JP4171280B2 - Rigid vinyl chloride resin tube - Google Patents
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- JP4171280B2 JP4171280B2 JP2002302163A JP2002302163A JP4171280B2 JP 4171280 B2 JP4171280 B2 JP 4171280B2 JP 2002302163 A JP2002302163 A JP 2002302163A JP 2002302163 A JP2002302163 A JP 2002302163A JP 4171280 B2 JP4171280 B2 JP 4171280B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、硬質塩化ビニル系樹脂管に関する。
【０００２】
【従来の技術】
塩化ビニル樹脂は機械的強度、耐薬品性などに優れており、管工機材や住宅資材等に広く使用されている。
しかし、硬質塩化ビニル管を太陽光が照射されるような状況下で保管した場合、塩化ビニル管が湾曲することがある。湾曲、すなわち反りの大きい塩化ビニル管は、管内を流れる流体の流動性が低下したり、施工が困難になるなどの問題があった。
この様な反りを防止する方法としては、塩化ビニル管に鉄製の線材を連着する方法がある（例えば、特許文献１参照）。この方法は塩化ビニル管の両端周縁面に山形状の突起部を形成した塩ビパイプ本体を設け、この突起部間に鉄製の線材を連着して、塩ビパイプ本体に発生する反りを防止するものである。しかし、この方法では、塩化ビニル管に鉄製の線材を一本一本連着する必要があり、非常に手間がかかってしまう。
【０００３】
【特許文献１】
特開平５−１４１５７４号公報（第１頁〜第４頁）
【０００４】
【発明が解決しようとする課題】
本発明は、上記に鑑み、太陽光等が照射されても湾曲し難たい又は湾曲量の小さい硬質塩化ビニル系樹脂管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、上記目的を達成するためになされたものであり、請求項１の発明（以下、発明１）は、外気温１５℃の雰囲気下において、波長０.７〜１００μｍ、熱量４ｋｗ／ｍ2の赤外及び遠赤外線が２時間照射された際に、管表面最大温度が６０℃以下であることを特徴とする硬質塩化ビニル系樹脂管を提供する。
また、請求項２の発明（以下、発明２）は、３５００ｋｃａｌ／m2・日以上の日射量が存在する環境下に２０日間静置された後の、下記式（１）から算出される周方向応力σの最大値と最小値の差△σが２．９４ＭＰａ以下であることを特徴とする硬質塩化ビニル系樹脂管を提供する。
σ＝[E／（１−Ｒ2)]・t／２・（1／r1−１／r0） （１）
E：引張弾性率 R：ポアソン比 t：肉厚 r0：切開前内半径 r1：切開後内半径
【０００６】
以下に本発明を詳述する。
本発明１の硬質塩化ビニル系樹脂管は、外気温１５℃の雰囲気下において、波長０.７〜１００μｍ、熱量４ｋｗ／ｍ2の赤外及び遠赤外線が２時間照射された際に、管表面最大温度が６０℃以下でなくてはならない。管表面最大温度が６０℃を超える硬質塩化ビニル系樹脂管は、特に夏場、太陽光の照射される環境下に保管した場合湾曲量が大きくなり、管体としての性能を発揮できなくなるため、この範囲に限定される。
本発明２の硬質塩化ビニル系樹脂管は、３５００ｋｃａｌ／m2・日以上の日射量が存在する環境下に２０日間静置された後の、式（１）から算出される周方向応力σの最大値と最小値の差△σが２．９４ＭＰａ以下でなくてはならない。
特に夏場、太陽光の照射される環境下に保管された場合、湾曲量が大きくなるため、この範囲に限定される。３５００ｋｃａｌ／m2・日とは、夏場の日射量に相当し、実際の暴露試験で３〜４週間で反り量は飽和するので、２０日間としたものである。
【０００７】
本発明1及び本発明２に用いられる塩化ビニル系樹脂としては、塩化ビニル単独重合休または塩化ビニルを主成分とする複合塩化ビニル系樹脂が挙げられる。これらは単独で用いられても良く、２種類以上併用して用いても良い。
【０００８】
本発明１及び本発明２に用いられる塩化ビニル系樹脂の平均重合度は６００〜３０００が好ましく、更に好ましくは８００〜２０００である。平均重合度が６００未満であると機械的強度が不足する可能性があり、逆に平均重合度が３０００を超えると成形が困難になることがある。
尚、上記の平均重合度とは、塩化ビニル単独重合体や複合塩化ビニル系樹脂をテトラヒドロフラン（THF）に溶解させ、濾過により不溶成分を除去した後、濾液中のTHFを乾燥除去して得た樹脂を試料とし、ＪＩＳ K−６７２１「塩化ビニル樹脂試験方法」に準拠して測定した平均重合度を意味する。
【０００９】
本発明1及び本発明２で用いられる塩化ビニルを主成分とする複合塩化ビニル系樹脂としては、塩化ビニルモノマーと共重合可能なモノマーや重合体との共重合体等が挙げられる。
【００１０】
塩化ビニルモノマーと共重合可能なモノマーとしては、例えば、エチレン、プロピレン、ブチレン等のαオレフイン類；プロピオン酸ビニル等のビニルエステル類；エチルビニルエーテル、ブチルビニルエ−テル等のビニルエーテル類；メチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヒドロキシ工チル（メタ）アクリレート等の（メタ）アクリレート類；スチレン、α−メチルスチレン等の芳香族ビニル類；フッ化ビニル、フッ化ビニリデン、塩化ビニリデン等のハロゲン化ビニル類；N−フェニルマレイミド、N−シクロヘキシルマレイミド等のN−置換マレイミド類等が挙げられる。これらの共重合性モノマーは、単独で用いられても良いし、２種類以上が併用されても良い。
