JP3076163B2 - Vinyl chloride resin composition - Google Patents
Vinyl chloride resin compositionInfo
- Publication number
- JP3076163B2 JP3076163B2 JP04338050A JP33805092A JP3076163B2 JP 3076163 B2 JP3076163 B2 JP 3076163B2 JP 04338050 A JP04338050 A JP 04338050A JP 33805092 A JP33805092 A JP 33805092A JP 3076163 B2 JP3076163 B2 JP 3076163B2
- Authority
- JP
- Japan
- Prior art keywords
- stabilizer
- vinyl chloride
- chloride resin
- weight
- parts
- 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 - Fee Related
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- Compositions Of Macromolecular Compounds (AREA)
Description
【００１】[0101]
【産業上の利用分野】本発明は、衛生的に安全で、耐熱
性、耐候性に優れた塩化ビニル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 which is hygienically safe and has excellent heat resistance and weather resistance.
【００２】[0092]
【従来技術】可塑剤、安定剤などを配合した塩化ビニル
樹脂組成物は、耐薬品性、加工性および耐候性などに優
れているので、顔料で着色することにより耐久性に優れ
た塩化ビニル樹脂積層金属板の製造に使用されている。
この金属板は、外装建材、内装建材、器物などに広く使
用されているが、耐久性に優れていることの一つは、安
定剤として耐熱性、耐候性に卓越した鉛系のものを用い
てある点にある。2. Description of the Related Art A vinyl chloride resin composition containing a plasticizer, a stabilizer and the like is excellent in chemical resistance, workability, weather resistance, and the like. Used in the manufacture of laminated metal sheets.
This metal sheet is widely used for exterior building materials, interior building materials, and fixtures, but one of the excellent durability is that it uses a lead-based material with excellent heat resistance and weather resistance as a stabilizer. There is a point.
【００３】しかし、鉛系安定剤のように重金属を用いた
ものは、劇物取締法により劇物に指定されており、ま
た、その製造や取扱いなどは労働安全衛生法に基づく鉛
中毒予防規則で環境、健康管理が厳しく規制されてい
る。さらに、塩化ビニル樹脂積層金属板製建材の廃材処
理も環境汚染に与える影響が大きいことから、処理方法
が問題になりつつある。However, those using heavy metals, such as lead-based stabilizers, are designated as deleterious substances by the Deleterious Substances Control Law, and their production and handling are regulated by the Occupational Safety and Health Law under the Prevention Rules for Lead Poisoning. Environment and health care are strictly regulated. Further, the treatment of waste materials of building materials made of a vinyl chloride resin-laminated metal sheet also has a large effect on environmental pollution.
【００４】[0093]
【発明が解決しようとする課題】そこで、本発明は、鉛
系安定剤を添加せずに耐熱性、耐候性に優れた塩化ビニ
ル樹脂組成物を提供するものである。Accordingly, an object of the present invention is to provide a vinyl chloride resin composition excellent in heat resistance and weather resistance without adding a lead-based stabilizer.
【００５】[0056]
【課題を解決するための手段】本発明は、安定剤とし
て、ジオクチルスズメルカプタイト安定剤、Ｍｇ−Ｚｎ
またはＢａ−Ｚｎ複合金属セッケン安定剤およびホスフ
ァイト系安定剤を添加し、それらの添加量を塩化ビニル
系樹脂１００重量部に対してジオクチルスズメルカプタ
イト安定剤１.０〜２.０重量部、Ｍｇ−ＺｎまたはＢａ
−Ｚｎ複合金属セッケン安定剤１.０〜３.０重量部、ホ
スファイト系安定剤１.０〜１５.０重量部にした。According to the present invention, dioctyltin mercaptite stabilizer, Mg-Zn is used as a stabilizer.
Alternatively, a Ba-Zn composite metal soap stabilizer and a phosphite-based stabilizer are added, and the added amounts thereof are 1.0 to 2.0 parts by weight of a dioctyltin mercaptite stabilizer per 100 parts by weight of a vinyl chloride-based resin. , Mg-Zn or Ba
-1.0 to 3.0 parts by weight of a Zn composite metal soap stabilizer and 1.0 to 15.0 parts by weight of a phosphite-based stabilizer.
