JP4446319B2 - Resin composition and molded product - Google Patents
Resin composition and molded product Download PDFInfo
- Publication number
- JP4446319B2 JP4446319B2 JP25403299A JP25403299A JP4446319B2 JP 4446319 B2 JP4446319 B2 JP 4446319B2 JP 25403299 A JP25403299 A JP 25403299A JP 25403299 A JP25403299 A JP 25403299A JP 4446319 B2 JP4446319 B2 JP 4446319B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- vinyl chloride
- weight
- parts
- chloride resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、優れた耐候性や耐熱変形性を付与し、圧縮永久歪を小さくした樹脂組成物、特に軟質樹脂組成物に関する。
【０００２】
【従来の技術】
従来より、可塑剤を配合した軟質塩化ビニル系樹脂は、窓枠等の建材用ガスケット、ベルトモール、ウィンドウモール及びサイドモール等の自動車用ガスケット等の材料として広く使われている。しかし、この塩化ビニル系樹脂は加硫ゴムに比べ高温時の形状保形性や圧縮永久歪が著しく劣るという欠点があった。
【０００３】
これらの欠点の改良方法としては、例えば平均重合度２５００〜３８００の高重合度塩化ビニル系樹脂を使用する方法が挙げられる。この方法を使用すると、例えば、ＪＩＳ Ｋ６３０１（７０℃×２２Ｈｒ）に定める圧縮永久歪を、従来品の６０〜７０％から、５０％近くへと低減させることができる。しかし、この方法により得られた塩化ビニル系樹脂は、更に低く良好な圧縮永久歪特性を要求される、ガスケット、チューブ又はパッキン類の材料としては不充分であった。この欠点を改良するために更に高重合度化した塩化ビニル系樹脂を使用しても、更なる圧縮永久歪の低減は図れず、塩化ビニル系樹脂の成形性が悪くなるという欠点があった。
【０００４】
この欠点を改良するために、塩化ビニル系樹脂及び可塑剤からなる軟質塩化ビニル系樹脂に部分架橋ニトリルゴムを添加し、圧縮永久歪特性を改良する方法が一般的に用いられている。
【０００５】
又、圧縮永久歪特性をより一層改良するために、塩化ビニル系樹脂、可塑剤及び部分架橋ニトリルゴムからなる軟質塩化ビニル系樹脂に架橋剤を添加し、成形加工時に部分架橋ニトリルゴムを動的に架橋させることにより、圧縮永久歪特性をより一層改良する方法が提案されている（特開平２−１２４９５８号公報参照）。
【０００６】
【発明が解決しようとする課題】
しかし、これらの方法により得られた塩化ビニル系樹脂は、高温時の形状保形性や圧縮永久歪特性が確かに改良されるけれども、成形加工時の溶融粘度が高い、成形性が劣る、更には樹脂組成物中に含まれる部分架橋ニトリルゴムに起因する屋外暴露による色調変化が大きい、物性の低下が大きく耐候性が劣るという課題があった。
【０００７】
本発明は、塩化ビニル系樹脂の成形加工性や耐候性を低下させることなく、高温時の形状保形性や圧縮永久歪特性を改良した樹脂組成物を提供することを目的とする。
【０００８】
【課題を解決するための手段】
即ち本発明は、平均重合度が８００〜１９００である塩化ビニル系樹脂、コア−シェル型構造を有するアクリル系ゴム重合体及び可塑剤を含有してなる樹脂組成物であり、アクリル系ゴム重合体の含有量が塩化ビニル系樹脂１００重量部に対して１０〜３００重量部である該樹脂組成物であり、さらに、充填剤を含有する該樹脂組成物である。
そして、該樹脂組成物を成形してなる成形品である。
【０００９】
【発明の実施の形態】
以下本発明を詳細に説明する。
【００１０】
