JPS6252774B2 - - Google Patents
Info
- Publication number
- JPS6252774B2 JPS6252774B2 JP54039117A JP3911779A JPS6252774B2 JP S6252774 B2 JPS6252774 B2 JP S6252774B2 JP 54039117 A JP54039117 A JP 54039117A JP 3911779 A JP3911779 A JP 3911779A JP S6252774 B2 JPS6252774 B2 JP S6252774B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- metal
- stabilizer
- cobalt
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 19
- 239000003381 stabilizer Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000344 soap Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 150000004696 coordination complex Chemical class 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VEYIMQVTPXPUHA-UHFFFAOYSA-N 3-hydroxypyran-4-one Chemical compound OC1=COC=CC1=O VEYIMQVTPXPUHA-UHFFFAOYSA-N 0.000 description 2
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- -1 organic acid salt Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 2
- MDYOLVRUBBJPFM-UHFFFAOYSA-N tropolone Chemical compound OC1=CC=CC=CC1=O MDYOLVRUBBJPFM-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- NCFNZZFMDWLVSL-UHFFFAOYSA-N 1,1,1-trifluoro-3-sulfinylpropan-2-one Chemical compound FC(F)(F)C(=O)C=S=O NCFNZZFMDWLVSL-UHFFFAOYSA-N 0.000 description 1
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- ILUMEPMGPCKGHH-UHFFFAOYSA-N 2-[(2,6-dioxocyclohexyl)methyl]cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1CC1C(=O)CCCC1=O ILUMEPMGPCKGHH-UHFFFAOYSA-N 0.000 description 1
- OLGHRLWDRJDQRS-UHFFFAOYSA-N 2-octyl-1-phenylbutane-1,3-dione Chemical compound CCCCCCCCC(C(C)=O)C(=O)C1=CC=CC=C1 OLGHRLWDRJDQRS-UHFFFAOYSA-N 0.000 description 1
- PKQIDSVLSKFZQC-UHFFFAOYSA-N 3-oxobutanal Chemical compound CC(=O)CC=O PKQIDSVLSKFZQC-UHFFFAOYSA-N 0.000 description 1
- BFXFNAKINNZZOQ-UHFFFAOYSA-N 3-oxobutanoic acid;hydrate Chemical compound O.CC(=O)CC(O)=O BFXFNAKINNZZOQ-UHFFFAOYSA-N 0.000 description 1
- REIYHFWZISXFKU-UHFFFAOYSA-N Butyl acetoacetate Chemical compound CCCCOC(=O)CC(C)=O REIYHFWZISXFKU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004287 Dehydroacetic acid Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- KYPVLDPQHIDKQJ-UHFFFAOYSA-N cobalt;ethyl 3-oxobutanoate Chemical compound [Co].CCOC(=O)CC(C)=O KYPVLDPQHIDKQJ-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- JEQRBTDTEKWZBW-UHFFFAOYSA-N dehydroacetic acid Chemical compound CC(=O)C1=C(O)OC(C)=CC1=O JEQRBTDTEKWZBW-UHFFFAOYSA-N 0.000 description 1
- 229940061632 dehydroacetic acid Drugs 0.000 description 1
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 description 1
- 235000019258 dehydroacetic acid Nutrition 0.000 description 1
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- BNLRKUSVMCIOGU-UHFFFAOYSA-N o-1-Hydroxyxanthone Natural products O1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O BNLRKUSVMCIOGU-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LZFIOSVZIQOVFW-UHFFFAOYSA-N propyl 2-hydroxybenzoate Chemical compound CCCOC(=O)C1=CC=CC=C1O LZFIOSVZIQOVFW-UHFFFAOYSA-N 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は屋外暴露に対して安定な塩化ビニル樹
脂組成物に関するものである。
塩化ビニル樹脂の着色成形品を日光の直射の下
で使用すると、日光暴露部の表面が粉をふいた如
く白つぽく着色して成形品本来の色調が大巾に変
化する結果、成形品の外観が著るしく損なわれる
ことは周知の通りである。この白つぽく着色する
現象は屋外暴露で発生するが、合成樹脂成形品の
耐候性促進試験機として汎用されているウエザオ
メーターでは再現し得ない特異な現象で、チヨー
キングと呼ばれている。
処で雨樋、デツキ材等は屋外で特に長期間使用
されるため、かかる用途に塩化ビニル樹脂成形品
を利用する場合、チヨーキングの発生を抑制して
発生時期を遅延させる目的で、従来より種々の安
定剤を塩化ビニル樹脂に添加することが行なわれ
ている。なかでも有機錫系化合物、カドミウムの
金属石鹸、鉛の金属石鹸はチヨーキング抑制効果
が秀でていることから汎用されているが、これら
安定剤を含む塩化ビニル樹脂組成物であつてもそ
の成形品を屋外暴露すると２〜10ケ月後にはチヨ
ーキングが発生し始める。このように従来チヨー
キング抑制効果の秀でている安定剤であつても、
長期間屋外暴露する用途には到底充分なものとは
言えなかつた。そのためチヨーキング抑制効果が
長期間持続する安定剤が強く要望され、広く研究
されていたが、末だ満足すべき安定剤は見い出さ
れていない。
本発明者等は、かかる状況に鑑み鋭意研究の結
果、或る種の金属のオキシケト錯体を金属石鹸系
安定剤と併用すると優れたチヨーキング抑制効果
が得られること、しかもその効果が従来汎用され
ていた有機錫系化合物に比べ著るしく長期間持続
することを見い出し、本発明に到つたのである。
即ち本発明はコバルト、ニツケルまたはマンガン
のオキシケト錯体（以後、金属錯体と称す）と金
属石鹸系安定剤とを含有する塩化ビニル樹脂組成
物に関するものである。
金属錯体はコバルト、ニツケルまたはマンガン
を中心原子とし、それにオキシケト錯体を形成し
うる配位子が付加した構造から成り立つている。
かかる金属錯体を形成する配位子として使用で
きるものには例えばアセト酢酸メチルエステル、
アセト酢酸エチルエステル、アセト酢酸プロピル
エステル、アセト酢酸ブチルエステル、アセトア
セトアルデヒド、アセトアセトアミド、アセトア
セトアニライド、アセチルアセト酢酸、トリ酢
酸、サリチル酸メチルエステル、サリチル酸エチ
ルエステル、サリチル酸プロピルエステル、サリ
チルアルデヒド、デヒドロ酢酸、ピロメコン酸、
アセチルアセトン、トリフルオルアセチルアセト
ン、ベンゾイルアセトン、１−オクチル−１−ベ
ンゾイルアセトン、チオニルトリフルオルアセト
ン、シクロヘキサン−１・３−ジオン、ジメド
ン、２・2′−メチレンビスシクロヘキサン−１・
３−ジオン、２−ベンジルシクロヘキサン−１・
３−ジオン、２−オン−３−アセチルテトラヒド
ロフラン、ｏ−オキシアセトフエノン、１−オキ
シキサントン、トロポロン等が含まれる。これら
のうち本発明の効果上特に好ましいものはアセチ
ルアセトン、アセト酢酸エステルであるが、コス
ト、毒性等の点からそれらのうちでもアセチルア
セトン、アセト酢酸エチルエステルが特に好まし
い。
これら配位子となる化合物をコバルト、ニツケ
ルまたはマンガンの塩化物、水酸化物、有機酸
塩、無機酸塩等の金属化合物と周知方法で反応さ
せることにより金属錯体を得ることができる。例
えばコバルトのアセト酢酸エチルエステル錯体
は、酢酸コバルトをアセト酢酸エチルエステルと
水との混合液に添加し常温乃至加熱温度で反応さ
せることにより得ることができる。
金属石鹸系安定剤としては、塩化ビニル樹脂の
熱安定剤として公知の金属石鹸がいずれも使用で
き、例えばカドミウム、鉛、カルシウム、亜鉛等
の金属石鹸が挙げられる。なかでもステアリン酸
カルシウムとステアリン酸亜鉛とを含有してなる
Ca／Zn系安定剤が好ましい。
ここで言う塩化ビニル樹脂とは、塩化ビニルを
構成単量体とする単独重合体または共重合体を指
す。これら重合体には、可塑剤、熱安定剤、変性
剤、滑剤等周知の性能向上成分が併存していても
かまわない。
本発明組成物は、金属錯体と金属石鹸系安定剤
とを塩化ビニル樹脂に混合することにより形成さ
れるものであつて、金属錯体の混合割合は塩化ビ
ニル樹脂100重量部（以後、部で示す）に対して
通常0.05〜２部好ましくは0.1〜1.5部の範囲であ
る。金属錯体を塩化ビニル樹脂に混合するに当つ
て注意することは、均一分散を目的とすることで
あつて、そのため微粉末状で使用すること、また
充分に混練することを要する。金属錯体と金属石
鹸系安定剤の混合方法としては塩化ビニル樹脂に
直接添加して混合する方法、または塩化ビニル樹
脂に配合することが周知の配合成分例えば着色剤
成分或いは可塑剤、変性剤、滑剤等の周知の性能
向上成分に金属錯体と金属石鹸系安定剤とを予か
じめ含有させておき、それを塩化ビニル樹脂に混
合する方法があるが、それらのうち均一に分散さ
せ易いという点で後者の方法が好ましい。特に着
色剤成分を利用する場合、着色剤成分が均一且つ
容易に塩化ビニル樹脂中に分散できるようその調
製には充分な配慮を払うので着色剤調製時に染顔
料に金属錯体を併存させておくと、それらの均一
分散性が特に優れたものになるので適当である。
かかる着色剤成分の形態としては微粉末状ドライ
カラー、練肉粉砕工程により製造される潤性タイ
プカラー、樹脂その他の賦形材により固化したペ
レツト状或いは板状のマスターバツチ、可塑剤そ
の他の液状或いは低温軟化点化合物をベヒクルと
するペーストカラー等のいずれにおいても良好な
結果が得られる。
かくして得られる本発明組成物は、屋外暴露に
対して安定であるため、屋外で使用する機器、用
具の用途に利用してもチヨーキングの発生が著る
しく長期間抑制されるので、雨樋、デツキ材等の
用途に最適である。
以下に本発明を実施例にて説明する。尚、実施
例中のチヨーキング抑制係数は以下の式から算出
したものである。
ΔＥＣ−ΔＥＩ／ΔＥＣ×100