【００６】[0086]
【作用】本発明での塩化ビニル系樹脂としては、塩化ビ
ニル単独重合樹脂、エチレン−塩化ビニル共重合体、塩
化ビニル−酢酸ビニル共重合体、エチレン−酢酸ビニル
共重合体に塩化ビニルをグラフト重合したグラフト樹
脂、塩素化塩化ビニル樹脂、架橋塩化ビニル樹脂などが
挙げられるが、これらは単独あるいは２種以上を任意の
比率で混合してもよい。The vinyl chloride resin in the present invention is a vinyl chloride homopolymer resin, an ethylene-vinyl chloride copolymer, a vinyl chloride-vinyl acetate copolymer, or a graft polymerization of vinyl chloride onto an ethylene-vinyl acetate copolymer. Examples thereof include a graft resin, a chlorinated vinyl chloride resin, and a cross-linked vinyl chloride resin. These may be used alone or as a mixture of two or more kinds at an arbitrary ratio.
【００７】可塑剤としては、ジ２−エチルヘキシルフタ
レ−ト（ＤＯＰ）、ｎ−ジオクチルフタレ−ト（ＤｎＯ
Ｐ）、ジイソデシルフタレ−ト（ＤＩＤＰ）などのフタ
ル酸エステル系、ジ２−エチルヘキシルアジペ−ト（Ｄ
ＯＡ）、ジ２−エチルヘキシルセバケ−ト（ＤＯＳ）な
どの脂肪酸二塩基性エステル系、トリクレジルホスヘ−
ト（ＴＣＰ）、トリキシレニルホスヘ−ト（ＴＸＰ）な
どの正燐酸エステル系、トリオクチルトリトリメ−ト
（ＴＯＴＭ）などのトリメット酸エステル系などが挙げ
られ、単独あるいは混合使用してもよい。As plasticizers, di-2-ethylhexyl phthalate (DOP), n-dioctyl phthalate (DnO)
P), phthalic acid esters such as diisodecyl phthalate (DIDP), di-2-ethylhexyl adipate (D
OA), dibasic esters of fatty acids such as di-2-ethylhexyl sebacate (DOS), tricresyl phos-
Orthophosphoric acid ester type such as octyl (TCP) and trixylenyl phosphate (TXP), and trimetic acid ester type such as trioctyltritrimate (TOTM). These may be used alone or in combination. .
【００８】また、安定剤としては、ジオクチルスズメル
カプタイト安定剤、Ｍｇ−ＺｎまたはＢａ−Ｚｎ複合金
属セッケン安定剤およびホスファイト系安定剤の３種を
併用する。ここで、３種の安定剤を用いるのは、ジオク
チルスズメルカプタイト安定剤は、卓越した耐熱性を付
与するが、耐候性が劣るため、紫外線によりラジカルを
生成して、塩化ビニル樹脂を劣化させる。そこで、ラジ
カル補足性能を有するホスファイト系安定剤で生成した
ラジカルを補足して、耐候性を付与するのである。ま
た、Ｍｇ−ＺｎまたはＢａ−Ｚｎ複合金属セッケン安定
剤は耐熱性に優れ、しかも、塩化ビニル樹脂が熱分解し
た時に発生する黄色若しくは黄褐色を色調的に補色する
作用があるため、見かけ上耐熱性を向上させる。As the stabilizer, three kinds of stabilizers are used in combination: a dioctyltin mercaptite stabilizer, a Mg-Zn or Ba-Zn composite metal soap stabilizer, and a phosphite-based stabilizer. Here, the three types of stabilizers are used because dioctyltin mercaptite stabilizers provide excellent heat resistance, but have poor weather resistance. Let it. Then, the radical generated by the phosphite-based stabilizer having the radical scavenging ability is supplemented to provide weather resistance. Further, the Mg-Zn or Ba-Zn composite metal soap stabilizer has excellent heat resistance, and also has an action of complementing the color tone of yellow or yellowish brown generated when the vinyl chloride resin is thermally decomposed. Improve the performance.
【００９】これらの安定剤は市販されており、例えば、
ジオクチルスズメルカプタイト安定剤の場合は、アデカ
スタブ４６５［旭電化工業（株）］、ＴＭ−１８８［勝
田化工（株）］として、また、Ｍｇ−Ｚｎ複合金属セッ
ケン安定剤の場合はアデカスタブＡＣ３１７「旭電化工
業（株）］、Ｂａ−Ｚｎ複合金属セッケン安定剤の場合
はアデカスタブＡＣ１７３［旭電化工業（株）］、ＢＺ
−１７１Ｊ、ＢＺ−１００Ｊ、ＢＺ−１００ＣＪ［勝田
化工（株）］として、さらに、ホスファイト系安定剤の
場合は、アデカスタブ１５００［旭電化工業（株）、
４，４’イソプロピリデン−ジフェノ−ルホスファイ
ト］として市販されている。These stabilizers are commercially available and include, for example,
In the case of dioctyltin mercaptite stabilizer, Adekastab 465 [Asahi Denka Kogyo Co., Ltd.] and TM-188 [Katsuta Kako Co., Ltd.], and in the case of Mg-Zn composite metal soap stabilizer, Adekastab AC317 " Asahi Denka Kogyo Co., Ltd.], and in the case of Ba-Zn composite metal soap stabilizer, ADK STAB AC173 [Asahi Denka Kogyo Co., Ltd.], BZ
-171J, BZ-100J, BZ-100CJ [Katsuta Kako Co., Ltd.]. In the case of a phosphite-based stabilizer, ADK STAB 1500 [Asahi Denka Kogyo Co., Ltd.
4,4'-isopropylidene-diphenol phosphite].
【０１０】安定剤の添加は、ジオクチルスズメルカプタ
イト安定剤の場合、塩化ビニル樹脂１００重量部に対し
て１.０〜２.０重量部にする。１.０重量部未満である
と、耐熱性安定剤のＭｇ−ＺｎまたはＢａ−Ｚｎ複合金
属セッケン安定剤の添加量を３.０重量部以上にしても
耐熱性が劣り、逆に２.０重量部より多くすると、耐候
性が低下してしまう。In the case of dioctyltin mercaptite stabilizer, the stabilizer is added in an amount of 1.0 to 2.0 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 1.0 part by weight, the heat resistance is inferior even if the addition amount of the heat-resistant stabilizer Mg-Zn or Ba-Zn composite metal soap stabilizer is 3.0 parts by weight or more, and conversely, 2.0. If the amount is more than the weight part, the weather resistance decreases.
【０１１】Ｍｇ−ＺｎまたはＢａ−Ｚｎ複合金属セッケ
ン安定剤の添加量は、ジオクチルスズメルカプタイト安
定剤添加量が１.０〜２.０重量部の場合、塩化ビニル樹
脂１００重量部に対して１.０〜３.０重量部にする。
１.０重量部未満であると、補色作用が十分でないた
め、塩化ビニル樹脂積層金属板のように、被膜を焼き付
けにより形成するものの場合、塩化ビニル樹脂の熱分解
により生じる着色の防止が困難となる。一方、３.０重
量部を越えると、補色作用は向上するが、耐候性の安定
剤であるホスファイト系安定剤を１５.０重量部添加し
ても紫外線で被膜表面が粉状の白亜化現象が生じ、耐候
性が低下してしまう。When the amount of the dioctyltin mercaptite stabilizer is 1.0 to 2.0 parts by weight, the added amount of the Mg—Zn or Ba—Zn composite metal soap stabilizer is based on 100 parts by weight of the vinyl chloride resin. To 3.0 to 3.0 parts by weight.
If the amount is less than 1.0 part by weight, the complementary color effect is not sufficient. Therefore, in the case of a film formed by baking such as a vinyl chloride resin laminated metal plate, it is difficult to prevent coloring caused by thermal decomposition of the vinyl chloride resin. Become. On the other hand, if the amount exceeds 3.0 parts by weight, the complementary color effect is improved, but even if 15.0 parts by weight of a phosphite-based stabilizer, which is a weather resistance stabilizer, is added, the surface of the coating film becomes chalky due to ultraviolet rays. A phenomenon occurs, and the weather resistance decreases.
【０１２】ホスファイト系安定剤の添加量は、ジオクチ
ルスズメルカプタイト安定剤とＭｇ−ＺｎまたはＢａ−
Ｚｎ複合金属セッケン安定剤の添加量が前記の場合、塩
化ビニル樹脂１００重量部に対して１.０〜１５.０重量
部にする。１.０重量部未満であると、発生ラジカルを
十分補足できないため、耐候性が劣り、１５.０重量部
を越えると、被膜表面にブリ−ドして、外観を著しく損
ねる。The amount of the phosphite-based stabilizer to be added depends on the dioctyltin mercaptite stabilizer, Mg-Zn or Ba-
When the amount of the Zn composite metal soap stabilizer is as described above, the amount is set to 1.0 to 15.0 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 1.0 part by weight, the generated radicals cannot be sufficiently captured, so that the weather resistance is inferior. If the amount exceeds 15.0 parts by weight, the surface of the coating film is bleed and the appearance is remarkably impaired.
【０１３】本発明の塩化ビニル樹脂組成物には必要に応
じて他の安定剤（例えば、エポキシ系安定剤）、難燃
剤、紫外線吸収剤などを適量添加してもよい。The vinyl chloride resin composition of the present invention may optionally contain other stabilizers (for example, epoxy stabilizers), flame retardants, ultraviolet absorbers and the like in appropriate amounts.
【０１４】[0141]
【実施例】塩化ビニル樹脂を１００重量部、可塑剤とし
てＤＯＰおよびＴＸＩＢをそれぞれ４０重量部および３
５重量部、顔料（キナクドリン系レッド）を１２.５重
量部配合した塩化ビニル樹脂組成物にジオクチルスズメ
ルカプタイト安定剤、Ｍｇ−ＺｎまたはＢａ−Ｚｎ複合
金属セッケン安定剤およびホスファイト系安定剤を種々
の割合で添加し、それを予め接着剤を塗布、乾燥した鋼
板にロ−ルコ−タ−にて乾燥塗膜換算で２００μｍにな
るように塗装し、２１０℃（最高到達温度）で６０秒間
焼き付けた。そして、得られた塩化ビニル樹脂積層鋼板
の耐熱性、耐候性を次の要領で調査した。この結果を第
１表に示す。EXAMPLE 100 parts by weight of vinyl chloride resin, 40 parts by weight of DOP and TXIB as plasticizers and 3 parts by weight, respectively.
Dioctyltin mercaptite stabilizer, Mg-Zn or Ba-Zn composite metal soap stabilizer and phosphite stabilizer are added to a vinyl chloride resin composition containing 5 parts by weight and 12.5 parts by weight of a pigment (quinacudrine red). Was added at various ratios, and the adhesive was applied in advance to the dried steel sheet. The coated steel sheet was coated with a roll coater so as to have a dry film equivalent of 200 μm. Bake for seconds. Then, the heat resistance and the weather resistance of the obtained vinyl chloride resin laminated steel sheet were investigated in the following manner. Table 1 shows the results.
【０１５】（１）耐熱性 塩化ビニル樹脂被膜を肉眼で観察して、着色（黄色若し
くは黄褐色）の認められないものを○、僅かに着色の認
められるものを△、著しく着色の認められるものを×の
記号で評価した。 （２）耐候性 スガ試験機（株）製のサンシャインウェザ−メ−タ−
（商品名、ＷＥＬ・ＳＵＮ・ＤＣＨ）を用いて、ＪＩＳ
・Ａ・１４１５（プラスチック建築材料の促進暴露試験
方法）に従い２０００時間行った。評価は白亜化抵抗性
試験をＪＩＳ・Ｋ・５４００ ９.６の白亜化度に従っ
て求め、８点以上を合格とした。(1) Heat resistance The vinyl chloride resin film was observed with the naked eye, and when the coloring (yellow or yellowish brown) was not observed, it was evaluated as ○, slightly colored as Δ, and markedly colored. Was evaluated by the symbol x. (2) Weather resistance Sunshine weather meter manufactured by Suga Test Instruments Co., Ltd.
(Product name, WEL, SUN, DCH)
-Performed for 2000 hours according to A.1415 (Promoted exposure test method for plastic building materials). For evaluation, a chalking resistance test was performed according to the chalking degree of JIS K 5400 9.6, and 8 or more points were judged as passing.
【０１６】[0162]
【第１表】 [Table 1]
【０１７】（注１）ジオクチルスズメルカプタイト安定
剤は、アデカスタブ４６５［旭電化工業（株）製］であ
る。 （注２）ホスファイト系安定剤は、アデカスタブ１５０
０［旭電化工業（株）製］である。(Note 1) The dioctyltin mercaptite stabilizer is ADK STAB 465 (manufactured by Asahi Denka Kogyo KK). (Note 2) Phosphite stabilizer is ADK STAB 150
0 [made by Asahi Denka Kogyo Co., Ltd.].
【０１８】[0182]
【発明の効果】以上のように、本発明の塩化ビニル樹脂
組成物は、鉛系安定剤を含有していなくても従来の鉛系
安定剤を添加したものと同等の耐熱性、耐候性を有して
いる。このため、塩化ビニル樹脂積層金属板のように、
製造時に塩化ビニル樹脂組成物の焼き付けを行う場合で
も被膜は熱分解により変色せず、また、外装建材、内装
建材、器物などに使用しても耐久性を発揮する。As described above, the vinyl chloride resin composition of the present invention has the same heat resistance and weather resistance as those obtained by adding a conventional lead-based stabilizer even if it does not contain a lead-based stabilizer. Have. For this reason, like a vinyl chloride resin laminated metal plate,
Even when the vinyl chloride resin composition is baked at the time of production, the coating does not discolor due to thermal decomposition, and exhibits durability even when used for exterior building materials, interior building materials, and articles.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｋ 5:524 5:58） (72)発明者 大久保 謙一 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社 鉄鋼研究所 塗覆装研究 部内 (72)発明者 輿石 謙二 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社 鉄鋼研究所 塗覆装研究 部内 (56)参考文献 特開 平２−127454（ＪＰ，Ａ) 特開 平２−77462（ＪＰ，Ａ) 特開 昭56−84741（ＪＰ，Ａ) 特開 昭54−58749（ＪＰ，Ａ) 特開 昭63−46248（ＪＰ，Ａ) 特開 昭61−285269（ＪＰ，Ａ) 特開 昭62−236861（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 27/06 C08K 5/00 - 5/58 C08L 51/06 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. 7 Identification code FI C08K 5: 524 5:58) (72) Inventor Kenichi Okubo 1-7-1 Takatani Shinmachi, Ichikawa City, Chiba Prefecture Nisshin Steel Corporation Tohoku Coating Research Department (72) Inventor Kenji Koshiishi 1 Nisshin Steel Co., Ltd., 7th Takatani Shinmachi, Ichikawa City, Chiba Prefectural Iron & Steel Research Laboratory Coating Coating Research Department (56) References JP-A-2-127454 (JP, A) JP-A-2-77462 (JP, A) JP-A-56-84741 (JP, A) JP-A-54-58749 (JP, A) JP-A-63-46248 (JP, A) JP-A-61 -285269 (JP, A) JP-A-62-28661 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08L 27/06 C08K 5/00-5/58 C08L 51/06 CA (STN)
Claims (1)
塩化ビニル樹脂組成物において、前記安定剤として、ジ
オクチルスズメルカプタイト安定剤、Ｍｇ−Ｚｎまたは
Ｂａ−Ｚｎ複合金属セッケン安定剤およびホスファイト
系安定剤を添加し、それらの添加量を塩化ビニル系樹脂
１００重量部に対してジオクチルスズメルカプタイト安
定剤１.０〜２.０重量部、Ｍｇ−ＺｎまたはＢａ−Ｚｎ
複合金属セッケン安定剤１.０〜３.０重量部、ホスファ
イト系安定剤１.０〜１５.０重量部にしたことを特徴と
する塩化ビニル樹脂組成物。1. A vinyl chloride resin composition containing a plasticizer, a stabilizer and a pigment, wherein the stabilizer is dioctyltin mercaptite stabilizer, Mg-Zn or Ba-Zn composite metal soap stabilizer, and phosphite. Based on 100 parts by weight of vinyl chloride resin, 1.0 to 2.0 parts by weight of dioctyltin mercaptite stabilizer, Mg-Zn or Ba-Zn.
A vinyl chloride resin composition comprising 1.0 to 3.0 parts by weight of a composite metal soap stabilizer and 1.0 to 15.0 parts by weight of a phosphite-based stabilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04338050A JP3076163B2 (en) | 1992-11-25 | 1992-11-25 | Vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04338050A JP3076163B2 (en) | 1992-11-25 | 1992-11-25 | Vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157853A JPH06157853A (en) | 1994-06-07 |
| JP3076163B2 true JP3076163B2 (en) | 2000-08-14 |
Family
ID=18314446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04338050A Expired - Fee Related JP3076163B2 (en) | 1992-11-25 | 1992-11-25 | Vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3076163B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11236478A (en) * | 1998-02-19 | 1999-08-31 | Miyoshi Oil & Fat Co Ltd | Chlorine-based polymer |
-
1992
- 1992-11-25 JP JP04338050A patent/JP3076163B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| JPH06157853A (en) | 1994-06-07 |
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