本発明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体、並びに、塩化ビニルと、それに共重合可能なビニル化合物との混合物を、懸濁重合法、塊状重合法、微細懸濁重合法又は乳化重合法等の通常の方法によって重合した樹脂組成物、並びに、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸エチル共重合体又は塩素化ポリエチレン等に塩化ビニルをグラフト共重合した樹脂組成物等が挙げられる。
又、塩素化塩素ビニル系樹脂を用いてもよい。
【００１１】
前記塩化ビニルと共重合可能なビニル化合物としては、酢酸ビニルやプロピオン酸ビニル等のビニルエステル類、メチルアクリレートやブチルアクリレート等のアクリル酸エステル類、メチルメタクリレートやエチルメタクリレート等のメタクリル酸エステル類、ブチルマレートやジエチルマレート等のマレイン酸エステル類、ジブチルフマレートやジエチルフマレート等のフマル酸エステル類、ビニルメチルエーテル、ビニルブチルエーテル及びビニルオクチルエーテル等のビニルエーテル類、アクリロニトリルやメタクリロニトリル等のシアン化ビニル類、エチレン、プロピレンやスチレン等のα−オレフィン類、塩化ビニリデンや臭化ビニル等の塩化ビニル以外のハロゲン化ビニリデンやハロゲン化ビニル類、並びに、ジアリルフタレート等のフタル酸エステル類が挙げられる。これらのビニル化合物は、塩化ビニル系樹脂の構成成分中３０重量％以下が好ましく、２０重量％以下がより好ましい。
【００１２】
これらの塩化ビニル系樹脂の平均重合度は、ＪＩＳ Ｋ６７２１により測定する平均重合度（以下重合度と称す）が８００〜１９００であり、１０００〜１８００が好ましい。重合度が８００未満だと得られた樹脂組成物の圧縮永久歪特性が劣り、１９００を越えると得られた樹脂組成物の成形加工時の溶融粘度が著しく高くなり、加工性が悪くなる。
【００１３】
本発明に用いられるアクリル系ゴム重合体は、コア材と、このコア材の表面を覆うシェル材とからなるコア−シェル型構造を有するアクリル系ゴム重合体である。
【００１４】
コア材とは、ブチルアクリレートを主成分として、ブチルアクリレートと反応性が等しく、２個以上の二重結合を有する単量体、例えばジビニルベンゼン等の芳香族ジビニル単量体やブチレングリコールジアクリレート等により架橋が施されたものをいう。
【００１５】
シェル材は、塩化ビニル系樹脂との相溶性に優れる単量体を最低１個以上含む構造が好ましい。塩化ビニル系樹脂との相溶性に優れるシェル材としては、ポリメタクリル酸メチルやポリメタクリル酸エチル等のポリメタクリル酸エステル類、ポリカプロラクトン等のポリエステル類、ポリエステル系ポリウレタン、エチレン−酢酸ビニル共重合体及びスチレン−アクリロニトリル共重合体等の樹脂組成物が挙げられる。
【００１６】
コア−シェル型構造を有するアクリル系ゴム重合体としては、サニガムＰ７３９５（ＧｏｏｄＹｅａｒ社製）等が挙げられる。
【００１７】
アクリル系ゴム重合体の含有量は、塩化ビニル系樹脂１００重量部に対して１０〜３００重量部が好ましく、２０〜２００重量部がより好ましい。１０重量部未満だと圧縮永久歪特性が劣るおそれがあり、３００重量部を越えると成形加工時の溶融粘度が著しく高くなり、加工性が悪くなるおそれがある。
【００１８】
本発明に用いられる可塑剤としては、特に限定されるものではなく、従来の軟質塩化ビニル系樹脂に使われるものを使用できる。可塑剤としては、ジ−２−エチルヘキシルフタレートやジブチルフタレート等のフタル酸エステル類、ジ−２−エチルヘキシルアジペート等のアジピン酸エステル類、ジブチルセバケート等のセバシン酸エステル、トリ−２−エチルヘキシルトリメリテート等のトリメリット酸エステル及びエポキシ化大豆油等のエポキシ系化合物等が挙げられる。
【００１９】
可塑剤の含有量は、製品に要求される硬さ、可撓性、物性及び成形加工性の点で、塩化ビニル系樹脂１００重量部に対して２０〜２００重量部が好ましく、３０〜１５０重量部がより好ましい。２０重量部未満だと柔軟性を付与しにくく、圧縮永久歪が大きく、加工性が悪くなるおそれがあり、２００重量部を越えると樹脂組成物中に可塑剤を吸収しにくく、成形品から可塑剤が滲み出て、形状保持性や成形加工性が悪くなるおそれがある。
【００２０】
本発明では、製品に要求される硬さ、可撓性、物性及び成形加工性を満たす点で、充填剤が好ましい。
【００２１】
充填剤としては、炭酸カルシウム、タルク、シリカ、クレー、水酸化アルミニウム及び酸化アンチモン等が挙げられる。これらの中では、軟質樹脂組成物の成形加工時の賦形性を大幅に改善する点で、炭酸カルシウム及び／又はタルクが好ましい。