ΔＥI＝金属錯体含有の本発明組成物のシートを
屋外暴露した後の色差
ΔＥC＝金属錯体不含有の他は上記と同一組成の
比較組成物のシートを上記と同一期間、同一条
件で屋外暴露した後の色差
従つて一定の屋外暴露期間においてこの係数の
値が100に近いほどチヨーキング抑制効果に優れ
ていることを意味する。
実施例 １
塩化ビニル樹脂（住友化学製、スミリツトＳ×
11F、重合度1100）100部にCa／Zn系安定剤〔大
日本インキ化学工業(株)製、インタースタブ
M62D、主成分：ステアリン酸カルシウムとステ
アリン酸亜鉛の混合物〕３部を添加混合してコン
パウンドを得た。かかるコンパウンド103部に弁
柄0.7部二酸化チタン0.5部及びアセチルアセト
ン・コバルト（）１部を添加混合し、155℃の
６インチ二本ロールにて５分間練肉した後、熱プ
レスで１mm厚のシートを作成し屋外暴露した。
実施例 ２〜９
実施例１において、アセチルアセトン・コバル
ト（）１部の代りに第一表記載の化合物をその
記載数量使用する以外は全く同様にしてシートを
作製し屋外暴露した。
比較例 １
実施例１において、アセチルアセトン・コバル
ト（）の代りに同量のジブチルチンジラウレー
トを使用する以外は全く同様にしてシートを作成
し屋外暴露した。
以上の各例における暴露16ケ月後、20ケ月後、
24ケ月後のチヨーキング抑制係数を第一表に示
す。
The present invention relates to a vinyl chloride resin composition that is stable against outdoor exposure. If a colored molded product made of vinyl chloride resin is used under direct sunlight, the surface of the exposed part will become white, as if it had been wiped with powder, and the original color tone of the molded product will change drastically, resulting in the molded product being damaged. It is well known that the appearance is significantly impaired. This phenomenon of whitish coloration occurs when exposed outdoors, but it is a unique phenomenon that cannot be reproduced with a weatherometer, which is commonly used as a weather resistance acceleration tester for synthetic resin molded products, and is called yoking. Rain gutters, decking materials, etc. are used outdoors for long periods of time, so when using vinyl chloride resin molded products for such purposes, various conventional methods have been used to suppress the occurrence of chocking and delay its occurrence. Stabilizers have been added to vinyl chloride resins. Among them, organotin compounds, cadmium metal soaps, and lead metal soaps are widely used because of their excellent anti-choke effect, but even if vinyl chloride resin compositions containing these stabilizers are used, their molded products cannot be processed. Chiyoking begins to occur after 2 to 10 months when exposed outdoors. In this way, even if the stabilizer has an excellent anti-yoking effect,
It could not be said to be sufficient for applications involving long-term outdoor exposure. Therefore, there has been a strong demand for a stabilizer that has a long-lasting inhibitory effect on choke, and has been extensively researched, but no satisfactory stabilizer has yet been found. In view of this situation, the present inventors have conducted extensive research and found that when a certain type of metal oxyketo complex is used in combination with a metal soap stabilizer, an excellent choke-inhibiting effect can be obtained, and that this effect has not been widely used in the past. The inventors discovered that this material lasts for a significantly longer period of time than other organic tin compounds, leading to the present invention.
That is, the present invention relates to a vinyl chloride resin composition containing an oxyketo complex of cobalt, nickel, or manganese (hereinafter referred to as a metal complex) and a metal soap stabilizer. Metal complexes consist of a structure in which a central atom of cobalt, nickel, or manganese is added with a ligand capable of forming an oxyketo complex. Examples of ligands that can be used to form such metal complexes include acetoacetic acid methyl ester,
Acetoacetic acid ethyl ester, acetoacetic acid propyl ester, acetoacetic acid butyl ester, acetoacetaldehyde, acetoacetamide, acetoacetanilide, acetylacetoacetic acid, triacetic acid, salicylic acid methyl ester, salicylic acid ethyl ester, salicylic acid propyl ester, salicylaldehyde, dehydroacetic acid , pyromeconic acid,
Acetylacetone, trifluoroacetylacetone, benzoylacetone, 1-octyl-1-benzoylacetone, thionyltrifluoroacetone, cyclohexane-1,3-dione, dimedone, 2,2'-methylenebiscyclohexane-1,
3-dione, 2-benzylcyclohexane-1.
Included are 3-dione, 2-one-3-acetyltetrahydrofuran, o-oxyacetophenone, 1-oxyxanthone, tropolone, and the like. Among these, acetylacetone and acetoacetate are particularly preferred from the viewpoint of the effects of the present invention, and among them, acetylacetone and ethyl acetoacetate are particularly preferred from the viewpoint of cost, toxicity, and the like. A metal complex can be obtained by reacting a compound serving as a ligand with a metal compound such as a chloride, hydroxide, organic acid salt, or inorganic acid salt of cobalt, nickel, or manganese by a well-known method. For example, a cobalt acetoacetate ethyl ester complex can be obtained by adding cobalt acetate to a mixture of acetoacetate ethyl ester and water and reacting the mixture at room temperature to heating temperature. As the metal soap stabilizer, any metal soap known as a heat stabilizer for vinyl chloride resin can be used, and examples thereof include metal soaps such as cadmium, lead, calcium, and zinc. Among them, it contains calcium stearate and zinc stearate.
Ca/Zn based stabilizers are preferred. The vinyl chloride resin referred to herein refers to a homopolymer or copolymer containing vinyl chloride as a constituent monomer. These polymers may contain well-known performance-enhancing components such as plasticizers, heat stabilizers, modifiers, and lubricants. The composition of the present invention is formed by mixing a metal complex and a metal soap stabilizer with a vinyl chloride resin, and the mixing ratio of the metal complex is 100 parts by weight of the vinyl chloride resin (hereinafter expressed in parts). ), usually 0.05 to 2 parts, preferably 0.1 to 1.5 parts. Care must be taken when mixing the metal complex with the vinyl chloride resin to achieve uniform dispersion, and therefore it is necessary to use it in the form of a fine powder and to thoroughly knead it. The metal complex and the metal soap stabilizer can be mixed by directly adding them to the vinyl chloride resin, or by adding ingredients that are well known to be added to the vinyl chloride resin, such as colorants, plasticizers, modifiers, and lubricants. There is a method of pre-containing a metal complex and a metal soap stabilizer in a well-known performance-enhancing component such as, and mixing it with vinyl chloride resin. The latter method is preferred. In particular, when using a colorant component, sufficient consideration must be given to the preparation so that the colorant component can be uniformly and easily dispersed in the vinyl chloride resin, so it is recommended that a metal complex be present in the dye and pigment when preparing the colorant. , are suitable because their uniform dispersibility is particularly excellent.
The form of the colorant component is a fine powder dry color, a wet type color produced by a grinding process, a pellet or plate masterbatch solidified with resin or other excipients, a plasticizer or other liquid or Good results can be obtained with any paste color using a low-temperature softening point compound as a vehicle. The thus obtained composition of the present invention is stable against outdoor exposure, and even when used for equipment and tools used outdoors, the occurrence of choking is significantly suppressed for a long period of time, so it is suitable for use in rain gutters, rain gutters, etc. Ideal for use as decking material, etc. The present invention will be explained below with reference to Examples. Note that the choke suppression coefficient in the examples was calculated from the following formula. ΔE C −ΔE I /ΔE C ×100 ΔE I = Color difference after outdoor exposure of a sheet of the composition of the present invention containing a metal complex ΔE C = Sheet of a comparative composition having the same composition as above except that it does not contain a metal complex Color difference after being exposed outdoors for the same period and under the same conditions as above. Therefore, the closer the value of this coefficient is to 100 for a certain outdoor exposure period, the better the yoking suppressing effect is. Example 1 Vinyl chloride resin (Sumitomo Chemical, Sumiritz S×
11F, degree of polymerization 1100) 100 parts of Ca/Zn stabilizer [manufactured by Dainippon Ink & Chemicals Co., Ltd., Interstub]
M62D, main component: mixture of calcium stearate and zinc stearate] was added and mixed to obtain a compound. To 103 parts of this compound, 0.7 parts of Bengara, 0.5 parts of titanium dioxide, and 1 part of acetylacetone cobalt () were added and mixed, kneaded for 5 minutes with two 6-inch rolls at 155°C, and then heated into a 1 mm thick sheet. Created and exposed outdoors. Examples 2 to 9 Sheets were prepared in exactly the same manner as in Example 1, except that 1 part of acetylacetone cobalt (2) was replaced by the compounds listed in Table 1 in the amounts listed, and exposed outdoors. Comparative Example 1 A sheet was prepared in exactly the same manner as in Example 1, except that the same amount of dibutyltin dilaurate was used instead of acetylacetone cobalt (2), and exposed outdoors. After 16 months and 20 months of exposure in each of the above cases,
Table 1 shows the Chiyoking inhibition coefficient after 24 months.
