JP2005015620A - Flame-retardant vinyl chloride resin molded form - Google Patents

Flame-retardant vinyl chloride resin molded form Download PDF

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Publication number
JP2005015620A
JP2005015620A JP2003182002A JP2003182002A JP2005015620A JP 2005015620 A JP2005015620 A JP 2005015620A JP 2003182002 A JP2003182002 A JP 2003182002A JP 2003182002 A JP2003182002 A JP 2003182002A JP 2005015620 A JP2005015620 A JP 2005015620A
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Prior art keywords
vinyl chloride
chloride resin
degree
flame
chlorination
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JP2003182002A
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Japanese (ja)
Inventor
Osamu Kouzui
治 洪水
Tadashi Kobayashi
正 小林
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Takiron Co Ltd
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Takiron Co Ltd
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Priority to JP2003182002A priority Critical patent/JP2005015620A/en
Publication of JP2005015620A publication Critical patent/JP2005015620A/en
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant vinyl chloride resin molded form having high flame retardancy and clear transparency free of yellowishness. <P>SOLUTION: The flame-retardant vinyl chloride resin molded form consists of a vinyl chloride resin. This molded form contains 56-59 wt.% of chlorine and gives a maximum rate of heat generation of ≤140 kW/m<SP>2</SP>when heated and combusted under a radiatively heating condition of 50 kW/m<SP>2</SP>in accordance with ISO-5660. For example, this molded form A may be obtained by laminating both sides of a core layer 1 of a low-chlorination degree vinyl chloride resin with surface layers 2 each of a high-chlorination degree vinyl chloride resin respectively, or may have a single-layer structure. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【0001】
【発明の属する技術分野】
本発明は、優れた難燃性と光学特性とを有する塩化ビニル樹脂成形体、特に透明性を有する難燃性塩化ビニル樹脂成形体に関する。
【0002】
【従来の技術】
塩化ビニル樹脂は、成形性が良く、機械的強度及び耐食性を有し、安価で、成形性に富んでいるので、あらゆる分野の材料として広く使用されていて、工業用特に耐食工業用材料としても半導体製造装置や液晶製造装置などの材料として用いられている。
【0003】
また、塩化ビニル樹脂は塩素を含有するので難燃性を有する反面、200℃以上に長時間接すると熱分解を起こし、発煙を生じると同時に、塩素ガスや塩化水素ガスなどの腐食性ガスを発生する。又難燃性の高い樹脂とは言え、600℃以上の高温下に晒されると着火し、燃焼する。そのため、この塩化ビニル樹脂を使用している装置に火災が生じると、延焼による直接的被害ではなく、発生する煙やガスにより半導体製造装置が置かれている室内の空気が汚れ、半導体に付着して不良品となったり、腐食性の塩素ガスや塩化水素ガスにより製造装置や精密機械や製品を侵して使用不能にしてしまう恐れがあった。
【0004】
そのため、リン系難燃剤やハロゲン系難燃剤等の難燃剤、或は水酸化マグネシウム等の含水化合物を添加して難燃性を向上させ、火災時の延焼抑制と発煙抑制が行なわれるようになってきている。本出願人も種々検討し、難燃性を向上させた成形体を発明した(特許文献1)。この特許文献1の成形体は、塩素化度が64.5%の後塩素化塩化ビニル樹脂に錫系安定剤とリン系難燃剤と塩素化ポリエチレンを添加し、全光線透過率を50%以上、ヘイズ値を60%以下になしたものである。
【0005】
【特許文献1】
特開2000−76369号公報
【0006】
【発明が解決しようとする課題】
上記の成形体はリン系難燃剤や塩素化ポリエチレンが添加されているため、実用に耐える全光線透過率とヘイズ値を有しているものの、さらにこれらの光学特性を向上させた難燃性塩化ビニル樹脂成形体が要求されるようになってきた。
【0007】
本発明は上記要求を満足する、光学特性に優れた難燃性の工業用、特に半導体製造装置用或は液晶製造装置用の塩化ビニル樹脂成形体を提供することを目的としている。
【0008】
【課題を解決するための手段】
本発明の難燃性塩化ビニル樹脂成形体は、塩化ビニル樹脂からなる成形体であって、該成形体に塩素が56〜59重量%含有され、ISO−5660に準拠して50kW/mの輻射加熱条件で加熱し燃焼させたときの最大発熱速度が140kW/m以下であることを特徴とするものである。
【0009】
この構成であると、成形体中に塩素を56〜59重量%含有するから最大発熱速度が140kW/m以下の優れた難燃性を有するものとすることができるうえに、成形体の製造も容易にできるので、難燃性と製造時の成形性に優れた成形体となる。
【0010】
本発明において、成形体が、塩素化度が低い塩化ビニル樹脂層と、塩素化度が高い塩化ビニル樹脂層とが積層されていて、成形体内の塩化ビニル樹脂の平均塩素化度が60%以上であること、特に、その平均塩素化度が60.0〜63.5%であることが好ましい。
【0011】
この構成であると、各層に用いる塩化ビニル樹脂の塩素化度を変えることにより、必要とする平均塩素化度を有する成形体の樹脂層を得ることができるので、要求される難燃性と製造時の成形性に適合したものとすることが容易にできる。
【0012】
また、本発明において、塩素化度が低い塩化ビニル樹脂層の両面に、塩素化度が高い塩化ビニル樹脂層が積層されていることが好ましい。この塩素化度が低い塩化ビニル樹脂としては、塩素化度が56.0〜57.0%の樹脂が、塩素化度が高い塩化ビニル樹脂としては、塩素化度が62.0〜66.0%の樹脂を用いることが好ましい。
【0013】
この構成であると、塩素化度の低い塩化ビニル樹脂層が熱に対する色相安定性に優れているので、成形体全体が塩素化度の高い塩化ビニル樹脂層からなる成形体に比べて色相ヤケの少ないものにすることができる。また、成形体の両面は、塩素化度の低いものに比べて難燃性に優れた塩素化度の高い塩化ビニル樹脂層であるので、成形体表面の難燃性が優れ、初期の難燃性を向上させたものにすることができる。
【0014】
また、本発明において、成形体中の塩化ビニル樹脂に占める塩素化度が低い塩化ビニル樹脂の割合が、60重量%以下であることが好ましい。この構成であると、塩素化度の高い塩化ビニル樹脂の割合が40重量%以上となるので、必要な難燃性を十分確保することができる。
【0015】