【００１１】
塩化ビニルモノマーと共重合可能な重合体としては、例えば、アルキル（メタ）アクリレートモノマーなどからなるアクリル系共重合体等が挙げられ、これらの共重合性重合体は、単独で用いられても良いし、２種類以上が併用されても良い。尚、ここで言う（メタ）アクリレートとはアクリレート又はメタクリレートを意味する。
【００１２】
塩化ビニルモノマーと、上記の共重合性モノマーや重合体とを併用する場合、共重合性モノマーや重合体の使用量は、得られる硬質塩化ビニル管の性能や目的に応じて適宜設定されれば良く、特に限定されるものではない。
【００１３】
塩化ビニル単独重合体や塩化ビニルを主成分とする複合塩化ビニル系樹脂の重合方法としては従来公知の方法で良く、例えば、懸濁重合法等が挙げられる。
【００１４】
本発明1及び本発明２の硬質塩化ビニル系樹脂管を得る場合には、必要に応じて熱安定剤、安定化助剤、滑剤、加工助剤、酸化防止剤、光安定剤、顔料、充填剤等を添加してもよい。
【００１５】
上記熟安定剤としては特に限定されず、例えば、ジメチル錫メルカプト、ジブチル錫メルカプト、ジオクチル錫メルカプト、ジブチル錫マレート、ジブチル錫マレートポリマー、ジオクチル錫マレート、ジオクチル錫マレートポリマー、ジブチル錫ラウレート、ジブチル錫ラウレートポリマー等の有機錫安定剤、ステアリン酸鉛、二塩基性亜リン酸鉛、三塩基性硫酸鉛等の鉛系安定剤、カルシウム−亜鉛系安定剤、バリウム−亜鉛系安定剤、バリウム−カドミウム系安定剤等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
【００１６】
上記の安定化助剤としては特に限定されず、例えば、エポキシ化大豆油、エポキシ化アマニ豆油、エポキシ化テトラヒドロフタレート、エポキシ化ポリブタジエン、リン酸エステル等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
【００１７】
上記の滑剤としては、内部滑剤、外部滑剤等が挙げられる。
上記の内部滑剤は、成形加工時の溶融樹脂の流動粘度を下げ、摩擦発熱を防止する目的で使用される。上記の内部滑剤としては特に限定されず、例えば、ブチルステアレート、ラウリルアルコール、ステアリルステアレート、エポキシ化大豆油、グリセリンモノステアレート、ステアリン酸、ビスアミド等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
【００１８】
上記の外部滑剤は、成形加工時の溶融樹脂と金属面との滑り効果を上げる目的で使用される。上記の外部滑剤としては特に限定されず、例えば、モンタン酸ワックス、パラフィンワックス、ポリオレフインワックス、エステルワックス等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
【００１９】
上記の加工助剤としては特に限定されず、例えば、重量平均分子１０万〜２００万のアルキルアクリレート／アルキルメタクリレート共重合体であるアクリル系加工助剤が挙げられ、具体例としては、n−ブチルアクリレート／メチルメタクリレート共重合体、２−エチルヘキシルアクリレート／メチルメタクリレート／ブチルメタクリレート共重合体等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
【００２０】
上記の酸化防止剤としては特に限定されず、例えば、フェノール系抗酸化剤等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
上記の光安定剤としては特に限定されず、例えば、サリチル酸エステル系、べンゾフェノン系、べンゾトリアゾール系、シアノアクリレート系等の紫外線吸収剤、あるいはヒンダードアミン系の光安定剤等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
【００２１】
上記の顔料としては特に限定されず、例えば、アゾ系、フタロシアニン系、スレン系、染料レーキ系等の有機顔料、酸化物系、クロム酸モリブデン系、硫化物・セレン化物系、フェロシアン化物系、カーボンブラック等の無機顔料等が挙げられる。しかし、赤外線を吸収しにくいという観点から、有機系の黒色顔料が望ましい。これらは単独で用いてもよく、２種以上を併用してもよい。
上記の充填剤としては特に限定されず、例えば、炭酸カルシウム、タルク等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
【００２２】
上記の各種配合剤を、上記の塩化ビニル系樹脂に混合する方法としては、特に限定されず、例えば、ホットブレンドによる方法、コールドブレンドによる方法等が挙げられる。
本発明1及び本発明２の硬質塩化ビニル系樹脂管の成形方法は、従来公知の方法で良く、例えば押出成形方法が好適に用いられる。
【００２３】
３５００kｃａｌ／m2・日以上の日射量が存在する環境下に２０日間静置された後の、式（１）から算出される周方向応力σの最大値と最小値の差△σを２．９４ＭＰａ以下にする方法は、得られる塩化ビニル系樹脂管の機能を損なわなければ、特に限定されず、例えば冷却水の水温を上げたりすることによる管の残留応力を低減させたり、塩化ビニル系樹脂管の赤外線吸収率を低減したりする方法が挙げられる。
【００２４】
【発明の実施の形態】
以下に実施例を挙げて、具体的に本発明の効果を鋭明するが、本発明はこれら実施例のみに限定されるものではない。
【００２５】
（実施例１）
