JPH04335056A - Vinyl chloride resin composition - Google Patents
Vinyl chloride resin compositionInfo
- Publication number
- JPH04335056A JPH04335056A JP10715691A JP10715691A JPH04335056A JP H04335056 A JPH04335056 A JP H04335056A JP 10715691 A JP10715691 A JP 10715691A JP 10715691 A JP10715691 A JP 10715691A JP H04335056 A JPH04335056 A JP H04335056A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- weight
- resin composition
- graft copolymer
- vinyl acetate
- 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.)
- Pending
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000011342 resin composition Substances 0.000 title claims description 10
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 150000003505 terpenes Chemical class 0.000 claims abstract description 11
- 235000007586 terpenes Nutrition 0.000 claims abstract description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 230000007423 decrease Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- -1 ethylene, propylene, phenoxymaleimide Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 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
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は成形性及び耐熱性に優れ
た塩化ビニル系樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition having excellent moldability and heat resistance.
【０００２】0002
【従来の技術】エチレン─酢酸ビニル共重合体に塩化ビ
ニルがグラフト共重合されたグラフト共重合体はよく知
られている。BACKGROUND OF THE INVENTION Graft copolymers in which vinyl chloride is grafted onto ethylene-vinyl acetate copolymers are well known.
【０００３】このグラフト共重合体は、塩化ビニルの単
独重合体と比較すれば流動性が改善されており、また耐
熱性にもすぐれているため、精密成形、薄肉成形の分野
に使用されてきている。それでも流動性は十分ではなく
、用途、デザインの多様化に伴い、より精密な成形品、
より薄肉な成形品が要求されてきている昨今においては
、上記グラフト共重合体では対応しきれないのが現状で
ある。[0003] This graft copolymer has improved fluidity compared to a vinyl chloride homopolymer and also has excellent heat resistance, so it has been used in the fields of precision molding and thin-wall molding. There is. However, fluidity is still not sufficient, and with the diversification of applications and designs, more precise molded products,
In recent years, there has been a demand for thinner molded products, and the current situation is that the above-mentioned graft copolymers cannot meet the demand.
【０００４】このため、上記グラフト共重合体の流動性
をさらに改善する方法として
■グラフト共重合体に可塑剤や内滑剤を添加する方法■
グラフト共重合体中の酢酸ビニルの比率を増加する方法
■グラフト共重合体の分子量を低下させる方法等がおこ
なわれている。[0004] Therefore, as a method for further improving the fluidity of the above-mentioned graft copolymer, there is a method of adding a plasticizer or an internal lubricant to the graft copolymer.
Methods such as increasing the ratio of vinyl acetate in the graft copolymer and reducing the molecular weight of the graft copolymer have been carried out.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記■
の方法では成形品の耐熱性及び耐衝撃性の低下が著しい
という問題がある。また、上記■の方法では成形品の耐
熱性の低下が著しく、上記■の方法では耐衝撃性の低下
が著しいという問題点を有している。[Problem to be solved by the invention] However, the above ■
This method has a problem in that the heat resistance and impact resistance of the molded product are significantly reduced. In addition, the above method (1) has the problem that the heat resistance of the molded product is significantly reduced, and the above method (2) has the problem that the impact resistance is significantly reduced.
【０００６】本発明は上記の課題を解決し、成形性が極
めて優れ、耐衝撃性および耐熱性が良好な塩化ビニル系
樹脂組成物を提供することにある。The object of the present invention is to solve the above-mentioned problems and provide a vinyl chloride resin composition which has extremely excellent moldability and good impact resistance and heat resistance.