さらに、本発明において、塩化ビニル樹脂の塩素化度が61.0〜63.5%の樹脂であることが好ましい。この構成であると、成形体中の塩素含有量を56〜59重量%とすることが出来、その最大発熱速度が140kW/m以下の優れた難燃性を有する成形体とすることができる。さらに、該樹脂による単一層の成形体であるので、成形体の製造も容易にできる。
【0016】
また、本発明において、塩化ビニル樹脂の平均重合度が500〜800であることが好ましい。この構成であると、低温での製造が可能であるので、製造時における塩化ビニル樹脂の熱劣化が少なくて色相が安定し、透明性を良好にすることができるうえ、ヘイズ値も小さな成形体とすることができる。
【0017】
また、本発明において、塩化ビニル樹脂の熱安定剤として錫系安定剤を使用し、厚さ5mmのときの全光線透過率が70〜80%、ヘイズ値が3〜5%であり、色相の黄変度が−30〜−5であることが好ましい。この構成であると、半導体製造工程や液晶製造工程などの間仕切り、機械カバーなどに必要な透明性を有していて、実用的な透明難燃性樹脂成形体とすることができる。
【0018】
【発明の実施の形態】
以下、図面に基づいて本発明の具体的な実施形態を説明する。
【0019】
図1は本発明に係る塩化ビニル樹脂成形体の一実施形態である樹脂板を示す断面図である。1は塩素化度が低い塩化ビニル樹脂(低塩素化塩化ビニル樹脂)よりなる塩化ビニル樹脂層(以下芯層という)であり、2は塩素化度の高い塩化ビニル樹脂(高塩素化塩化ビニル樹脂)よりなる塩化ビニル樹脂層(以下表面層という)であって、この芯層1の上下両表面に表面層2が積層された3層構造の難燃性塩化ビニル樹脂板Aを形成している。
【0020】
芯層1に用いられる低塩素化塩化ビニル樹脂としては、塩素化度が56〜60%と低くて、重合度が400〜1300の塩化ビニル樹脂、特に塩素化度が56〜57%で重合度が500〜800の塩化ビニル樹脂が好ましく用いられる。また、表面層2に用いる高塩素化塩化ビニル樹脂としては、塩素化度が60〜70%と高くて、重合度が400〜1000の後塩素化塩化ビニル樹脂、好ましくは塩素化度が62.0〜66.0%で重合度が500〜800の後塩素化塩化ビニル樹脂が用いられる。
【0021】
芯層1に用いる低塩素化塩化ビニル樹脂の塩素化度が60%より高いと、難燃性は良くなるものの、塩素含有割合が多くなるので樹脂の熱劣化が進んで色相が悪くなるので好ましくない。重合度は塩素化度が低いので特に限定されることはないが、重合度が400〜1300程度の樹脂が用いられる。
【 22】
表面層2に用いる高塩素化塩化ビニル樹脂の塩素化度が60%より低いと、塩化ビニル樹脂板Aの中に含まれる塩素を56〜59重量%にすることができないし、必要とする難燃性を得ることも困難となる。特に、該樹脂を用いた表面層2は、樹脂板Aの表面に位置し最初に熱に晒されるため、芯層1よりも塩素化度の高い樹脂を使用して難燃性を高め、樹脂板A全体の難燃性を、特に初期の難燃性を高めるために、塩素化度が60%以上の樹脂を使用することが好ましいのである。しかし、あまり塩素化度を高くしすぎると、色相・光学特性が悪くなるし成形性も悪くなるので、好ましくは62.0〜66.0%であることがより好ましい。
【0023】
また、高塩素化塩化ビニル樹脂の重合度を400以下にすると、低温での成形が可能となり樹脂の劣化が少なく光学特性や色相を良好にすることができるが、機械的強度が得難く実使用が困難となる。一方、重合度が1000より高いと、高温での製造が必要で樹脂の劣化が進んで色相の黄色味が強くなるので、この黄色味を補色する青色顔料を多く添加することが必要となり、その結果全光線透過率が低下する。
【0024】
ここで難燃性は、ISO−5660に準拠して、50kW/mの輻射加熱条件で、コーンカロリーメーターを用いて燃焼させたときの成形体の最大発熱速度を測定して判断するが、その速度を140kW/m以下にすることで、半導体製造装置などの材料としては実使用上問題のない難燃性となる。また、黄変度は成形体の黄色の程度を示す価であり、黄変度が小さいほど黄色に着色していない成形体であることを示し、ガラス色に近似した色相を有する。
【0025】
そして、低塩素化塩化ビニル樹脂よりなる芯層1と高塩素化塩化ビニル樹脂よりなる表面層2とを積層した塩化ビニル樹脂板Aに含有される塩素が56〜59重量%となるように、各層の樹脂の塩素化度と、芯層1と表面層2との厚みとを考慮して積層する。
【0026】
例えば、塩素化度が56.8%の低塩素化塩化ビニル樹脂100重量部と熱安定剤などの添加剤8重量部よりなる芯層1の厚みを1.2mmにし、塩素化度が64.5%の高塩素化塩化ビニル樹脂100重量部と熱安定剤などの添加剤8重量部よりなる表面層2の各厚みをそれぞれ0.9mmとすると、厚さ3mmの塩化ビニル樹脂板Aに含有される塩素は56.9重量%となる。また、芯層1の厚みを1.0mmとし、表面層2の各厚みを2.0mmとすると、厚さ5mmの塩化ビニル板Aに含有される塩素は58.3重量%となる。このように、芯層1と表面層2の各厚みにより、成形体Aに含有される塩素は異なるので、各樹脂の塩素化度と厚みには十分注意する必要がある。
【0027】
また、塩化ビニル樹脂板Aに占める低塩素度塩化ビニル樹脂の割合は、40重量%以下にすることが好ましい。この40重量%以下にすることで、高塩素化塩化ビニル樹脂の割合を60重量%以上とすることができるので、成形体中の塩素の含有量を56〜59重量%とすることができ、これにより必要な難燃性を得ることができるし、低塩素塩化ビニル樹脂により化光学特性も良好にすることができる。上記における厚さ3mmの塩化ビニル樹脂板Aは、樹脂板Aに占める低塩素化塩化ビニル樹脂が40.0重量%となる。そして、平均塩素化度は61.4%となる。
【0028】
この低塩素化塩化ビニル樹脂にも高塩素化塩化ビニル樹脂にも、成形に必要な錫系や鉛系の熱安定剤、滑剤、加工助剤、補強剤、抗酸化剤、顔料などの添加剤が必要に応じて添加される。透明性塩化ビニル樹脂成形体を得るには、樹脂100重量部に対して錫系熱安定剤を1〜5重量部添加し、良好な透明性と樹脂の劣化を防止するのが好ましい。
【0029】
さらに、樹脂板Aの製造時の熱により、塩化ビニル樹脂の劣化は避けがたく、大なり小なり黄色に着色するのは必至であるから、青色顔料を添加して黄色味を相殺しガラス色の成形体とすることが好ましい。このような青色顔料としては、群青、フタロシアンブルー、アントラキノン系顔料などが用いられ、これを0.001〜0.150重量%、好ましくは0.001〜0.015重量%添加するのが好ましい。
【0030】
このような塩化ビニル樹脂板Aにおいて、錫系熱安定剤を添加した低塩素化塩化ビニル樹脂を用いた芯層1と錫系熱安定剤を添加した高塩素化度塩化ビニル樹脂を用いた表面層2とを積層して、厚みが5mmのときの全光線透過率を70〜80%、ヘイズ値を3〜5%となし、黄変度を−20〜−5にした透明成形体を得ることが好ましい。
【0031】
そして、前記青色顔料は、その添加量を0.001〜0.008重量部と少なく添加することで、全光線透過率を75〜80%程度に良くすることができるし、黄変度を−10〜−5となしてガラス色に近似した色相とすることができる。一方、添加量を0.008〜0.015重量部と多くすると、顔料が多くなっただけ全光線透過率が55〜75%と若干悪くなり、黄変度は−30〜−10となってガラス色より僅かに青味を帯びた色相となる。このように、青色顔料の添加量の多少で色相が若干変化するので、用途などに応じて使い分けて使用すればよい。
【0032】
上記のような塩化ビニル樹脂板Aを得るには、上記の低塩素化塩化ビニル樹脂並びに高塩素化塩化ビニル樹脂に、それぞれ熱安定剤(透明性成形体を得る場合は錫系安定剤)、滑剤、加工助剤、補強剤、顔料などの添加剤を均一に混合した各配合物で芯層用カレンダーシート並びに表面層用カレンダーシートを作成し、複数枚の芯層用カレンダーシートの上下両面に、複数枚の表面層用カレンダーシートを重ね合わせて熱圧プレスし積層一体化することにより容易に製造できる。また、上記各配合物を3層用共押出し金型を使用し共押出し成形することによって、芯層1の上下に表面層2を積層した塩化ビニル樹脂板を容易に製造することができる。
【0033】
図2は本発明の他の実施形態の塩化ビニル樹脂成形体Bである樹脂板を示す断面図である。3は塩素化度が61.0〜63.5%の塩化ビニル樹脂よりなる塩化ビニル樹脂層であり、該樹脂層3の1層のみで難燃性塩化ビニル樹脂板Bを形成している。
【0034】
この実施形態に使用する塩化ビニル樹脂は、塩素化度が56.8%で重合度が500〜800の塩化ビニル樹脂と塩素化度が64%以上(好ましくは64.5%)で重合度が500〜800の後塩素化塩化ビニル樹脂とを混合して、平均塩素化度を60.0〜63.5%、平均重合度を500〜800とした混合塩化ビニル樹脂が用いられている。その他、塩素化度が60.0〜63.5%で重合度が500〜800の後塩素化塩化ビニル樹脂を単独で用いることも好ましい。混合又は単独塩化ビニル樹脂の重合度が500以下になると、成形性は良好となるが機械的強度が得難く実使用が困難となる。一方、重合度が800より高いと、高温での成形が必要となり樹脂の劣化が進んで色相の黄色味が強くなるので、この黄色味を補色する青色顔料を多く添加する必要に迫られ、その結果全光線透過率が悪くなる。