【００２２】
本発明に用いられる炭酸カルシウムは、重質炭酸カルシウムや軽質炭酸カルシウムの何れでも良い。
【００２３】
炭酸カルシウムの平均粒径は特に制限はないが、通常、０．０３〜４．０μｍが好ましく、０．０４〜２．０μｍがより好ましい。０．０３μｍ未満だと賦形性の付与効果が認められないおそれがあり、４．０μｍを越えるとは成形品表面が平滑にならず、外観不良となるおそれがある。
【００２４】
本発明に用いられるタルクは、ケイ酸マグネシウム系の鉱物を微粉砕した市販品が使用できる。これらの中では、ゴムや合成樹脂充填用に市販されているものが好ましい。
【００２５】
タルクの平均粒径は特に制限はないが、通常、０．８〜１２μｍが好ましく、１．０〜９μｍがより好ましく、１．５〜５μｍが最も好ましい。０．８μｍ皆だと変形やソリが大きいおそれがあり、１２μｍを越えると表面が平滑にならず、外観不良となるおそれがある。
【００２６】
充填剤の含有量は、塩化ビニル系樹脂１００重量部に対して３〜２００重量部が好ましく、５〜１５０重量部がより好ましい。３重量部未満だと成形性や加工性が悪いおそれがあり、２００重量部を越えると加工性が悪く、成形品表面が平滑にならないおそれがある。
【００２７】
本発明の樹脂組成物には、その性能を極端に低下させない範囲内で、エチレン−酢酸ビニル共重合体、アクリル系樹脂、塩素化ポリエチレン、ポリウレタン及びアクリロニトリル−ブタジエン共重合体等の塩化ビニル系樹脂との相溶性に優れる熱可塑性樹脂、塩化ビニル系樹脂に通常添加される三酸化アンチモンやホウ酸亜鉛に代表される難燃剤、ステアリン酸バリウム、ステアリン酸亜鉛及び三塩基性硫酸鉛等の熱安定剤、酸化防止剤、紫外線吸収剤、滑剤、並びに、着色剤等の各種添加剤を必要に応じて添加できる。
【００２８】
本発明において樹脂組成物を構成する各成分を混合、混練する方法や、得られた樹脂組成物を成形加工する方法は特に限定されるものではなく、一般的な混練方法及び成形加工方法を用いることができる。
【００２９】
即ち、塩化ビニル系樹脂、アクリル系ゴム重合体、可塑剤、充填剤及び必要に応じて各種添加剤を、ヘンシェルミキサーやスーパーミキサーのような高速ミキサーやリボンブレンダー等の混合機に投入し、例えば１５０℃以下の温度でそれぞれの混合機に見合った時間、均一にブレンドする。得られた混合物をバンバリーミキサー、ミキシングロール及び押出機等といった、通常の塩化ビニル系樹脂の製造に用いられる混練機を使い、常法により造粒することができる。更にこのようにして得られた樹脂組成物は通常の成形加工方法、即ちプレス成形機、押出成形機及び射出成形機等を用いて容易に加熱溶融成形することができる。
【００３０】
本発明の樹脂組成物を用いた成形品は耐候性及び圧縮永久歪特性に優れることから、ウェザーストリップ、グラスランチャンネル、ウィンドウモール、ベルトモール及びドアミラーパッキング等の自動車外装用部材、シフトレバーブーツ、サイドブレーキカバー、ヘッドレスト及びアームレスト等の自動車内装用部材、各種シール材及び各種ガスケットを含む工業用パッキン材料、ケーブル、カールコード及びマイクロホンコード等の電線被覆用部材、並びに、防水用土木シート、止水用土木シート及び窓枠用グレージング等の建築用部材等に幅広く利用することができる。
【００３１】
【実施例】
以下、本発明を実施例により説明する。
【００３２】
実験例１
表１に示す配合の使用原料を７５リットルのヘンシェルミキサーに投入した。撹拌混合後、９０ｍ／ｍ単軸押出機〔池貝鉄工（株）製〕にて混練ペレット化を行い、樹脂組成物のペレット１５ｋｇを得た。
得られたペレットを８インチロールを用いて１７０℃で５分間溶融混練した後、プレス成形し、圧縮永久歪と耐候性の各材料試験の評価に供した。
又、得られた樹脂組成物について、成形加工性及び形状保持性の評価を行った。
【００３３】
（使用原料）
塩化ビニル系樹脂−１：平均重合度８００
塩化ビニル系樹脂−２：平均重合度１０００
塩化ビニル系樹脂−３：平均重合度１７００
塩化ビニル系樹脂−４：平均重合度１８００
塩化ビニル系樹脂−５：平均重合度１９００
塩化ビニル系樹脂−６：平均重合度２０００
アクリル系ゴム重合体−１：コア−シェル型構造を有するもの、サニガムＰ７３９５、ＧｏｏｄＹｅａｒ社製
