JP3953844B2 - Polybutylene terephthalate resin composition and molded product using the same - Google Patents

Description

【００２１】
その内でも特に２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−｛（ヘキシル）オキシ｝フェノール（チヌビン１５７７ＦＦ チバスペシャリティーケミカルズ社製）が市販されており、入手が容易であるので好ましい。
該紫外線吸収剤の配合量は、ＰＢＴと各種添加剤を合計した重量に対して０．０５〜４ｗｔ％である。０．０５ｗｔ％以下の添加量では、紫外線を照射したとき、短時間でｂ値が高くなり、樹脂が黄色く変色したのが目視でもわかるので、好ましくない。４ｗｔ％を越えると紫外線吸収剤自体で樹脂への着色が目立つようになり、各種着色し難くなるばかりではなく、成形品やフィルム表面にブリードアウトして粉吹き状態となり、好ましくない。さらに好ましい添加量としては０．１〜２ｗｔ％であり、より好ましくは０．２〜１ｗｔ％の範囲である。
紫外線吸収剤としては、上記のトリアジン系の他に、本発明の目的を損なわない範囲で、例えばベンゾトリアゾール系、ベンゾフェノン系、ベンゾエート系等と併用しても良い。しかし、トリアジン系以外のものが多く含まれると、樹脂と混合し、成形品を成形した時点で黄色着色が強くなって好ましくない。
【００２２】
本発明では、上記トリアジン系紫外線吸収剤とラクトン系熱安定剤を併用する。ラクトン系熱安定剤もそのもの自体が白色であり、ＰＢＴの色目に影響を与えない。また融点が比較的高く、主に２００℃以上で成形するＰＢＴに配合しやすい特徴がある。
本発明で使用するラクトン系熱安定剤は下記式２で示される構造式で表されるものが好ましい。
【００２３】
【化２】

【００２４】
具体例としては、３−ヒドロキシ−５，７−ジ−tert−ブチル−フラン−２−オンとｏ−キシレンの反応生成物等が上げられ、具体的にはＨＰ−１３６（チバスペシャリティーケミカルズ社製）が市販されており、入手が容易であるので好ましい。
該ラクトン系熱安定剤の配合量は０．０１〜３ｗｔ％である。添加量が０．０１ｗｔ％以下では、熱安定剤としての効果が小さく、紫外線照射時のｂ値の変化が大きくなってしまう。添加量が３ｗｔ％より多いと、成形品やフィルムの表面にブリードアウトして粉吹き状態となったり、原料コストが上がるので好ましくない。さらに好ましい添加量としては０．０５〜１ｗｔ％であり、より好ましい範囲としては０．０５〜０．５ｗｔ％である。
【００２５】
本発明に使用する熱安定剤は、前述のラクトン系熱安定剤のみでも十分であるが、更にフェノール系やリン系の熱安定剤を併用すると更に効果的である。フェノール系熱安定剤としては例えばペンタエルスリトールテトラキス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ’−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニルプロピオナミド］、オクタデシル−３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート、チオジエチレンビス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート］、ヘキサメチレンビス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート］、エチレンビス（オキシエチレン）ビス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート］、４，６−ビス（オクチルチオメチル）−ｏ−クレゾール、３，３’，３”，５，５’，５”−ヘキサ−tert−ブチル−ａ，ａ’，ａ”−（メシチレン−２，４，６−トリイル）トリ−ｐ−クレゾール、ベンゼンプロパン酸、３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシアルキルエステル等が挙げられる。特に好ましい物質としては、ペンタエリスリトールテトラキス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート、チオジエチレンビス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート］、ヘキサメチレンビス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート］が挙げられる。
【００２６】
本発明で使用するリン原子を含むリン系熱安定剤は、たとえばトリス（２，４−ジ−tert−ブチルフェニル）フォスファイト、ビス［２，４−ビス（１，１−ジメチルエチル）−６−メチルフェニル］エチルフォスファイト、テトラキス（２，４−ジ-tert-ブチルフェニル）［１，１−ビフェニル］−４，４−ジイルビスフォスファイト、ビス（２，４−ｔｅｒｔ−ブチルフェニル）ペンタエルスリトールジフォスファイト、トリス（モノノニルフェニル）フォスファイト等が挙げられる。特に好ましい物質としてはビス（２，４−ジ−tert−ブチルフェニル）フォスファイト、ビス（２，４−ｔｅｒｔ−ブチルフェニル）ペンタエルスリトールジフォスファイトが挙げられる。
