JP6568679B2 - Vinyl chloride resin composition - Google Patents
Vinyl chloride resin composition Download PDFInfo
- Publication number
- JP6568679B2 JP6568679B2 JP2014172276A JP2014172276A JP6568679B2 JP 6568679 B2 JP6568679 B2 JP 6568679B2 JP 2014172276 A JP2014172276 A JP 2014172276A JP 2014172276 A JP2014172276 A JP 2014172276A JP 6568679 B2 JP6568679 B2 JP 6568679B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- resin composition
- tube
- component
- mol
- 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.)
- Active
Links
Landscapes
- Materials For Medical Uses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、塩化ビニル系樹脂組成物に関する。更に詳しくは、成形性、特に押出チューブ成形性に優れ、耐蒸気滅菌性、耐γ線滅菌性、及び耐キンク性の良好な医療用途に好適なチューブを得ることのできる、塩化ビニル系樹脂組成物に関する。
The present invention relates to a vinyl chloride resin composition. More specifically, a vinyl chloride resin composition that is excellent in moldability, particularly extruded tube moldability, and can provide a tube suitable for medical use having good steam sterilization resistance, γ-ray sterilization resistance, and kink resistance. Related to things.
塩化ビニル系樹脂は、その優れた機械的特性と経済性から、医療用器具、例えばカテーテル等の医療用チューブ；血液バッグ、薬液バッグ及びドレインバッグ等の医療用バック；医療用血液回路のジョイント部材；及び医療用容器などの材料として広く用いられている。 Due to its excellent mechanical properties and economic efficiency, the vinyl chloride resin is a medical instrument such as a medical tube such as a catheter; a medical bag such as a blood bag, a drug solution bag and a drain bag; a joint member of a medical blood circuit And widely used as a material for medical containers and the like.
医療チューブとしては、例えば、「塩化ビニル系樹脂１００重量部に対して、シクロヘキサン−１，２−ジカルボン酸系エステル２０〜１００重量部を配合してなる軟質塩化ビニル樹脂から構成されるカテーテル。」が提案されている（特許文献１）。しかし、押出チューブ成形性、成形されたチューブが巻状態で蒸気滅菌された場合の、特に所謂高圧蒸気滅菌器を用いて、温度１２１℃において蒸気滅菌された場合の耐くっつき性、及び耐キンク性の全てに満足できるものではなかった。
As a medical tube, for example, “a catheter composed of a soft vinyl chloride resin in which 20 to 100 parts by weight of cyclohexane-1,2-dicarboxylic acid ester is blended with 100 parts by weight of vinyl chloride resin”. Has been proposed (Patent Document 1). However, extrusion tube formability, sticking resistance and kink resistance when the molded tube is steam sterilized in a wound state, particularly when steam sterilized at a temperature of 121 ° C. using a so-called high pressure steam sterilizer. I was not satisfied with all of the above.
本発明の課題は、押出チューブ成形性、成形されたチューブが巻状態で、所謂高圧蒸気滅菌器を用いて、温度１２１℃において蒸気滅菌された場合の耐くっつき性、及び耐キンク性に優れ、医療用途に好適なチューブを得ることのできる、塩化ビニル系樹脂組成物を提供することにある。
The subject of the present invention is excellent in extrusion tube formability, sticking resistance when the molded tube is wound, and steam sterilization at a temperature of 121 ° C. using a so-called high pressure steam sterilizer, and kink resistance. The object is to provide a vinyl chloride resin composition capable of obtaining a tube suitable for medical use.
本発明者は、鋭意研究した結果、特定の可塑剤を含む塩化ビニル系樹脂組成物により、上記課題を達成できることを見出した。 As a result of intensive studies, the present inventor has found that the above problems can be achieved by a vinyl chloride resin composition containing a specific plasticizer.
すなわち、本発明は、成分（ａ）塩化ビニル系樹脂１００質量部；及び成分（ｂ）ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステルを水素添加して得られるシス異性体９０〜１００モル％、トランス異性体１０〜０モル％のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル１５〜１５０質量部；を含む医療用塩化ビニル系樹脂組成物である。 That is, the present invention relates to component (a) 100 parts by mass of vinyl chloride resin; and component (b) casNo. 28553-12-0 phthalic acid diisononyl ester obtained by hydrogenation 90 to 100 mol%, trans isomer 10 to 0 mol% cyclohexane-1,2-dicarboxylic acid di (isononyl) ester 15 to A medical vinyl chloride resin composition containing 150 parts by mass.