【0035】
この樹脂板Bは、樹脂板Bに含有される塩素が56〜59重量%となり、難燃性を有する塩化ビニル樹脂板とすることができる。例えば、平均塩素化度が61.0%の塩化ビニル樹脂100重量部と熱安定剤などの添加剤8重量部よりなる組成物で成形された塩化ビニル樹脂板Bに含有される塩素は56.5重量%となる。また、塩素化度が63.5%の塩化ビニル樹脂を用いると、樹脂板Bに含有される塩素は58.8重量%となる。
【0036】
この成形板Bであっても、その中に含有される塩素が56〜59重量%であるから、コーンカロリーメーターによる最大発熱速度は140kW/m以下とすることができて、実使用上問題のない難燃性を有するものとなる。
【0037】
この塩化ビニル樹脂にも、成形に必要な錫系や鉛系の熱安定剤、滑剤、加工助剤、補強剤、抗酸化剤、顔料などの添加剤が必要に応じて添加される。透明性塩化ビニル樹脂成形体を得るには、樹脂100重量部に対して錫系熱安定剤を1〜5重量部添加し、樹脂の劣化を防止するのが好ましい。さらに、塩素化度が高いので樹脂板製造時の熱により樹脂の劣化は避けがたいので、青色顔料を添加して補色し、黄色味を相殺したガラス色の樹脂板とすることが好ましい。このような青色顔料としては、前述の群青、フタロシアニンブルー、アントラキノン系顔料などが用いられる。
【0038】
このような塩素化度が60.0〜63.5%で且つ重合度が500〜800の塩化ビニル樹脂に、錫系安定剤を1〜5重量部添加することで、全光線透過率を70〜80%で、ヘイズ値を3〜5%にした透光性を有する塩化ビニル樹脂板Bを得ることができる。
【0039】
そして、これに前述の青色顔料を0.001〜0.150重量%、好ましくは0.001〜0.015重量%添加することで、成形体の黄変度を−30〜−5にまで色相を変化させることが出来、需要者の要望により変更することできる。
【0040】
上記のような塩化ビニル樹脂樹脂板Bを得るには、上記の塩化ビニル樹脂に熱安定剤(透明性成形体を得る場合は錫系安定剤)、滑剤、加工助剤、補強剤、顔料などの添加剤を均一に混合した配合物でカレンダーシートを作成し、これを複数枚重ね合わせて熱圧プレスし積層一体化することにより容易に製造できる。また、上記配合物を押出し成形することによっても容易に製造することができる。
【0041】
上記各実施形態においては、板状の塩化ビニル樹脂樹脂板について説明したが、板以外の他形状であるのアングル形状、丸棒形状、その他異形形状などの如何なる形状であってもよい。
【0042】
以下、実施例に基づいて更に具体的に説明する。
【0043】
(実施例1)
塩素化度が56.8%、重合度が700の塩化ビニル樹脂100重量部に対して、マレート錫系熱安定剤を2重量部、ステアリン酸滑剤を1重量部、アクリル系加工助剤を2重量部、MBS系補強剤を3重量部、アントラキノン青色顔料を0.01重量部それぞれ添加して均一に混合した後に、厚さ0.5mmの芯層用カレンダーシートを作成した。一方、塩素化度が64.5%、重合度が700の塩素化塩化ビニル樹脂100重量部に対して、マレート錫系熱安定剤を2重量部、ステアリン酸滑剤を1重量部、アクリル系加工助剤を2重量部、MBS系補強剤を3重量部、アントラキノン青色顔料を0.01重量それぞれ添加して均一に混合した後に、厚さ0.5mmの表面層用カレンダーシートを作成した。
【0044】
芯層用カレンダーシートを4枚重ね、この上下に表面層用カレンダーシートをそれぞれ3枚ずつ重ね、これを熱圧して厚さ5mmの実施例1のプレートを作成した。このプレートに含有される塩素量は56.9重量%、塩化ビニル樹脂の平均塩素化度は61.4%、塩素化度56.8%の塩化ビニル樹脂のプレートに占める割合は40.0%である。
【0045】
この実施例1のプレートの全光線透過率、ヘイズ値をJIS K−7361−1に基づき測定し、色相(黄変度)をJIS Z8722に基づき測定した。難燃性は、ISO−5660に準拠して、50kW/mの輻射加熱条件で、コーンカロリーメーターを用いて燃焼させたときのプレートの最大発熱速度を測定した。その結果を表1に記載する。
【0046】
(実施例2)
実施例1の芯層用カレンダーシートを2枚と、その上下に表面層用カレンダーシートをそれぞれ4枚ずつ用いた以外は実施例1と同様にして、このプレートに含有される塩素量が58.3重量%、塩化ビニル樹脂の平均塩素化度が63.0%、塩素化度56.8%の塩化ビニル樹脂のプレートに占める割合が20%である実施例2のプレートを得た。
【0047】
このプレートについて、実施例1と同様にして、全光線透過率、ヘイズ値、黄変度、最大発熱速度をそれぞれ測定して求め、その結果を表1に併記する。
【0048】
(実施例3)
実施例1の表面層用カレンダーシート6枚の上下両面に芯層用カレンダーシートをそれぞれ2枚ずつ重ね、これを熱圧して厚さ5mmのプレートを作成した。このプレートに含有される塩素量は56.9%、塩化ビニル樹脂の平均塩素化度が61.4%、塩素化度56.8%の塩化ビニル樹脂のプレートに占める割合が40%である実施例3のプレートを得た。
【0049】
このプレートについて、実施例1と同様にして、全光線透過率、ヘイズ値、黄変度、最大発熱速度をそれぞれ測定して求め、その結果を表1に併記する。
【0050】
(実施例4)
塩素化度が56.8%、重合度が700の塩化ビニル樹脂と、塩素化度が64.5%、重合度が700の後塩素化塩化塩化ビニル樹脂とを30:70の割合で均一に混合して、平均塩素化度が62.2%の混合塩化ビニル樹脂を得た。この混合塩化ビニル樹脂100重量部に対して、マレート錫系熱安定剤を2重量部、ステアリン酸滑剤を1重量部、アクリル系加工助剤を2重量部、MBS系補強剤を3重量部、アントラキノン青色顔料を0.01重量部それぞれ添加して均一に混合した後に、厚さ0.5mmのカレンダーシートを作成した。このカレンダーシートを10枚重ねて熱圧し厚さ5mmの実施例4のプレートを作成した。このプレートに含有される塩素量は57.6重量%、塩化ビニル樹脂の平均塩素化度は62.2%、塩素化度56.8%の塩化ビニル樹脂のプレートに占める割合は30.0%である。
【0051】
このプレートについて実施例1と同様にして、全光線透過率、ヘイズ値、黄変度、最大発熱速度をそれぞれ測定して求め、その結果を表1に併記する。
【0052】
(比較例1)
実施例1の芯層用カレンダーシートを8枚と、表面層用カレンダーシートをそれぞれ1枚ずつ用いて熱圧した以外は実施例1と同様にして、このプレートに含有される塩素量が54.0重量%、塩化ビニル樹脂の平均塩素化度が58.3%、塩素化度56.8%の塩化ビニル樹脂のプレートに占める割合は80%である比較例1のプレートを作成した。このプレートを実施例1と同様にして、全光線透過率、ヘイズ値、黄変度、最大発熱速度をそれぞれ測定して求め、その結果を表1に併記する。
【0053】
(比較例2、3)
実施例1の芯層用カレンダーシートのみを10枚重ねて熱圧して厚さ5mmの比較例2のプレートを得た。また実施例1の表面層用カレンダーシートのみを10枚重ねて熱圧して厚さ5mmの比較例3のプレートを得た。これらのプレートを実施例1と同様にして、全光線透過率、ヘイズ値、黄変度、最大発熱速度をそれぞれ測定して求め、その結果を表1に併記する。
【0054】
(比較例4)
塩素化度が64.5%、重合度が700の塩素化塩化ビニル樹脂100重量部に対して、錫系熱安定剤を2重量部、滑剤を1重量部、加工助剤を2重量部、補強剤を3重量部、青色顔料を0.01重量部、リン系難燃剤を7重量部、塩素化ポリエチレンを5重量部それぞれ添加して均一に混合した後に、厚さ0.5mmのカレンダーシートを作成した。このカレンダーシートを10枚重ねて熱圧して厚さ5mmの比較例4のプレートを得た。このプレートを実施例1と同様にして、全光線透過率、ヘイズ値、黄変度、最大発熱速度をそれぞれ測定して求め、その結果を表1に併記する。
【0055】
【表1】

Figure 2005015620
【0056】
この表1からわかるように、最大発熱速度は、実施例1、2、3、4及び比較例3、4において、130kW/m以下と低くなっていて難燃性を有しているが、比較例1、2はそれが182kW/m、241kW/mと極めて高くて難燃性に劣っていることがわかる。これは、プレートに占める塩素含有率が比較例1においては54.0%、比較例2においては52.6%と、他の実施例・比較例に比べて4%以上低く、また平均塩素化率も他の実施例・比較例に比べて3〜6%程度低いためである。なお、比較例4はリン系や塩素化ポリエチレンの難燃剤を添加しているために、塩素含有率が低くても難燃性を有しているものである。このことより、プレートに含有される塩素量が夫々55重量%以上、平均塩素化度が59以上あれば難燃性を有することが理解できる。
【0057】