可塑剤：市販品、ジ−２−エチルヘキシルフタレート
熱安定剤−１：市販品、ステアリン酸バリウム
熱安定剤−２：市販品、ステアリン酸亜鉛
部分架橋ニトリルゴム：部分架橋アクリロニトリル−ブタジエン共重合体、市販品
【００３４】
〔試験方法〕
（圧縮永久歪の評価）
ＪＩＳ Ｋ６２６２に準拠し、試験条件７０℃×２２時間で圧縮永久歪の評価を行った。
（耐候性の評価）
ＪＩＳ Ｋ６３０１に規定される３号ダンベルをカーボンアーク式サンシャインウエザオメータ（スガ試験機（株）製）を用い、ブラックパネル温度６３℃、晴１０８分／雨１２分のサイクルで１０００時間暴露し、暴露前後の色調変化を色差計（カラーコンピュータＳＭ５、スガ試験機（株）製）を用いて評価した。色差ΔＥはＪＩＳ Ｚ８７３０により算出した。
（成形加工性の評価）
４０ｍ／ｍ単軸押出機〔池貝鉄工（株）製〕に窓枠用グレージング型ダイスを取り付け、得られた樹脂組成物について、ダイス温度１７０℃で成形加工性の評価を行った。成形品が平滑で形状の良好なものを○(その中でも表面状態が特に平滑で、金型形状が細部まで賦形されたものを◎)、成形品表面が平滑ではあるが粗いものを△、成形品の表面に波打ちが見られ、端部が裂けているものを×とした。
（形状保持性の評価）
成形加工性の評価で得られた窓枠用グレージング型を、２００℃に保持した恒温層内に１０分間放置した。放置後窓枠用グレージング型を取り出し、形状変化の有無を確認した。形状が変化しないものを○、形状変化が僅かで使用上問題とならないものを△、形状変化が大きく使用できないものを×とした。
【００３５】
【表１】
実験例２
表２に示す配合の使用原料を使用したこと以外は、実験例１と同様の条件により目的とする組成物を得、評価を行った。その結果を表２に示す。
【００３７】
（使用原料）
アクリル系ゴム重合体−２：コア−シェル型構造を有しないもの、市販品
【００３８】
【表２】
実験例３
表３に示す配合の使用原料を使用したこと以外は、実験例１と同様の条件により目的とする組成物を得、評価を行った。その結果を表３に示す。
【００４０】
【表３】
実験例４
表４に示す配合の使用原料を使用したこと以外は、実験例１と同様の条件により目的とする組成物を得、評価を行った。その結果を表４に示す。
【００４２】
（使用原料）
充填剤−１：市販品、炭酸カルシウム、平均粒径１．８μｍ
充填剤−２：市販品、タルク、平均粒径４μｍ、３ＭｇＯ・４ＳｉＯ2・Ｈ2Ｏの組成を有するもの
【００４３】
【表４】
【発明の効果】
本発明により得られた樹脂組成物は成形加工性、耐候性及び圧縮永久歪特性に優れるので、窓枠用グレージング等の建材用ガスケット、並びに、ベルトモール、ウィンドウモール及びサイドモール等の自動車用モールディングの材料といった、高温時の保形性を必要とし、耐候性や圧縮永久歪特性を要求される用途に好適に使用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition, particularly a soft resin composition, which has excellent weather resistance and heat distortion resistance and reduced compression set.
[0002]
[Prior art]
Conventionally, a soft vinyl chloride resin blended with a plasticizer has been widely used as a material for building material gaskets such as window frames, automobile gaskets such as belt moldings, window moldings, and side moldings. However, this vinyl chloride resin has the disadvantage that its shape retention at high temperatures and compression set are significantly inferior to vulcanized rubber.