ラクトン系、フェノール系、リン系、それぞれの熱安定剤の添加量は上記の範囲内であれば問題なく、特にそれぞれの量比に制限はない。好ましい配合比は前述添加剤の順番で、例えば１：２：３〜１：３：２であり、ラクトン系に対してその他のものが２〜３倍量を配合するのがよい。本発明においては、該熱安定剤としてラクトン系のものを使用すれば、リン系やフェノール系を添加しても着色がほとんど起こらない。ただし、フェノール系が多すぎると、その色が樹脂組成物中で目立つようになり、また、リン系が多すぎると、ＰＢＴがゲル化したり、分解したりして好ましくない。
【００２７】
上記紫外線吸収剤と熱安定剤をＰＢＴに添加する方法は、公知の方法が採用できる。すなわち所定量の紫外線吸収剤及び熱安定剤をＰＢＴに予めドライブレンドした後に直接成形するドライブレンド法；所定量の紫外線吸収剤及び熱安定剤をＰＢＴに添加した後、一旦２軸混練機等で混練しその後、直接成形する方法；一旦２軸混練したものをストランド状に押し出してカットし、ペレットとした後、成形する全練り法；紫外線吸収剤及び熱安定剤を高濃度に配合した後に、加圧ニーダー、バンバリーミキサー、１軸または２軸混練機を用いてＰＢＴに練り込んだ後、ペレット化し、その高濃度ペレット（マスターバッチ）を所定の濃度になるように成形時に希釈して使用するマスターバッチ法等が採用できる。
また紫外線吸収剤を重合時に配合したＰＢＴ（特開平１０−１５９９）、又は熱安定剤の一部を重合時に配合したＰＢＴを使用することもできる。
【００２８】
成形品を成形する際には、たとえばフィルムの場合は、前述の紫外線吸収剤と熱安定剤を配合した樹脂組成物を、１軸押出機にＴダイやインフレーションダイを結合させたフィルム成形機やカレンダーロールを用いて通常フィルム成形を行う。Ｔダイを結合させたフィルム成形機では、平面上のフィルムやシートが得られ、インフレーションダイを結合させた場合は、チューブ状のフィルムを成形することが出来る。インフレーション成形においては、溶融樹脂を吐出させた後に空気を吹き付けて冷却する空冷インフレーション法、水を直接かけて冷却する水冷インフレーション法のいずれも可能である。壁紙など、広い幅の平面上のフィルム成形品が必要な場合は、Ｔダイ成形法が好ましい。
【００２９】
射出成形する場合は、金型を用いて通常各種成形品を成形することが出来る。金型温度は特に制限はなく、成形サイクル、成形品の寸法、ソリ、外観等が最適化するように設定すればよい。
成形するに当たって、前述以外のヒンダードフェノール系、リン系、硫黄系やヒンダードアミン系の熱安定剤、着色のための染顔料、離型剤や結晶核剤としての無機や有機のフィラー類、可塑剤、難燃材を、樹脂組成物に配合したものを用いても良い。
また、得られた成形品は、必要に応じて印刷したり、塗装したり、他の材料、例えば他の樹脂フィルムやシート、紙、金属板等と積層するなど、複合化したりすることも可能である。
【００３０】
ＰＢＴは、ポリエステル樹脂であるので、通常は成形する前に熱風、真空、窒素雰囲気下等、適当な環境下で乾燥する。また押出機の種類によっては原料樹脂組成物を乾燥せず、押出機で溶融押出しながら、途中に真空ベントを設置することで、事前乾燥に替えることもできる。
このような本発明の樹脂組成物を用いた成形品は、紫外線照射前に色差計で測定したときのｂ値が５以下であるのが好ましい。ｂ値は青色〜黄色への色を評価する項目で、数値が大きくなると黄色みを帯びてくる。ｂ値が５以上であるとかなり黄色みが有ることを示し、着色する際、特に白系統の色への着色が困難となるので好ましくない。特に、純白に近い着色を行うためにはｂ値が４以下であるのが好ましい。
【００３１】
得られた成形品は、紫外線での変色が少なく、室内や屋外で使用する壁紙や表面部材として好適である。紫外線による変色については促進試験としてウエザーメーターと呼ばれる評価装置で、通常より強い紫外線を照射して、促進試験を行うことで確認できる。ウエザーメーターでの紫外線照射試験条件は、用途によって様々ではあるが、建材の耐紫外線性評価の条件としては、ブラックパネル温度：６３℃、１０２分紫外線照射、１８分暗黒で雨のトータル１２０分の周期で連続的に紫外線照射と雨、暗黒を繰り返す試験が一般的である。この条件で、耐紫外線性照射試験２００時間を行って、ｂ値が１０以下であるのがより好ましい。ｂ値が１０より大きくては、黄色みが強く、例えば壁紙などにした場合、短時間で壁が黄変して見苦しくなり、好ましくない。更に長期に使用される用途では、前述条件で紫外線照射をした後のｂ値は８以下がより好ましい。
【００３２】
【実施例】
以下、実施例により本発明を更に詳細に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。
［使用したＰＢＴ樹脂］
ＰＢＴ−１：ＩＶ値１．２５、融点２２４℃、ホモＰＢＴ樹脂、ガラス転移温度８０℃（商品名：ＮＯＶＡＤＵＲＡＮ（登録商標）５０２０Ｓ 三菱エンジニアリングプラスチックス（株）製品）
ＰＢＴ−２：ＩＶ値１．１５、融点２２２℃、ジオール成分の１０ｗｔ％が分子量１０００のポリブチレングリコールである共重合ＰＢＴ樹脂、ガラス転移温度５８℃（商品名：ＮＯＶＡＤＵＲＡＮ（登録商標）５５０５Ｓ 三菱エンジニアリングプラスチックス（株）製品）
ＰＢＴ−３：ＩＶ値１．３０、融点２１９℃、ジオール成分の２０ｗｔ％が分子量１０００のポリブチレングリコールである共重合ＰＢＴ樹脂、ガラス転移温度２２℃（商品名：ＮＯＶＡＤＵＲＡＮ（登録商標）５５１０Ｓ 三菱エンジニアリングプラスチックス（株）製品）
【００３３】
［使用した紫外線吸収剤］
ＵＶ−１：トリアジン系紫外線吸収剤 ２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）オキシ］−フェノール（商品名；チヌビン１５７７ＦＦ、チバスペシャリティーケミカルズ社製品）
