminating or heat embossing, which is disclosed in JP-A-11-343353. Describes that, when a sheet is formed by calendering, adhesion is suppressed by using a fatty acid ester lubricant to enable calendering.
However, since the melt viscosity is not so high even if a fatty acid ester lubricant is used, it is difficult to produce a relatively thin sheet of 0.05 to 0.2 mm or to perform secondary processing with high-temperature embossing or the like. There are drawbacks.
[0004]
[Problems to be solved by the invention]
The present invention is a polyester resin composition comprising a specific amorphous / low crystalline polyester resin as a main component, and by blending a specific resin or compound, the peelability from the calender roll and the emboss heat resistance Another object of the present invention is to provide a polyester resin composition capable of imparting solvent resistance.
[0005]
[Means for Solving the Problems]
The present invention is an amorphous material composed of a dicarboxylic acid component composed mainly of terephthalic acid and a diol component composed of 15 to 80 mol% 1,4-cyclohexanedimethanol and 20 to 85 mol% ethylene glycol. 100 parts by weight of a polyester resin component of 60 to 95% by weight of a low crystalline polyester resin and 5 to 40% by weight of at least one high crystalline polyester resin selected from polybutylene terephthalate resin and polyethylene telesterate resin On the other hand, a polyester-based resin composition comprising 0.1 to 3 parts by weight of an organic phosphate triester compound as a lubricant, wherein the organic phosphate triester compound is represented by the following formula: A polyester resin composition characterized by being a compound obtained from the above.
[R O (CH 2 CH 2 O) m ] 3 PO
(In the formula, R represents the same or different alkyl group or alkylaryl group having 10 to 22 carbon atoms, and m represents an integer of 1 to 10)
The organophosphate triester compound is added in an amount of 0.1 to 3 parts by weight, preferably 0.3 to 2.5 parts by weight, based on 100 parts by weight of the polyester resin component. When the blending amount is less than 0.1 parts by weight, the calendering processability and the workability at high temperature embossing are deteriorated, and when it exceeds 3 parts by weight, the transparency is deteriorated and the blowout to the sheet surface is large. This is not preferable because printability is impaired.
[0006]
When the transparency is not necessary, the core-shell type modifier 1 to 20 weights in which a vinyl monomer is graft-polymerized to the core portion of the rubber component to constitute the shell portion with respect to 100 weight parts of the polyester resin component. The polyester resin composition according to claim 1, wherein the polyester resin composition is formed by blending parts.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The amorphous / low crystalline polyester resin in the present invention comprises a dicarboxylic acid component whose main component is terephthalic acid, 15 to 80 mol% 1,4-cyclohexanedimethanol and 20 to 85 mol% ethylene glycol. A diol component, specifically, an amorphous polyester resin in which 1,4-cyclohexanedimethanol is about 30 mol%: trade names “PETG 6763” and “Provista” manufactured by Eastman Chemical Co., Ltd. Moreover, low crystalline polyester resins having a 1,4-cyclohexanedimethanol component of around 70 mol%: trade names “PCTG” and “PCTA” manufactured by Eastman Chemical Co., Ltd. can be mentioned.
[0008]
In the present invention, in addition to the above amorphous / low crystalline polyester resin, a high crystalline polyester resin is blended. Specific examples include polybutylene terephthalate resin and polyethylene terephthalate resin.
The blending ratio of the high crystalline polyester resin to the polyester resin component composed of the amorphous / low crystalline polyester resin and the high crystalline polyester resin is 5 to 40% by weight. it can.
If the blending ratio of the high crystalline polyester resin is less than 5% by weight, the improvement in solvent resistance is insufficient, and if it exceeds 40% by weight, crystallization occurs due to reheating of the sheet and transparency is impaired. Or the melt viscosity is lowered and the high temperature embossability is deteriorated.
[0010]
As a core-shell type modifier compounded as necessary, 100 parts by weight of the above-mentioned polyester resin component is a core-shell type modifier in which a vinyl monomer is graft-polymerized to the core part of the rubber component to form a shell part. 1 to 20 parts by weight can be blended with respect to.