また、黄変度は、各実施例及び比較例1、2において,約−20〜−8の値を示し、ガラス色に似た色相を有しているが、比較例3、4は約−4及び−2の値となっていて、黄色味を帯びた色相を呈している。これは、比較例3においては塩素含有量が約60%と多く、また平均塩素化度も64.5%と高いので、プレート作成時の熱により塩化ビニル樹脂が熱分解したためである。また比較例4はリン系や塩素化ポリエチレンの難燃剤の影響である。このことより、プレートに含有される塩素量は59重量%以下、平均塩素化度は64%以下であれば、黄色味のないクリヤーな色相のプレートを得ることができる。
【0058】
一方、全光線透過率は各実施例及び比較例共に70〜76%であり、十分透光性を有している。しかし、ヘイズ値において、比較例4のみが10%と非常に高く、スカットした透明性を有していないことがわかり、透明性に劣ることがわかる。これはリン系難燃剤、特に塩素化ポリエチレンが添加されているためであり、難燃性は良好であっても透明性成形体とてしは使用できない。
【0059】
【発明の効果】
以上の説明から明らかなように、本発明の難燃性塩化ビニル樹脂成形体は、最大発熱速度が140kW/m以下である難燃性を有する上に、色相も黄色味のないクリヤーなものとすることができ、透明性を要求される用途に実使用可能な成形体を得ることができる。そして、塩素化度の低い塩化ビニル樹脂層の両側に塩素化度の高い塩化ビニル樹脂層を積層すると、難燃性の高い高塩素化樹脂層が外側に位置するので、初期の難燃性に優れた成形体することができる。特に、成形体に含有される塩素量を56〜59重量%、平均塩素化度を60.0〜63.5%とすると、クリヤーな透明で難燃性を有する成形体を容易に得ることができる。
【図面の簡単な説明】
【図1】本発明の一実施形態に係る難燃性塩化ビニル樹脂成形体を示す断面図である。
【図2】本発明の他の実施形態に係る難燃性塩化ビニル樹脂成形体を示す断面図である。
【符号の説明】
1 芯層(塩素化度が低い塩化ビニル樹脂層)
2 表面層(塩素化度の高い塩化ビニル樹脂層)
3 塩素化度が60.0〜63.5%の塩化ビニル樹脂層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a vinyl chloride resin molded article having excellent flame retardancy and optical properties, and more particularly to a flame retardant vinyl chloride resin molded article having transparency.
[0002]
[Prior art]
Vinyl chloride resin has good moldability, has mechanical strength and corrosion resistance, is inexpensive, and has good moldability. Therefore, it is widely used as a material in various fields, and it can be used as an industrial material, particularly as a material for the corrosion-resistant industry. It is used as a material for semiconductor manufacturing equipment and liquid crystal manufacturing equipment.
[0003]
In addition, vinyl chloride resin contains chlorine and is therefore flame retardant. On the other hand, when it comes into contact with 200 ° C or more for a long time, it decomposes thermally and generates smoke, and at the same time, generates corrosive gases such as chlorine gas and hydrogen chloride gas. To do. Although it is a highly flame-retardant resin, it is ignited and combusted when exposed to a high temperature of 600 ° C. or higher. Therefore, when a fire occurs in a device using this vinyl chloride resin, the air in the room where the semiconductor manufacturing equipment is located is contaminated by the generated smoke and gas, and not attached directly to the semiconductor. There is a risk that the product may become defective or corrosive chlorine gas or hydrogen chloride gas may invade the manufacturing equipment, precision machine, or product and make it unusable.
[0004]
Therefore, flame retardants such as phosphorus-based flame retardants and halogen-based flame retardants, or water-containing compounds such as magnesium hydroxide are added to improve the flame retardancy, and fire spread and smoke are suppressed in the event of a fire. It is coming. The present applicant has also studied variously and invented a molded body having improved flame retardancy (Patent Document 1). This molded article of Patent Document 1 has a total light transmittance of 50% or more by adding a tin-based stabilizer, a phosphorus-based flame retardant and chlorinated polyethylene to a chlorinated vinyl chloride resin having a chlorination degree of 64.5%. The haze value is 60% or less.
[0005]
[Patent Document 1]
Japanese Patent Laid-Open No. 2000-76369 [0006]
[Problems to be solved by the invention]
The above-mentioned molded body has a total light transmittance and a haze value that can withstand practical use because of addition of a phosphorus-based flame retardant and chlorinated polyethylene, but has further improved these optical properties. Vinyl resin moldings have been required.
[0007]
It is an object of the present invention to provide a vinyl chloride resin molded article satisfying the above requirements and having excellent optical properties and flame retardancy for industrial use, particularly for semiconductor production equipment or liquid crystal production equipment.