ＵＶ−２：トリアゾール系紫外線吸収剤 ２−（２Ｈベンゾトリアゾール−２−イル）−４，６−ビス（１−メチル−１−フェニルエチル）フェノール（商品名；チヌビン２３４、チバスペシャリティーケミカルズ社製品）
【００３４】
［使用した熱安定剤］
熱安１：３ーヒドロキシ−５，７−ジ−ｔｅｒｔ−ブチル−フラン−２−オンとｏ−キシレンの反応生成物（ラクトン系、商品名；ＨＰ−１３６、チバスペシャリティーケミカルズ社製品）
熱安２：ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］（商品名；ＩＲＧＡＮＯＸ１０１０、チバスペシャリティ−ケミカルズ社製品）
熱安３：トリス（２、４ージーｔｅｒｔ−ブチルフェニル）フォスファイト（商品名：ＩＲＧＡＦＯＳ１６８、チバスペシャリティーケミカルズ社製品）
熱安４：熱安１＝１５ｗｔ％、熱安２＝２８．３ｗｔ％、熱安３＝５６．７ｗｔ％の混合物（商品名：ＩＲＧＡＮＯＸ ＨＰ２２１５ＦＦ、チバスペシャリティーケミカルズ社製品）
【００３５】
実施例１〜８、比較例１〜５
紫外線吸収剤：ＵＶ−１、ＵＶ−２、熱安定剤：熱安１、熱安２、熱安３は、それぞれ別々にＰＢＴ−２に５ｗｔ％添加してドライブレンドしたあと、２軸押出機（ＴＥＸ３０−ＨＣＴ 日本製鋼社製）で樹脂温２６０℃でコンパウンドした後、ペレット化し、それぞれ添加剤濃度５ｗｔ％の高濃度マスターバッチを作製した。
この高濃度マスターバッチを使用し、下記表１及び表２に示すように、成形時の樹脂組成物中の添加剤濃度が、表に示した所定量になるよう、各々所定の使用樹脂（ＰＢＴ−１、ＰＢＴ−２、ＰＢＴ−３）で希釈した樹脂組成物を用い、下記の条件で成形した。
（成形条件）
ＡＳＴＭ１号引張試験用ダンベルをＪ７５ＥＤ（日本製鋼社製）を用いて、シリンダー設定温度２６０℃、樹脂温２６５℃、金型温度８０℃の条件、成形サイクル５０秒で成形した。
紫外線照射試験はスガ試験機（株）社製サンシャインスーパーロングライフウエザーメーター 商品名：ＷＥＬ−ＳＵＮ−ＤＣ型を使ってブラックパネル温度６３℃、１２０分サイクル（うち雨１８分）の条件で紫外線照射試験を行った。色の変化は日本電色工業社製スペクトロカラーメーター 商品名：ＳＥ２０００を用いて、紫外線照射前後の引張試験片の中央部付近で色（ｂ値）を測定し、その変化について表１、表２にまとめて示した。
【００３６】
【表１】

【００３７】
【表２】

【００３８】
実施例９
実施例８の樹脂組成物を用いて、以下の条件で厚み７０μｍのフィルムを作製した。作製したフィルムを１０ｃｍ角の鋼板にエポキシ系接着剤を用いて貼り付け、紫外線照射試験を行った。紫外線照射前のｂ値は３．０であり、２００時間紫外線照射後のｂ値は７．５であった。
（フィルム成形条件）
押出機（口径４０ｍｍφ、Ｌ／Ｄ＝２５の単軸押出機、ＦＳ４０−２５、池貝社製品）の先端に、コートハンガータイプＴダイ（幅６００ｍｍ）を取り付け、シリンダー設定温度２５０〜２６０℃、ダイス設定温度２６０℃、冷却ロール温度４０℃の条件で、単層フィルムをキャスト法により作製した。
【００３９】
【発明の効果】
１．トリアジン系紫外線吸収剤とラクトン系熱安定剤を併用したポリブチレンテレフタレート系樹脂組成物は、この樹脂組成物から得られる成形品は、初期のｂ値が小さく、白い成形品の製造が可能である（実施例１〜実施例３、比較例５）。
２．トリアジン系紫外線吸収剤とラクトン系熱安定剤を併用したポリブチレンテレフタレート系樹脂組成物は、この樹脂組成物から得られる成形品は、紫外線照射後のｂ値変化が小さく、長期間光に曝される部品（製品）、壁紙などの製造用に使用しても、部品の黄変が少なく、良好なものが得られる（実施例１〜実施例３、比較例１）。
３．ポリブチレンテレフタレート系樹脂組成物には、トリアジン系紫外線吸収剤とラクトン系熱安定剤に、更にフェノール系やリン系の熱安定剤を添加すると、この樹脂組成物から得られる成形品は、更に紫外線照射後のｂ値変化が小さく、より白い状態を保つことが出来る（実施例４〜実施例６、実施例８）。
４．ポリブチレンテレフタレート系樹脂組成物に、トリアジン系紫外線吸収剤を多量に添加すると、この樹脂組成物から得られる成形品は、紫外線照射前のｂ値が高く、黄色くなるばかりでなく、成形品表面に滲み出てきて粉吹き状態となり、実用に耐えられなくなる（比較例３）。[0001]
BACKGROUND OF THE INVENTION
The present invention is such that the color of the resin composition itself is close to white so that it is easy to color the molded product in a desired color tone, and the discoloration with respect to light including the ultraviolet region such as sunlight and fluorescent lamps is small. Resin molded products (especially films) used for interior and exterior decorative panels and various parts with reduced behavior of discoloration when used in an environment exposed to light over a long period of time The present invention relates to a polybutylene terephthalate resin composition for producing the same.
