JPS6342934B2 - - Google Patents
Info
- Publication number
- JPS6342934B2 JPS6342934B2 JP5650681A JP5650681A JPS6342934B2 JP S6342934 B2 JPS6342934 B2 JP S6342934B2 JP 5650681 A JP5650681 A JP 5650681A JP 5650681 A JP5650681 A JP 5650681A JP S6342934 B2 JPS6342934 B2 JP S6342934B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- composition
- weight
- present
- 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
- 239000000203 mixture Substances 0.000 claims description 19
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 16
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000010292 electrical insulation Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- PUFGCEQWYLJYNJ-UHFFFAOYSA-N didodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCC PUFGCEQWYLJYNJ-UHFFFAOYSA-N 0.000 description 2
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- -1 ethylhexyl Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Description
本発明は、軟質製品用の塩化ビニル樹脂の組成
物に関するものである。
従来使用されてきた軟質製品用の塩化ビニル樹
脂の組成物は、耐揮発性、耐寒性および電気絶縁
性を釣り合い良く具備するものがなく、いずれか
がすぐれていても他が劣るうらみがあつた。たと
えば、塩化ビニル樹脂にトリメリツト酸トリアル
キルを配合してなる組成物は、耐揮発性、電気絶
縁性は良好なるものの、耐寒性が不十分である。
また、炭素数10〜12個のノルマルアルキル基をも
つジアルキルフタレートを塩化ビニル樹脂に配合
してなる組成物は電気絶縁性が不十分の上アルキ
ル基鎖長の増大に伴ない塩化ビニル樹脂との相溶
性も低下する。
本発明者らは以上の欠点を改良し釣り合いのと
れた性質を有する塩化ビニル樹脂組成物を得るべ
く研究の結果、塩化ビニル樹脂にシクロペンタン
テトラカルボン酸テトラアルキルを配合してなる
組成物が良好なる性質を有することを見出し、本
発明を完成させるに到つた。
すなわち、本発明の塩化ビニル樹脂の組成物
は、塩化ビニル樹脂につぎの一般式で示されるシ
クロペンタンテトラカルボン酸テトナアルキルを
配合してなる。
（式中、Ｒは炭素数４〜13個のアルキル基を示
す）。
更に詳しくは、塩化ビニル樹脂100重量部に対
してシクロペンタンテトラカルボン酸テトラアル
キル20〜200重量部を配合てなる。
本発明の組成物に使用する塩化ビニル樹脂は懸
濁重合、塊状重合もしくは懸濁重合／乳化重合併
用など、特に重合方法によつて限定されるもので
はなく、塩化ビニルホモポリマーもしくは塩化ビ
ニルと他のビニル化合物とのコポリマーまたはこ
れらの混合物が用いられる。シクロペンタンテト
ラカルボン酸テトラアルキルは、アルキル基の炭
素原子数４〜13個のものであれば、単独または混
合物いずれにも使用できるが、シクロペンタンテ
トラカルボン酸テトラ２―エチルヘキシルが好ま
しく用いられる。このシクロペンタンテトラカル
ボン酸テトラ２―エチルヘキシルは、市販のシク
ロペンタテトラカルボン酸と市販の２―エチルヘ
キサノールをエステル化反応により合成すること
ができる。
本発明の組成物の塩化ビニル樹脂とシクロペン
タンテトラカルボン酸テトラアルキルの混合は、
公知の混合機たとえばヘンセルミキサー、リボン
ブレンダーなどを用いて容易に実施できる。混合
に際して、公知の種々の安定剤のほか種々の公知
の塩化ビニル樹脂組成物用添加剤を本発明の目的
を損わない範囲内で配合できる。
一般的に用いられる可塑剤を用いた組成物と、
本発明とを比べると、可塑剤トリメリツト酸トリ
２―エチルヘキシルを用いた組成物の柔軟温度は
−11℃に対し、本発明の組成物の柔軟温度は−15
℃であり、機械特性、老化性、耐油性、電気絶縁
性を損なうことなく低温柔軟性に優れている。ジ
ラウリルフタレートを用いた組成物の粉吹き性は
ブルームありに対し、本発明の組成物の粉吹き性
は変化なしであり、機械特性、老化性、耐油性、
低温柔軟性、電気絶縁性を損なうことなく粉吹性
も優れている。またDOPを用いた組成物は、老
化試験の重量変化率が−7.5％と、可塑材量の24
％が揮発しているのに対し、本発明の重量変化率
は−0.1と少なく、機械特性、耐油性、低温柔軟
性、ブリード・ブルーム性、電気絶縁性を損なう
ことなく老化性、耐揮発性に優れている。このた
め本発明の組成物は、耐熱電線被覆材料、自動車
の内装材料として用いられる。本発明の組成物に
よつて得られるフイルム、シートはブリードブル
ームを起すこともなく、また、電線被覆は電気絶
縁性がすぐれている。
以下、実施例、比較例にし本発明を説明する。
実施例、比較例で用いた各種の物性測定はつぎに
示す方法で行なつた。
引張試験 ：JIS Ｋ−6723による。
加熱老化試験：JIS Ｋ−6723による。
耐油性試験 ： 〃 〃
硬 さ ：JIS Ｋ−6301Aによる。
柔軟温度 ：JIS Ｋ−6745による。
体積抵抗率 ：JIS Ｋ−6723による。
ブリード・ブルーム性：試験シートを70℃、相
対湿度80％の定温定湿状態におき経時的に
シートを観察し、液状物のにじみ出し（ブ
リード）、粉状物のふき出し（ブルーム）
の有無をしらべる。
実施例 １
塩化ビニルホモポリマー（＝1030）100重量
部、シクロペンタンテトラカルボン酸テトラ２―
エチルヘキシル50重量部をCa−Zn系安定剤〔ア
デカアーガス化学(株)製品Mark37、以下Ca−Zn
系安定剤という〕２重量部を混合し、150℃で８
インチミキシングロールにて５分間混練後、厚さ
1.3mmのシートとなし、170℃にて５分間プレスし
て厚さ１mmまたは２mmのシートを作成した。これ
らのシートから所定の試験法による試験片を作成
して試験を行なつた。結果を表１に示した。
実施例 ２
実施例１において、Ca−Zn系安定剤の代りに、
三塩基性硫酸鉛４重量部、ステアリン酸１重量部
を使用し、他は同様に行つた。結果を表２に示
す。
比較例 １，２，３
シクロペンタンテトラカルボン酸テトラ２−エ
チルヘキシルに代えて、トリメリツト酸トリ―２
―エチルヘキシル、ジラウリルフタレート、ジ―
２―エチルヘキシルフタレート（DOPと略す）
を使用し、同様に行つた。結果を表１に示す。
比較例 ４，５，６
比較例１，２，３のそれぞれのCa−Zn系安定
剤に代えて、三塩基性硫酸鉛４重量部、ステアリ
ン酸鉛１重量部を使用し同様に行つた。結果を表
２に示す。
The present invention relates to a vinyl chloride resin composition for soft products. Conventionally used vinyl chloride resin compositions for soft products do not have a good balance of volatility resistance, cold resistance, and electrical insulation, and even if one is superior, the other is inferior. . For example, a composition prepared by blending trialkyl trimellitate with a vinyl chloride resin has good volatility resistance and electrical insulation, but has insufficient cold resistance.
In addition, compositions made by blending dialkyl phthalate with a normal alkyl group having 10 to 12 carbon atoms in vinyl chloride resin have insufficient electrical insulation properties, and due to the increase in the alkyl group chain length, the compositions have poor electrical insulation properties. Compatibility also decreases. The present inventors conducted research to improve the above-mentioned drawbacks and obtain a vinyl chloride resin composition having balanced properties. As a result, a composition obtained by blending a vinyl chloride resin with a tetraalkyl cyclopentanetetracarboxylate was found to be favorable. The present inventors have discovered that the present invention has the following properties, and have completed the present invention. That is, the vinyl chloride resin composition of the present invention is formed by blending a vinyl chloride resin with a tetonaalkyl cyclopentanetetracarboxylate represented by the following general formula. (In the formula, R represents an alkyl group having 4 to 13 carbon atoms). More specifically, 20 to 200 parts by weight of tetraalkyl cyclopentanetetracarboxylate is blended with 100 parts by weight of vinyl chloride resin. The vinyl chloride resin used in the composition of the present invention is not particularly limited by the polymerization method, such as suspension polymerization, bulk polymerization, suspension polymerization/emulsion polymerization, etc. copolymers with vinyl compounds or mixtures thereof are used. Tetraalkyl cyclopentanetetracarboxylate can be used alone or as a mixture as long as the alkyl group has 4 to 13 carbon atoms, but tetra-2-ethylhexyl cyclopentanetetracarboxylate is preferably used. This tetra-2-ethylhexyl cyclopentanetetracarboxylate can be synthesized by esterifying commercially available cyclopentatetracarboxylic acid and commercially available 2-ethylhexanol. The mixture of vinyl chloride resin and tetraalkyl cyclopentanetetracarboxylate in the composition of the present invention is
This can be easily carried out using a known mixer such as a Hensel mixer or a ribbon blender. At the time of mixing, in addition to various known stabilizers, various known additives for vinyl chloride resin compositions can be added within a range that does not impair the object of the present invention. A composition using a commonly used plasticizer,
In comparison with the present invention, the softening temperature of the composition using the plasticizer tri2-ethylhexyl trimellitate is -11°C, while the softening temperature of the composition of the present invention is -15°C.
℃, and has excellent low-temperature flexibility without compromising mechanical properties, aging resistance, oil resistance, and electrical insulation properties. The composition using dilauryl phthalate showed blooming, while the composition of the present invention showed no change in powdering property, and the mechanical properties, aging resistance, oil resistance,
Excellent powder blowing properties without compromising low temperature flexibility and electrical insulation properties. In addition, the composition using DOP showed a weight change rate of -7.5% in the aging test, which was 24% of the amount of plasticizer.
% is volatile, whereas the weight change rate of the present invention is as small as -0.1, and it has excellent aging resistance and volatility resistance without compromising mechanical properties, oil resistance, low temperature flexibility, bleed/bloom properties, and electrical insulation properties. Excellent. Therefore, the composition of the present invention is used as a heat-resistant wire coating material and an automobile interior material. Films and sheets obtained using the composition of the present invention do not cause bleed bloom, and the wire coating has excellent electrical insulation properties. The present invention will be explained below using Examples and Comparative Examples.
Various physical property measurements used in Examples and Comparative Examples were performed by the methods shown below. Tensile test: According to JIS K-6723. Heat aging test: According to JIS K-6723. Oil resistance test: Hardness: According to JIS K-6301A. Soft temperature: According to JIS K-6745. Volume resistivity: According to JIS K-6723. Bleeding/blooming properties: The test sheet was kept at a constant temperature and humidity of 70°C and 80% relative humidity, and the sheet was observed over time to see if liquid matter oozed out (bleed) or powdered matter came out (bloom).
Find out if there is. Example 1 100 parts by weight of vinyl chloride homopolymer (=1030), cyclopentanetetracarboxylic acid tetra2-
Add 50 parts by weight of ethylhexyl to a Ca-Zn stabilizer [Adeka Argus Chemical Co., Ltd. product Mark 37, hereinafter Ca-Zn]
Mix 2 parts by weight of the system stabilizer and heat it at 150°C.
After kneading for 5 minutes on an inch mixing roll, the thickness
A 1.3 mm sheet was formed and pressed at 170°C for 5 minutes to produce a 1 mm or 2 mm thick sheet. Test pieces were prepared from these sheets according to a predetermined test method and tested. The results are shown in Table 1. Example 2 In Example 1, instead of the Ca-Zn stabilizer,
The same procedure was used except that 4 parts by weight of tribasic lead sulfate and 1 part by weight of stearic acid were used. The results are shown in Table 2. Comparative Example 1, 2, 3 Tri-2 trimellistate was used instead of tetra-2-ethylhexyl cyclopentanetetracarboxylate.
-Ethylhexyl, dilauryl phthalate, di-
2-Ethylhexyl phthalate (abbreviated as DOP)
I did the same thing using . The results are shown in Table 1. Comparative Examples 4, 5, 6 The same procedure was carried out using 4 parts by weight of tribasic lead sulfate and 1 part by weight of lead stearate in place of each of the Ca-Zn stabilizers in Comparative Examples 1, 2, and 3. The results are shown in Table 2.
【表】【table】
【表】【table】
Claims (1)
クロペンタンテトラカルボン酸テトラアルキルを
配合してなる塩化ビニル樹脂の組成物。 （式中、Ｒは炭素数４〜13個のアルキル基を示
す） ２ 塩化ビニル樹脂100重量部に対してテトラカ
ルボン酸テトラアルキル20〜200重量部を配合し
てなる特許請求の範囲第１項記載の組成物。[Scope of Claims] 1. A vinyl chloride resin composition comprising a vinyl chloride resin and a tetraalkyl cyclopentanetetracarboxylate represented by the following general formula. (In the formula, R represents an alkyl group having 4 to 13 carbon atoms.) 2. Claim 1 wherein 20 to 200 parts by weight of tetraalkyl tetracarboxylate is blended with 100 parts by weight of vinyl chloride resin. Compositions as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5650681A JPS57170948A (en) | 1981-04-15 | 1981-04-15 | Composition of vinyl chloride resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5650681A JPS57170948A (en) | 1981-04-15 | 1981-04-15 | Composition of vinyl chloride resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57170948A JPS57170948A (en) | 1982-10-21 |
| JPS6342934B2 true JPS6342934B2 (en) | 1988-08-26 |
Family
ID=13029004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5650681A Granted JPS57170948A (en) | 1981-04-15 | 1981-04-15 | Composition of vinyl chloride resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57170948A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61195145A (en) * | 1985-02-25 | 1986-08-29 | Mitsubishi Monsanto Chem Co | Vinyl chloride resin composition for wire coating |
| US8815992B2 (en) | 2010-04-14 | 2014-08-26 | Exxonmobil Research And Engineering Company | Tetracarboxylic ester plasticizers |
-
1981
- 1981-04-15 JP JP5650681A patent/JPS57170948A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57170948A (en) | 1982-10-21 |
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