［塩化ビニル系樹脂組成物の作製］
塩化ビニル系単独重合体（商品名「ＴＳ−１０００Ｒ」、徳山積水工業社製）１００重量部に、有機錫系安定剤（商品名「ＯＮＺ−１４２Ｆ」、三共有機社製）１部、ポリエチレンワックス系滑剤（商品名「Ｈｉｗａｘ２２０ＭＰ」、三井石油化学工業社製）０.５部、ステアリン酸（商品名「Ｓ−３０」、花王社製）０.５部、炭酸カルシウム（商品名「ホワイトン３０５Ｓ」、白石カルシウム社製）５部、黒色顔料（有機系）（商品名「Ｂｌａｃｋ Ａ−１１０３」、大日精化社製）０.５重量部、及び酸化チタン（商品名「Ｒ−３Ｌ」、堺化学社製）２重量部をスーパーミキサー（１００Ｌ、カワタ社製）にて攪拌混合して塩化ビニル系樹脂組成物を得た。
【００２６】
［塩化ビニル系樹脂管継手の成形］
得られた塩化ビニル系樹脂組成物を直径５０ｍｍの２軸異方向回転押出機（商品名「ＳＬＭ−５０」、長田製作所社製）に供給し、外径６０ｍｍ、肉厚４．５ｍｍ、長さ１ｍの塩化ビニル系樹脂管を得た。
【００２７】
（実施例２）
塩化ビニル単独重合体を用いる代わりに、下記要領で作成した複合塩化ビニル系樹脂を用いたこと以外は実施例１と同様にして塩化ビニル系樹脂管を得た。
〔アクリル系共重合体の作製〕
アクリル系モノマー成分としてｎ−ブチルアクリレート（単独重合体のＴｇ：−５４℃）９５％及び多官能性モノマー成分としてトリメチロールプロパントリアクリレート５％を含有してなるアクリル系混合モノマー２.３６ｋｇ、乳化分散剤（商品名「ハイテノールＮ−０８」、第一工業製薬社製）の１０％水溶液５０ｇ及び純水１.５ｋｇからなる乳化モノマー液を予め調製した。
【００２８】
攪拌機及び温度調整機を備えた重合反応器（内容積１０リットル）内に、純水４ｋｇ、重合開始剤として過硫酸アンモニウムの１０％水溶液２４ｇを仕込み、重合容器内を窒素ガスで置換した後、攪拌下、重合反応器内を７５℃に昇温した。 次いで、予め調製した上記乳化モノマー液を昇温後の重合反応器内に一定の滴下速度で滴下した。乳化モノマー液の全量の滴下を３時間で終了し、その後、１時間攪拌を続けた後、重合反応を終了し、固形分の濃度が３０％のアクリル系共重合体エマルジョンを作製した。
【００２９】
〔複合塩化ビニル系樹脂の作製〕
攪拌機及び温度調整機を備えた重合反応器（内容積１５リットル）内に、純水７.５ｋｇ、上記で得られたアクリル系共重合体エマルジョン０.５ｋｇ（固形分０.１５ｋｇ）、乳化分散剤として部分鹸化ポリビニルアルコール（商品名「クラレポバールＬ−８」、クラレ社製）の３％水溶液３３０ｇ、重合開始剤としてｔ−ブチルパーオキシデカネート及びα−クミルパーオキシネオデカネートを各々１.１ｇを仕込み、重合反応器内の空気を真空ポンプで排出した後、攪拌下、塩化ビニルモノマー３.０ｋｇを添加した。次いで、重合反応器内を５０℃に昇温して、グラフト重合反応を開始した。重合反応器内の圧力の低下でグラフト重合反応の終了を確認した後、未反応の塩化ビニルモノマーを排出して、複合塩化ビニル系樹脂を作製した。得られた複合塩化ビニル系樹脂中の塩化ビニルのグラフト量は９４％であり、アクリル系共重合体の含有量は６％であった。又、得られた複合塩化ビニル系樹脂の平均重合度をＪＩＳ Ｋ ６７２１に準拠して測定したところ、平均重合度は１４００であった。
【００３０】
（比較例１）
黒色顔料を添加する代わりに、カーボンブラック（商品名「トーカブラック＃７３５０」、東海カーボン社製）を０.５重量部添加したこと以外は実施例１と同様にして塩化ビニル系樹脂管を得て、評価を行った。
【００３１】
［塩化ビニル系樹脂管の物性評価］
実施例１，２及び比較例１で得られた塩化ビニル系樹脂管について、管表面温度及び湾曲量を以下の方法で評価し、その結果を表１に示した。
（管表面温度、湾曲量）
外気温１５℃の雰囲気下において、赤外線ランプを用い、熱量４ｋｗ／ｍ2の赤外線を塩化ビニル系樹脂管に３時間照射し、塩化ビニル系樹脂管の表面温度を測定した。尚、赤外線ランプと塩化ビニル系樹脂管との距離は４０ｃｍであった。 照射後、一昼夜放置し最も湾曲している部位のパイプの両端間にピアノ線を張り、ピアノ線とパイプとの距離を測定する。上記作業を５本のパイプについて行い、測定したピアノ線とパイプとの距離のうち最大のものを湾曲量とした。
【００３２】
【表１】
（実施例３）
［塩化ビニル系樹脂組成物の作製］
実施例１の黒色顔料（商品名「Ｂｌａｃｋ Ａ−１１０３」、大日精化社製）０.５重量部の代わりに、カーボンブラック（商品名「トーカブラック＃７３５０」、東海カーボン社製）０．０５重量部を用いたこと以外は実施例１と同じ方法で塩化ビニル系樹脂組成物を得た。
【００３４】
［塩化ビニル系樹脂管継手の成形］
得られた塩化ビニル系樹脂樹脂組成物を直径５０ｍｍの２軸異方向回転押出機（商品名「ＳＬＭ−５０」、長田製作所社製）に供給し、外径６０ｍｍ、肉厚４．５ｍｍの成形体を５０℃の温水で冷却後、長さ４ｍに切断し硬質塩化ビニル系樹脂管を得た。
【００３５】
［塩化ビニル系樹脂管の物性評価］
実施例３で得られた塩化ビニル系樹脂管について、湾曲量、引張弾性率、ポアソン比、応力を以下の方法で評価し、その結果を表２に示した。
・湾曲量
硬質塩化ビニル管が動かないよう、管の両端から５ｃｍの場所を支持し、３５００Ｋｃａｌ／m2・日以上の日射量が存在する環境下に２０日間静置された後、硬質塩化ビニル管の両端にピアノ線を張り、ピアノ線と硬質塩化ビニル管との距離を測定し、その最大値を湾曲量とした。
・引張弾性率、ポアソン比
ＪＩＳ Ｋ７１６１に準拠して測定した。
【００３６】
・応力