[0002]
[Prior art]
Conventionally, polyvinyl chloride, polycarbonate, modified polyphenylene ether, and the like have been frequently used as interior and exterior resin component materials that cannot be replaced over a long period of time once they are constructed. These resins are inexpensive, can improve UV resistance relatively easily, and because the surface appearance of the molded product can be molded beautifully, they are particularly frequently used as parts that are exposed to normal light, called external parts, and are exposed to the human eye. It has been.
[0003]
Of these materials, vinyl chloride has been widely used as wallpaper, flooring, and the like because it is flexible and has good scratch resistance. However, in recent years, it has not been used as an interior material in particular as a toxic gas generation problem at the time of disposal and incineration and a toxic gas generation substance at the time of fire. Also, polycarbonate and modified polyphenylene ether (m-PPE) are non-crystalline resins, and their chemical resistance is inferior to crystalline resins, so kitchens that use alcohol or hypochlorous acid chemicals for cleaning or sterilization purposes There were problems that could not be used in laboratories and food production sites.
[0004]
Of the crystalline resins with high hygiene and chemical resistance, wallpaper and flooring using olefin resins such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer are partly put into practical use. Since the surface resin has low surface hardness and poor scratch resistance, it can be damaged by touching something, especially on wallpaper, etc., and the appearance may be deteriorated or the adhesion to other materials may be poor. However, they were easily peeled off during cutting and bending, or peeled off immediately from the wall or floor after construction.
[0005]
Cellulose-based paper turns yellow easily with ultraviolet rays, but burns easily, and in places where many people come and go and live, such as housing complexes, schools, hospitals, and offices. Use has been a material that is difficult to say.
A polybutylene terephthalate resin blended with an ultraviolet absorber having a triazine skeleton is described in, for example, JP-A No. 10-1599. This technique is a method in which an ultraviolet absorber is charged into a polymerization can together with a monomer during polymerization and reacted. This method is excellent in production efficiency, but is not suitable for small-quantity production of other varieties when the polymerization can is time-consuming and coloring is performed. Further, it is not preferable because it is scattered in a high-temperature vacuum environment at the time of polycondensation and the amount of the UV-absorbing material in the resulting polymer is not constant. Furthermore, in this publication, the result after the UV exposure test for ΔE, which is a comprehensive color change, is described. From this result, the b value (blue to yellow / the larger the value, the stronger the yellowness). ) Is not disclosed and cannot be predicted.
In addition, in JP-A-10-306209, there is no description of using a triazine-based ultraviolet absorber and a lactone-based heat stabilizer in combination with a polybutylene terephthalate-based resin, and there is no suggestion of the effect in that case. There is no disclosure of data about the color before the ultraviolet irradiation test, and there is no technical idea of making the color of the resin before the ultraviolet irradiation test as close to white as possible.
[0006]
[Problems to solve the problem]
  An object of the present invention is to provide a molded article produced from a polybutylene terephthalate resin composition.The initial color is close to white, has good chemical resistance and scratch resistance, and has little yellow discoloration when exposed to ultraviolet rays over a long period of time, and does not generate toxic gas even in the event of fire or incinerationPolybutylene terephthalate-based resin composition from which a molded product exhibiting characteristics can be obtainedTo provideIt is in.
[0007]
[Means for Solving the Problems]
  In order to achieve the above object, the present invention has been repeatedly studied, and when a specific ultraviolet absorber is blended with a polybutylene terephthalate resin, the b value indicating that the color has changed to yellow in particular, the initial color tone immediately after the blending It was found to be low enough to show that it is close to white, and that the change in b value can be kept small over a long period of time.CompleteIt came to. That is, the gist of the present invention is that a polybutylene terephthalate resin having a glass transition temperature of 0 ° C. to 85 ° C. measured by a dynamic viscoelastic method and an ultraviolet absorber 0.05 to 4 having a triazine skeleton.% By weight (wt%)Lactone heat stabilizer 0.01-3wt%TheIncludingMukoAnd featuresThatThe present invention resides in a ribylene terephthalate resin composition and a molded article produced from this composition.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The polybutylene terephthalate resin (hereinafter abbreviated as PBT) used in the present invention comprises terephthalic acid and / or an ester derivative thereof as a dicarboxylic acid, and a diol component having 1,4-butanediol as a main component as a diol component. The starting material is obtained by condensation polymerization, and the glass transition temperature measured by the dynamic viscoelastic method is 0 ° C to 85 ° C.