Examples of the core part of the core-shell type modifier include acrylic rubber, olefin rubber, diene rubber, and acrylic-siloxane composite rubber. For example, the core-shell type modifier of acrylic rubber is representative. In particular, a vinyl monomer such as methyl methacrylate, acrylonitrile, or styrene is grafted onto a core portion made of an acrylic rubber obtained by polymerizing an acrylic ester such as butyl acrylate and a small amount of a crosslinking monomer, and a shell portion is formed. Constructed modifier, “HIA-80” manufactured by Kureha Chemical Co., Ltd., “Acryloid KM-330” manufactured by Rohm and Haas, “Metabrene W-300”, “Metabrene W-” manufactured by Mitsubishi Rayon Co., Ltd. Resin commercially available as “530” or the like is preferably used.
A core-shell type modifier for acrylic-siloxane composite rubber is obtained by graft polymerization of the above vinyl monomer on a core portion made of composite rubber made of acrylic polymer and polyorganosiloxane. It is commercially available as “Metabrene S2001” and “Metabrene SX006” manufactured by Rayon.
These core-shell type modifiers can impart lubricity to the resin composition and increase the melt viscosity, facilitating the transfer of the composition in a heated gel state, and providing a quantitative feed to the calender roll. The accuracy is increased, the sheet thickness accuracy is improved, and a sheet having excellent smoothness can be produced.
[0011]
If necessary, lubricants and acrylic processing aids other than the above-mentioned organophosphate triester compounds can be blended within a range that does not impair the performance of the present invention.
For example, acrylic processing aids include acrylic acid esters such as acrylic acid, methyl acrylate, ethyl acrylate, nbutyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, A copolymer having a weight average molecular weight of 1,000,000 to 5,000,000 based on a methacrylic acid ester such as n-butyl methacrylate, isobutyl methacrylate, or 2-ethylhexyl methacrylate is preferred. 551 "," Metabrene P-530A "," Kaneace PA-30 "," Kaneace PA-100 "manufactured by Kaneka Chemical Co., Ltd., and the like.
[0012]
The blending ratio of these acrylic processing aids is 10 parts by weight or less, preferably 0.5 to 8 parts by weight, more preferably 1 to 6 parts by weight with respect to 100 parts by weight of the polyester resin composition. can do. By blending, there is an effect that lubricity is imparted and melt viscosity is increased, and a thin and uniform surface property can be imparted.
[0013]
Furthermore, in the present invention, various additives conventionally added, for example, pigments, hindered amine light stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic and organic fillers, and compatibility. Resins and the like can be blended.
[0014]
The polyester resin composition of the present invention was prepared by mixing the above-mentioned resin component, organophosphate triester compound, and various additives as described above as required, respectively, and melt-kneading to adjust the raw materials. Thereafter, the sheet is produced by a normal calendering method. The roll temperature of the calendar is usually 165 to 190 ° C, preferably 175 to 185 ° C.
[0015]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to this. Each evaluation item and its evaluation were performed under the following conditions.
[0016]
(1) Solvent resistance:
A sheet of 0.3 mm thickness produced by a calender was cut into a size of 50 mm in width and 150 mm in length, and with absorbent cotton (about 30 mm square, 170 mg) containing 1 cc of each solvent shown in Table 1, The surface was rubbed back and forth 20 times and allowed to stand for 20 minutes, then the sheet state was observed and evaluated according to the following evaluation criteria.
○: No deformation of the appearance of the sheet.
Δ: Some change in appearance.
X: Attacked by the solvent and the appearance change is large.
[0017]
(2) High temperature embossability:
The maximum surface temperature of the embossing roll when the depth of the embossing roll can be maintained at 80% or more on the surface of the sheet when the embossing is transferred and molded with an embossing roll with an uneven depth of 20 μm and a surface temperature of 110 ° C. to 150 ° C. It was measured.
A: 150 ° C. or higher ○: 130 ° C. or higher, lower than 150 ° C. Δ: 110 ° C. or higher, lower than 130 ° C. x: lower than 110 ° C.
(3) Transparency (haze value):
A haze value was measured on a 0.3 mm thick sheet produced by a calender according to JIS-K7105.