第２の発明は、チューブ用であることを特徴とする第１の発明に記載の医療用塩化ビニル系樹脂組成物である。 2nd invention is a vinyl chloride resin composition for medical use as described in 1st invention characterized by using for tubes.
第３の発明は、第１の発明又は第２の発明に記載の樹脂組成物からなる医療用チューブである。
3rd invention is a medical tube which consists of a resin composition as described in 1st invention or 2nd invention.
本発明の塩化ビニル系樹脂組成物は、成形性、特に押出チューブ成形性に優れる。また本発明の塩化ビニル系樹脂組成物からなるチューブは、巻状態で所謂高圧蒸気滅菌器を用い、温度１２１℃において蒸気滅菌された場合の耐くっつき性、及び耐キンク性に優れる。そのため医療用チューブとして好適に用いることができる。
The vinyl chloride resin composition of the present invention is excellent in moldability, particularly extrusion tube moldability. The tube made of the vinyl chloride resin composition of the present invention is excellent in sticking resistance and kink resistance when a so-called high pressure steam sterilizer is used in a wound state and steam sterilized at a temperature of 121 ° C. Therefore, it can be suitably used as a medical tube.
成分（ａ）「塩化ビニル樹脂」（必須成分）：
本発明の成分（ａ）として用いる塩化ビニル系樹脂は、−ＣＨ２−ＣＨＣｌ−で表される基を有する全ての重合体を指し、塩化ビニルの単独重合体；塩化ビニル・酢酸ビニル共重合体、塩化ビニル・（メタ）アクリル酸共重合体、塩化ビニル・（メタ）アクリル酸メチル共重合体、塩化ビニル・（メタ）アクリル酸エチル共重合体、塩化ビニル・マレイン酸エステル共重合体、塩化ビニル・エチレン共重合体、塩化ビニル・プロピレン共重合体、塩化ビニル・スチレン共重合体、塩化ビニル・イソブチレン共重合体、塩化ビニル・塩化ビニリデン共重合体、塩化ビニル・スチレン・無水マレイン酸三元共重合体、塩化ビニル・スチレン・アクリロニトリル三元共重合体、塩化ビニル・ブタジエン共重合体、塩化ビニル・イソプレン共重合体、塩化ビニル・塩素化プロピレン共重合体、塩化ビニル・塩化ビニリデン・酢酸ビニル三元共重合体、塩化ビニル・アクリロニトリル共重合体、塩化ビニル・各種ビニルエーテル共重合体等の塩化ビニルと塩化ビニルと共重合可能な他のモノマーとの共重合体；後塩素化ビニル共重合体等の塩化ビニル単独重合体や塩化ビニル系共重合体を改質したもの；さらには塩素化ポリエチレン等の構造上塩化ビニル樹脂と類似の塩素化ポリオレフィンを包含する。
Component (a) “vinyl chloride resin” (essential component):
The vinyl chloride resin used as component (a) of the present invention refers to all polymers having a group represented by —CH 2 —CHCl—, a vinyl chloride homopolymer; a vinyl chloride / vinyl acetate copolymer. , Vinyl chloride / (meth) acrylic acid copolymer, vinyl chloride / (meth) methyl acrylate copolymer, vinyl chloride / (meth) ethyl acrylate copolymer, vinyl chloride / maleic acid ester copolymer, chloride Vinyl / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride ternary Copolymer, vinyl chloride / styrene / acrylonitrile terpolymer, vinyl chloride / butadiene copolymer, vinyl chloride / isoprene copolymer Copolymerized with vinyl chloride and vinyl chloride, such as vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinylidene chloride / vinyl acetate terpolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / various vinyl ether copolymers, etc. Copolymers with other possible monomers; Post-chlorinated vinyl copolymers and other vinyl chloride homopolymers and modified vinyl chloride copolymers; and structurally vinyl chloride resins such as chlorinated polyethylene And similar chlorinated polyolefins.