[0009]
Specific examples of the dicarboxylic acid component other than terephthalic acid and / or its ester derivative component (hereinafter abbreviated as terephthalic acid component) used as a raw material of the PBT include, for example, phthalic acid, isophthalic acid, 4,4′- Diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,6-naphthalene dicarboxylic acid Aromatic dicarboxylic acids such as acids, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. Bonn acid and / or the like of these ester derivatives.
[0010]
In addition to the dicarboxylic acid component, for example, hydroxycarboxylic acids such as glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid, etc. And alkoxycarboxylic acids, and monofunctional components such as stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, and benzoylbenzoic acid, or ester derivatives thereof, tricarballylic acid, trimellitic acid, trimesic acid, pyro Trifunctional or higher polyfunctional components such as merit acid, gallic acid, trimethylol ethane, trimethylol propane, glycerol, pentaerythritol, or one or two or more ester derivatives thereof may be used as the copolymer component.
[0011]
As the other diol component of PBT, 1,4-butanediol is the main component, and other diol components include, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propane. Diol, polytetramethylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, aliphatic diol such as 1,8-octanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol and other alicyclic diols, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, bis (4-Hydro Shifeniru) aromatic diol such as sulfone and the like.
[0012]
These dicarboxylic acid components and diol components are used in combination with the terephthalic acid component and 1,4-butanediol, which are the main components, and two or more types may be used simultaneously. The PBT of the present invention is essentially composed of a homo PBT composed essentially of a terephthalic acid component and 1,4-butanediol, or a dicarboxylic acid component composed of terephthalic acid and / or an ester derivative thereof, and 1,4-butanediol. A polycondensate of a diol component comprising a mixture of two or more diols, a dicarboxylic acid component comprising two or more dicarboxylic acid mixtures mainly comprising terephthalic acid and / or an ester derivative thereof, and 1,4-butanediol A polycondensate of a diol component composed of a mixture of two or more diols containing as a main component is preferred.
[0013]
The amount of terephthalic acid and / or its ester derivative, 1,4-butanediol, and the dicarboxylic acid component and / or its ester derivative and diol component used in combination with these, depends on the dynamic viscosity of the copolymer PBT obtained. The glass transition temperature measured by the elastic method is appropriately selected in such an amount that it is in the range of 0 to 85 ° C. From the viewpoint of chemical resistance and ultraviolet resistance, terephthalic acid and / or its ester derivative is 50% by weight or more of the dicarboxylic acid component, and 1,4-butanediol is 50% by weight or more of the diol component. Is desirable.
The melt viscosity of PBT is not particularly limited, but considering the ease of film forming, 250 ° C., shear rate 91.2 (1 / second), nozzle diameter 1 mmφ, nozzle flow path length 30 mm (L / D = 30) The melt viscosity measured under the condition of 400 to 2500 Pa · s is preferable, and 600 to 1300 Pa · s is more preferable.
[0014]
The manufacturing method of PBT used by this invention is not specifically limited, Basically, the conventional manufacturing method of polybutylene terephthalate-type resin is employable. That is, the dicarboxylic acid component mainly composed of terephthalic acid and / or an ester derivative thereof and the diol component mainly composed of 1,4-butanediol are esterified in one or a plurality of esterification reaction vessels. In the presence of the reaction catalyst, the temperature is usually 150 to 280 ° C., preferably 180 to 265 ° C., usually 50 to 1000 torr (6666 to 133322 Pa), preferably 70 to 760 torr (9333 to 101325 Pa), with stirring. The esterification reaction is carried out for 2 to 5 hours, and the resulting oligomer as an esterification reaction product is transferred to a polycondensation reaction tank, and usually in the presence of a polycondensation reaction catalyst in one or a plurality of polycondensation reaction tanks. 210 to 280 ° C, preferably 220 to 265 ° C, usually 200 torr (26664 Pa) or less, Mashiku in the following reduced pressure 150torr (19998Pa), thereby 2-5 hours polycondensation reaction under stirring. The reaction mode may be any of continuous type, semi-continuous type, or batch type. In addition, the resin obtained by the polycondensation reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die and extracted into a strand shape, cooled with water, or after being cooled with water and cut with a cutter to form a pellet. It is a granular material such as a chip.
[0015]
As an esterification reaction catalyst, at least a titanium compound is used, for example, titanium alcoholate such as tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, titanium phenolate such as tetraphenyl titanate, etc. For example, in the case of tetrabutyl titanate, the amount used is usually 30 to 300 ppm, preferably 50 to 200 ppm as titanium atoms with respect to the theoretical yield of the polybutylene terephthalate resin. In addition to the titanium compound, for example, a tin compound, a magnesium compound, a calcium compound, a zirconium compound, or the like can be used as the esterification reaction catalyst.
[0016]
As the polycondensation reaction catalyst, it is not necessary to add a new catalyst by using the esterification reaction catalyst added at the time of esterification reaction as the polycondensation reaction catalyst, but the esterification reaction added at the time of esterification reaction. The same catalyst as the catalyst may be further added, and the amount used is, for example, in the case of tetrabutyl titanate, usually 300 ppm or less, preferably 150 ppm or less as a titanium atom with respect to the theoretical yield of polybutylene terephthalate resin. is there. Further, for example, an antimony compound such as antimony trioxide or a germanium compound such as germanium dioxide or germanium tetroxide different from the esterification reaction catalyst added during the esterification reaction may be added.