○: Haze value is less than 5.0% Δ: Haze value is 5.0% or more and less than 10.0% ×: Haze value is 10.0% or more
Example 1
Polyester comprising 90% by weight of an amorphous polyester resin (trade name “PETG6763” manufactured by Eastman Chemical Co., Ltd.) and 10% by weight of polybutylene terephthalate resin (trade name “600FP” manufactured by Polyplastics Co., Ltd.) as a highly crystalline polyester resin. For 100 parts by weight of the resin component, 1 part by weight of an organic phosphate triester compound (manufactured by Kawaken Fine Chemical Co., Ltd., trade name “LTP-2”, (polyoxyethylene lauryl ether) phosphate triester) as a lubricant and a phenol type 1 part by weight of an antioxidant was blended, and a transparent polyester resin sheet having a thickness of 0.3 mm was produced by a normal calendering method. Thickness accuracy and calendar workability were good.
Table 1 shows the evaluation of solvent resistance, high temperature embossability and transparency.
[0020]
Example 2
As amorphous polyester resin (Eastman Chemical Co., trade name “PETG6763”) 40% by weight, low crystalline polyester resin (Eastman Chemical Co., trade name “PCTG”) 40% by weight, as high crystalline polyester resin For 100 parts by weight of a polyester resin component comprising 20% by weight of a polybutylene terephthalate resin (polyplastics, trade name “600FP”), an organophosphate triester compound (made by Kawaken Fine Chemicals, trade name “LTP”) is used as a lubricant. -2 ") 1 part by weight and 1 part by weight of a phenolic antioxidant were blended, and a transparent polyester resin sheet having a thickness of 0.3 mm was produced by an ordinary calendering method. Thickness accuracy and calendar workability were good.
Table 1 shows the evaluation of solvent resistance, high temperature embossability and transparency.
[0021]
Example 3
40% by weight of amorphous polyester resin (Eastman Chemical Co., trade name “PETG6763”), 30% by weight of low crystalline polyester resin (trade name “PCTG”, Eastman Chemical Co., Ltd.), as high crystalline polyester resin An organic phosphate triester compound (manufactured by Kawaken Fine Chemical Co., Ltd., trade name “LTP”) is used as a lubricant with respect to 100 parts by weight of a polyester resin component comprising 30% by weight of polybutylene terephthalate resin (polyplastics, trade name “600FP”). -2 ") 1 part by weight and 1 part by weight of a phenolic antioxidant were blended, and a transparent polyester resin sheet having a thickness of 0.3 mm was produced by an ordinary calendering method. Thickness accuracy and calendar workability were good.
Table 1 shows the evaluation of solvent resistance, high temperature embossability and transparency.
[0022]
Example 4
As amorphous polyester resin (Eastman Chemical Co., trade name “PETG6763”) 50% by weight, low crystalline polyester resin (Eastman Chemical Co., trade name “PCTA”) 20% by weight, as high crystalline polyester resin For 100 parts by weight of a polyester resin component comprising 30% by weight of a polyethylene terephthalate resin (trade name “MA521H” manufactured by Mitsubishi Rayon Co., Ltd.), an organophosphate triester compound (manufactured by Kawaken Fine Chemical Co., Ltd., trade name “LTP-”) is used. 2 ") 1 part by weight and 1 part by weight of a phenolic antioxidant were blended, and a transparent polyester resin sheet having a thickness of 0.3 mm was produced by an ordinary calendering method. Thickness accuracy and calendar workability were good.
Table 1 shows the evaluation of solvent resistance, high temperature embossability and transparency.
[0023]
Comparative Example 1
1 weight of organophosphate triester compound (trade name “LTP-2” manufactured by Kawaken Fine Chemical Co., Ltd.) as a lubricant with respect to 100 parts by weight of amorphous polyester resin (trade name “PETG6763” manufactured by Eastman Chemical Co., Ltd.) Part and 1 part by weight of a phenolic antioxidant were blended, and a transparent polyester resin sheet having a thickness of 0.3 mm was produced by an ordinary calendering method. Thickness accuracy and calendar workability were good.
Table 1 shows the evaluation of solvent resistance, high temperature embossability and transparency.
[0024]
Comparative Example 2
Comparative Example 1 was the same as Comparative Example 1 except that the lubricant was replaced with 1 part by weight of an organic phosphoric diester compound (Akishima Chemical Industry Co., Ltd., (polyoxyethylene tridecyl ether) phosphoric diester). A transparent polyester resin sheet was produced by an ordinary calendering method. Thickness accuracy and calendar workability were good.
Table 1 shows the evaluation of solvent resistance, high temperature embossability and transparency.