[0003]
As a method for improving these drawbacks, for example, a method using a vinyl chloride resin having a high degree of polymerization of 2500 to 3800 and a high degree of polymerization can be mentioned. When this method is used, for example, the compression set defined in JIS K6301 (70 ° C. × 22 Hr) can be reduced from 60 to 70% of the conventional product to nearly 50%. However, the vinyl chloride resin obtained by this method is insufficient as a material for gaskets, tubes or packings which are required to have a lower compression and good compression set characteristics. Even if a vinyl chloride resin having a higher degree of polymerization is used to improve this drawback, the compression set cannot be further reduced, and the moldability of the vinyl chloride resin is deteriorated.
[0004]
In order to improve this drawback, a method is generally used in which a partially crosslinked nitrile rubber is added to a soft vinyl chloride resin composed of a vinyl chloride resin and a plasticizer to improve compression set characteristics.
[0005]
In order to further improve the compression set characteristics, a cross-linking agent is added to a soft vinyl chloride resin composed of a vinyl chloride resin, a plasticizer, and a partially crosslinked nitrile rubber, and the partially crosslinked nitrile rubber is dynamically changed during molding processing. There has been proposed a method for further improving the compression set characteristics by cross-linking (see JP-A-2-124958).
[0006]
[Problems to be solved by the invention]
However, the vinyl chloride resin obtained by these methods certainly improves the shape retention at high temperatures and compression set properties, but has a high melt viscosity during molding, poor moldability, However, there is a problem that the color change due to outdoor exposure due to the partially crosslinked nitrile rubber contained in the resin composition is large, the physical properties are greatly deteriorated, and the weather resistance is inferior.
[0007]
An object of this invention is to provide the resin composition which improved the shape retention property and compression set property at the time of high temperature, without reducing the molding workability and weather resistance of a vinyl chloride resin.
[0008]
[Means for Solving the Problems]
That is, the present invention is a resin composition comprising a vinyl chloride resin having an average degree of polymerization of 800 to 1900, an acrylic rubber polymer having a core-shell structure, and a plasticizer, and the acrylic rubber polymer. Is a resin composition having a content of 10 to 300 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, and further containing the filler.
And it is a molded article formed by shape | molding this resin composition.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
[0010]
As the vinyl chloride resin used in the present invention, a vinyl chloride homopolymer, and a mixture of vinyl chloride and a vinyl compound copolymerizable therewith are prepared by suspension polymerization, bulk polymerization, and fine suspension polymerization. Or a resin composition polymerized by a usual method such as an emulsion polymerization method, and a resin composition obtained by graft-copolymerizing vinyl chloride to an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, a chlorinated polyethylene or the like. Etc.
A chlorinated chlorovinyl resin may also be used.
[0011]
Examples of the vinyl compound copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid esters such as methyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, and butyl maleate. And maleic esters such as diethyl malate, fumaric esters such as dibutyl fumarate and diethyl fumarate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile , Α-olefins such as ethylene, propylene and styrene, vinylidene halides and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, and diallyl phthalate Phthalic acid esters such as bets and the like. These vinyl compounds are preferably 30% by weight or less, more preferably 20% by weight or less, in the constituent components of the vinyl chloride resin.
[0012]
As for the average degree of polymerization of these vinyl chloride resins, the average degree of polymerization (hereinafter referred to as the degree of polymerization) measured according to JIS K6721 is 800 to 1900, preferably 1000 to 1800. If the degree of polymerization is less than 800, the compression set characteristic of the obtained resin composition is inferior. If it exceeds 1900, the melt viscosity at the time of molding of the obtained resin composition becomes remarkably high, and the processability deteriorates.
[0013]
The acrylic rubber polymer used in the present invention is an acrylic rubber polymer having a core-shell type structure composed of a core material and a shell material covering the surface of the core material.
[0014]
The core material is a monomer having butyl acrylate as a main component and having the same reactivity as butyl acrylate and having two or more double bonds, for example, aromatic divinyl monomers such as divinylbenzene, butylene glycol diacrylate, etc. The thing which was bridge | crosslinked by.