[0008]
[Means for Solving the Problems]
The flame-retardant vinyl chloride resin molded body of the present invention is a molded body made of a vinyl chloride resin, wherein the molded body contains 56 to 59% by weight of chlorine, and is 50 kW / m 2 in accordance with ISO-5660. The maximum heat generation rate when heated and burned under radiant heating conditions is 140 kW / m 2 or less.
[0009]
With this configuration, since the molded body contains 56 to 59% by weight of chlorine, it can have excellent flame retardancy with a maximum heat generation rate of 140 kW / m 2 or less, and the production of the molded body. Therefore, it becomes a molded article excellent in flame retardancy and moldability during production.
[0010]
In the present invention, the molded body is formed by laminating a vinyl chloride resin layer having a low chlorination degree and a vinyl chloride resin layer having a high chlorination degree, and the average chlorination degree of the vinyl chloride resin in the molded body is 60% or more. It is preferable that the average chlorination degree is 60.0 to 63.5%.
[0011]
With this configuration, by changing the chlorination degree of the vinyl chloride resin used for each layer, a molded resin layer having the required average chlorination degree can be obtained. It can be easily adapted to the moldability at the time.
[0012]
Moreover, in this invention, it is preferable that the vinyl chloride resin layer with a high chlorination degree is laminated | stacked on both surfaces of the vinyl chloride resin layer with a low chlorination degree. As the vinyl chloride resin having a low chlorination degree, a resin having a chlorination degree of 56.0 to 57.0% is used. As a vinyl chloride resin having a high chlorination degree, the chlorination degree is 62.0 to 66.0. % Resin is preferably used.
[0013]
With this configuration, the vinyl chloride resin layer with a low degree of chlorination is excellent in hue stability against heat, so that the entire molded body has a hue burn that is less than that of a molded body composed of a vinyl chloride resin layer with a high degree of chlorination. It can be reduced. In addition, since both surfaces of the molded body are vinyl chloride resin layers with a high degree of chlorination and excellent flame retardancy compared to those with a low degree of chlorination, the flame resistance of the surface of the molded body is excellent and the initial flame resistance Can be improved.
[0014]
Moreover, in this invention, it is preferable that the ratio of the vinyl chloride resin with a low chlorination degree to the vinyl chloride resin in a molded object is 60 weight% or less. With this configuration, since the proportion of the vinyl chloride resin having a high degree of chlorination is 40% by weight or more, the necessary flame retardance can be sufficiently ensured.
[0015]
Furthermore, in the present invention, the vinyl chloride resin is preferably a resin having a chlorination degree of 61.0 to 63.5%. With this configuration, the chlorine content in the molded body can be 56 to 59% by weight, and the molded body having excellent flame retardancy with a maximum heat generation rate of 140 kW / m 2 or less can be obtained. . Furthermore, since it is a single layer molded body made of the resin, the molded body can be easily manufactured.
[0016]
In the present invention, the average degree of polymerization of the vinyl chloride resin is preferably 500 to 800. With this configuration, it is possible to produce at low temperature, so that the vinyl chloride resin has little thermal deterioration during production, the hue is stable, transparency can be improved, and the haze value is also small. It can be.
[0017]
In the present invention, a tin-based stabilizer is used as a thermal stabilizer for the vinyl chloride resin, the total light transmittance at a thickness of 5 mm is 70 to 80%, the haze value is 3 to 5%, The yellowing degree is preferably -30 to -5. With this configuration, it has transparency required for partitions such as semiconductor manufacturing processes and liquid crystal manufacturing processes, machine covers, and the like, and a practical transparent flame-retardant resin molded product can be obtained.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.
[0019]
FIG. 1 is a cross-sectional view showing a resin plate which is an embodiment of a vinyl chloride resin molded body according to the present invention. 1 is a vinyl chloride resin layer (hereinafter referred to as a core layer) made of a vinyl chloride resin having a low chlorination degree (low chlorination vinyl chloride resin), and 2 is a vinyl chloride resin having a high chlorination degree (high chlorination vinyl chloride resin). ), A flame retardant vinyl chloride resin plate A having a three-layer structure in which the surface layer 2 is laminated on both upper and lower surfaces of the core layer 1 is formed. .
[0020]
The low chlorinated vinyl chloride resin used for the core layer 1 has a low chlorination degree of 56 to 60% and a polymerization degree of 400 to 1300, particularly a chlorination degree of 56 to 57% and a polymerization degree. Of 500 to 800 is preferably used. The highly chlorinated vinyl chloride resin used for the surface layer 2 has a high chlorination degree of 60 to 70% and a post-chlorination vinyl chloride resin having a polymerization degree of 400 to 1000, preferably a chlorination degree of 62. A post-chlorinated vinyl chloride resin is used at 0-66.0% and a degree of polymerization of 500-800.
[0021]
When the degree of chlorination of the low-chlorinated vinyl chloride resin used for the core layer 1 is higher than 60%, the flame retardancy is improved, but the chlorine content is increased, so that the resin deteriorates and the hue deteriorates. Absent. The degree of polymerization is not particularly limited because the degree of chlorination is low, but a resin having a degree of polymerization of about 400 to 1300 is used.
[22]
If the degree of chlorination of the highly chlorinated vinyl chloride resin used for the surface layer 2 is lower than 60%, the chlorine contained in the vinyl chloride resin plate A cannot be made 56 to 59% by weight, and it is a necessary difficulty. It is also difficult to obtain flammability. In particular, since the surface layer 2 using the resin is located on the surface of the resin plate A and is first exposed to heat, a resin having a higher chlorination degree than the core layer 1 is used to increase the flame retardancy, and the resin In order to improve the flame retardancy of the entire plate A, particularly the initial flame retardancy, it is preferable to use a resin having a chlorination degree of 60% or more. However, if the degree of chlorination is too high, the hue and optical properties are deteriorated and the moldability is also deteriorated. Therefore, the content is preferably 62.0 to 66.0%.
[0023]
In addition, when the degree of polymerization of the highly chlorinated vinyl chloride resin is 400 or less, molding at low temperature is possible and the resin is less deteriorated and the optical properties and hue can be improved. It becomes difficult. On the other hand, if the degree of polymerization is higher than 1000, it is necessary to produce at a high temperature, the deterioration of the resin proceeds and the yellowness of the hue becomes strong, so it is necessary to add a large amount of blue pigment that complements this yellowness. As a result, the total light transmittance is reduced.
[0024]
Here, flame retardancy is determined by measuring the maximum heat generation rate of the molded product when burned using a corn calorimeter under a radiation heating condition of 50 kW / m 2 in accordance with ISO-5660. By setting the speed to 140 kW / m 2 or less, the material for a semiconductor manufacturing apparatus or the like becomes flame retardant without problems in actual use. The degree of yellowing is a value indicating the degree of yellowness of the molded body. The smaller the degree of yellowing, the more molded body is not colored yellow, and the hue approximates the glass color.
[0025]
And the chlorine contained in the vinyl chloride resin plate A obtained by laminating the core layer 1 made of low chlorinated vinyl chloride resin and the surface layer 2 made of high chlorinated vinyl chloride resin is 56 to 59% by weight. The layers are laminated in consideration of the degree of chlorination of the resin of each layer and the thickness of the core layer 1 and the surface layer 2.
[0026]
For example, the thickness of the core layer 1 consisting of 100 parts by weight of a low chlorinated vinyl chloride resin having a chlorination degree of 56.8% and 8 parts by weight of an additive such as a heat stabilizer is 1.2 mm, and the chlorination degree is 64. When each thickness of the surface layer 2 consisting of 100 parts by weight of 5% highly chlorinated vinyl chloride resin and 8 parts by weight of additives such as a heat stabilizer is 0.9 mm, it is contained in the vinyl chloride resin plate A having a thickness of 3 mm. Chlorine is 56.9% by weight. If the thickness of the core layer 1 is 1.0 mm and each thickness of the surface layer 2 is 2.0 mm, the chlorine contained in the vinyl chloride plate A having a thickness of 5 mm is 58.3 wt%. Thus, since the chlorine contained in the molded product A differs depending on the thicknesses of the core layer 1 and the surface layer 2, it is necessary to pay sufficient attention to the chlorination degree and thickness of each resin.