[0025]
Comparative Example 3
In Example 1 above, a polyester resin sheet was produced by the usual calendering method in the same manner as in Example 1 except that the lubricant was replaced with 1 part by weight of montanic acid wax (manufactured by Clariant Japan). Thickness accuracy and calendar workability were good.
Table 1 shows the evaluation of solvent resistance, high temperature embossability and transparency.
[0026]
Comparative Example 4
Polyester comprising 50% by weight of an amorphous polyester resin (made by Eastman Chemical Co., trade name “PETG6763”) and 50% by weight of a polybutylene terephthalate resin (made by Polyplastics, trade name “600FP”) as a highly crystalline polyester resin 1 part by weight of an organic phosphate triester compound (trade name “LTP-2”, manufactured by Kawaken Fine Chemical Co., Ltd.) and 1 part by weight of a phenolic antioxidant are blended as a lubricant with respect to 100 parts by weight of the resin component. A transparent polyester resin sheet having a thickness of 0.3 mm was produced by a calendering method. Thickness accuracy and calendar workability were good.
Table 1 shows the evaluation of solvent resistance, high temperature embossability and transparency.
[0027]
[Table 1]
【The invention's effect】
The polyester-based resin composition of the present invention is excellent in calendar moldability because it has excellent peelability from a calender roll, high-temperature embossing and solvent resistance, and can be used for applications such as decorative sheets and packaging materials. .
Claims (4)
該有機リン酸トリエステル化合物が、次式によって示される化合物であることを特徴とする。
〔ＲＯ（ＣＨ２ＣＨ２Ｏ）ｍ〕３ＰＯ
（式中、Ｒは、同一或いは異なる炭素数１０〜２２のアルキル基またはアルキルアリール基、ｍは１〜１０の整数を表す）Amorphous and low crystalline material composed of a dicarboxylic acid component composed mainly of terephthalic acid and a diol component composed of 15 to 80 mol% 1,4-cyclohexanedimethanol and 20 to 85 mol% ethylene glycol. A lubricant for 100 parts by weight of a polyester resin component of 60 to 95% by weight of a polyester resin and 5 to 40% by weight of at least one highly crystalline polyester resin selected from a polybutylene terephthalate resin and a polyethylene telesterate resin. A polyester-based resin composition comprising 0.1 to 3 parts by weight of an organic phosphate triester compound as
The organophosphate triester compound is a compound represented by the following formula:
[R O (CH 2 CH 2 O) m ] 3 PO
(In the formula, R represents the same or different alkyl group or alkylaryl group having 10 to 22 carbon atoms, and m represents an integer of 1 to 10)
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| JP2003020386A (en) * | 2001-07-10 | 2003-01-24 | Tsutsunaka Plast Ind Co Ltd | Method for manufacturing hot press molding noncrystalline polyester resin composition and noncrystalline polyester resin sheet |
| JP3988113B2 (en) * | 2001-09-10 | 2007-10-10 | 東洋紡績株式会社 | POLYESTER RESIN COMPOSITION FOR CALENDAR PROCESSING AND SHEET USING THE SAME |
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| US8071695B2 (en) | 2004-11-12 | 2011-12-06 | Eastman Chemical Company | Polyeste blends with improved stress whitening for film and sheet applications |
| KR101139130B1 (en) | 2004-12-20 | 2012-04-30 | 에스케이케미칼주식회사 | Blend of PET resin and transparent copolyester resin, preparing method thereof and articles using the same |
| KR101204136B1 (en) * | 2005-08-30 | 2012-11-22 | 에스케이케미칼주식회사 | Method for Preparing Profile Extruded Articles Using Copolyester Resin Composition |
| JP5271486B2 (en) * | 2006-08-16 | 2013-08-21 | 株式会社ブリヂストン | Release agent, method for forming concave / convex pattern using the same, method for producing optical information recording medium, and optical information recording medium |
| JP2008222995A (en) * | 2007-03-08 | 2008-09-25 | Okamoto Ind Inc | Pbt resin composition for calendering use |
| KR100903683B1 (en) * | 2007-12-27 | 2009-06-18 | 제일모직주식회사 | Chemical-resistant, impact-resistant, thermoplastic resin composition with excellent hydrolysis resistance |
| JP5886026B2 (en) * | 2011-12-20 | 2016-03-16 | 帝人デュポンフィルム株式会社 | Laminated film |
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