[0015]
The shell material preferably has a structure including at least one monomer excellent in compatibility with the vinyl chloride resin. Shell materials excellent in compatibility with vinyl chloride resins include polymethacrylates such as polymethyl methacrylate and polyethyl methacrylate, polyesters such as polycaprolactone, polyester polyurethanes, and ethylene-vinyl acetate copolymers. And a resin composition such as a styrene-acrylonitrile copolymer.
[0016]
Examples of the acrylic rubber polymer having a core-shell structure include Sanigam P7395 (manufactured by GoodYear).
[0017]
The content of the acrylic rubber polymer is preferably 10 to 300 parts by weight and more preferably 20 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. If the amount is less than 10 parts by weight, the compression set characteristics may be inferior. If the amount exceeds 300 parts by weight, the melt viscosity at the time of molding may be extremely high, and the workability may be deteriorated.
[0018]
The plasticizer used in the present invention is not particularly limited, and those used in conventional soft vinyl chloride resins can be used. Examples of plasticizers include phthalates such as di-2-ethylhexyl phthalate and dibutyl phthalate, adipates such as di-2-ethylhexyl adipate, sebacates such as dibutyl sebacate, tri-2-ethylhexyl trimelli Examples thereof include trimellitic acid esters such as tate and epoxy compounds such as epoxidized soybean oil.
[0019]
The content of the plasticizer is preferably 20 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the vinyl chloride resin, in terms of hardness, flexibility, physical properties and moldability required for the product. Part is more preferred. If it is less than 20 parts by weight, it is difficult to impart flexibility, the compression set is large, and workability may be deteriorated. If it exceeds 200 parts by weight, it is difficult to absorb the plasticizer in the resin composition and The agent may ooze out and shape retention and molding processability may deteriorate.
[0020]
In the present invention, a filler is preferred in that it satisfies the hardness, flexibility, physical properties and moldability required for the product.
[0021]
Examples of the filler include calcium carbonate, talc, silica, clay, aluminum hydroxide, and antimony oxide. Among these, calcium carbonate and / or talc are preferable in that the shapeability during molding of the soft resin composition is greatly improved.
[0022]
The calcium carbonate used in the present invention may be either heavy calcium carbonate or light calcium carbonate.
[0023]
The average particle size of calcium carbonate is not particularly limited, but is usually preferably 0.03 to 4.0 μm, and more preferably 0.04 to 2.0 μm. If it is less than 0.03 μm, the effect of imparting formability may not be recognized, and if it exceeds 4.0 μm, the surface of the molded product may not be smooth and the appearance may be poor.
[0024]
As the talc used in the present invention, a commercially available product obtained by pulverizing a magnesium silicate mineral can be used. In these, what is marketed for rubber | gum and synthetic resin filling is preferable.
[0025]
The average particle size of talc is not particularly limited, but is usually preferably 0.8 to 12 μm, more preferably 1.0 to 9 μm, and most preferably 1.5 to 5 μm. If the thickness is 0.8 μm, deformation and warping may be large. If the thickness exceeds 12 μm, the surface may not be smooth and the appearance may be poor.
[0026]
The content of the filler is preferably 3 to 200 parts by weight and more preferably 5 to 150 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. If it is less than 3 parts by weight, the moldability and workability may be poor, and if it exceeds 200 parts by weight, the workability is poor and the surface of the molded product may not be smooth.
[0027]
The resin composition of the present invention includes vinyl chloride resins such as ethylene-vinyl acetate copolymer, acrylic resin, chlorinated polyethylene, polyurethane, and acrylonitrile-butadiene copolymer within a range that does not extremely deteriorate the performance. Heat-stabilization of thermoplastic resins with excellent compatibility with antimony, flame retardants such as antimony trioxide and zinc borate, which are usually added to vinyl chloride resins, barium stearate, zinc stearate and tribasic lead sulfate Various additives such as additives, antioxidants, ultraviolet absorbers, lubricants, and colorants can be added as necessary.
[0028]
In the present invention, the method for mixing and kneading the components constituting the resin composition and the method for molding the obtained resin composition are not particularly limited, and general kneading methods and molding methods are used. be able to.
[0029]
That is, a vinyl chloride resin, an acrylic rubber polymer, a plasticizer, a filler, and various additives as necessary are charged into a mixer such as a high-speed mixer such as a Henschel mixer or a super mixer, or a ribbon blender. Blend uniformly at a temperature below 150 ° C. for a time commensurate with each mixer. The obtained mixture can be granulated by a conventional method using a kneader such as a Banbury mixer, a mixing roll, an extruder, or the like, which is used for producing a normal vinyl chloride resin. Furthermore, the resin composition thus obtained can be easily melt-molded by heating using a normal molding method, that is, a press molding machine, an extrusion molding machine, an injection molding machine or the like.
[0030]
Molded articles using the resin composition of the present invention are excellent in weather resistance and compression set characteristics, such as weather strips, glass run channels, window moldings, belt moldings, door mirror packings and other automotive exterior members, shift lever boots, side Automotive interior parts such as brake covers, headrests and armrests, industrial packing materials including various sealing materials and various gaskets, members for covering wires such as cables, curl cords and microphone cords, and civil engineering sheets for waterproofing, for water stopping It can be widely used for construction members such as civil engineering sheets and window frame glazing.
[0031]
【Example】
Hereinafter, the present invention will be described with reference to examples.
[0032]
Experimental example 1
Raw materials having the composition shown in Table 1 were charged into a 75 liter Henschel mixer. After stirring and mixing, the mixture was kneaded and pelletized with a 90 m / m single screw extruder (manufactured by Ikekai Tekko Co., Ltd.) to obtain 15 kg of pellets of the resin composition.
The obtained pellets were melt-kneaded at 170 ° C. for 5 minutes using an 8-inch roll, then press-molded, and subjected to evaluation of each material test of compression set and weather resistance.
Further, the obtained resin composition was evaluated for moldability and shape retention.
[0033]
(Raw material)
Vinyl chloride resin-1: Average polymerization degree 800
Vinyl chloride resin-2: Average polymerization degree 1000
Vinyl chloride resin-3: Average polymerization degree 1700
Vinyl chloride resin-4: average polymerization degree 1800
Vinyl chloride resin-5: Average polymerization degree 1900
Vinyl chloride resin-6: Average polymerization degree 2000
Acrylic rubber polymer-1: having a core-shell structure, Sanigam P7395, plasticizer manufactured by GoodYear: commercial product, di-2-ethylhexyl phthalate thermal stabilizer-1: commercial product, barium stearate thermal stabilizer -2: Commercially available product, zinc stearate partially crosslinked nitrile rubber: partially crosslinked acrylonitrile-butadiene copolymer, commercially available product
〔Test method〕
(Evaluation of compression set)
Based on JIS K6262, the compression set was evaluated under test conditions of 70 ° C. × 22 hours.
(Evaluation of weather resistance)
No. 3 dumbbell specified in JIS K6301 is exposed for 1000 hours using a carbon arc type sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ° C. and a cycle of fine 108 minutes / rain 12 minutes. The change in color tone before and after exposure was evaluated using a color difference meter (color computer SM5, manufactured by Suga Test Instruments Co., Ltd.). The color difference ΔE was calculated according to JIS Z8730.
(Evaluation of moldability)
A glazing die for window frames was attached to a 40 m / m single-screw extruder (manufactured by Ikekai Tekko Co., Ltd.), and the molding processability of the obtained resin composition was evaluated at a die temperature of 170 ° C. ○ that the molded product is smooth and good in shape (in particular, the surface state is particularly smooth and the shape of the mold is shaped in detail ◎), the molded product surface is smooth but rough, Δ, The case where the surface of the molded product was wavy and the end was torn was marked with x.
(Evaluation of shape retention)
The window frame glazing mold obtained by the evaluation of molding processability was left for 10 minutes in a thermostatic layer maintained at 200 ° C. After leaving, the window frame glazing mold was taken out, and the presence or absence of a shape change was confirmed. The case where the shape did not change was indicated as ◯, the case where the shape change was slight and no problem in use was indicated by Δ, and the case where the shape change was not large was indicated as ×.
[0035]
[Table 1]
Experimental example 2
A target composition was obtained and evaluated under the same conditions as in Experimental Example 1 except that the raw materials used in the formulations shown in Table 2 were used. The results are shown in Table 2.
[0037]
(Raw material)
Acrylic rubber polymer-2: one having no core-shell structure, commercially available product
[Table 2]
Experimental example 3
A target composition was obtained and evaluated under the same conditions as in Experimental Example 1 except that the raw materials used in the formulations shown in Table 3 were used. The results are shown in Table 3.
[0040]
[Table 3]
Experimental Example 4
A target composition was obtained and evaluated under the same conditions as in Experimental Example 1 except that the raw materials used in the formulations shown in Table 4 were used. The results are shown in Table 4.
[0042]
(Raw material)
Filler-1: Commercial product, calcium carbonate, average particle size 1.8 μm
Filler-2: Commercial product, talc, average particle size 4 μm, 3MgO.4SiO 2 .H 2 O composition
[Table 4]
【The invention's effect】
Since the resin composition obtained by the present invention is excellent in molding processability, weather resistance and compression set characteristics, gaskets for building materials such as glazing for window frames, and automotive moldings such as belt moldings, window moldings and side moldings. It can be suitably used for applications that require shape retention at high temperatures and require weather resistance and compression set properties.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25403299A JP4446319B2 (en) | 1998-09-10 | 1999-09-08 | Resin composition and molded product |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25688598 | 1998-09-10 | ||
| JP10-256885 | 1998-09-10 | ||
| JP25403299A JP4446319B2 (en) | 1998-09-10 | 1999-09-08 | Resin composition and molded product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000143917A JP2000143917A (en) | 2000-05-26 |
| JP4446319B2 true JP4446319B2 (en) | 2010-04-07 |
Family
ID=26541509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25403299A Expired - Lifetime JP4446319B2 (en) | 1998-09-10 | 1999-09-08 | Resin composition and molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4446319B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023085813A1 (en) * | 2021-11-12 | 2023-05-19 | 한화솔루션 주식회사 | Plasticizer composition and vinylchloride resin composition comprising same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001347604A (en) * | 2000-06-06 | 2001-12-18 | Denki Kagaku Kogyo Kk | Extruded molding and automobile molding |
| JP2010235834A (en) * | 2009-03-31 | 2010-10-21 | Kaneka Corp | Thermoplastic elastomer composition |
| CN103739990B (en) * | 2013-12-16 | 2016-03-02 | 重庆驰象建材有限责任公司 | PVC profile |
| US20210017372A1 (en) * | 2018-04-09 | 2021-01-21 | Dow Global Technologies Llc | Pvc-based composition |
-
1999
- 1999-09-08 JP JP25403299A patent/JP4446319B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023085813A1 (en) * | 2021-11-12 | 2023-05-19 | 한화솔루션 주식회사 | Plasticizer composition and vinylchloride resin composition comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000143917A (en) | 2000-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2515155B2 (en) | Thermoplastic elastomer composition | |
| US5736605A (en) | Vinyl chloride resin composition | |
| US5554683A (en) | Vinyl chloride resin elastomer composition | |
| JP4446319B2 (en) | Resin composition and molded product | |
| US20060155024A1 (en) | Polyvinyl chloride-base thermoplastic elastomer composition | |
| JP4407852B2 (en) | Architectural gaskets and glazing channels | |
| JP2000095912A (en) | Resin composition | |
| JPH11151742A (en) | Coextrusion molded product of soft/rigid vinyl chloride resin composition | |
| JP6961920B2 (en) | Vinyl chloride resin composition and extruded product for window frame | |
| JPS6145659B2 (en) | ||
| JP4311935B2 (en) | Thermoplastic elastomer composition | |
| JP2000117806A (en) | Extrusion molded product and resin composition | |
| JP2001270052A (en) | Co-extruded item and window molding | |
| JP2001347604A (en) | Extruded molding and automobile molding | |
| JPH09292063A (en) | Pipe and joint excellent in flexibility and shock resistance | |
| JP3506586B2 (en) | Soft vinyl chloride resin composition and molded article thereof | |
| JP3322087B2 (en) | ABS resin composite | |
| JP4792633B2 (en) | Extruded products for window frames | |
| JP2805681B2 (en) | Thermoplastic elastomer composition | |
| JP3438302B2 (en) | Vinyl chloride resin-based elastomer composition | |
| JP2001234015A (en) | Trim | |
| JPH11151743A (en) | Coextrusion molded product of soft/rigid vinyl chloride resin composition | |
| JP2006002066A (en) | Thermoplastic elastomer composition | |
| JP3508958B2 (en) | Seal material | |
| JPH06228394A (en) | Thermoplastic elastomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060623 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080115 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20090317 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090714 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090831 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091002 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20091002 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100113 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130129 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4446319 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130129 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160129 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |