JPS6210535B2 - - Google Patents
Info
- Publication number
- JPS6210535B2 JPS6210535B2 JP13814279A JP13814279A JPS6210535B2 JP S6210535 B2 JPS6210535 B2 JP S6210535B2 JP 13814279 A JP13814279 A JP 13814279A JP 13814279 A JP13814279 A JP 13814279A JP S6210535 B2 JPS6210535 B2 JP S6210535B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- parts
- mercapto
- tin
- 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
Links
- -1 aryl mercapto Chemical class 0.000 claims description 19
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 14
- 230000005251 gamma ray Effects 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 3
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 2
- YLFRJROMPGNJRP-UHFFFAOYSA-L [dibutyl(3-sulfanylpropanoyloxy)stannyl] 3-sulfanylpropanoate Chemical compound [O-]C(=O)CCS.[O-]C(=O)CCS.CCCC[Sn+2]CCCC YLFRJROMPGNJRP-UHFFFAOYSA-L 0.000 description 2
- VWVMXINFNLYXDW-UHFFFAOYSA-L dioctyltin(2+);8-methyl-2-(6-methylheptyl)-2-sulfanylnonanoate Chemical compound CCCCCCCC[Sn+2]CCCCCCCC.CC(C)CCCCCC(S)(C([O-])=O)CCCCCC(C)C.CC(C)CCCCCC(S)(C([O-])=O)CCCCCC(C)C VWVMXINFNLYXDW-UHFFFAOYSA-L 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- VNPRJHMMOKDEDZ-UHFFFAOYSA-L 6-methylheptyl 2-[dibutyl-[2-(6-methylheptoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCCCCCC(C)C VNPRJHMMOKDEDZ-UHFFFAOYSA-L 0.000 description 1
- GFAOOHPSQZQJEI-UHFFFAOYSA-L CCCCCCCCCCCCCCCCCCC(CCCCCCCCCCCCCCCCCC)(C(=O)O[Sn](CCCC)(CCCC)OC(=O)C(CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)S)S Chemical compound CCCCCCCCCCCCCCCCCCC(CCCCCCCCCCCCCCCCCC)(C(=O)O[Sn](CCCC)(CCCC)OC(=O)C(CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)S)S GFAOOHPSQZQJEI-UHFFFAOYSA-L 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は放射線特にγ線に対して優れた抵抗性
を有する塩化ビニル樹脂組成物に関するものであ
る。
従来医療器具例えば注射針等の殺菌は、プラス
チツク等による包装体の状態でエチレンオキサイ
ドガスあるいは、コバルト60によるγ線処理が採
用されている。
最近はガス処理に比し、取り扱いの容易さから
γ線処理に移行しつゝあるが、これらの包装材料
として用いられる材料群の中でもよく使用される
塩化ビニル樹脂は、γ線照射によつて変色を起す
という欠点があつた。
本発明は、放射線の中でも透過性に優れ殺菌力
の強いγ線を塩化ビニル樹脂による包装体に照射
しても塩化ビニル樹脂の脱塩酸反応等による黄変
色等を防止し得る、γ線に対し強い抵抗性を有
し、且つフイルム、シート等の加工性を損うこと
なく生産できる塩化ビニル樹脂配合組成物で、そ
の要旨は、塩化ビニル樹脂100重量部に対し錫ア
ルキルメルカプト、錫アリールメルカプト又は／
および錫メルカプト酸エステルを0.1〜５重量部
および下記(1)式で示される化合物を１〜５重量部
添加してなる耐γ線性良好な塩化ビニル樹脂組成
物である。
Ｘ−（CH2−CH2−Ｏ）o−Ｈ
（式中、Ｘは水酸基、アルコキシ基またはアルキ
ルフエノキシ基）
すなわちこの発明に用いられる錫アルキルメル
カプトはジメチル錫ジドデシルメルカプト、ジブ
チル錫ジドデシルメルカプト、ジフエニル錫ジド
デシルメルカプト等であり、錫アリールメルカプ
トとしてはジブチル錫ジフエニルメルカプト等、
また錫メルカプト酸エステルとしては、ジブチル
錫ジイソオクチルチオグリコレート、ジブチル錫
ジｎ−オクタデシルチオグリコレート、ジオクチ
ル錫ジイソオクチルチオグリコレート、トリメチ
ルヘキシル錫ジブチルチオグリコレート、シクロ
ヘキシル錫ジブチルチオグリコレート、ノニル錫
ジブチルチオグリコレート、ジブチル錫βメルカ
プトプロピオネート等が用いられる。
また上記(1)式で示される化合物としては、ポリ
エチレングリコール（上式でＸが水酸基）、ポリ
オキシエチレンオレイルエーテル（Ｘ＝−
OC18H35）、ポリオキシエチレンセチルエーテル
（Ｘ＝−OC16H33）、ポリオキシエチレンラウリル
エーテル（Ｘ＝−OC12H25）、ポリオキシエチレ
ンノニルフエニルエーテル
The present invention relates to a vinyl chloride resin composition having excellent resistance to radiation, particularly gamma rays. Conventionally, medical instruments such as injection needles have been sterilized by γ-ray treatment using ethylene oxide gas or cobalt-60 while packaged in plastic or the like. Recently, there has been a shift towards gamma ray treatment due to its ease of handling compared to gas treatment, but vinyl chloride resin, which is commonly used among these packaging materials, has been shown to be more susceptible to gamma ray irradiation. It had the disadvantage of causing discoloration. The present invention provides anti-gamma rays that can prevent yellowing due to dehydrochlorination reactions of vinyl chloride resin even when irradiating packaging made of vinyl chloride resin with γ-rays, which are highly transparent and have strong sterilizing power among radiation types. It is a vinyl chloride resin compounded composition that has strong resistance and can be produced without impairing the processability of films, sheets, etc. Its gist is that tin alkyl mercapto, tin aryl mercapto, or /
and 0.1 to 5 parts by weight of tin mercapto acid ester and 1 to 5 parts by weight of a compound represented by the following formula (1), which is a vinyl chloride resin composition with good gamma ray resistance. X-(CH 2 -CH 2 -O) o -H (wherein, Dodecyl mercapto, diphenyltin didodecyl mercapto, etc., and tin aryl mercapto includes dibutyltin diphenyl mercapto, etc.
Examples of tin mercapto acid esters include dibutyltin diisooctylthioglycolate, dibutyltin di-n-octadecylthioglycolate, dioctyltin diisooctylthioglycolate, trimethylhexyltin dibutylthioglycolate, and cyclohexyltin dibutylthioglycolate. , nonyltin dibutylthioglycolate, dibutyltin β-mercaptopropionate, and the like. In addition, as compounds represented by the above formula (1), polyethylene glycol (X in the above formula is a hydroxyl group), polyoxyethylene oleyl ether (X = -
OC 18 H 35 ), polyoxyethylene cetyl ether (X=-OC 16 H 33 ), polyoxyethylene lauryl ether (X=-OC 12 H 25 ), polyoxyethylene nonyl phenyl ether
【式】ポリオキシエチレン
オクチルフエニルエーテル
[Formula] Polyoxyethylene octyl phenyl ether
【式】等が用いられる。
これらの化合物としては、常温で液状のものが
好ましく、(1)式におけるｎでいえば１〜15のもの
を主成分とする化合物が好適である。
ｎが15を越えて常温でワツクス状ないし粉状に
なると、塩化ビニル樹脂中に均一に分散させ緊密
に相溶させることが難しく、実用性が極めて乏し
くなる。
また主体となる塩化ビニル樹脂は、従来から成
形用として用いられている通常の樹脂でよく、成
形法（押圧法、カレンダー法、射出成形法等）に
応じて適当な単独重合体または共重合体を選択す
る。
次に各成分の添加量について説明するが、以
下、添加割合を示す「部」は「重量部」を意味す
る。
錫アルキルメルカプト、錫アリールメルカプト
および錫メルカプト酸エステルは、単独でまたは
混合して使用し得るが、その添加量は塩化ビニル
樹脂100部に対し0.1〜５部である。0.1部未満で
はγ線に対する抵抗がなくなり黄変色等を起し、
また５部を越えると吹出しを生じ好ましくない。
耐γ線性からみれば１部以上添加するのが好まし
い。
また上記(1)式に示される化合物は１〜５部添加
するのが好ましく、１部未満では耐γ線性が不足
し、５部を越えると吹出しやべとつきを生じる。
本発明の化合物がなぜ耐γ線性を有するかは現
在明確ではないが、錫アルキルメルカプト等を添
加することによつて安定なイオンラジカルを生
じ、γ線照射の照射エネルギーがこれに移行して
安定なイオンラジカルとして停止し、塩化ビニル
樹脂内の連鎖崩壊が阻止されることが一因と推測
される。しかし、上記の特定の錫化合物と(1)式の
化合物とを併用した場合にのみ顕著なγ線抵抗性
を示す理由はさだかでない。
更に、本発明の組成物に、必要に応じ、他の安
定剤、可塑剤、着色剤を加工性、耐γ線性を損な
わない程度に添加してもよい。
本発明組成物は、フイルム・シート状に成形し
て袋、真空成形容器等として使用するほか、ブロ
ー成形びん、厚手のシートからなる箱等の各種容
器として使用し得る。特に本発明組成物は塩化ビ
ニル樹脂の特性を生かして、押出成形法またはカ
レンダー成形法により無延伸シートとしこれを真
空成形または圧空成形で容器状に成形して用いる
のに好適である。
以下実施例について述べる。
実施例 １
下記表−１に示す各種配合物を190℃でカレン
ダー圧延を行い150μのシートを得た。これを線
量5.0Mradのコバルト60線源でγ線照射を行い、
その照射後の試料の400ｍμ波長での光線透過率
を測定した。その結果を表−１に併記する。な
お、照射前のシートの光線透過率は93％である。
表−１からわかる如く、本発明組成物から得たシ
ート（実験No.４〜８及び11〜12）はγ線照射後も
黄変が小さく高い光線透過率を維持している。な
お表−１に示すシートは、いずれも良好な真空成
形性を示した。[Formula] etc. are used. These compounds are preferably liquid at room temperature, and compounds whose main component is n in formula (1) from 1 to 15 are preferred. If n exceeds 15 and the resin becomes waxy or powdery at room temperature, it will be difficult to uniformly disperse it in the vinyl chloride resin and make it closely compatible with it, making it extremely impractical. The main vinyl chloride resin may be any ordinary resin conventionally used for molding, and may be an appropriate homopolymer or copolymer depending on the molding method (pressing method, calendar method, injection molding method, etc.). Select. Next, the amount of each component added will be explained. Hereinafter, "parts" indicating the addition ratio means "parts by weight." Tin alkyl mercapto, tin aryl mercapto and tin mercapto acid ester can be used alone or in combination, and the amount added is 0.1 to 5 parts per 100 parts of vinyl chloride resin. If it is less than 0.1 part, there will be no resistance to gamma rays, causing yellowing, etc.
Moreover, if it exceeds 5 parts, blowing may occur, which is undesirable.
From the viewpoint of γ-ray resistance, it is preferable to add 1 part or more. It is preferable to add 1 to 5 parts of the compound represented by formula (1) above; less than 1 part results in insufficient gamma ray resistance, and more than 5 parts causes blistering and stickiness. It is currently not clear why the compound of the present invention has gamma ray resistance, but by adding tin alkyl mercapto, etc., stable ion radicals are generated, and the irradiation energy of gamma ray irradiation is transferred to this, resulting in stabilization. It is presumed that one reason is that the ion radicals are stopped as ion radicals, and chain collapse within the vinyl chloride resin is prevented. However, there is no obvious reason why remarkable gamma ray resistance is exhibited only when the above-mentioned specific tin compound and the compound of formula (1) are used together. Furthermore, other stabilizers, plasticizers, and colorants may be added to the composition of the present invention, if necessary, to the extent that processability and gamma ray resistance are not impaired. The composition of the present invention can be formed into a film or sheet and used as bags, vacuum-formed containers, etc., and can also be used as various containers such as blow-molded bottles and boxes made of thick sheets. In particular, the composition of the present invention is suitable for use by taking advantage of the properties of vinyl chloride resin and forming a non-stretched sheet by extrusion molding or calendar molding into a container shape by vacuum molding or pressure molding. Examples will be described below. Example 1 Various formulations shown in Table 1 below were calender rolled at 190°C to obtain sheets of 150μ. This was irradiated with gamma rays using a cobalt-60 radiation source with a dose of 5.0 Mrad.
After the irradiation, the light transmittance of the sample at a wavelength of 400 mμ was measured. The results are also listed in Table-1. Note that the light transmittance of the sheet before irradiation was 93%.
As can be seen from Table 1, the sheets obtained from the compositions of the present invention (Experiments Nos. 4 to 8 and 11 to 12) showed little yellowing and maintained high light transmittance even after irradiation with gamma rays. Note that all the sheets shown in Table 1 exhibited good vacuum formability.
【表】【table】
【表】
実施例 ２
下記表−２に示す各種配合を押出温度190℃で
押圧加工して150μのシートを得た。このシート
について実施例１と同一の条件でγ線照射及び光
線透過率の測定を行つた。なお照射前のシートの
光線透過率は95％である。表−２からわかる如く
ジオクチルスズジイソオクチルチオグリコレート
又はジブチルスズβメルカプトプロピオネートあ
るいはノニオンが規定量未満の場合、黄変のため
透過率は60％以下となる（No.１〜３、８）。
本発明組成物から得たシート（No.４〜６及び
９）は良好な耐γ線性を示した。
なおNo.７及び10は、添加物の量が多すぎるた
め、シートに吹出しを生じ好ましくなかつた。[Table] Example 2 Various formulations shown in Table 2 below were pressed at an extrusion temperature of 190°C to obtain sheets of 150μ. This sheet was subjected to gamma ray irradiation and measurement of light transmittance under the same conditions as in Example 1. Note that the light transmittance of the sheet before irradiation was 95%. As can be seen from Table 2, if the amount of dioctyltin diisooctylthioglycolate, dibutyltin β-mercaptopropionate, or nonion is less than the specified amount, the transmittance will be 60% or less due to yellowing (Nos. 1 to 3, 8). ). Sheets obtained from the compositions of the present invention (Nos. 4 to 6 and 9) exhibited good gamma ray resistance. In No. 7 and No. 10, the amount of additives was too large, which caused the sheet to blow out, which was not preferable.
Claims (1)
ルメルカプト、錫アリールメルカプト又は／およ
び錫メルカプト酸エステルを0.1〜５重量部およ
び下記(1)式で示される化合物を１〜５重量部添加
してなる耐γ線性良好な塩化ビニル樹脂組成物。 Ｘ−（CH2−CH2−Ｏ）o−Ｈ…………(1) （式中、Ｘは水酸基、アルコキシ基またはアルキ
ルフエノキシ基）[Scope of Claims] 1. 0.1 to 5 parts by weight of tin alkyl mercapto, tin aryl mercapto or/and tin mercapto acid ester and 1 to 5 parts of a compound represented by the following formula (1) to 100 parts by weight of vinyl chloride resin. A vinyl chloride resin composition with good gamma ray resistance, which is obtained by adding part by weight of the vinyl chloride resin composition. X-( CH2 - CH2 -O) o -H…………(1) (wherein, X is a hydroxyl group, an alkoxy group, or an alkylphenoxy group)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13814279A JPS5661448A (en) | 1979-10-25 | 1979-10-25 | Vinyl resin composition having good gamma radiation resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13814279A JPS5661448A (en) | 1979-10-25 | 1979-10-25 | Vinyl resin composition having good gamma radiation resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5661448A JPS5661448A (en) | 1981-05-26 |
| JPS6210535B2 true JPS6210535B2 (en) | 1987-03-06 |
Family
ID=15214979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13814279A Granted JPS5661448A (en) | 1979-10-25 | 1979-10-25 | Vinyl resin composition having good gamma radiation resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5661448A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4726928A (en) * | 1983-11-15 | 1988-02-23 | American Hoechst Corporation | Radiation-resistant vinyl halide resin compositions and a process for their production |
| JPS6466257A (en) * | 1987-09-07 | 1989-03-13 | Nitto Kasei Co Ltd | One-pack stabilizer for halogen-containing resin |
| US5599863A (en) * | 1994-06-17 | 1997-02-04 | Cyro Industries | Gamma radiation sterilizable acrylic polymer |
| US5527842A (en) * | 1995-03-10 | 1996-06-18 | Witco Corporation | Alkyl-thio-glycolate PVC stabilizers with added aromatic ether alcohol to prevent precipitation |
| US5567751A (en) * | 1995-06-01 | 1996-10-22 | Witco Corporation | Alkyl-tin PVC stabilizers with added aromatic ether alcohol to prevent precipitation |
| US6348517B1 (en) * | 2000-09-01 | 2002-02-19 | Oxy Services, Inc. | Preparing sterile articles from polymers containing a stabilizer based on a poly(oxyalkylene) |
| EP2920242A1 (en) * | 2012-11-13 | 2015-09-23 | Resilia S.r.l. | Use of pvc for manufacturing sterilisable containers |
| KR20160139001A (en) | 2014-03-27 | 2016-12-06 | 신닛폰 리카 가부시키가이샤 | Plasticizer for vinyl chloride resin containing non-phthalate ester and vinyl chloride resin composition containing such plasticizer |
| KR20180012318A (en) | 2015-05-27 | 2018-02-05 | 신닛폰 리카 가부시키가이샤 | Epoxy cyclohexane dicarboxylic acid diester, plasticizer, stabilizer, and resin composition |
-
1979
- 1979-10-25 JP JP13814279A patent/JPS5661448A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5661448A (en) | 1981-05-26 |
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