硬質塩化ビニル管から長さ２ｃｍのサンプルを切り出し、肉厚及び内半径（r0）を測定する。静置時、最も下になった部分を切り取りＣ字型のサンプルを作成し、内半径（r1）を測定する。即ち図１において、符号１で示した部分を中心に左側は２まで、右側は８まで切り取り、全円周の１／４を切り取ったサンプルを作成した。尚、中心を通る各線は応力測定時のサンプルの切り取り方向と位置を示している。
この作業を図１の２〜８についても同様にして行い、それぞれの部位での応力σを式（１）に従って算出し、その最大値から最小値を差し引き、応力差Δσを算出する。
σ＝[E／（１−Ｒ2)]・t／２・（1／r1−１／r0） （１）
Ｅ：引張弾性率 Ｒ：ポアソン比 t：肉厚 r0：切開前内半径 r1：切開後内半径
【００３７】
（実施例４）
得られた塩化ビニル系樹脂樹脂組成物を直径５０ｍｍの２軸異方向回転押出機（商品名「ＳＬＭ−５０」、長田製作所社製）に供給し、４０℃の温水で冷却したこと以外は実施例３と同様にして評価を行った。
（実施例５）
カーボンブラックを添加する代わりに、黒色顔料（商品名「Ｂｌａｃｋ Ａ−１１０３」、大日精化社製）０．０５重量部添加したこと以外は実施例３と同様にして評価を行った。
【００３８】
（実施例６）
カーボンブラックを添加する代わりに、黒色顔料（商品名「Ｂｌａｃｋ Ａ−１１０３」、大日精化社製）０．０５重量部添加したこと以外は実施例４と同様にして評価を行った。
（実施例７）
得られた塩化ビニル系樹脂樹脂組成物を直径５０ｍｍの２軸異方向回転押出機（商品名「ＳＬＭ−５０」、長田製作所社製）に供給し、２５℃の温水で冷却したこと以外は実施例３と同様にして評価を行った。
【００３９】
（比較例２）
得られた塩化ビニル系樹脂樹脂組成物を直径５０ｍｍの２軸異方向回転押出機（商品名「ＳＬＭ−５０」、長田製作所社製）に供給し、２５℃の水で冷却したこと以外は実施例４と同様にして評価を行った。
黒色顔料を添加する代わりに、カーボンブラック（商品名「トーカブラック＃７３５０」、東海カーボン社製）を０．５重量部添加したこと以外は実施例３と同様にして評価を行った。
【００４０】
【表２】
【発明の効果】
以上述べたように、本発明により、太陽光等の照射による湾曲が生じにくいか湾曲量の小さい硬質塩化ビニル系樹脂管を得ることが出来る。
【００４２】
【図面の簡単な説明】
【図１】本発明により得られる硬質塩化ビニル系樹脂管の管軸方向に直角な断面図である。
【００４３】
【符号の説明】
１〜８ 応力測定時のサンプルの切り取り位置[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hard vinyl chloride resin tube.
[0002]
[Prior art]
Vinyl chloride resin is excellent in mechanical strength, chemical resistance, etc., and is widely used in pipework equipment and housing materials.
However, when the hard vinyl chloride tube is stored under the condition where sunlight is irradiated, the vinyl chloride tube may be bent. A vinyl chloride pipe having a large curvature, that is, a large warp, has problems such as a decrease in fluidity of a fluid flowing in the pipe and difficulty in construction.
As a method for preventing such warping, there is a method of continuously connecting an iron wire to a vinyl chloride pipe (see, for example, Patent Document 1). This method is to provide a PVC pipe body with mountain-shaped projections on the peripheral edges of both ends of the vinyl chloride pipe, and to connect the wire made of iron between the projections to prevent warping that occurs in the PVC pipe body. It is. However, in this method, it is necessary to attach iron wires to the polyvinyl chloride pipes one by one, which is very troublesome.
[0003]
[Patent Document 1]
JP-A-5-141574 (pages 1 to 4)
[0004]
[Problems to be solved by the invention]
In view of the above, an object of the present invention is to provide a hard vinyl chloride resin tube that is difficult to bend even when irradiated with sunlight or the like or has a small amount of bending.