上記成分（ａ）は、成形性、耐くっつき性、及び耐キンク性の観点から、数平均重合度が、好ましくは３００〜７０００、より好ましくは１０００〜２５００である。 The component (a) has a number average polymerization degree of preferably 300 to 7000, more preferably 1000 to 2500 from the viewpoints of moldability, sticking resistance, and kink resistance.
本発明の成分（ａ）としては、これらの塩化ビニル系樹脂の１種又は２種以上の混合物を用いることができる。 As the component (a) of the present invention, one or a mixture of two or more of these vinyl chloride resins can be used.
成分（ｂ）「ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステルを水素添加して得られるシス異性体９０〜１００モル％、トランス異性体１０〜０モル％のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル」（必須成分）：
本発明の塩化ビニル系樹脂組成物は、成分（ｂ）ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステル（以下、ＤＩＮＰと略すことがある。）を水素添加して得られるシス異性体９０〜１００モル％、トランス異性体１０〜０モル％のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステルを含む。上記成分（ｂ）が、ＤＩＮＰを水素添加して得られるものであるため、本発明の樹脂組成物は、成形性、耐くっつき性、及び耐キンク性の特に優れた樹脂組成物になる。
Component (b) “cyclohexane-1,2-dicarboxylic acid having 90 to 100 mol% of cis isomer and 10 to 0 mol% of trans isomer obtained by hydrogenation of diisononyl phthalate of cas No. 28553-12-0 Di (isononyl) ester "(essential component):
The vinyl chloride resin composition of the present invention comprises component (b) casNo. 28553-12-0 phthalic acid diisononyl ester (hereinafter sometimes abbreviated as DINP) obtained by hydrogenation of 90 to 100 mol% of cis isomer, 10 to 0 mol% of cyclohexane-1, 2-dicarboxylic acid di (isononyl) ester. Since the component (b) is obtained by hydrogenating DINP, the resin composition of the present invention is a resin composition particularly excellent in moldability, sticking resistance, and kink resistance.
上記ＤＩＮＰとしては、特に制限されず、公知の方法で合成されたＤＩＮＰを用いることができる。 The DINP is not particularly limited, and DINP synthesized by a known method can be used.
上記成分（ｂ）は、シス異性体９０〜１００モル％と、トランス異性体１０〜０モル％との混和物である。そのため成形性、耐くっつき性、及び耐キンク性の特に優れた樹脂組成物を得ることができる。好ましくは、シス異性体９５〜１００モル％と、トランス異性体５〜０モル％との混和物である。ここでシス異性体とトランス異性体との和は１００モル％である。 The component (b) is a mixture of 90 to 100 mol% of cis isomer and 10 to 0 mol% of trans isomer. Therefore, a resin composition having particularly excellent moldability, sticking resistance, and kink resistance can be obtained. A mixture of 95 to 100 mol% of cis isomer and 5 to 0 mol% of trans isomer is preferable. Here, the sum of the cis isomer and the trans isomer is 100 mol%.
上記シス異性体とトランス異性体との混和物は、ＤＩＮＰを公知の方法（例えば、特表２０１３−５１３４７７号公報に記載された技術。）で水素添加することにより得ることができる。 The mixture of the cis isomer and the trans isomer can be obtained by hydrogenating DINP by a known method (for example, a technique described in JP 2013-513477 A).
上記成分（ｂ）のシス異性体とトランス異性体との比率は、プロトンの核磁気共鳴スペクトル（以下、１Ｈ−ＮＭＲと略すことがある。）により求めることができる。ジアルキルヘキサヒドロフタレートのメチンのプロトンは２．５〜３．０ｐｐｍにシグナルが現れ、該シグナルのうち２．７〜３．０ｐｐｍはシス異性体に、２．５〜２．７ｐｐｍはトランス異性体に帰属される。従って、シス異性体の比率は２．５〜３．０ｐｐｍの積分面積に対する２．７〜３．０ｐｐｍの積分面積として、トランス異性体の比率は２．５〜３．０ｐｐｍの積分面積に対する２．５〜２．７ｐｐｍの積分面積として、求めることができる。１Ｈ−ＮＭＲの測定は、例えば、特表２００５−５０４１１９号公報などを参照して行うことができる。また株式会社三井化学分析センターなどに測定を依頼して行うこともできる。 The ratio of the cis isomer to the trans isomer of the component (b) can be determined from a nuclear magnetic resonance spectrum of proton (hereinafter sometimes abbreviated as 1 H-NMR). The methine proton of dialkyl hexahydrophthalate shows a signal at 2.5-3.0 ppm, of which 2.7-3.0 ppm is in the cis isomer and 2.5-2.7 ppm is in the trans isomer. Be attributed. Thus, the cis isomer ratio is 2.7-3.0 ppm integrated area to 2.5-3.0 ppm integrated area, and the trans isomer ratio is 2.5-3.0 ppm integrated area 2. It can be determined as an integrated area of 5 to 2.7 ppm. The measurement of 1 H-NMR can be performed with reference to, for example, JP-T-2005-504119. It can also be done by requesting measurements from Mitsui Chemical Analysis Center.
上記成分（ｂ）の配合量は、成形性、耐くっつき性、及び耐キンク性の観点から、上記成分（ａ）１００質量部に対して、１５〜１５０質量部、好ましくは２０〜１２０質量部である。 The blending amount of the component (b) is 15 to 150 parts by mass, preferably 20 to 120 parts by mass with respect to 100 parts by mass of the component (a) from the viewpoints of moldability, sticking resistance, and kink resistance. It is.
本発明の樹脂組成物には、本発明の目的に反しない限度において、上記成分（ｂ）以外の可塑剤、例えば、シス異性体とトランス異性体との比が規定範囲外のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル、ｃａｓＮｏ．６８５１５−４８−０のフタル酸ジイソノニルエステルを水素添加して得られるシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル、フタル酸エステル、トリメリット酸エステル、脂肪酸２塩基性エステル、リン酸エステル、エポキシ系可塑剤、及びポリエステル系可塑剤を１種又は２種以上含ませてもよい。 In the resin composition of the present invention, the plasticizer other than the component (b), for example, cyclohexane-1, whose ratio of cis isomer to trans isomer is outside the specified range, is not limited to the object of the present invention. 2-dicarboxylic acid di (isononyl) ester, casNo. Cyclohexane-1,2-dicarboxylic acid di (isononyl) ester, phthalic acid ester, trimellitic acid ester, fatty acid dibasic ester, phosphoric acid ester obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester, One or more epoxy plasticizers and polyester plasticizers may be included.
本発明の樹脂組成物には、塩化ビニル系樹脂及びその樹脂組成物に通常用いられる安定剤を、更に含ませることができる。上記安定剤としては、例えば、有機スズ化合物系、バリウム−亜鉛系、カルシウム−亜鉛系、及び鉛系の安定剤などをあげることができる。これらの中で、環境問題の観点から、有機スズ化合物系、バリウム−亜鉛系、及びカルシウム−亜鉛系の安定剤が好ましい。安定剤としては、これらの１種、又は２種以上の混合物を用いることができる。安定剤の配合量は、上記成分（ａ）１００質量部に対して、０．１〜１０質量部が好ましい。 The resin composition of the present invention may further contain a vinyl chloride resin and a stabilizer usually used for the resin composition. Examples of the stabilizer include organotin compound-based, barium-zinc-based, calcium-zinc-based, and lead-based stabilizers. Among these, from the viewpoint of environmental problems, organotin compound-based, barium-zinc-based, and calcium-zinc-based stabilizers are preferable. As a stabilizer, these 1 type, or 2 or more types of mixtures can be used. As for the compounding quantity of a stabilizer, 0.1-10 mass parts is preferable with respect to 100 mass parts of said components (a).
本発明の樹脂組成物には、各種金属セッケン、脂肪酸、及びポリエチレンワックスなどの滑剤を、更に含ませることができる。滑剤の配合量は、上記成分（ａ）１００質量部に対して、０．１〜１０質量部が好ましい。 The resin composition of the present invention may further contain various metal soaps, fatty acids, and lubricants such as polyethylene wax. The blending amount of the lubricant is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (a).
本発明の樹脂組成物には、本発明の目的に反しない限度において、所望により、塩化ビニル系樹脂及びその樹脂組成物に通常用いられる各種添加剤（例えば、熱安定剤、充填剤、滑剤、発泡剤、顔料、紫外線吸収剤など。）や各種充填材（例えば、炭酸カルシウム、クレー、タルクなど。）を更に含ませることができる。 In the resin composition of the present invention, the vinyl chloride resin and various additives usually used in the resin composition (for example, heat stabilizer, filler, lubricant, Foaming agents, pigments, ultraviolet absorbers, etc.) and various fillers (for example, calcium carbonate, clay, talc, etc.) can be further included.