[0027]
Moreover, it is preferable that the ratio of the low chlorine degree vinyl chloride resin to the vinyl chloride resin plate A is 40% by weight or less. By making this 40% by weight or less, the proportion of the highly chlorinated vinyl chloride resin can be made 60% by weight or more, so the chlorine content in the molded body can be made 56 to 59% by weight, Thereby, the required flame retardancy can be obtained, and the low optical properties can be improved by the low chlorine vinyl chloride resin. In the vinyl chloride resin plate A having a thickness of 3 mm in the above, the low chlorinated vinyl chloride resin in the resin plate A is 40.0% by weight. The average degree of chlorination is 61.4%.
[0028]
Additives such as tin-based and lead-based heat stabilizers, lubricants, processing aids, reinforcing agents, antioxidants, and pigments required for molding both low and high chlorinated vinyl chloride resins Is added as needed. In order to obtain a transparent vinyl chloride resin molded article, it is preferable to add 1 to 5 parts by weight of a tin-based heat stabilizer with respect to 100 parts by weight of the resin to prevent good transparency and deterioration of the resin.
[0029]
Furthermore, since the deterioration of the vinyl chloride resin is unavoidable due to the heat during the production of the resin plate A, it is inevitable that the resin is colored yellow. It is preferable to use the molded body. As such a blue pigment, ultramarine blue, phthalocyanine blue, anthraquinone pigment or the like is used, and 0.001 to 0.150 wt%, preferably 0.001 to 0.015 wt% is preferably added. .
[0030]
In such a vinyl chloride resin plate A, a surface using a core layer 1 using a low chlorinated vinyl chloride resin to which a tin heat stabilizer is added and a high chlorination degree vinyl chloride resin to which a tin heat stabilizer is added. Layer 2 is laminated to obtain a transparent molded article having a total light transmittance of 70 to 80%, a haze value of 3 to 5% and a yellowing degree of -20 to -5 when the thickness is 5 mm. It is preferable.
[0031]
The blue pigment can be added in a small amount of 0.001 to 0.008 parts by weight, so that the total light transmittance can be improved to about 75 to 80%, and the yellowing degree is − It can be set to 10-5, and it can be set as the hue approximated to the glass color. On the other hand, when the addition amount is increased to 0.008 to 0.015 parts by weight, the total light transmittance is slightly deteriorated to 55 to 75% as the pigment is increased, and the yellowing degree is −30 to −10. The hue is slightly bluish than the glass color. As described above, since the hue slightly changes depending on the amount of the blue pigment added, it may be used depending on the application.
[0032]
In order to obtain the vinyl chloride resin plate A as described above, the above low chlorinated vinyl chloride resin and high chlorinated vinyl chloride resin are each provided with a heat stabilizer (in the case of obtaining a transparent molded body, a tin-based stabilizer), Create a calendar sheet for the core layer and a calendar sheet for the surface layer with each compound that is uniformly mixed with additives such as lubricants, processing aids, reinforcing agents, and pigments. It can be easily manufactured by superimposing a plurality of calendar sheets for the surface layer, hot pressing and laminating and integrating them. Moreover, the vinyl chloride resin board which laminated | stacked the surface layer 2 on the upper and lower sides of the core layer 1 can be easily manufactured by co-extrusion molding each said compound using the co-extrusion die for 3 layers.
[0033]
FIG. 2 is a cross-sectional view showing a resin plate which is a vinyl chloride resin molded product B according to another embodiment of the present invention. 3 is a vinyl chloride resin layer made of a vinyl chloride resin having a chlorination degree of 61.0 to 63.5%, and the flame retardant vinyl chloride resin plate B is formed by only one layer of the resin layer 3.
[0034]
The vinyl chloride resin used in this embodiment is a vinyl chloride resin having a degree of chlorination of 56.8% and a degree of polymerization of 500 to 800, and a degree of polymerization of 64% or more (preferably 64.5%). A mixed vinyl chloride resin having an average degree of chlorination of 60.0 to 63.5% and an average degree of polymerization of 500 to 800 by mixing with 500 to 800 post-chlorinated vinyl chloride resin is used. In addition, it is also preferable to use a post-chlorinated vinyl chloride resin alone after the chlorination degree is 60.0 to 63.5% and the polymerization degree is 500 to 800. When the degree of polymerization of the mixed or single vinyl chloride resin is 500 or less, the moldability is good, but the mechanical strength is difficult to obtain and the actual use becomes difficult. On the other hand, if the degree of polymerization is higher than 800, molding at a high temperature is required, and the deterioration of the resin progresses to increase the yellowness of the hue. Therefore, it is necessary to add a large amount of blue pigment that complements this yellowness. As a result, the total light transmittance is deteriorated.
[0035]
The resin plate B can be a vinyl chloride resin plate having a flame retardance of 56 to 59% by weight of chlorine contained in the resin plate B. For example, the chlorine contained in the vinyl chloride resin plate B formed of a composition comprising 100 parts by weight of a vinyl chloride resin having an average degree of chlorination of 61.0% and 8 parts by weight of an additive such as a heat stabilizer is 56. 5% by weight. When a vinyl chloride resin having a chlorination degree of 63.5% is used, the chlorine contained in the resin plate B is 58.8% by weight.
[0036]
Even in this molded plate B, since the chlorine contained therein is 56 to 59% by weight, the maximum heat generation rate by the cone calorimeter can be 140 kW / m 2 or less, which is a problem in practical use. It will have no flame retardancy.
[0037]
Additives such as tin-based and lead-based heat stabilizers, lubricants, processing aids, reinforcing agents, antioxidants, and pigments necessary for molding are also added to this vinyl chloride resin as necessary. In order to obtain a transparent vinyl chloride resin molded article, it is preferable to add 1 to 5 parts by weight of a tin-based heat stabilizer to 100 parts by weight of the resin to prevent the resin from deteriorating. Furthermore, since the degree of chlorination is high, it is difficult to avoid the deterioration of the resin due to the heat during the production of the resin plate. Therefore, it is preferable to add a blue pigment to complement the glass to make a glass-colored resin plate that offsets the yellowness. As such a blue pigment, the above-mentioned ultramarine blue, phthalocyanine blue, anthraquinone pigments and the like are used.
[0038]
By adding 1 to 5 parts by weight of a tin stabilizer to the vinyl chloride resin having a chlorination degree of 60.0 to 63.5% and a polymerization degree of 500 to 800, the total light transmittance is 70. A light-transmitting vinyl chloride resin plate B having a haze value of 3 to 5% at -80% can be obtained.
[0039]
Further, by adding 0.001 to 0.150% by weight, preferably 0.001 to 0.015% by weight of the blue pigment described above, the yellowing degree of the molded body is set to −30 to −5. Can be changed, and can be changed according to the demands of consumers.
[0040]
In order to obtain the vinyl chloride resin plate B as described above, a heat stabilizer (tin stabilizer if a transparent molded body is obtained), a lubricant, a processing aid, a reinforcing agent, a pigment, etc. It can be easily manufactured by preparing a calender sheet with a blend in which the above additives are uniformly mixed, stacking a plurality of these, hot pressing and integrating them. Moreover, it can manufacture easily also by extruding the said compound.