【０００７】[0007]
【課題を解決するための手段】本発明で用いられるエチ
レン─酢酸ビニル共重合体は、酢酸ビニル１０〜４０重
量％を含有する。酢酸ビニル含有量が１０重量％未満で
は塩化ビニルをグラフト共重合する際の重合効率が低下
し、４０重量％を超えるとグラフト共重合体の熱安定性
が低下する。The ethylene-vinyl acetate copolymer used in the present invention contains 10 to 40% by weight of vinyl acetate. If the vinyl acetate content is less than 10% by weight, the polymerization efficiency during graft copolymerization of vinyl chloride will decrease, and if it exceeds 40% by weight, the thermal stability of the graft copolymer will decrease.
【０００８】本発明で用いられるグラフト共重合体とは
、上記エチレン─酢酸ビニル共重合体５〜２０重量％に
、塩化ビニル８０〜９５重量％がグラフト共重合されて
いるものであり、必要に応じて、塩化ビニルと共重合可
能なエチレン、プロピレン、フェノキシマレイミド、ア
クリレ─ト等の不飽和結合を有するモノマ─がグラフト
共重合してもよい。グラフト共重合体中のエチレン─酢
酸ビニル共重合体が５重量％未満では流動性の向上は見
られず、２０重量％を超えると耐熱性が低下する。The graft copolymer used in the present invention is one in which 80 to 95% by weight of vinyl chloride is graft copolymerized to 5 to 20% by weight of the above ethylene-vinyl acetate copolymer. Accordingly, a monomer having an unsaturated bond such as ethylene, propylene, phenoxymaleimide, acrylate, etc. which can be copolymerized with vinyl chloride may be graft copolymerized. If the amount of ethylene-vinyl acetate copolymer in the graft copolymer is less than 5% by weight, no improvement in fluidity will be observed, and if it exceeds 20% by weight, heat resistance will decrease.
【０００９】上記グラフト共重合体の重合度は特に限定
されるものではないが、例えばＪＩＳ Ｋ ６７２
１に準拠して測定された粘度から換算された平均重合度
は、３００未満では耐衝撃性が低下し、１，２００以上
では流動性が向上しないため３００〜１，２００が好ま
しい。[0009] The degree of polymerization of the graft copolymer is not particularly limited, but for example, JIS K 672
The average degree of polymerization calculated from the viscosity measured according to No. 1 is preferably from 300 to 1,200, since impact resistance decreases when it is less than 300, and fluidity does not improve when it is 1,200 or more.
【００１０】本発明で用いられる水素化テルペン樹脂は
下記構成単位からなる数平均分子量が４００〜１，００
０の重合体である。[0010] The hydrogenated terpene resin used in the present invention consists of the following structural units and has a number average molecular weight of 400 to 1,00.
0 polymer.
【００１１】[0011]
【化２】[Case 2]
【００１２】数平均分子量４００未満では水素化テルペ
ン樹脂は非常に脆く、グラフト塩化ビニル系共重合体に
添加して成形すると成形体の耐衝撃性が低下する。また
、１，０００を超えると水素化テルペン樹脂の粘度が高
くなりすぎるため流動性が低下し、グラフト共重合体に
添加しても成形性が向上しない。[0012] When the number average molecular weight is less than 400, the hydrogenated terpene resin is very brittle, and when it is added to a grafted vinyl chloride copolymer and molded, the impact resistance of the molded product decreases. Moreover, when it exceeds 1,000, the viscosity of the hydrogenated terpene resin becomes too high, resulting in a decrease in fluidity, and even if it is added to the graft copolymer, moldability does not improve.
【００１３】本発明の塩化ビニル系樹脂組成物は、上記
グラフト共重合体１００重量部と上記水素化テルペン樹
脂１〜１０重量部からなる。水素化テルペン樹脂の添加
量は少なすぎると、流動性は向上はせず、多すぎると滑
性が強くなりすぎるため、例えば本発明の塩化ビニル系
樹脂組成物を用いて押出成形で成形する場合において、
ペレットのスクリュ─への食い込みが悪くなるなどの原
因で滞留時間が長くなるため、塩化ビニル樹脂の分解の
原因となる。また、射出成形で成形する場合においても
同様の理由で充填不良などの原因となり耐衝撃性が低下
する。The vinyl chloride resin composition of the present invention comprises 100 parts by weight of the above graft copolymer and 1 to 10 parts by weight of the above hydrogenated terpene resin. If the amount of hydrogenated terpene resin added is too small, the fluidity will not improve, and if it is too large, the slipperiness will become too strong. For example, when molding by extrusion using the vinyl chloride resin composition of the present invention. In,
The residence time becomes longer due to factors such as poor penetration of the pellets into the screw, which causes decomposition of the vinyl chloride resin. Furthermore, when molding is performed by injection molding, the impact resistance decreases due to insufficient filling for the same reason.