本発明の樹脂組成物は、上記成分（ａ）、上記成分（ｂ）、及び所望に応じて用いる任意成分を、任意の溶融混練機（例えば、単軸押出機、二軸押出機、ロール、ミキサー、及び各種のニーダーなど。）を使用して溶融混練することにより得ることができる。好ましくは加圧ニーダーを用い、樹脂温度１５０〜１８０℃で溶融混練することにより得ることができる。
In the resin composition of the present invention, the above component (a), the above component (b), and an optional component used as desired can be mixed with any melt kneader (for example, a single screw extruder, a twin screw extruder, a roll, It can be obtained by melt-kneading using a mixer and various kneaders. Preferably, it can be obtained by melt kneading at a resin temperature of 150 to 180 ° C. using a pressure kneader.
以下、本発明を実施例により説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
使用した原材料
成分（ａ）：
（ａ−１）数平均重合度Ｐ＝１０５０の塩化ビニル単独重合体。
（ａ−２）数平均重合度Ｐ＝１４００の塩化ビニル単独重合体。
（ａ−３）数平均重合度Ｐ＝１７００の塩化ビニル単独重合体。
（ａ−４）数平均重合度Ｐ＝２０００の塩化ビニル単独重合体。
（ａ−５）数平均重合度Ｐ＝２５００の塩化ビニル単独重合体。
Raw materials used Component (a):
(A-1) A vinyl chloride homopolymer having a number average degree of polymerization P = 1050.
(A-2) Vinyl chloride homopolymer having a number average degree of polymerization P = 1400.
(A-3) Vinyl chloride homopolymer having a number average polymerization degree P = 1700.
(A-4) A vinyl chloride homopolymer having a number average polymerization degree P = 2000.
(A-5) A vinyl chloride homopolymer having a number average degree of polymerization P = 2500.
成分（ｂ）：
（ｂ−１）ＤＩＮＰを水素添加して得られるシス異性体９２モル％、トランス異性体８モル％のジイソノニルシクロヘキサン−１，２−ジカルボキシレート可塑剤。
（ｂ−２）ＤＩＮＰを水素添加して得られるシス異性体１００モル％、トランス異性体０モル％のジイソノニルシクロヘキサン−１，２−ジカルボキシレート可塑剤。
Component (b):
(B-1) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 92 mol% of cis isomer and 8 mol% of trans isomer obtained by hydrogenating DINP.
(B-2) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 100 mol% of cis isomer and 0 mol% of trans isomer obtained by hydrogenating DINP.
比較成分（ｂ’）：
（ｂ’−１）ＤＩＮＰを水素添加して得られるシス異性体８５モル％、トランス異性体１５モル％のジイソノニルシクロヘキサン−１，２−ジカルボキシレート可塑剤。
（ｂ’−２）ｃａｓＮｏ．６８５１５−４８−０のフタル酸ジイソノニルエステルを水素添加して得られるシス異性体９５モル％、トランス異性体５モル％のジイソノニルシクロヘキサン−１，２−ジカルボキシレート可塑剤。
Comparative component (b ′):
(B′-1) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 85 mol% of cis isomer and 15 mol% of trans isomer obtained by hydrogenating DINP.
(B′-2) casNo. A diisononylcyclohexane-1,2-dicarboxylate plasticizer containing 95 mol% of cis isomer and 5 mol% of trans isomer obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester.
任意成分（Ｃ）：
（Ｃ−１）株式会社ＡＤＥＫＡのジオクチル錫メルカプト系安定剤「アデカスタブ４６５（商品名）」。
（Ｃ−２）株式会社ＡＤＥＫＡのバリウム−亜鉛系複合安定性。
（Ｃ−３）三井化学株式会社のポリエチレンワックス系滑剤「ハイワックス４２０２Ｅ（商品名）」。
Optional component (C):
(C-1) Dioctyl tin mercapto stabilizer “ADEKA STAB 465 (trade name)” by ADEKA Corporation.
(C-2) Barium-zinc composite stability of ADEKA Corporation.