[0005]
[Means for Solving the Problems]
The present invention has been made to achieve the above object, and the invention of claim 1 (hereinafter referred to as invention 1) has a wavelength of 0.7 to 100 μm and a calorific value of 4 kw / m in an atmosphere having an outside air temperature of 15 ° C. when 2 of infrared and far-infrared radiation is irradiated 2 hours, to provide a rigid vinyl chloride resin tube, wherein the maximum temperature pipe surface is 60 ° C. or less.
The invention of claim 2 (hereinafter referred to as invention 2) is a circuit calculated from the following formula (1) after standing for 20 days in an environment where an amount of solar radiation of 3500 kcal / m 2 · day or more exists. A rigid vinyl chloride resin pipe characterized in that the difference Δσ between the maximum value and the minimum value of the directional stress σ is 2.94 MPa or less.
σ = [E / (1-R 2 )] · t / 2 · (1 / r 1 −1 / r 0 ) (1)
E: Tensile modulus R: Poisson's ratio t: Wall thickness r 0 : Inner radius before incision r 1 : Inner radius after incision [0006]
The present invention is described in detail below.
The hard vinyl chloride resin tube of the present invention 1 has a tube surface when irradiated with infrared rays and far infrared rays having a wavelength of 0.7 to 100 μm and a calorific value of 4 kw / m 2 in an atmosphere having an outside air temperature of 15 ° C. for 2 hours. The maximum temperature must be below 60 ° C. Hard vinyl chloride resin pipes with a maximum tube surface temperature exceeding 60 ° C have a large bending amount when stored in an environment where they are exposed to sunlight, especially in summer. Limited to range.
The rigid vinyl chloride resin pipe of the present invention 2 has a circumferential stress σ calculated from the equation (1) after being left for 20 days in an environment where a solar radiation amount of 3500 kcal / m 2 · day or more exists. The difference Δσ between the maximum value and the minimum value must be 2.94 MPa or less.
In particular, when stored in an environment that is irradiated with sunlight in summer, the amount of bending becomes large, so the range is limited. 3500 kcal / m 2 · day corresponds to the amount of solar radiation in the summer, and the warping amount is saturated in 3 to 4 weeks in the actual exposure test, so it is 20 days.
[0007]
Examples of the vinyl chloride resin used in the present invention 1 and the present invention 2 include a vinyl chloride homopolymerization holiday or a composite vinyl chloride resin mainly composed of vinyl chloride. These may be used alone or in combination of two or more.
[0008]
The average degree of polymerization of the vinyl chloride resin used in the present invention 1 and the present invention 2 is preferably 600 to 3000, more preferably 800 to 2000. If the average degree of polymerization is less than 600, the mechanical strength may be insufficient. Conversely, if the average degree of polymerization exceeds 3000, molding may be difficult.
The average degree of polymerization is obtained by dissolving a vinyl chloride homopolymer or a composite vinyl chloride resin in tetrahydrofuran (THF), removing insoluble components by filtration, and drying and removing THF in the filtrate. It means the average degree of polymerization measured using a resin as a sample and according to JIS K-6721 “Testing methods for vinyl chloride resin”.
[0009]
Examples of the composite vinyl chloride resin containing vinyl chloride as a main component used in the present invention 1 and the present invention 2 include monomers copolymerizable with vinyl chloride monomers and copolymers with polymers.
[0010]
Examples of monomers copolymerizable with vinyl chloride monomer include α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl propionate; vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; methyl (meth) acrylate , (Meth) acrylates such as butyl (meth) acrylate and hydroxy-modified til (meth) acrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinyl fluoride, vinylidene fluoride and vinylidene chloride And N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. These copolymerizable monomers may be used alone or in combination of two or more.
[0011]
Examples of the polymer copolymerizable with the vinyl chloride monomer include acrylic copolymers composed of alkyl (meth) acrylate monomers and the like, and these copolymerizable polymers may be used alone. And two or more types may be used together. In addition, the (meth) acrylate said here means an acrylate or a methacrylate.
[0012]
When the vinyl chloride monomer is used in combination with the above copolymerizable monomer or polymer, the amount of the copolymerizable monomer or polymer used can be appropriately set according to the performance and purpose of the obtained rigid vinyl chloride tube. Good, not particularly limited.
[0013]
As a polymerization method of a vinyl chloride homopolymer or a composite vinyl chloride resin mainly composed of vinyl chloride, a conventionally known method may be used, and examples thereof include a suspension polymerization method.
[0014]
When obtaining the rigid vinyl chloride resin pipes of the present invention 1 and the present invention 2, heat stabilizers, stabilizing aids, lubricants, processing aids, antioxidants, light stabilizers, pigments, fillings are used as necessary. An agent or the like may be added.
[0015]
The ripening stabilizer is not particularly limited. Organotin stabilizers such as tin laurate polymer, lead-based stabilizers such as lead stearate, dibasic lead phosphite, tribasic lead sulfate, calcium-zinc stabilizer, barium-zinc stabilizer, barium -A cadmium stabilizer etc. are mentioned. These may be used alone or in combination of two or more.
[0016]
The stabilization aid is not particularly limited, and examples thereof include epoxidized soybean oil, epoxidized linseed bean oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphate ester. These may be used alone or in combination of two or more.
[0017]
Examples of the lubricant include an internal lubricant and an external lubricant.
The internal lubricant is used for the purpose of lowering the flow viscosity of the molten resin during molding and preventing frictional heat generation. The internal lubricant is not particularly limited, and examples thereof include butyl stearate, lauryl alcohol, stearyl stearate, epoxidized soybean oil, glycerin monostearate, stearic acid, and bisamide. These may be used alone or in combination of two or more.
[0018]
The above external lubricant is used for the purpose of increasing the sliding effect between the molten resin and the metal surface during the molding process. The external lubricant is not particularly limited, and examples thereof include montanic acid wax, paraffin wax, polyolefin wax, and ester wax. These may be used alone or in combination of two or more.
[0019]
The processing aid is not particularly limited, and examples thereof include acrylic processing aids that are alkyl acrylate / alkyl methacrylate copolymers having a weight average molecular weight of 100,000 to 2,000,000. Specific examples include n-butyl. Examples thereof include acrylate / methyl methacrylate copolymers, 2-ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymers, and the like. These may be used alone or in combination of two or more.
[0020]
The antioxidant is not particularly limited, and examples thereof include phenolic antioxidants. These may be used alone or in combination of two or more.
The light stabilizer is not particularly limited, and examples include salicylic acid ester-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like. These may be used alone or in combination of two or more.
[0021]
The pigment is not particularly limited, for example, organic pigments such as azo-based, phthalocyanine-based, selenium-based, dye lake-based, oxide-based, molybdenum chromate-based, sulfide / selenide-based, ferrocyanide-based, Examples thereof include inorganic pigments such as carbon black. However, an organic black pigment is desirable from the viewpoint that it hardly absorbs infrared rays. These may be used alone or in combination of two or more.
The filler is not particularly limited, and examples thereof include calcium carbonate and talc. These may be used alone or in combination of two or more.
[0022]
The method of mixing the various compounding agents with the vinyl chloride resin is not particularly limited, and examples thereof include a method using hot blending and a method using cold blending.
The molding method of the hard vinyl chloride resin pipe of the present invention 1 and the present invention 2 may be a conventionally known method, for example, an extrusion molding method is suitably used.
[0023]
The difference Δσ between the maximum value and the minimum value of the circumferential stress σ calculated from the equation (1) after being allowed to stand for 20 days in an environment where an amount of solar radiation of 3500 kcal / m 2 · day or more exists is 2. The method of 94 MPa or less is not particularly limited as long as the function of the obtained vinyl chloride resin tube is not impaired. For example, the residual stress of the tube by increasing the temperature of the cooling water is reduced, or the vinyl chloride resin is used. A method of reducing the infrared absorption rate of the tube is mentioned.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES Examples are given below to specifically clarify the effects of the present invention, but the present invention is not limited only to these examples.
[0025]
(Example 1)
[Preparation of vinyl chloride resin composition]
100 parts by weight of a vinyl chloride homopolymer (trade name “TS-1000R”, manufactured by Tokuyama Sekisui Kogyo Co., Ltd.), 1 part of an organic tin stabilizer (trade name “ONZ-142F”, manufactured by Sansha Co., Ltd.), polyethylene Wax-based lubricant (trade name “Hiwax220MP”, manufactured by Mitsui Petrochemical Co., Ltd.) 0.5 part, stearic acid (trade name “S-30”, manufactured by Kao Corporation) 0.5 part, calcium carbonate (trade name “Whiteon” 305S ", manufactured by Shiraishi Calcium Co., Ltd. 5 parts, black pigment (organic) (trade name" Black A-1103 ", manufactured by Dainichi Seika Co., Ltd.) 0.5 part by weight, and titanium oxide (trade name" R-3L ") 2 parts by weight, manufactured by Sakai Chemical Co., Ltd.) was stirred and mixed with a super mixer (100 L, manufactured by Kawata Corp.) to obtain a vinyl chloride resin composition.
[0026]
[Molding of vinyl chloride resin pipe fittings]
The obtained vinyl chloride resin composition was supplied to a biaxial counter-rotating extruder having a diameter of 50 mm (trade name “SLM-50”, manufactured by Nagata Seisakusho Co., Ltd.), and had an outer diameter of 60 mm, a wall thickness of 4.5 mm, and a length. A 1-m vinyl chloride resin tube was obtained.
[0027]
(Example 2)
Instead of using a vinyl chloride homopolymer, a vinyl chloride resin tube was obtained in the same manner as in Example 1 except that a composite vinyl chloride resin prepared as described below was used.
[Production of acrylic copolymer]
2.36 kg of acrylic mixed monomer containing 95% n-butyl acrylate (Tg of homopolymer: −54 ° C.) as acrylic monomer component and 5% trimethylolpropane triacrylate as polyfunctional monomer component, emulsified An emulsified monomer solution consisting of 50 g of a 10% aqueous solution of a dispersant (trade name “Hitenol N-08”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 1.5 kg of pure water was prepared in advance.
[0028]
In a polymerization reactor (internal volume 10 liters) equipped with a stirrer and a temperature controller, 4 kg of pure water and 24 g of a 10% aqueous solution of ammonium persulfate as a polymerization initiator were charged, and the inside of the polymerization vessel was replaced with nitrogen gas, and then stirred. The temperature inside the polymerization reactor was raised to 75 ° C. Subsequently, the emulsion monomer solution prepared in advance was dropped into the polymerization reactor after the temperature increase at a constant dropping rate. The dropping of the total amount of the emulsified monomer liquid was completed in 3 hours, and then the stirring was continued for 1 hour, and then the polymerization reaction was terminated to prepare an acrylic copolymer emulsion having a solid content of 30%.