【表】【table】
【表】
実施例 10
塩化ビニル樹脂（住友化学製、スミリツトSX
−11F、重合度1100）100部にCa／Zn系安定剤
（インタースタブM62D）３部を添加混合してコ
ンパウンドを得た。かかるコンパウンド103部に
アセチルアセトン・コバルト（）１部を添加混
合し、155℃の６インチ二本ロールにて５分間練
肉した後、熱プレスで１mm厚のシートを作成し屋
外暴露した。
実施例 11〜18
実施例10において、アセチルアセトン・コバル
ト（）１部の代りに第二表記載の化合物をその
記載数量使用する以外は全く同様にしてシートを
作製し屋外暴露した。
比較例 ２
実施例10において、アセチルアセトン・コバル
ト（）の代りに同量のジブチルチンジラウレー
トを使用する以外は全く同様にしてシートを作成
し屋外暴露した。
以上の各例における暴露16ケ月後、20ケ月後、
24ケ月後のチヨーキング抑制係数を第二表に示
す。[Table] Example 10 Vinyl chloride resin (Sumitomo Chemical, Sumiritz SX
-11F, degree of polymerization 1100) and 3 parts of a Ca/Zn stabilizer (Interstub M62D) were added and mixed to obtain a compound. 1 part of acetylacetone cobalt () was added and mixed to 103 parts of the compound, kneaded for 5 minutes using two 6-inch rolls at 155°C, and then heated to form a sheet with a thickness of 1 mm and exposed outdoors. Examples 11 to 18 Sheets were prepared in exactly the same manner as in Example 10, except that 1 part of acetylacetone cobalt (2) was replaced by the compounds listed in Table 2 in the amounts listed, and exposed outdoors. Comparative Example 2 A sheet was prepared in exactly the same manner as in Example 10, except that the same amount of dibutyltin dilaurate was used instead of acetylacetone cobalt (2), and exposed outdoors. After 16 months and 20 months of exposure in each of the above cases,
Table 2 shows the Chiyoking inhibition coefficient after 24 months.
【表】【table】
【表】【table】
Claims (1)
ケト錯体と金属石鹸系安定剤とを含有する塩化ビ
ニル樹脂組成物。1. A vinyl chloride resin composition containing an oxyketo complex of cobalt, nickel, or manganese and a metal soap stabilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3911779A JPS55131036A (en) | 1979-03-31 | 1979-03-31 | Polyvinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3911779A JPS55131036A (en) | 1979-03-31 | 1979-03-31 | Polyvinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55131036A JPS55131036A (en) | 1980-10-11 |
| JPS6252774B2 true JPS6252774B2 (en) | 1987-11-06 |
Family
ID=12544132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3911779A Granted JPS55131036A (en) | 1979-03-31 | 1979-03-31 | Polyvinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55131036A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09208777A (en) * | 1996-01-29 | 1997-08-12 | Asahi Denka Kogyo Kk | Vinyl chloride resin composition |
| JP4731011B2 (en) * | 2000-12-18 | 2011-07-20 | 株式会社Ａｄｅｋａ | Vinyl chloride resin composition for wire coating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5329351A (en) * | 1976-08-31 | 1978-03-18 | Matsushita Electric Works Ltd | Vinyl chloride resin compositions |
-
1979
- 1979-03-31 JP JP3911779A patent/JPS55131036A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5329351A (en) * | 1976-08-31 | 1978-03-18 | Matsushita Electric Works Ltd | Vinyl chloride resin compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55131036A (en) | 1980-10-11 |
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