【００１４】本発明の塩化ビニル系樹脂組成物には、必
要に応じて耐熱性や流動性を著しく損なわない範囲で、
従来から使用されているジブチル錫マレ─ト、ジブチル
錫ジマレ─ト、ジブチル錫メルカプト、ステアリン酸鉛
、ステアリン酸亜鉛等の安定剤、ステアリン酸、ステア
リン酸カルシウム、ステアリン酸ブチルエステル、ステ
アリルアルコ─ル、ポリエチレンワックス等の滑剤、酸
化防止剤、ＭＢＳゴム、ＡＢＳゴム等の耐衝撃改良剤、
ガラス繊維等の補強材、炭酸カルシウム等の充填剤、酸
化チタン等の着色剤、紫外線吸収剤等が適宜添加されて
もよい。[0014] The vinyl chloride resin composition of the present invention may contain, if necessary, as long as the heat resistance and fluidity are not significantly impaired.
Conventionally used stabilizers such as dibutyltin maleate, dibutyltin dimaleate, dibutyltin mercapto, lead stearate, zinc stearate, stearic acid, calcium stearate, butyl stearate, stearyl alcohol, Lubricants such as polyethylene wax, antioxidants, impact improvers such as MBS rubber and ABS rubber,
Reinforcing materials such as glass fibers, fillers such as calcium carbonate, coloring agents such as titanium oxide, ultraviolet absorbers, etc. may be added as appropriate.
【００１５】本発明の塩化ビニル系樹脂組成物から成形
品を製造する方法は従来公知の任意の方法が採用でき、
例えば押出成形法、射出成形法等が挙げられる。[0015] Any conventionally known method can be used to produce a molded article from the vinyl chloride resin composition of the present invention.
Examples include extrusion molding, injection molding, and the like.
【００１６】[0016]
【実施例】次に本発明を実施例をもってさらに詳細に説
明する。
実施例１〜６、比較例１〜４
表１に示した所定量のグラフト共重合体Ｉ、ＩＩ（組成
は表２に示した）、水素化テルペン樹脂Ｉ（ヤスハラケ
ミカル社製：クリアロンＰ１２５、数平均分子量７００
）、水素化テルペン樹脂ＩＩ（ヤスハラケミカル社製：
クリアロンＰ１０５、数平均分子量６３０）、ジブチル
錫マレ─ト（三共有機合成社製：ＲＣ４０ＦＴ）、ジブ
チル錫メルカプト（三共有機合成社製、ＪＦ−９Ｂ）及
びステアリン酸ブチルエステル（花王社製：エキセパ─
ルＢＳ）をヘンシェルミキサ─に供給し、約６０℃で１
５分間混合した。その後１８０℃のロ─ルで３分間溶融
混練した。EXAMPLES Next, the present invention will be explained in more detail with reference to examples. Examples 1 to 6, Comparative Examples 1 to 4 Predetermined amounts of graft copolymers I and II shown in Table 1 (compositions shown in Table 2), hydrogenated terpene resin I (manufactured by Yasuhara Chemical Co., Ltd.: Clearon P125, number Average molecular weight 700
), hydrogenated terpene resin II (manufactured by Yasuhara Chemical Co., Ltd.:
Clearon P105, number average molecular weight 630), dibutyltin maleate (manufactured by Sankyoki Gosei Co., Ltd.: RC40FT), dibutyltin mercapto (manufactured by Sankyoki Gosei Co., Ltd., JF-9B), and butyl stearate (manufactured by Kao Corporation: EXCEPA
BS) was fed to a Henschel mixer and heated to about 60°C.
Mixed for 5 minutes. Thereafter, the mixture was melt-kneaded for 3 minutes using rolls at 180°C.
【００１７】このようにして得られた混練物を高化式フ
ロ─テスタ─に供給し、吐出孔の直径１ｍｍ、長さ１０
ｍｍのダイを用いて荷重１５０ｋｇｆ／ｃｍ２ 、１８
０℃の条件で吐出量（ｍｌ／ｓｅｃ）を測定した。又、
得られた混練物を１８０℃、１５０ｋｇｆ／ｃｍ２ の
条件でプレス成形し、得られた成形体を切断して試験片
を得、ＪＩＳ Ｋ ７２０７に準拠し、曲げ応力４
．６ｋｇｆ／ｃｍ２ で撓み温度（ＨＤＴ）を測定した
。測定結果を表２に示した。The kneaded material thus obtained was supplied to a Koka-type flow tester, and the discharge hole had a diameter of 1 mm and a length of 10 mm.
Load 150kgf/cm2 using mm die, 18
The discharge amount (ml/sec) was measured at 0°C. or,
The obtained kneaded product was press-molded under the conditions of 180°C and 150 kgf/cm2, and the obtained molded product was cut to obtain test pieces.
．． Deflection temperature (HDT) was measured at 6 kgf/cm2. The measurement results are shown in Table 2.
【００１８】[0018]
【表１】[Table 1]
【００１９】[0019]
【表２】[Table 2]
【００２０】[0020]
【発明の効果】本発明の塩化ビニル系樹脂組成物の構成
は上述の通りであり、特定のグラフト共重合体に特定量
の水素化テルペン樹脂が添加されているので、流動性に
優れ成形性が格段に良好であるばかりでなく、耐熱性、
耐衝撃性にも優れているため、より精密な成形品、より
薄肉な成形品を成形することができる。Effects of the Invention The composition of the vinyl chloride resin composition of the present invention is as described above, and since a specific amount of hydrogenated terpene resin is added to a specific graft copolymer, it has excellent fluidity and moldability. Not only is it significantly better in heat resistance,
Because it has excellent impact resistance, it is possible to mold more precise molded products and thinner molded products.
Claims (1)
成単位からなる数平均分子量４００〜１，０００の水素
化テルペン樹脂１〜１０重量部からなる樹脂組成物であ
って、 【化１】 上記グラフト重合体が、酢酸ビニル１０〜４０重量％を
含有するエチレン─酢酸ビニル共重合体５〜２０重量％
に、塩化ビニル８０〜９５重量％がグラフト共重合され
ていることを特徴とする塩化ビニル系樹脂組成物。1. A resin composition comprising 100 parts by weight of a graft copolymer and 1 to 10 parts by weight of a hydrogenated terpene resin having a number average molecular weight of 400 to 1,000 and consisting of the following structural units: The above-mentioned graft polymer is an ethylene-vinyl acetate copolymer containing 5-20% by weight of vinyl acetate 10-40% by weight.
A vinyl chloride resin composition characterized in that 80 to 95% by weight of vinyl chloride is graft copolymerized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10715691A JPH04335056A (en) | 1991-05-13 | 1991-05-13 | Vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10715691A JPH04335056A (en) | 1991-05-13 | 1991-05-13 | Vinyl chloride resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04335056A true JPH04335056A (en) | 1992-11-24 |
Family
ID=14451925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10715691A Pending JPH04335056A (en) | 1991-05-13 | 1991-05-13 | Vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04335056A (en) |
-
1991
- 1991-05-13 JP JP10715691A patent/JPH04335056A/en active Pending
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