[0029]
[Production of composite vinyl chloride resin]
In a polymerization reactor (with an internal volume of 15 liters) equipped with a stirrer and a temperature controller, 7.5 kg of pure water, 0.5 kg of the acrylic copolymer emulsion obtained above (solid content 0.15 kg), emulsified dispersion 330 g of a 3% aqueous solution of partially saponified polyvinyl alcohol (trade name “Kuraray Poval L-8”, manufactured by Kuraray Co., Ltd.) as an agent, and 1 each of t-butyl peroxydecanate and α-cumyl peroxyneodecane as polymerization initiators After charging 0.1 g, the air in the polymerization reactor was discharged with a vacuum pump, and then 3.0 kg of vinyl chloride monomer was added with stirring. Next, the temperature in the polymerization reactor was raised to 50 ° C. to initiate the graft polymerization reaction. After confirming the completion of the graft polymerization reaction by lowering the pressure in the polymerization reactor, the unreacted vinyl chloride monomer was discharged to produce a composite vinyl chloride resin. The graft amount of vinyl chloride in the obtained composite vinyl chloride resin was 94%, and the content of the acrylic copolymer was 6%. Moreover, when the average degree of polymerization of the obtained composite vinyl chloride resin was measured according to JIS K 6721, the average degree of polymerization was 1400.
[0030]
(Comparative Example 1)
A vinyl chloride resin tube was obtained in the same manner as in Example 1 except that 0.5 parts by weight of carbon black (trade name “Toka Black # 7350”, manufactured by Tokai Carbon Co., Ltd.) was added instead of adding the black pigment. And evaluated.
[0031]
[Physical property evaluation of vinyl chloride resin pipe]
For the vinyl chloride resin tubes obtained in Examples 1 and 2 and Comparative Example 1, the tube surface temperature and the amount of bending were evaluated by the following methods, and the results are shown in Table 1.
(Tube surface temperature, bending amount)
In an atmosphere with an external temperature of 15 ° C., an infrared lamp was used to irradiate the vinyl chloride resin tube with infrared rays having a heat amount of 4 kw / m 2 for 3 hours, and the surface temperature of the vinyl chloride resin tube was measured. The distance between the infrared lamp and the vinyl chloride resin tube was 40 cm. After irradiation, leave it for a whole day and night and put a piano wire between the ends of the most curved part of the pipe, and measure the distance between the piano wire and the pipe. The above operation was performed on five pipes, and the maximum distance among the measured distances between the piano wire and the pipe was defined as the bending amount.
[0032]
[Table 1]
(Example 3)
[Preparation of vinyl chloride resin composition]
Instead of 0.5 parts by weight of the black pigment of Example 1 (trade name “Black A-1103”, manufactured by Dainichi Seika Co., Ltd.), carbon black (trade name “Toka Black # 7350”, manufactured by Tokai Carbon Co., Ltd.) A vinyl chloride resin composition was obtained in the same manner as in Example 1 except that 05 parts by weight was used.
[0034]
[Molding of vinyl chloride resin pipe fittings]
The obtained vinyl chloride resin resin composition was supplied to a biaxial different direction rotary extruder (trade name “SLM-50”, manufactured by Nagata Seisakusho Co., Ltd.) having a diameter of 50 mm, and molded with an outer diameter of 60 mm and a wall thickness of 4.5 mm. The body was cooled with hot water at 50 ° C. and then cut to a length of 4 m to obtain a hard vinyl chloride resin tube.
[0035]
[Physical property evaluation of vinyl chloride resin pipe]
The vinyl chloride resin tube obtained in Example 3 was evaluated for the bending amount, tensile elastic modulus, Poisson's ratio, and stress by the following methods. The results are shown in Table 2.
・ Because the curved hard vinyl chloride tube does not move, it is supported at a location 5 cm from both ends of the tube, and after standing for 20 days in an environment with a solar radiation of 3500 Kcal / m 2 · day or more, the hard vinyl chloride tube A piano wire was stretched at both ends of the tube, the distance between the piano wire and the hard vinyl chloride tube was measured, and the maximum value was defined as the amount of bending.
-Tensile modulus, Poisson's ratio Measured according to JIS K7161.
[0036]
-A 2 cm long sample is cut out from the stress-hard vinyl chloride tube, and the wall thickness and inner radius (r 0 ) are measured. At rest, the lowermost part is cut out to make a C-shaped sample, and the inner radius (r 1 ) is measured. That is, in FIG. 1, a sample was created by cutting out the left side up to 2 and the right side up to 8, centering on the portion indicated by reference numeral 1 and cutting out 1/4 of the entire circumference. Each line passing through the center indicates the cutting direction and position of the sample at the time of stress measurement.
This operation is similarly performed for 2 to 8 in FIG. 1, and the stress σ at each part is calculated according to the equation (1), and the minimum value is subtracted from the maximum value to calculate the stress difference Δσ.
σ = [E / (1-R 2 )] · t / 2 · (1 / r 1 −1 / r 0 ) (1)
E: Tensile modulus R: Poisson's ratio t: Wall thickness r 0 : Radius before incision r 1 : Radius after incision
Example 4
The obtained vinyl chloride resin resin composition was supplied to a biaxial different-direction rotary extruder (trade name “SLM-50”, manufactured by Nagata Seisakusho Co., Ltd.) having a diameter of 50 mm and cooled with 40 ° C. hot water. Evaluation was carried out in the same manner as in Example 3.
(Example 5)
Evaluation was performed in the same manner as in Example 3 except that 0.05 part by weight of a black pigment (trade name “Black A-1103”, manufactured by Dainichi Seika Co., Ltd.) was added instead of adding carbon black.
[0038]
(Example 6)
Evaluation was performed in the same manner as in Example 4 except that 0.05 part by weight of a black pigment (trade name “Black A-1103”, manufactured by Dainichi Seika Co., Ltd.) was added instead of adding carbon black.
(Example 7)
The obtained vinyl chloride-based resin resin composition was supplied to a biaxial different-direction rotary extruder (trade name “SLM-50”, manufactured by Nagata Seisakusho Co., Ltd.) having a diameter of 50 mm, and was cooled except with 25 ° C. warm water. Evaluation was carried out in the same manner as in Example 3.
[0039]
(Comparative Example 2)
The obtained vinyl chloride resin resin composition was supplied to a biaxial different-direction rotary extruder (trade name “SLM-50”, manufactured by Nagata Seisakusho Co., Ltd.) having a diameter of 50 mm and cooled with water at 25 ° C. Evaluation was performed in the same manner as in Example 4.
Evaluation was performed in the same manner as in Example 3 except that 0.5 parts by weight of carbon black (trade name “Toka Black # 7350”, manufactured by Tokai Carbon Co., Ltd.) was added instead of adding the black pigment.
[0040]
[Table 2]
【The invention's effect】
As described above, according to the present invention, it is possible to obtain a hard vinyl chloride resin tube that is less likely to be bent by irradiation with sunlight or the like or has a small bending amount.
[0042]
[Brief description of the drawings]
FIG. 1 is a cross-sectional view perpendicular to the tube axis direction of a hard vinyl chloride resin tube obtained by the present invention.
[0043]
[Explanation of symbols]
1-8 Cutting position of sample when measuring stress
Claims (2)
σ＝[E／（１−Ｒ2)]・t／２・（1／r1−１／r0） （１）
E：引張弾性率 R：ポアソン比 t：肉厚 r0：切開前内半径 r1：切開後内半径The difference Δσ between the maximum value and the minimum value of the circumferential stress σ calculated from the following formula (1) after standing for 20 days in an environment where the amount of solar radiation of 3500 kcal / m 2 · day or more exists is 2 A hard vinyl chloride resin tube characterized by having a pressure of 94 MPa or less.
σ = [E / (1-R 2 )] · t / 2 · (1 / r 1 −1 / r 0 ) (1)
E: Tensile modulus R: Poisson's ratio t: Wall thickness r 0 : Internal radius before incision r 1 : Internal radius after incision
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| JP2002302163A JP4171280B2 (en) | 2002-03-06 | 2002-10-16 | Rigid vinyl chloride resin tube |
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| JP2002302163A JP4171280B2 (en) | 2002-03-06 | 2002-10-16 | Rigid vinyl chloride resin tube |
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| JP5108224B2 (en) * | 2004-12-16 | 2012-12-26 | 積水化学工業株式会社 | Rigid vinyl chloride resin tube |
| JP6894545B2 (en) * | 2016-03-31 | 2021-06-30 | 積水化学工業株式会社 | Gutter rehabilitation method |
| JP6997613B2 (en) * | 2017-12-15 | 2022-01-17 | アロン化成株式会社 | Hard vinyl chloride resin molded product |
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| JP2000088155A (en) * | 1998-09-09 | 2000-03-31 | Sekisui Chem Co Ltd | Belt-like body for forming spiral pipe and molding method therefor |
| JP2001139698A (en) * | 1999-11-17 | 2001-05-22 | Shin Etsu Chem Co Ltd | Polyvinyl chloride resin hard molded article for outdoor building material |
| JP2002136920A (en) * | 2000-11-06 | 2002-05-14 | Sekisui Chem Co Ltd | Method for coating outer surface of synthetic resin pipe with hot melt adhesive |
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| NL176804C (en) * | 1977-04-06 | 1985-06-03 | Wavin Bv | PLASTIC TUBE WITH LONG CHANNELS IN HIS WALL, AND METHOD FOR MANUFACTURING SUCH PLASTIC TUBE. |
| JPS6030347B2 (en) * | 1978-07-06 | 1985-07-16 | 積水化学工業株式会社 | Thermoplastic resin molded products |
| JPS5512151A (en) * | 1978-07-11 | 1980-01-28 | Sekisui Chem Co Ltd | Chlorine-containing resin compostion |
| JPS6230202A (en) * | 1985-08-01 | 1987-02-09 | Dainichi Color & Chem Mfg Co Ltd | Infrared reflective material |
| JP2626391B2 (en) * | 1991-12-27 | 1997-07-02 | 住友金属工業株式会社 | Polybutene resin deformed tube and method for producing the same |
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2002
- 2002-10-16 JP JP2002302163A patent/JP4171280B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000088155A (en) * | 1998-09-09 | 2000-03-31 | Sekisui Chem Co Ltd | Belt-like body for forming spiral pipe and molding method therefor |
| JP2001139698A (en) * | 1999-11-17 | 2001-05-22 | Shin Etsu Chem Co Ltd | Polyvinyl chloride resin hard molded article for outdoor building material |
| JP2002136920A (en) * | 2000-11-06 | 2002-05-14 | Sekisui Chem Co Ltd | Method for coating outer surface of synthetic resin pipe with hot melt adhesive |
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