(C-3) Polyethylene wax lubricant “High Wax 4202E (trade name)” manufactured by Mitsui Chemicals, Inc.
測定方法
（１）押出チューブ成形性：
スパイラルダイ出口の樹脂温度１８８℃、冷却水温度１５℃、引取速度１０ｍ／分、及び真空水槽の真空度−７．０ＫＰａの条件で、内径２．１ｍｍ、外径３．３ｍｍの押出チューブを成形する際の、ドローダウン性、押出チューブ表面外観、及び押出チューブ形状を目視観察し、以下の基準で評価した。
◎：ドローダウン性、押出チューブ表面外観、及び押出チューブ形状の全てが良好である。
○：押出チューブの表面にやや肌荒れがあるが、ドローダウン性と押出チューブ形状は良好である。
△：押出チューブの表面に肌荒れがあり、形状にも乱れがあるが、ドローダウン性は良好である。
×：押出チューブの表面に顕著な肌荒れがあり、形状にも大きな乱れがある。またドローダウン性も悪い。
Measuring method (1) Extruded tube formability:
Forming extruded tube with inner diameter of 2.1mm and outer diameter of 3.3mm under the conditions of spiral die outlet resin temperature 188 ° C, cooling water temperature 15 ° C, take-up speed 10m / min and vacuum water tank vacuum degree -7.0KPa The drawdown property, the extruded tube surface appearance, and the extruded tube shape were visually observed and evaluated according to the following criteria.
A: The drawdown property, the extruded tube surface appearance, and the extruded tube shape are all good.
○: Although the surface of the extruded tube is somewhat rough, the drawdown property and the extruded tube shape are good.
Δ: The surface of the extruded tube is rough and the shape is disordered, but the drawdown property is good.
X: The surface of the extruded tube has significant skin roughness, and the shape is greatly disturbed. Also, the drawdown property is bad.
（２）押出チューブが巻状態で蒸気滅菌された場合の耐くっつき性：
上記押出チューブ成形性の評価で得た押出チューブから長さ５メートルのサンプルを採取し、ドーナッツ状（ドーナッツの穴の大きさを直径２０ｃｍにした。）に巻き束ね、高圧蒸気滅菌器内に静置し、温度１２１℃で１時間の蒸気滅菌処理を行い、温度２３度、相対湿度５０％の環境で２４時間状態調整した後、以下の基準で評価した。
◎：チューブ間のくっつきは全く生じておらず、簡単にほどけた。
○：チューブ間のくっつきが僅かに生じている。
△：チューブ間のくっつきがあり、かつチューブを手で触るとややべたつき感がある。
×：チューブ間のくっつきがあり、かつチューブの表面にやや肌荒れが目視観察される。
(2) Sticking resistance when the extruded tube is steam sterilized in a wound state:
A sample having a length of 5 meters was taken from the extruded tube obtained by the above-described evaluation of the extruded tube formability, wound in a donut shape (the size of the hole of the donut was 20 cm in diameter), and statically placed in a high pressure steam sterilizer. Then, steam sterilization treatment was performed at a temperature of 121 ° C. for 1 hour, and the condition was adjusted for 24 hours in an environment of a temperature of 23 degrees and a relative humidity of 50%, and then evaluated according to the following criteria.
(Double-circle): The sticking between tubes did not arise at all, but was easily unwound.
○: Slight sticking between tubes.
(Triangle | delta): There exists sticking between tubes, and when a tube is touched by hand, there exists a feeling of stickiness a little.
X: There exists sticking between tubes, and a rough skin is visually observed on the surface of the tube.
（３）耐キンク性
上記押出チューブ成形性の評価で得た押出チューブから長さ１０ｃｍのサンプルを採取し、温度２３度、相対湿度５０％の環境で２４時間状態調整した後、同環境下で、引張圧縮試験機を使用し、圧縮速度１２０ｍｍ／分、チャック間距離５０ｍｍの条件でチューブを圧縮し、サンプルの長さ方向の中央部周辺においてキンクが発生した時点のチャック移動距離（Ｌ）を求め、以下の基準で評価した。ここで「キンク」とは、チューブが折れ曲がる等して閉塞され、導通管としての機能を果たせなくなった状態をいう。
○：Ｌ≧４５ｍｍ
×：Ｌ＜４５ｍｍ
(3) Kink resistance A sample having a length of 10 cm was taken from the extruded tube obtained by the above-described evaluation of the extruded tube formability, and after being conditioned for 24 hours in an environment of a temperature of 23 degrees and a relative humidity of 50%, Using a tensile / compression tester, compress the tube under the conditions of a compression speed of 120 mm / min and a distance between chucks of 50 mm, and determine the chuck travel distance (L) when kinks occur around the center of the sample in the longitudinal direction. And evaluated according to the following criteria. Here, “kink” refers to a state in which the tube is blocked by bending or the like and cannot function as a conducting tube.