[0041]
In each of the above embodiments, the plate-like vinyl chloride resin resin plate has been described. However, any shape other than the plate, such as an angle shape, a round bar shape, and other irregular shapes may be used.
[0042]
Hereinafter, it demonstrates more concretely based on an Example.
[0043]
(Example 1)
For 100 parts by weight of vinyl chloride resin having a degree of chlorination of 56.8% and a degree of polymerization of 700, 2 parts by weight of malate tin-based heat stabilizer, 1 part by weight of stearic acid lubricant, 2 parts of acrylic processing aid After adding parts by weight, 3 parts by weight of the MBS reinforcing agent, and 0.01 parts by weight of anthraquinone blue pigment and mixing them uniformly, a calendar sheet for a core layer having a thickness of 0.5 mm was prepared. On the other hand, for 100 parts by weight of chlorinated vinyl chloride resin having a chlorination degree of 64.5% and a polymerization degree of 700, 2 parts by weight of malate tin-based heat stabilizer, 1 part by weight of stearic acid lubricant, acrylic processing After adding 2 parts by weight of an auxiliary agent, 3 parts by weight of an MBS-based reinforcing agent and 0.01 parts by weight of an anthraquinone blue pigment and mixing them uniformly, a calendar sheet for a surface layer having a thickness of 0.5 mm was prepared.
[0044]
Four calender sheets for the core layer were stacked, and three calender sheets for the surface layer were stacked on the top and bottom, respectively, and these were hot-pressed to prepare a plate of Example 1 having a thickness of 5 mm. The amount of chlorine contained in this plate is 56.9% by weight, the average chlorination degree of vinyl chloride resin is 61.4%, and the proportion of vinyl chloride resin with a chlorination degree of 56.8% in the plate is 40.0%. It is.
[0045]
The total light transmittance and haze value of the plate of Example 1 were measured based on JIS K-7361-1, and the hue (degree of yellowing) was measured based on JIS Z8722. The flame retardancy was measured in accordance with ISO-5660 by measuring the maximum heat generation rate of the plate when burned using a cone calorimeter under a radiation heating condition of 50 kW / m 2 . The results are listed in Table 1.
[0046]
(Example 2)
The amount of chlorine contained in this plate was 58. 5 in the same manner as in Example 1, except that two core layer calender sheets of Example 1 and four surface layer calender sheets were used above and below. A plate of Example 2 was obtained in which the proportion of vinyl chloride resin in the plate of 3% by weight, vinyl chloride resin with an average chlorination degree of 63.0% and chlorination degree of 56.8% was 20%.
[0047]
For this plate, the total light transmittance, haze value, yellowing degree, and maximum heat generation rate were determined in the same manner as in Example 1, and the results are also shown in Table 1.
[0048]
Example 3
Two calender sheets for the core layer were stacked on each of the upper and lower surfaces of the six calender sheets for the surface layer of Example 1, and these were hot-pressed to prepare a plate having a thickness of 5 mm. The amount of chlorine contained in this plate is 56.9%, the average chlorination degree of the vinyl chloride resin is 61.4%, and the proportion of vinyl chloride resin with the chlorination degree of 56.8% in the plate is 40%. The plate of Example 3 was obtained.
[0049]
For this plate, the total light transmittance, haze value, yellowing degree, and maximum heat generation rate were determined in the same manner as in Example 1, and the results are also shown in Table 1.
[0050]
(Example 4)
Uniform proportion of vinyl chloride resin with a chlorination degree of 56.8% and a polymerization degree of 700 and a post-chlorination vinyl chloride resin with a chlorination degree of 64.5% and a polymerization degree of 700 at a ratio of 30:70 By mixing, a mixed vinyl chloride resin having an average chlorination degree of 62.2% was obtained. 2 parts by weight of a malate tin heat stabilizer, 1 part by weight of a stearic acid lubricant, 2 parts by weight of an acrylic processing aid, 3 parts by weight of an MBS reinforcing agent, relative to 100 parts by weight of this mixed vinyl chloride resin After 0.01 parts by weight of anthraquinone blue pigment was added and mixed uniformly, a calendar sheet having a thickness of 0.5 mm was prepared. Ten calendar sheets were stacked and hot pressed to produce a plate of Example 4 having a thickness of 5 mm. The amount of chlorine contained in this plate is 57.6% by weight, the average chlorination degree of the vinyl chloride resin is 62.2%, and the proportion of the vinyl chloride resin with the chlorination degree of 56.8% in the plate is 30.0%. It is.
[0051]
About this plate, it carried out similarly to Example 1, and measured and calculated | required each of the total light transmittance, the haze value, the yellowing degree, and the maximum heat release rate, and the result is written together in Table 1.
[0052]
(Comparative Example 1)
The amount of chlorine contained in this plate was 54. 5 in the same manner as in Example 1 except that eight core layer calender sheets and one surface layer calender sheet of Example 1 were used for hot pressing. A plate of Comparative Example 1 was prepared in which the proportion of vinyl chloride resin with respect to the plate of 0% by weight, vinyl chloride resin having an average chlorination degree of 58.3% and chlorination degree of 56.8% was 80%. This plate was obtained in the same manner as in Example 1 by measuring the total light transmittance, haze value, degree of yellowing, and maximum heat generation rate, and the results are also shown in Table 1.
[0053]
(Comparative Examples 2 and 3)
Only 10 calendar sheets for the core layer of Example 1 were stacked and hot-pressed to obtain a plate of Comparative Example 2 having a thickness of 5 mm. Further, only the calender sheets for the surface layer of Example 1 were stacked and hot pressed to obtain a plate of Comparative Example 3 having a thickness of 5 mm. These plates were obtained in the same manner as in Example 1 by measuring the total light transmittance, haze value, yellowing degree, and maximum heat generation rate, and the results are also shown in Table 1.
[0054]
(Comparative Example 4)
2 parts by weight of a tin-based heat stabilizer, 1 part by weight of a lubricant, 2 parts by weight of a processing aid for 100 parts by weight of a chlorinated vinyl chloride resin having a chlorination degree of 64.5% and a polymerization degree of 700, After adding 3 parts by weight of the reinforcing agent, 0.01 parts by weight of the blue pigment, 7 parts by weight of the phosphorus flame retardant, and 5 parts by weight of the chlorinated polyethylene, and mixing them uniformly, a calendar sheet having a thickness of 0.5 mm It was created. Ten calendar sheets were stacked and hot-pressed to obtain a plate of Comparative Example 4 having a thickness of 5 mm. This plate was obtained in the same manner as in Example 1 by measuring the total light transmittance, haze value, degree of yellowing, and maximum heat generation rate, and the results are also shown in Table 1.
[0055]
[Table 1]
Figure 2005015620
[0056]
As can be seen from Table 1, the maximum heat generation rate in Examples 1, 2, 3, 4 and Comparative Examples 3 and 4 is as low as 130 kW / m 2 or less and has flame retardancy. It can be seen that Comparative Examples 1 and 2 are extremely high at 182 kW / m 2 and 241 kW / m 2 and inferior in flame retardancy. This is because the chlorine content in the plate is 54.0% in Comparative Example 1 and 52.6% in Comparative Example 2, 4% or more lower than other Examples / Comparative Examples, and the average chlorination. This is because the rate is about 3 to 6% lower than other examples and comparative examples. In addition, since the comparative example 4 has added the flame retardant of phosphorus type | system | group and chlorinated polyethylene, it has a flame retardance even if chlorine content rate is low. From this, it can be understood that if the amount of chlorine contained in the plate is 55% by weight or more and the average chlorination degree is 59 or more, it has flame retardancy.
[0057]
Moreover, yellowing degree shows the value of about -20--8 in each Example and Comparative Examples 1 and 2, and has a hue similar to glass color, but Comparative Examples 3 and 4 are about-. It has values of 4 and -2, and has a yellowish hue. This is because in Comparative Example 3, the chlorine content is as high as about 60%, and the average chlorination degree is as high as 64.5%, so that the vinyl chloride resin was thermally decomposed by the heat during plate preparation. Comparative Example 4 is the influence of a phosphorus-based or chlorinated polyethylene flame retardant. From this, if the amount of chlorine contained in the plate is 59% by weight or less and the average chlorination degree is 64% or less, a plate having a clear hue without yellowishness can be obtained.
[0058]
On the other hand, the total light transmittance is 70 to 76% in each of the examples and comparative examples, and has sufficient translucency. However, in the haze value, only Comparative Example 4 is very high as 10%, and it can be seen that it does not have scutted transparency and is inferior in transparency. This is because a phosphorus-based flame retardant, particularly chlorinated polyethylene, is added. Even if the flame retardancy is good, it cannot be used as a transparent molded article.
[0059]
【The invention's effect】
As is clear from the above description, the flame-retardant vinyl chloride resin molded article of the present invention has a flame retardancy with a maximum heat generation rate of 140 kW / m 2 or less and a clear hue without yellowishness. Therefore, it is possible to obtain a molded body that can be practically used for applications requiring transparency. And if a high chlorinated vinyl chloride resin layer is laminated on both sides of a low chlorinated vinyl chloride resin layer, the highly flammable high chlorinated resin layer is located on the outside, so the initial flame retardancy is improved. An excellent molded product can be obtained. In particular, when the amount of chlorine contained in the molded product is 56 to 59% by weight and the average degree of chlorination is 60.0 to 63.5%, a clear transparent and flame-retardant molded product can be easily obtained. it can.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a flame-retardant vinyl chloride resin molded article according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view showing a flame-retardant vinyl chloride resin molded article according to another embodiment of the present invention.
[Explanation of symbols]
1 Core layer (vinyl chloride resin layer with low chlorination degree)
2 Surface layer (highly chlorinated vinyl chloride resin layer)
3 Vinyl chloride resin layer with a chlorination degree of 60.0-63.5%

Claims (9)

塩化ビニル樹脂からなる成形体であって、該成形体には塩素が56〜59重量%含有され、ISO−5660に準拠して50kW/mの輻射加熱条件で加熱し燃焼させたときの最大発熱速度が140kW/m以下であることを特徴とする難燃性塩化ビニル樹脂成形体。A molded body made of a vinyl chloride resin, wherein the molded body contains 56 to 59% by weight of chlorine and is maximum when heated and burned under a radiation heating condition of 50 kW / m 2 in accordance with ISO-5660. A flame-retardant vinyl chloride resin molded article having a heat generation rate of 140 kW / m 2 or less. 成形体が、塩素化度が低い塩化ビニル樹脂層と、塩素化度が高い塩化ビニル樹脂層とが積層されていて、成形体内の塩化ビニル樹脂の平均塩素化度が60%以上であることを特徴とする請求項1に記載の難燃性塩化ビニル樹脂成形体。The molded body is formed by laminating a vinyl chloride resin layer having a low chlorination degree and a vinyl chloride resin layer having a high chlorination degree, and the average chlorination degree of the vinyl chloride resin in the molded body is 60% or more. The flame-retardant vinyl chloride resin molded article according to claim 1, wherein 平均塩素化度が60.0〜63.5%であることを特徴とする請求項2に記載の難燃性塩化ビニル樹脂成形体。The flame-retardant vinyl chloride resin molded article according to claim 2, wherein the average degree of chlorination is 60.0 to 63.5%. 塩素化度が低い塩化ビニル樹脂層の両面に、塩素化度が高い塩化ビニル樹脂層が積層されたことを特徴とする請求項2又は請求項3に記載の難燃性塩化ビニル樹脂成形体。The flame-retardant vinyl chloride resin molded article according to claim 2 or 3, wherein a vinyl chloride resin layer having a high chlorination degree is laminated on both surfaces of a vinyl chloride resin layer having a low chlorination degree. 塩素化度が低い塩化ビニル樹脂の塩素化度が56.0〜57.0%で、塩素化度が高い塩化ビニル樹脂の塩素化度が62.0〜66.0%であることを特徴とする請求項2ないし請求項4のいずれかに記載の難燃性塩化ビニル樹脂成形体。The vinyl chloride resin having a low chlorination degree has a chlorination degree of 56.0 to 57.0%, and the vinyl chloride resin having a high chlorination degree is 62.0 to 66.0%. The flame-retardant vinyl chloride resin molded article according to any one of claims 2 to 4. 成形体中の塩化ビニル樹脂に占める塩素化度が低い塩化ビニル樹脂の割合が、60重量%以下であることを特徴とする請求項2ないし請求項5のいずれかに記載の難燃性塩化ビニル樹脂成形体。The flame retardant vinyl chloride according to any one of claims 2 to 5, wherein a ratio of the vinyl chloride resin having a low chlorination ratio to the vinyl chloride resin in the molded body is 60% by weight or less. Resin molded body. 塩化ビニル樹脂の塩素化度が60.0〜63.5%であることを特徴とする請求項1に記載の難燃性塩化ビニル樹脂成形体。The flame-retardant vinyl chloride resin molded article according to claim 1, wherein the chlorination degree of the vinyl chloride resin is 60.0 to 63.5%. 塩化ビニル樹脂の平均重合度が500〜800であることを特徴とする請求項1ないし請求項8のいずれかに記載の難燃性塩化ビニル樹脂成形体。The flame-retardant vinyl chloride resin molded article according to any one of claims 1 to 8, wherein an average degree of polymerization of the vinyl chloride resin is 500 to 800. 塩化ビニル樹脂の熱安定剤として錫系安定剤を使用し、厚みが5mmのときの全光線透過率が70〜80%、ヘイズ値が3〜5%であり、色相の黄変度が−30〜−5であることを特徴とする請求項1ないし請求項8のいずれかに記載の難燃性塩化ビニル樹脂成形体。A tin stabilizer is used as a heat stabilizer for the vinyl chloride resin, the total light transmittance is 70 to 80% when the thickness is 5 mm, the haze value is 3 to 5%, and the yellowing degree of the hue is -30. It is --5, The flame-retardant vinyl chloride resin molding in any one of Claim 1 thru | or 8 characterized by the above-mentioned.
JP2003182002A 2003-06-26 2003-06-26 Flame-retardant vinyl chloride resin molded form Pending JP2005015620A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009013208A (en) * 2007-06-29 2009-01-22 Takiron Co Ltd Vinyl chloride-based resin molding
WO2011142263A1 (en) 2010-05-10 2011-11-17 日東電工株式会社 Flame-retardant polymer member, flame-retardant product, and flame-retarding method
WO2012053418A1 (en) 2010-10-19 2012-04-26 日東電工株式会社 Highly flame-retardant polymer member, flame-retardant article, and flame-retarding method
CN110423421A (en) * 2018-09-21 2019-11-08 安徽滁州德威新材料有限公司 A kind of cable jacket color inhibition anti-flaming transparent material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009013208A (en) * 2007-06-29 2009-01-22 Takiron Co Ltd Vinyl chloride-based resin molding
WO2011142263A1 (en) 2010-05-10 2011-11-17 日東電工株式会社 Flame-retardant polymer member, flame-retardant product, and flame-retarding method
WO2012053418A1 (en) 2010-10-19 2012-04-26 日東電工株式会社 Highly flame-retardant polymer member, flame-retardant article, and flame-retarding method
CN110423421A (en) * 2018-09-21 2019-11-08 安徽滁州德威新材料有限公司 A kind of cable jacket color inhibition anti-flaming transparent material and preparation method thereof

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