[0017]
In the esterification reaction or / and polycondensation reaction, in addition to the catalyst, orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphorus compounds such as esters and metal salts thereof, sodium hydroxide, benzoic acid, etc. Reaction aids such as alkali metal or alkaline earth metal compounds such as sodium acid, magnesium acetate, calcium acetate, 2,6-di-t-butyl-4-octylphenol, pentaerythrityl-tetrakis [3- (3 ′, 5′-t-butyl-4′-hydroxyphenyl) propionate] and other thioether compounds such as dilauryl-3,3′-thiodipropionate and pentaerythrityl-tetrakis (3-laurylthiodipropionate) , Triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butyl) Antioxidants such as phosphorous compounds such as ruphenyl) phosphite, paraffin wax, microcrystalline wax, polyethylene wax, long-chain fatty acids represented by montanic acid and montanic acid esters, and release agents such as silicone oil Other additives may be present.
[0018]
The esterification reaction tank may be, for example, a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower type continuous reaction tank, or the like. It is good also as multiple tanks which connected the tank of this in series. Further, the polycondensation reaction tank may be of any type such as a vertical stirring polymerization tank, a horizontal stirring polymerization tank, a thin film evaporation type polymerization tank, and the like or different tanks as a single tank. It is good also as a plurality of tanks in series.
[0019]
The ultraviolet absorber used in the present invention must be triazine-based. A triazine-based ultraviolet absorber having a high melting point of 100 ° C. or higher.
This is because the bite is stable because there is no melting near the screw feed portion during compounding or molding. In addition, triazine-based ultraviolet absorbers are less colored themselves and have little effect on the color of the resin when blended with the resin. In ordinary white PBT, the white color is hardly changed, and various colors can be obtained. In this case, it is easy to adjust the color, which is particularly desirable for white goods.
The triazine-based ultraviolet absorber used in the present invention preferably has a structure represented by the following formula 1.
[0020]
[Chemical 1]

[0021]
Among them, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-{(hexyl) oxy} phenol (Tinuvin 1577FF manufactured by Ciba Specialty Chemicals) is commercially available. It is preferable because it is easily available.
The blending amount of the ultraviolet absorber is 0.05 to 4 wt% with respect to the total weight of PBT and various additives. An addition amount of 0.05 wt% or less is not preferable because the b value is increased in a short time when the ultraviolet rays are irradiated, and it can be seen visually that the resin has turned yellow. If it exceeds 4 wt%, the resin is noticeably colored by the ultraviolet absorber itself, and various colors are difficult to color. A more preferable addition amount is 0.1 to 2 wt%, and more preferably 0.2 to 1 wt%.
As the ultraviolet absorber, in addition to the above triazine, it may be used in combination with, for example, a benzotriazole, a benzophenone, a benzoate or the like as long as the object of the present invention is not impaired. However, it is not preferable that a large amount other than triazine is contained because yellow coloring becomes strong at the time of mixing with the resin and molding the molded product.
[0022]
In the present invention, the above triazine ultraviolet absorber and a lactone heat stabilizer are used in combination. Lactone heat stabilizers themselves are white and do not affect the color of PBT. In addition, it has a relatively high melting point and is easily blended with PBT molded mainly at 200 ° C. or higher.
The lactone heat stabilizer used in the present invention is preferably one represented by the structural formula shown by the following formula 2.
[0023]
[Chemical 2]

[0024]
Specific examples include a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Specifically, HP-136 (Ciba Specialty Chemicals Co., Ltd.) Manufactured) is commercially available and is easy to obtain.
The amount of the lactone heat stabilizer is 0.01 to 3 wt%. When the addition amount is 0.01 wt% or less, the effect as a heat stabilizer is small, and the change of the b value at the time of ultraviolet irradiation becomes large. When the addition amount is more than 3 wt%, it is not preferable because it bleeds out on the surface of the molded product or film and powder is blown, or the raw material cost increases. A more preferable addition amount is 0.05 to 1 wt%, and a more preferable range is 0.05 to 0.5 wt%.
[0025]
As the heat stabilizer used in the present invention, only the above-mentioned lactone-based heat stabilizer is sufficient, but it is more effective when a phenol-based or phosphorus-based heat stabilizer is used in combination. Examples of the phenol-based heat stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,6-bis (octylthiomethyl) -o Cresol, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, benzene And propanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxyalkyl ester, etc. A particularly preferred substance is pentaerythritol tetrakis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].
[0026]
Examples of the phosphorus-based heat stabilizer containing a phosphorus atom used in the present invention include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6. -Methylphenyl] ethyl phosphite, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4-diylbisphosphite, bis (2,4-tert-butylphenyl) penta Examples include erythritol diphosphite and tris (monononylphenyl) phosphite. Particularly preferred materials include bis (2,4-di-tert-butylphenyl) phosphite and bis (2,4-tert-butylphenyl) pentaerythritol diphosphite.
The addition amount of each of the lactone type, phenol type, and phosphorus type heat stabilizers is not a problem as long as it is within the above range, and the amount ratio of each is not particularly limited. A preferable blending ratio is, for example, 1: 2: 3 to 1: 3: 2 in the order of the above-mentioned additives. In the present invention, if a lactone type is used as the heat stabilizer, coloration hardly occurs even if a phosphorus type or phenol type is added. However, if the phenolic type is too much, the color becomes conspicuous in the resin composition, and if the phosphorus type is too much, the PBT is gelled or decomposed.
[0027]
As a method of adding the ultraviolet absorber and the heat stabilizer to the PBT, a known method can be adopted. That is, a dry blend method in which a predetermined amount of an ultraviolet absorber and a heat stabilizer are previously dry-blended with a PBT and then directly molded; after a predetermined amount of an ultraviolet absorber and a heat stabilizer is added to the PBT, once in a biaxial kneader or the like A method of kneading and then directly molding; a biaxially kneaded one extruded into strands, cut into pellets, and then molded into a whole kneading method; after blending a high concentration of UV absorber and heat stabilizer, Kneaded into PBT using a pressure kneader, Banbury mixer, uniaxial or biaxial kneader, then pelletized, and the high-concentration pellets (masterbatch) are diluted at the time of molding to a predetermined concentration and used. A master batch method can be employed.
Moreover, PBT which mix | blended the ultraviolet absorber at the time of superposition | polymerization (Unexamined-Japanese-Patent No. 10-1599) or PBT which mix | blended a part of heat stabilizer at the time of superposition | polymerization can also be used.
[0028]
When molding a molded article, for example, in the case of a film, a film molding machine in which a T-die or an inflation die is bonded to a single-screw extruder using a resin composition containing the above-described ultraviolet absorber and heat stabilizer, Usually, film forming is performed using a calender roll. In a film forming machine to which a T-die is bonded, a flat film or sheet is obtained. When an inflation die is bonded, a tubular film can be formed. In the inflation molding, any of an air-cooled inflation method in which air is blown to cool after discharging a molten resin and a water-cooled inflation method in which water is directly cooled to cool can be used. The T-die molding method is preferable when a film molded product on a wide plane such as wallpaper is required.
[0029]
In the case of injection molding, various molded products can usually be molded using a mold. The mold temperature is not particularly limited, and may be set so that the molding cycle, the dimension of the molded product, the warp, the appearance, and the like are optimized.
In molding, hindered phenol, phosphorus, sulfur and hindered amine heat stabilizers other than those described above, dyes and pigments for coloring, inorganic and organic fillers as mold release agents and crystal nucleating agents, plasticizers A flame retardant mixed with a resin composition may be used.
In addition, the obtained molded product can be combined as required by printing, painting, or laminating with other materials such as other resin films, sheets, paper, metal plates, etc. It is.
[0030]
Since PBT is a polyester resin, it is usually dried in a suitable environment such as hot air, vacuum or nitrogen atmosphere before molding. Depending on the type of the extruder, the raw resin composition may not be dried, but may be replaced with pre-drying by installing a vacuum vent in the middle while melt-extruding with the extruder.
Such a molded article using the resin composition of the present invention preferably has a b value of 5 or less when measured with a color difference meter before ultraviolet irradiation. The b value is an item for evaluating the color from blue to yellow, and becomes yellowish as the value increases. If the b value is 5 or more, it indicates that there is a considerable yellowishness, and when coloring, it is particularly difficult to color white color, which is not preferable. In particular, the b value is preferably 4 or less in order to perform coloring close to pure white.
[0031]
The obtained molded article has little discoloration by ultraviolet rays and is suitable as a wallpaper or a surface member used indoors or outdoors. Discoloration due to ultraviolet rays can be confirmed by performing an accelerated test by irradiating ultraviolet rays stronger than usual with an evaluation device called a weather meter as an accelerated test. The conditions of UV irradiation test using a weather meter vary depending on the application, but the conditions for evaluating the UV resistance of building materials are as follows: Black panel temperature: 63 ° C, 102 minutes UV irradiation, 18 minutes dark, total 120 minutes of rain In general, the test repeats UV irradiation, rain, and darkness continuously in a cycle. Under these conditions, the UV resistance irradiation test is conducted for 200 hours, and the b value is more preferably 10 or less. If the b value is larger than 10, the yellowness is strong. For example, when the wallpaper is used, the wall turns yellow in a short time and becomes unsightly. In applications that are used for a longer period of time, the b value after UV irradiation under the aforementioned conditions is more preferably 8 or less.
[0032]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.
[PBT resin used]
PBT-1: IV value 1.25, melting point 224 ° C., homo PBT resin, glass transition temperature 80 ° C. (trade name: NOVADURAN (registered trademark) 5020S manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
PBT-2: Copolymerized PBT resin having an IV value of 1.15, a melting point of 222 ° C., and a polybutylene glycol having a molecular weight of 10 wt% of a diol component, glass transition temperature of 58 ° C. (trade name: NOVADURAN® 5505S Mitsubishi Engineering) Plastics products)
PBT-3: Copolymer PBT resin having an IV value of 1.30, a melting point of 219 ° C., and a polybutylene glycol having a molecular weight of 20 wt% of the diol component, glass transition temperature of 22 ° C. (trade name: NOVADURAN® 5510S Mitsubishi Engineering) Plastics products)
[0033]
[Used UV absorber]
UV-1: Triazine-based UV absorber 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (trade name; Tinuvin 1577FF, Ciba Specialty Tea Chemicals products)
UV-2: Triazole-based UV absorber 2- (2Hbenzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (trade name; Tinuvin 234, product of Ciba Specialty Chemicals )
[0034]
[Thermal stabilizer used]
Hotan 1: Reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (lactone type, trade name: HP-136, product of Ciba Specialty Chemicals)
Hotan 2: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name; IRGANOX 1010, product of Ciba Specialty Chemicals)
Hotan 3: Tris (2, 4-ji tert-butylphenyl) phosphite (trade name: IRGAFOS168, Ciba Specialty Chemicals product)
Heat-an 4: Heat-an 1 = 15 wt%, Heat-an 2 = 28.3 wt%, Heat-an 3 = 56.7 wt% (trade name: IRGANOX HP2215FF, Ciba Specialty Chemicals product)
[0035]
Examples 1-8, Comparative Examples 1-5
UV absorbers: UV-1, UV-2, heat stabilizers: heat-an 1, heat-an 2 and heat-an 3 were each separately added to PBT-2 by 5 wt% and dry blended, then a twin screw extruder (TEX30-HCT manufactured by Nippon Steel Co., Ltd.) was compounded at a resin temperature of 260 ° C. and then pelletized to prepare high concentration master batches each having an additive concentration of 5 wt%.
Using this high-concentration masterbatch, as shown in Tables 1 and 2 below, each of the predetermined resins used (PBT) was used so that the additive concentration in the resin composition at the time of molding would be the predetermined amount shown in the table. -1, PBT-2, PBT-3) and molded under the following conditions.
(Molding condition)
An ASTM No. 1 tensile test dumbbell was molded using a J75ED (manufactured by Nippon Steel Co., Ltd.) under the conditions of a cylinder set temperature of 260 ° C., a resin temperature of 265 ° C., a mold temperature of 80 ° C., and a molding cycle of 50 seconds.
Ultraviolet irradiation test was conducted by Suga Test Instruments Co., Ltd. Sunshine Super Long Life Weather Meter Product name: WEL-SUN-DC type, black panel temperature 63 ° C, 120 minutes cycle (including rain 18 minutes) A test was conducted. The color change is a spectro color meter manufactured by Nippon Denshoku Industries Co., Ltd. Product name: SE2000 is used to measure the color (b value) near the center of the tensile test piece before and after UV irradiation. Are summarized in
[0036]
[Table 1]

[0037]
[Table 2]

[0038]
Example 9
Using the resin composition of Example 8, a film having a thickness of 70 μm was produced under the following conditions. The produced film was attached to a 10 cm square steel plate using an epoxy adhesive, and an ultraviolet irradiation test was conducted. The b value before UV irradiation was 3.0, and the b value after 200 hours UV irradiation was 7.5.
(Film forming conditions)
A coat hanger type T die (width 600mm) is attached to the tip of an extruder (single screw extruder with a caliber of 40mmφ, L / D = 25, FS40-25, product of Ikegai Co., Ltd.). A single layer film was produced by a casting method under conditions of a set temperature of 260 ° C. and a cooling roll temperature of 40 ° C.
[0039]
【The invention's effect】
1. A polybutylene terephthalate resin composition using a triazine UV absorber and a lactone heat stabilizer in combination,Molded products obtained from this resin composition are:initialofb value is small, white molded productManufacturing(Examples 1 toExample3, Comparative Example 5).
2. A polybutylene terephthalate resin composition using a triazine UV absorber and a lactone heat stabilizer in combination,Molded products obtained from this resin composition are:Parts with small change in b value after UV irradiation and exposed to light for a long time(Product), Wallpaper, etc.Used for manufacturingIn addition, the yellowing of the parts is small and good ones can be obtained (Examples 1 toExample3, Comparative Example 1).
3.In the polybutylene terephthalate resin composition,If you add a phenolic or phosphorus heat stabilizer to the triazine UV absorber and lactone heat stabilizer,Molded products obtained from this resin composition are:B value after UV irradiationchangeIs smaller and can maintain a whiter state (Example 4 toExample 6 and Example 8).
4).In the polybutylene terephthalate resin composition,Triazine UV absorberTheIf you add a large amount,Molded products obtained from this resin composition are:B value before UV irradiation is high and not only yellow, but also molded productOoze out on the surfaceIt becomes a powder-blown state and cannot withstand practical use (Comparative Example 3).

Claims (6)

Polybutylene terephthalate resin having a glass transition temperature of 0 ° C. to 85 ° C. measured by a dynamic viscoelastic method, 0.05 to 4 % by weight (wt%) of an ultraviolet absorber having a triazine skeleton, and a lactone thermal stability agent characterized the early days including the 0.01 to 3%, Po polybutylene terephthalate resin composition. Polybutylene terephthalate resin composition further polybutylene terephthalate described phenol-based heat stabilizer 0.01～3.0Wt% and a phosphorus-based heat stabilizer to claim 1 comprising a 0.01～3.0Wt% -Based resin composition. A molded article produced using the polybutylene terephthalate resin composition according to claim 1 or 2 as a raw material . The molded product according to claim 3, wherein the molded product has a b value measured by a color difference meter of 5 or less. The molded product according to claim 3, wherein the molded product has a b value of 10 or less after 200 hours of ultraviolet treatment in a weather meter under conditions of black panel 63 ° C, 120 minutes (18 minutes of internal rain). Moldings Ru film der,請 Motomeko 3 to forming molded article according to any one of claims 5.