○: L ≧ 45 mm
×: L <45 mm
実施例１〜１２、比較例１〜２
表１又は２に示す量（質量部）の成分を、加圧ニーダーを使用して排出時樹脂温度１６０℃の条件で溶融混練し、塩化ビニル樹脂組成物を得た。上記（１）〜（３）の評価を行った。結果を表１又は２に示す。
Examples 1-12, Comparative Examples 1-2
The components (parts by mass) shown in Table 1 or 2 were melt-kneaded using a pressure kneader at a resin temperature at discharge of 160 ° C. to obtain a vinyl chloride resin composition. The above evaluations (1) to (3) were performed. The results are shown in Table 1 or 2.
本発明の塩化ビニル樹脂組成物は、押出チューブ成形性に優れる。また得られたチューブは、巻状態で蒸気滅菌された場合の耐くっつき性、及び耐キンク性に優れる。 The vinyl chloride resin composition of the present invention is excellent in extrusion tube moldability. The obtained tube is excellent in sticking resistance and kink resistance when steam-sterilized in a wound state.
一方、成分（ｂ）の替わりに、シス／トランス比が規定範囲外の可塑剤を用いた比較例１は、得られたチューブの巻状態で蒸気滅菌された場合の耐くっつき性、及び耐キンク性に劣る。成分（ｂ）（ＤＩＮＰ（ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステル）を水素添加して得た可塑剤）の替わりに、ｃａｓＮｏ．６８５１５−４８−０のフタル酸ジイソノニルエステルを水素添加して得た可塑剤を用いた比較例２は、得られたチューブの巻状態で蒸気滅菌された場合の耐くっつき性、及び耐キンク性に劣る。 On the other hand, Comparative Example 1 using a plasticizer having a cis / trans ratio outside the specified range instead of the component (b) is sticking resistance and kink resistance when steam sterilization is performed in a wound state of the obtained tube. Inferior to sex. Instead of component (b) (a plasticizer obtained by hydrogenating DINP (casino diesteronyl phthalate of cas No. 28553-12-0)), casNo. Comparative Example 2 using a plasticizer obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester is superior in sticking resistance and kink resistance when steam sterilized in a wound state of the obtained tube. Inferior.
Claims (2)
成分（ｂ）ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステルを水素添加して得られるシス異性体９０〜１００モル％、トランス異性体１０〜０モル％のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル １５〜１５０質量部；
を含む医療用塩化ビニル系樹脂組成物であって、チューブ用であり、かつ高圧蒸気滅菌用の上記医療用塩化ビニル系樹脂組成物。
Component (a) vinyl chloride resin 100 parts by mass; and component (b) casNo. Cycloisomer-1,2-dicarboxylic acid di (isononyl) ester 15 to 90 mol% obtained by hydrogenation of 28553-12-0 phthalic acid diisononyl ester 90 to 100 mol%, trans isomer 10 to 0 mol% 150 parts by weight;
A medical vinyl chloride resin composition comprising: a medical use vinyl chloride resin composition for a tube and for high-pressure steam sterilization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014172276A JP6568679B2 (en) | 2014-08-27 | 2014-08-27 | Vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014172276A JP6568679B2 (en) | 2014-08-27 | 2014-08-27 | Vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016044297A JP2016044297A (en) | 2016-04-04 |
| JP6568679B2 true JP6568679B2 (en) | 2019-08-28 |
Family
ID=55635157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014172276A Active JP6568679B2 (en) | 2014-08-27 | 2014-08-27 | Vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6568679B2 (en) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3549246B2 (en) * | 1994-05-18 | 2004-08-04 | テルモ株式会社 | Medical equipment |
| DE10146848A1 (en) * | 2001-09-24 | 2003-04-24 | Oxeno Olefinchemie Gmbh | Mixture of alicyclic polycarboxylic acid esters with a high cis content |
| EP2045286B1 (en) * | 2001-09-25 | 2013-04-24 | ExxonMobil Chemical Patents Inc. | Plasticised polyvinyl chloride |
| JP2004097599A (en) * | 2002-09-11 | 2004-04-02 | Kawasumi Lab Inc | Blood circuit for high-pressure steam sterilization |
| US7591887B2 (en) * | 2003-03-14 | 2009-09-22 | Basf Se | Printing inks comprising cyclohexane polycarboxylic acid derivatives |
| JP2005040397A (en) * | 2003-07-23 | 2005-02-17 | Sumitomo Bakelite Co Ltd | Catheter |
| JP5291294B2 (en) * | 2007-02-15 | 2013-09-18 | 昭和化成工業株式会社 | Rigid medical vinyl chloride resin composition and rigid medical parts using the same |
| KR101099127B1 (en) * | 2008-10-16 | 2011-12-26 | 한화케미칼 주식회사 | Method of preparing of 60% or more cis-di(C4-C20)alkyl cyclohexane-1,4-dicarboxylate |
| CN101899188A (en) * | 2010-08-31 | 2010-12-01 | 威海洁瑞医用制品有限公司 | Medical PVC granular material |
| JP2012255104A (en) * | 2011-06-09 | 2012-12-27 | Riken Technos Corp | Vinyl chloride resin composition |
| WO2014046158A1 (en) * | 2012-09-20 | 2014-03-27 | 東洋紡株式会社 | Pellet-type composition for medical use, and molded article |
| CN102863720A (en) * | 2012-10-29 | 2013-01-09 | 成都市新津事丰医疗器械有限公司 | Medical polyvinyl chloride (PVC) material sterilized by gamma ray radiation |
-
2014
- 2014-08-27 JP JP2014172276A patent/JP6568679B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016044297A (en) | 2016-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105555859B (en) | Molding resin composition containing chlorinated vinyl chloride resin and molded article thereof | |
| US20110264080A1 (en) | Medical Devices Having Extremely High Radiopacity Containing Ytterbium Compound | |
| JP6461542B2 (en) | Vinyl chloride resin composition | |
| CA2971399A1 (en) | Poly(oxyalkylene) polymer processing additive, compositions, and methods | |
| JP6556427B2 (en) | Biodegradable resin composition | |
| JP6148565B2 (en) | Medical radiation sterilized vinyl chloride resin composition and medical device comprising the same | |
| US20170121513A1 (en) | Medical Tube | |
| JP4757649B2 (en) | Radiation shielding sheet | |
| ES2998547T3 (en) | Flexible tube | |
| TW201815845A (en) | Compositions including copolymers of vinylidene fluoride and tetrafluoroethylene and methods of using the same | |
| JP6333045B2 (en) | Vinyl chloride resin composition | |
| JP6148566B2 (en) | Medical radiation sterilized vinyl chloride resin composition and medical device comprising the same | |
| JP6568679B2 (en) | Vinyl chloride resin composition | |
| JP2012067257A (en) | Polyvinyl chloride resin composition and flexible cable protecting tube | |
| JP6246527B2 (en) | Medical vinyl chloride resin composition and medical device comprising the same | |
| JP6219133B2 (en) | Medical vinyl chloride resin composition and medical device comprising the same | |
| JP6425460B2 (en) | Vinyl chloride resin composition | |
| JPWO2020008923A1 (en) | Fluororesin-containing resin composition and its manufacturing method | |
| JP6385219B2 (en) | Vinyl chloride resin composition for foam molding | |
| JP4889007B2 (en) | Tearable tube made of fluororesin | |
| JP6495677B2 (en) | Medical vinyl chloride resin composition | |
| JP2006342343A (en) | Elastomer composition | |
| JP6461531B2 (en) | Vinyl chloride resin composition | |
| JP6148570B2 (en) | Medical radiation sterilized vinyl chloride resin composition and medical device comprising the same | |
| JP6178658B2 (en) | Medical radiation sterilized vinyl chloride resin composition and medical device comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170714 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180713 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180727 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180913 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181219 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20190215 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190403 |
|
| 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: 20190717 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190805 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6568679 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |