JPS59108055A - Postchlorinated vinyl chloride molding resin composition - Google Patents
Postchlorinated vinyl chloride molding resin compositionInfo
- Publication number
- JPS59108055A JPS59108055A JP21706482A JP21706482A JPS59108055A JP S59108055 A JPS59108055 A JP S59108055A JP 21706482 A JP21706482 A JP 21706482A JP 21706482 A JP21706482 A JP 21706482A JP S59108055 A JPS59108055 A JP S59108055A
- Authority
- JP
- Japan
- Prior art keywords
- elastomer
- vinyl chloride
- resistance
- parts
- composition
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、優れた低温落錘耐衝撃性、優れた高温時耐内
水圧破壊性、優れた耐染品性、優れた耐熱性、優れた耐
候性及び優れた実用削久性などの改善賄性質を示し、且
つこ几ら優れた6ti+!+−、責をバランスよく兼備
したユニークな符性を元1軍できる後塙紫化塩化ビニル
側脂/鳴化ビニル佃脂/エラストマー系の成フ裟用叫脂
組反物に関する。Detailed Description of the Invention The present invention has excellent low-temperature falling weight impact resistance, excellent internal hydraulic rupture resistance at high temperatures, excellent dye resistance, excellent heat resistance, excellent weather resistance, and excellent practical use. 6ti+ shows improved cutting properties such as durability, and is also excellent! The present invention relates to a synthetic resin composite fabric made of vinyl chloride resin, vinyl resin resin, and elastomer, which has a unique characteristic that combines positive and negative characteristics in a well-balanced manner.
更に評しくは1本発明は、下記(1)及び(11)(1
)後塩累化塩化ビニル切J府
55重重部〜70車友部未満
(好ましくld55〜65重前部)
(好ましくは35〜45重前部)
の合計100重量部に対し、下記((i)及びGv)(
iii) 後塩素化ポリエチレン・エラストマー1重
重部〜6爪量部未満
(好ましくは2〜5重世部)
たエラストマー
1車量部〜8■量部
(好ましくは2〜7屯量部)
但し、上記(ii)及び(iv)の合計が25重量部〜
12緻憤部である、
を含有して成ることftW徴とする後塩素化塩化ビニル
系成形用樹脂組成物に関する。More particularly, the present invention provides the following (1) and (11) (1)
) For a total of 100 parts by weight of 55 parts to less than 70 parts (preferably 1d 55 to 65 parts) (preferably 35 to 45 parts), the following ((i ) and Gv)(
iii) Post-chlorinated polyethylene elastomer 1 part by weight to less than 6 parts by weight (preferably 2 to 5 parts by weight) of elastomer from 1 part by weight to 8 parts by weight (preferably 2 to 7 parts by weight) However, The total of (ii) and (iv) above is 25 parts by weight or more
The present invention relates to a post-chlorinated vinyl chloride molding resin composition having an ftW characteristic of containing the following:
従来、耐錆本性、耐熱性などの穀物を主目的として後塩
累化塙化ビニル4阿脂/塩化ビニル樹脂/エラストマー
系の樹脂組成物及びその成形品について、後垣累化塩化
ビニル樹脂リッチな組成物、力・ら塩化ビニル・1シj
月旨リッチh :4’+Ii a Q’14にわたるい
くつかの提案が刈られており、それぞれの→1案の〔×
善目的に応じて種々の組成割合及びエラストマーの種類
からなる組み合わせが連条されている。Conventionally, the main purpose of grains such as rust resistance and heat resistance has been to use a polyvinyl chloride resin-rich polyvinyl chloride resin composition and its molded products. composition, strength, vinyl chloride, 1
Monthly rich h: 4'+Ii a Several proposals over Q'14 have been cut, and each →1 proposal [×
Various composition ratios and combinations of elastomer types are available depending on the purpose.
しかしながら、それぞれ一長一短のあることか回避でき
ず、苛酷な使用栄件下においても満足す永き耐衝撃性、
耐熱性その他の性質を示し且つそれら性質をバランスよ
く兼備した樹脂組成物を提供することは極めて困難なの
が実情である。However, each has its own merits and demerits that cannot be avoided.
The reality is that it is extremely difficult to provide a resin composition that exhibits heat resistance and other properties and has these properties in a well-balanced manner.
例えば、特公昭45−27905号には、耐:11Ii
撃性、耐熱性を有し、加工性の良好な樹脂組成物を提供
する目的で、95〜50重徽部の後塩素化ポリビニルク
ロライド及び5〜50重余部の、191Jビニルクロラ
イド又は塩化ビニルを主体とする共重合物との□混合物
100 箪嘱部に対して、アクリルニトリル/ブタジェ
ン/スチレン共重合体(ABS・エラストマー)が1〜
50重−坑部配合された三成分系の後塩票化塩化ビニル
糸仙脂組成物が従来されている。For example, in Japanese Patent Publication No. 45-27905, resistance: 11Ii
For the purpose of providing a resin composition that has impact resistance, heat resistance, and good processability, 95 to 50 parts by weight of post-chlorinated polyvinyl chloride and 5 to 50 parts by weight of 191J vinyl chloride or vinyl chloride are added. Acrylonitrile/butadiene/styrene copolymer (ABS/elastomer) is 1 to 100% of the mixture with the main copolymer (ABS/elastomer)
A 3-component post-salt vinyl chloride resin composition containing 50 parts of polyvinyl chloride has been conventionally used.
しかしながら、この提案には本蛇明に時延された前記(
iii)及U (iv)ニジストマーについても、更に
その併用についても全く開示されていない。この提案の
@IIW庸成物は、たとえは耐候性が悲〈、耐候性テス
ト倭耐イ曲湛テストの如き耐衝撃性試験においては、実
用にl(シ得る耐衝撃性を示さない。更に、嗣榮品件か
劣る難点に加えて、実用耐久性テストの精米も不τii
4足であり、比較1」す苛陥斤咬用条件にさらされる用
途には実用に供し得ない姉一点がある。However, this proposal has been postponed for some time.
There is no disclosure whatsoever regarding iii) and U(iv) nidistomers or their combined use. This proposed @IIW material has poor weather resistance, but does not show any impact resistance that is practical in impact resistance tests such as the weather resistance test and the curvature resistance test. , In addition to the disadvantages of inferior products, the polishing of the practical durability test was also poor.
There are 4 pairs of shoes, and there is one piece that cannot be put to practical use in applications exposed to harsh conditions such as Comparison 1.
更に、前開昭54−22454号には、耐衝撃性、成ル
時加工適性、後場系化項化ビニル糸柚脂との相陪性、耐
候性、その他の銭械的1主賓の改岩を目的として、後塩
素化り脆化ビニル詞脂もしくは後塩素化塩化ビニル14
脂か50 ri’c f+jチ以上を占める混合梢脂例
えば恢塩業化塙化ビニル1lIJ ilt’rとポリ塩
化ビニル樹脂との混合憎81f用の印悔零件改善剤が提
案されている。この連条によれば、上記樹脂組成物の樹
脂合計重合に卆いて約2〜約10重量係程度で配合する
該(ズ善R’Jとして、寅(什平均分子鉱の比が約4以
下であるエチレン・プロピレン・ジエン共重合体エラス
トマーを幹ポリマーとし塩化ビニルをグラフトモノマー
としてなる環化ビニルグラフト懸涌共厘合体を有効成分
とする側備零性改善剤が提案されている。In addition, Maekai No. 54-22454 includes improvements in impact resistance, suitability for processing during molding, compatibility with post-processed vinyl resin, weather resistance, and other features of the main guest. For the purpose, post-chlorinated brittle vinyl resin or post-chlorinated vinyl chloride 14
A zero-impression improver has been proposed for use in mixed fats, such as polyvinyl chloride resins, which account for more than 50 ri'c f+j of fat. According to this series of articles, the ratio of the average molecular weight of the resin compound (R'J), which is added in the total resin polymerization of the resin composition at a ratio of about 2 to about 10% by weight, is about 4 or less. A lateral zero property improving agent has been proposed which contains as an active ingredient a cyclized vinyl graft suspended copolymer comprising an ethylene-propylene-diene copolymer elastomer as a backbone polymer and vinyl chloride as a graft monomer.
し刀・しながら、この提案にも本発明に刊・雉された前
記(iii)及ヒ(iv)エラストマーについても、更
にその併用についても全<自゛及されていナーシ、低温
落錘耐1!lJ撃性、劇薬品性、実用劇久住などにおい
て苛酷な条件下の耐性になお改笹が望寸れる。However, this proposal does not include any mention of the elastomers mentioned in (iii) and (iv) published and published in the present invention, nor the combination thereof. ! It is expected that the bamboo will be improved in terms of resistance under harsh conditions such as lJ impact resistance, strong chemical resistance, and practical durability.
又更に、特開昭55−127455+jには、塩先住ポ
リ塩化ビニルの含弔゛週が塩系化ポリ順化ビニルとポリ
塩化ビニルの金言」財にヌ](、TO〜84屯tt俤、
71?す態化ビニル含有太iが30〜16車量係である
」″d系先住化ビニル釧月盲、咀h/、物)を190〜
220℃の成形温度で成形した塙先住塙化ビニル411
脂成形%りが提案されている。この提案によれば、とく
にすぐれた耐熱水性を有する成形物がイIIられるとし
、上6已ヂリ塩化ビニルの1汁が16重1仕係より少々
すぎても、30.4:rftk’tより多すぎても、こ
の提案の効果とくにすぐれた1岨熱水41−が得られ拭
:Cくなると記載している。Furthermore, in JP-A-55-127455+J, the inclusion of salt-containing polyvinyl chloride in the golden words of salt-based polyvinyl chloride and polyvinyl chloride] (, TO~84 tons,
71? The indigenous vinyl content is 30 to 16, and the indigenous vinyl content is 190 to 190.
Hanawajiju Hanawa Vinyl 411 molded at a molding temperature of 220°C
Fat molding has been proposed. According to this proposal, a molded product with particularly excellent hot water resistance is required, and even if the amount of 16-layer vinyl chloride is a little more than 16-layer, 30.4:rftk't It is stated that even if the amount is too much, the effect of this proposal is particularly excellent, and the result is that 41-C of hot water can be obtained.
更に、この提案においては、上記・、・λ先住j′、(
化ビニ11柿削1?j+I且威、物が耐衝撃性改良の罠
め少〉tのエラストマーを含有してよいことが記載され
、塩素化ぼり塩化ビニルとポリ塩化ビニルとの会計1ね
・100屯阪稀に対し10市量部以下のA B S 、
jf、J脂が好適でイ・)ると記載されている・
この提案にも本発明にItf定された前記(iii)及
びGy)エラストマーについても、史にその併用につイ
テも全く開示されていないし、且つ又、30屯景部を超
える塩化ビニル141]αの1更用は祷′極H′づに排
除されている。この提案の組成物はl:j)′’J、’
:、品性が劣り、耐候性及び実用耐久性も悪く、比1数
的苛酷斤凹用条件にさらされる用途には実用に:、・4
、し待かい欠陥がある。Furthermore, in this proposal, the above...
Vinyl 11 persimmon shavings 1? It is stated that the material may contain an elastomer of less than 100% to improve impact resistance, and the ratio of chlorinated vinyl chloride and polyvinyl chloride is 100 to 100. ABS below the market weight department,
It is stated that jf and J fats are preferred and a). Regarding this proposal and the above-mentioned (iii) and Gy) elastomers specified in the present invention, there has been no disclosure in the history of their combined use. Furthermore, the use of vinyl chloride 141]α in excess of 30 tons is strictly prohibited. The composition of this proposal is l:j)''J,'
:, Poor quality, poor weather resistance and practical durability, not practical for applications exposed to relatively severe conditions:, ・4
, there is a long-awaited flaw.
又、他の(8!業として特開昭56−117’519号
の地中線用ケーブル防禮憤・についての提案が知られて
いる。この提’3Kには、ポリ塩化ビニル+’;I4
It汀に、J盆紫化ポリ1,1化ビニル1σ4脂と1j
針候性1dii零vfi化剤とを適量配合してなる・1
4脂組1戊物を1更用した耐熱性、耐雨撃性及び耐候性
に漬れていることを将偵とする池中線用ケーブル防護装
置が請求されている。そして、該耐候性衝撃・独化剤と
してアクリツク・エラストマーが記載され上記’[(J
et¥及びアクリツク・エラストマーのfilに関して
、本発明でいうところのポリ塙化ビニル樹脂、咀成Ii
9/J中のPVc(ポリ1;4化ビニル)に対するCP
VCCr品素化ポリ塩素化ポリ塩化ビニル化剤との割合
は、cpvcl 5〜50 % 量Q3 f P Vo
85〜50−r@ fd部混合した4dJ脂召1成物
100屯量部に対して、4rl撃強化剤は5〜20市最
部の範囲であると記載されている。In addition, as another (8!) proposal for cable protection for underground cables in JP-A-56-117'519 is known. I4
It is J-bon purple polyvinyl 1,1ide 1σ4 fat and 1j
Contains an appropriate amount of needle-climate 1dii zero vfi agent.・1
A cable protection device for the Ikenaka line is claimed to have excellent heat resistance, rain shock resistance, and weather resistance by using 4 resins and 1 material. Acrylic elastomer is described as the weather-resistant impact/uniforming agent, and the above-mentioned '[(J
Regarding et¥ and the film of acrylic elastomer, polyvinyl resin as defined in the present invention, mastication Ii
CP for PVc (poly 1; vinyl tetrachloride) in 9/J
The ratio with the VCCr-grade polychlorinated polyvinylating agent is cpvcl 5 to 50% Amount Q3 f P Vo
It is stated that the 4rl impact strength agent is in the range of 5 to 20 parts per 100 parts by weight of the 4dJ resin composition mixed with 85 to 50 parts of fd.
この提案には本発明に誉;(された前記<1il)エラ
ストマーについては画及されていないし、(iii)及
びGy)エラストマーの併/4−11cついては、勿論
、全く開示されてい7Zい、史に、上記のとおり壇素化
ポリ塩化ビニル1例脂の反用量が、側面組成物100[
有]鑵部中50屯口19部以下のポリ塩化ビニル嗣ノ信
・リッチの組成吻か推奨されている。しかしながら、こ
のタイプの組成物は尚温時嗣円水圧破壊性及び耐榮品・
141〜が不満足であり、史に、耐候性が劣り、実用耐
久性も不充分であって、比較的に苛酷な条件にさらされ
る用途には実用に供し得ない欠点がある。This proposal does not mention the elastomer (said <1il), and the combination of (iii) and Gy) elastomer is, of course, not disclosed at all. Then, as described above, the reverse amount of the base composition 100 [
It is recommended that the composition of polyvinyl chloride is 50 parts or less and 19 parts or less of polyvinyl chloride. However, this type of composition has excellent hydraulic rupture resistance and resistance to corrosion.
141~ are unsatisfactory, and have disadvantages such as poor weather resistance and insufficient practical durability, making them impractical for applications exposed to relatively harsh conditions.
又更に%特開昭56−117520号にも地中線用ケー
ブル防護管が提案さrしている。この提案には、塩化ビ
ニル初詣と後塩先住塩化ビニル例脂とが重賞比で4+6
〜614のホ1)囲で混合された混合物に、塩素化ポリ
エチレンが該混合q勿100市量部に対し6重量部以上
で且つ前記後塩素化塩イヒビニル・囮脂ioo’1旬部
に対(〜で12〜20重量部の範囲で添加された組成物
から成る地中線用ケーブル防穫管が提案されている。Further, a cable protection tube for underground cables is also proposed in JP-A-56-117520. In this proposal, the major award ratio is 4 + 6 for vinyl chloride hatsumode and aftershio indigenous vinyl chloride example fat.
~ 614 E1) chlorinated polyethylene is added in an amount of 6 parts by weight or more based on 100 parts of the mixture, and chlorinated polyethylene is added to the mixture in an amount of 6 parts by weight or more based on 1 part of the post-chlorinated salt vinyl/decoy fat. (A cable protection pipe for underground cables comprising a composition in which 12 to 20 parts by weight of . . . is added is proposed.
この提案VCは、本発明にqす足された前記Ov)エラ
ストマーについては全く開示されていないし、前Fee
(iii)及び(v)エラストマーの併)1→につぃ
ても全く8及されていない。この提案の組成物は畠温時
耐内水圧破壊性に劣り、更に耐候性も不満足であり、実
用耐久性テストの結果も悪く、比較的苛酷な使用条件に
さらされる用途には実用に洪し得ない欠点がある。This proposed VC does not disclose at all the above Ov) elastomer which is added to the present invention, and the previous Fee
(iii) and (v) elastomer combination) 1→8 is not mentioned at all. This proposed composition has poor internal hydraulic rupture resistance at warm temperatures, unsatisfactory weather resistance, and poor practical durability test results, making it impractical for applications exposed to relatively harsh usage conditions. There are disadvantages that cannot be gained.
本発明者等は、前述の如き、従来提案における後塩素化
塩化ビニル樹脂/塩化ビニル四脂/エラストマー系の成
形用側脂組成物における改善の望まれる技術的昧題を克
服し得る組成物をN発1−べく研究を進めてきた。The present inventors have proposed a composition capable of overcoming the technical problems that are desired to be improved in the post-chlorinated vinyl chloride resin/vinyl chloride tetrapolymer/elastomer molding side fat compositions as described above. We have been conducting research to achieve N-1.
その結果、前記の特だ常軛囲割合の(1)後塩素化塩化
ビニル樹脂及び(It)塩化ビニル側面の合計100重
量部に対し、各々特定量範囲割合で且つそれらの合計搦
がltf定量範囲を充足する(ii) (友塩累化ポリ
エチレン・エラストマー及びQ■)アクリツク・エラス
トマー及びMB2・エラストマーよ9成る群からえらは
れたエラストマーから成る複合エラストマーの配合によ
って、優れた低温落輝耐(IJi撃性、優れた高温時耐
内水圧破壊性、優れた耐薬品性・優れた耐熱性、優れた
耐候性及び優れた実用耐久性などの改嵜諸性質を兼備し
、且つこれらの優れた諸性質をバランスよく兼備したユ
ニークな特性を発揮できる後塩累化塩化ビニル・リッチ
な後塩素化塩化ビニル系成形用樹脂、41成物が提供で
きることを発見した。As a result, with respect to a total of 100 parts by weight of (1) post-chlorinated vinyl chloride resin and (It) vinyl chloride side surface of the above-mentioned special normal range ratio, it was determined that each of them was in a specified amount range ratio and that the total ratio was ltf quantitative. (ii) Excellent low-temperature flash resistance due to the compounding of a composite elastomer consisting of an elastomer selected from the group consisting of acrylic elastomer and MB2 elastomer. (It has various properties such as IJi impact resistance, excellent internal hydraulic pressure fracture resistance at high temperatures, excellent chemical resistance, excellent heat resistance, excellent weather resistance, and excellent practical durability, and has these excellent properties. It has been discovered that it is possible to provide post-chlorinated vinyl chloride-rich post-chlorinated vinyl chloride-based molding resin, product No. 41, which exhibits unique properties that have a well-balanced combination of properties.
従って、本発明の目的ld優れた改”?j Wb性質を
7,1F備した後垣素化塩化ビニル系成形用樹脂組成物
Jを提供するにある。Therefore, it is an object of the present invention to provide a trailing polyvinyl chloride molding resin composition J having excellent modified Wb properties of 7.1F.
本発明の上記目的及び更に多くの他の目的ならびに利点
は、以下の記載から一層明らかとなるであろう。The above objects and many other objects and advantages of the present invention will become more apparent from the following description.
本発明で用いる(1)後塩素化塩化ビニル樹脂の例とし
ては1例えば、塩紮含蛍糺60〜7011輌係。Examples of the (1) post-chlorinated vinyl chloride resin used in the present invention include, for example, 60 to 7011 salt-containing fluorescent glues.
比粘度(JIS K6T21準拠)約0.20〜0.
70のものが例示でき、例えば塊化ビニル病脂粉末を気
相中で又は水中に勝陶した状態で、もしくは溶媒に溶解
した状態で塩素化することによシ製這できる。塩化ビニ
ル樹脂の塩紫化方法についてはよく知られており、例え
ば特公昭36−888号公報及び特公昭45−3083
3号公報々どに詳しく祝明されている。Specific viscosity (according to JIS K6T21) approximately 0.20 to 0.
For example, it can be produced by chlorinating agglomerated vinyl fat powder in a gas phase, in water, or dissolved in a solvent. The method of turning vinyl chloride resin into purple is well known, for example, as disclosed in Japanese Patent Publication No. 36-888 and Japanese Patent Publication No. 45-3083.
The congratulations are detailed in the third bulletin.
また前記後塩素化塩化ビニル・1g1脂を製造するのに
使用する塩化ビニル樹脂の例としては、塩化ビニルホモ
、l 17マーのほかに、塩化ビニルと共重合可能な他
のコーモノマーとの塩化ビニル系共重合体樹脂を挙げる
ことができる。In addition, examples of vinyl chloride resins used to produce the post-chlorinated vinyl chloride 1g1 fat include vinyl chloride homo, l 17mer, and vinyl chloride resins with other comonomers copolymerizable with vinyl chloride. Copolymer resins can be mentioned.
この除、該コーモノマーの・1史用11澹、は塩化ビニ
ルモノマー100重量部に基いて、約15重電部以下、
好ましくは約6重量部以下であ石のがよい。Excluding this, 11 parts of the comonomer is about 15 parts by weight or less, based on 100 parts by weight of vinyl chloride monomer,
Preferably, the amount is about 6 parts by weight or less.
斯かるに川口」能な他の共献合性モノマーの例としては
、例えば酢酸ビニル、プロピオン咳ビニル、ラウリル目
にビニル等のビニルエステル迎;メチルアクリレート、
エチレンアクリレート、ブチルアクリレート等のアクリ
ル咳エステル類茎メチ■メタアクリレート、エチルメタ
アクリレート咎のメタアクリル戚エステル類;ジプチル
マレート、ソエチルマレート等のマレインに7エステル
類;ジプチルフマレート、ジエチルフマレート専ノフマ
ール改エステル類;ビニルメチルエーテル、ビニルブチ
ルエーテル、ビニルオクチルエーテル等のビニルエーテ
ル類;アクリロニトリル、メタアクリロニトリル等のシ
アン化ビニル?(11エチレン、プロピレン、ノルマル
ブテン等のオレフィン尖自;塩化ビニリデン、臭化ビニ
ル寺の塩化ビニル以外のハロダン化ビニリデン類又ハハ
ログン化ビニル類逼等をあげることができる。Examples of other codonating monomers that can be used in this way include vinyl esters such as vinyl acetate, propionic vinyl, vinyl lauryl; methyl acrylate;
Acrylic cough esters such as ethylene acrylate and butyl acrylate; methacrylic related esters of methacrylate and ethyl methacrylate; 7-esters of maleic such as diptyl maleate and soethyl maleate; dibutyl fumarate and diethyl fumarate Esters; Vinyl ethers such as vinyl methyl ether, vinyl butyl ether, vinyl octyl ether; Vinyl cyanide such as acrylonitrile and methacrylonitrile? (Olefins such as 11 ethylene, propylene, n-butene, etc.; vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide; and vinyl halide compounds).
また1本発明で使用する(11)塩化ビニル樹脂の例と
しては%塩化ビニルホモポリマーのほかに、前記後塩素
化塩化ビニル蝮]脂の製造に利用する塩化ビニル樹脂の
形成に使用する塩化ビニルと共血合可能な他のモノマー
として例示したと同様々他のコーモノマーとの塩化ビニ
ル系共重合体・1y1脂を革げることができる。これら
のコーモノマーの使用方正も、塩化ビニル七ツマー10
0車虚部に基いて約15城量部以下のものが好凍しい。Examples of the vinyl chloride resin (11) used in the present invention include vinyl chloride homopolymer, as well as vinyl chloride used to form the vinyl chloride resin used in the production of the post-chlorinated vinyl chloride resin. Similarly to the examples of other monomers that can be copolymerized with other comonomers, vinyl chloride copolymers and 1y1 fats can be produced with other comonomers. The correct usage of these comonomers is vinyl chloride heptamer 10
Based on the 0 car imaginary part, it is preferable to freeze something with a weight of about 15 parts or less.
更に、本発明で利用する(ii)後塩素化、J5 リエ
チレン・エラストマー及びその製法も知られており。Furthermore, (ii) post-chlorinated, J5 polyethylene elastomers and processes for their production are also known for use in the present invention.
このような陵塩業化ポリエチレン・エラストマーの・列
としては、好ましく1l−1:壜某含量約20〜45重
i−チ、より好ましくは約30〜40卓重係の後塩素化
ポリエチレン・エラストマーをνり示できる。The column of such chlorinated polyethylene elastomer preferably has a chlorinated polyethylene elastomer content of about 20 to 45 parts per bottle, more preferably about 30 to 40 parts per bottle. can be shown.
該後塩素化ポリエチレン・エラストマーとしては非結晶
性のものが好ましい。このような後塩素化ポリエチレン
・エラストマーは箱鳴でも入手でき、例えば、エラスレ
ン301A、351,4,401A(昭和電工(株)製
)1ダインラックR−135(大阪曹達(株)製) s
CPE−a 614.CPE−3615(タウケミカ
ル(休)裏)等を挙げることができる。The post-chlorinated polyethylene elastomer is preferably amorphous. Such post-chlorinated polyethylene elastomers are also available from Hakounaki, such as Elaslen 301A, 351, 4,401A (manufactured by Showa Denko Co., Ltd.), 1 Dynelac R-135 (manufactured by Osaka Soda Co., Ltd.)
CPE-a 614. Examples include CPE-3615 (Tau Chemical (Kyu) Ura).
又、本発明で利用する(IV)アクリツク・エラストマ
ー及びその製法も知られており本扼明で利用できる。ア
クリツク・エラストマーとはアクリル酸エステル類を主
体とする共重合ゴムにメチルメタ7りIJレ−)、スチ
レン、アクリロニトリル等の単量体をグラフト重合した
多成分系樹脂である。Furthermore, the (IV) acrylic elastomer used in the present invention and its manufacturing method are also known and can be used in this invention. Acrylic elastomer is a multi-component resin made by graft polymerizing monomers such as methylmethane (IJ-ray), styrene, and acrylonitrile to a copolymer rubber mainly composed of acrylic acid esters.
この多成分系樹脂の製造方法については既に公知であシ
1例えば特公昭51−5674.特公昭51−2811
7、特開昭50−881 9、特開昭50−88169
.特開昭50−98951等に記載されている方法で製
造できる。製造法について更に詳しく例を用いて説明す
る。The method for producing this multi-component resin is already known. Special Public Service 51-2811
7, JP-A-50-881 9, JP-A-50-88169
.. It can be produced by the method described in JP-A-50-98951 and the like. The manufacturing method will be explained in more detail using an example.
共重合ゴムの主体となるアクリル酸エステルには、アル
キル基の炭素数が2〜8であるアクリル酸アルキルエス
テル又はアクリル敏アルキルエステルを少なくとも80
重t%以上便用し、これに共重合可能なモノビニリデン
化合物及び多官能性架欄剤を反応させて、まずゴム状共
重合体の水性分散液を作る。次に、このゴム状共重合体
20〜80重祉部の水性分散液にグラフト用単量体とし
て、アルキル基の炭素数が1〜4のメタクリル酸アルキ
ルエステル、ビニル芳香族化合物、不飽和ニトリル及び
これらの単量体と共重合可能なモノビニリデン基を含む
単量体の全部又は2〜3種類からなる混合物20〜80
重量部をグラフト重合して多成分系樹脂を得る。The acrylic ester that is the main component of the copolymer rubber contains at least 80 acrylic alkyl esters or acrylic sensitive alkyl esters in which the alkyl group has 2 to 8 carbon atoms.
First, an aqueous dispersion of a rubbery copolymer is prepared by using at least t% by weight and reacting it with a copolymerizable monovinylidene compound and a polyfunctional crosslinking agent. Next, a methacrylic acid alkyl ester whose alkyl group has 1 to 4 carbon atoms, a vinyl aromatic compound, an unsaturated nitrile, etc. are added to the aqueous dispersion of this rubbery copolymer containing 20 to 80 heavy polymers as a grafting monomer. and a mixture of all or 2 to 3 monomers containing a monovinylidene group copolymerizable with these monomers 20 to 80
A multicomponent resin is obtained by graft polymerizing parts by weight.
このようなアクリツク・エラストマーは市場でも入手で
き、例えば、クレハHIA−15,l1IA−28(呉
羽化学(株)製);カネエースFM(鐘淵化学(株)製
)!メタプレンW−3o o、メタプレンW−529(
三菱レーヨン(株)製)等を挙げることができる。更に
又、本発明で利用するrJv)MBS・エラストマー及
びその製法は仰られておシ、本発明で利用できる。例え
ば、ブタジェンを主成分とするゴムに、メチルメタアク
リレート、スチレン等をグラフト町今した多成分系樹脂
を例示できる。このよりなGy)MBS・エラストマー
は市場でも入手でき、例えば、メタブレンC1−223
(三菱レーヨン(株)製)IクレハBTAmNX(呉羽
化学(株)製);カネエースB−56(鐘淵化学(株)
製)などを挙げることができる。Such acrylic elastomers are available on the market, such as Kureha HIA-15, l1IA-28 (manufactured by Kureha Chemical Co., Ltd.); Kane Ace FM (manufactured by Kanebuchi Chemical Co., Ltd.)! Metaprene W-3o, Metaprene W-529 (
(manufactured by Mitsubishi Rayon Co., Ltd.). Furthermore, the MBS elastomer used in the present invention and its manufacturing method can be used in the present invention. For example, a multicomponent resin in which methyl methacrylate, styrene, etc. are grafted onto a rubber containing butadiene as a main component can be exemplified. This higher Gy) MBS elastomer is available on the market, for example Metablane C1-223
(Mitsubishi Rayon Co., Ltd.) I Kureha BTAmNX (Kureha Chemical Co., Ltd.); Kane Ace B-56 (Kanebuchi Chemical Co., Ltd.)
(manufactured by).
本発明の後塩素化塩化ビニル系成形用m1UN組成物に
於ては、上に例示した如@(I)麦塩素化塙化ビニル樹
脂成分及び(it)塩化ビニル::+4脂成分から成る
複合樹脂成分に対して、(ii)後塩素化ポリエチレン
・エラストマーと(iv)アクリツク・エラストマー及
びMBS・エラストマーよりなる群刀・らえらばれたエ
ラストマーとから成る複合ニジストマー成分の組み合わ
せ成分が必須である。In the post-chlorinated vinyl chloride molding m1UN composition of the present invention, as exemplified above, a composite consisting of (I) a chlorinated vinyl resin component and (it) a vinyl chloride::+4 fat component is used. For the resin component, a combination of (ii) a post-chlorinated polyethylene elastomer and (iv) a composite nystomer component consisting of a selected elastomer consisting of an acrylic elastomer and an MBS elastomer is essential.
該複合エラストマー成分中、(iii)後塩素化ポリエ
チレン・エラストマーを省略すると、本発明組成物のt
、ψれた諸性質をバランスよく兼備させることは困稀で
あって、たとえば、耐薬品性が著しく悪化し、−に、耐
候性も著しく低下する傾向があり。If (iii) post-chlorinated polyethylene elastomer is omitted in the composite elastomer component, t of the composition of the present invention
It is difficult to combine these properties in a well-balanced manner; for example, chemical resistance tends to deteriorate significantly, and weather resistance also tends to deteriorate significantly.
加えて、実用耐久性も不満足となり、比較的苛酷な条件
下での実用に耐えない。又、該複合エラストマー成分中
、(iv)アクリツク・エラストマー及びMilS・エ
ラストマーよりなる群からえらばれたエラストマーを省
111hすると、本発明m成9勿の優れたm 41 情
”itバランスよく兼備させることが同様に困難であっ
て、たとえば#ll温時円内水圧破壊性顕著に低下し、
耐熱性も低下傾向を生ずるほかに、1劇候性及び実用鋼
久住に著しい悪化を生じて、比較的苛酷な条件での実用
には全く不1両足な結果となる。In addition, its practical durability is unsatisfactory, and it cannot withstand practical use under relatively harsh conditions. In addition, by omitting (iv) an elastomer selected from the group consisting of acrylic elastomer and MilS elastomer in the composite elastomer component, it is possible to combine the excellent properties of the present invention in a well-balanced manner. It is similarly difficult, for example, the internal hydraulic rupture property decreases markedly at #ll temperature,
In addition to a tendency to decrease in heat resistance, there is also a significant deterioration in the severity and durability of the steel, resulting in a result that is completely unsatisfactory for practical use under relatively harsh conditions.
従って1本発明に於ては、前記(iii)及びGy)か
ら成る複合エラストマー成分の吠用が必須であり、これ
ら両エラストマー成分の1、口み合Jっせが、前記(D
及び(11)からなる被合樹脂成分と互いに影砕し合っ
て本発明4成分糸組成物が示す前化lk hた品性性を
バランスよく兼備するのに役立っている。これら4成分
を必須とする多成分系m11成吻における個餉の成分が
、該組成物に及ぼす上り己ヘイ符件の兼備の作用機構は
不明であるが、恢に実/I也例と共に比1奴例をあけて
示すように、エラストマーの配合により耐衝撃性を向上
させるという従来技術の知見からは全く予想し得なかっ
た意外な結果であった。Therefore, in the present invention, it is essential to use a composite elastomer component consisting of the above (iii) and Gy), and the mouth contact of both of these elastomer components is the above (D
and (11), and they interact with each other to help the four-component yarn composition of the present invention exhibit the preformed properties in a well-balanced manner. The mechanism of action of the individual components in the multi-component system M11, which requires these four components, on the composition is unknown, but it is possible to As shown in one example, this was a completely unexpected result that could not have been expected based on the knowledge of the prior art that impact resistance can be improved by adding an elastomer.
更に1本発明組成物においては、上述の如き4成分系ホ
11み合わせが示す條れた低温洛錘耐備撃性、優れた市
温時耐内水圧破壊性、1)X11−た耐薬品性、優れた
耐熱性、′&れた耐候性及び梗れた実用耐久性をバラン
スよく兼備したユニークyxm性の発コ小を、最もよく
賦与するために4上記成分組み合わせと共にそれら相互
の置割合本重要な因子となる。Furthermore, in the composition of the present invention, the above-mentioned four-component system H11 combination exhibits excellent low-temperature ramming resistance, excellent internal hydraulic pressure fracture resistance at room temperature, and (1) X11-chemical resistance. In order to best provide a unique YXM property with a well-balanced combination of heat resistance, excellent heat resistance, excellent weather resistance, and excellent practical durability, the combination of the above four components and their relative proportions should be used. This is an important factor.
その址割合として、下記の量割合が選択される。The following amount ratio is selected as the waste ratio.
(1)C1−PVCs5重”74部〜70車量部未満(
好ましくは55〜65藺鼠部)
(!I)PV C30床虜MBe1Mf〜45 ’*、
M、部(好ましくは35〜45助貰部)
の合計100貞酸部に対し、
(iii)Cl−PE 1用量部〜6I七部未満(
好ましくは2〜5庸麓部)
MBS (好ましくけ2〜7這柚部)州し、(i
ii) +(iv)の合計がZ 5 、!Nfgpij
I 〜12 ’M flit部好ましくは5.5財産部
〜12虫瓜部。(1) C1-PVCs 5-layer” 74 parts to less than 70 vehicle parts (
Preferably 55 to 65 groin) (!I) PV C30 floor captive MBe1Mf ~ 45 '*,
M, parts (preferably 35 to 45 parts) for a total of 100 parts of stetanic acid, (iii) Cl-PE 1 part to less than 6I7 parts (
(preferably 2 to 5 bases) MBS (preferably 2 to 7 bases), (i
ii) The sum of +(iv) is Z 5 ,! Nfgpij
I to 12'M flit part preferably 5.5 property parts to 12 milliparts.
史に、上記業割合に於て、好筐しくは、更に下記賞条帥
(イ)及び(ロ)を充足するのが有利でめる。Historically, with the above business ratio, it would be advantageous to further satisfy the following award conditions (a) and (b).
(イ)(iii) I Gv)の埴夏比が1+1〜2(
ロ) (iii)の童が(+) 100重量部に対し
て11車量部以下
尚、上記に於て、ct pvcは(支)塩素化塩化ビ
ニル樹脂、PVCIrit4化ヒー ル・b5J脂、
Cl −pEFi後塩累化1止りエチレン・エラストマ
ー。(a) (iii) Hanika ratio of I Gv) is 1+1~2(
(b) The child of (iii) is (+) 11 parts by weight or less per 100 parts by weight. In the above, ct pvc is (support) chlorinated vinyl chloride resin, PVCIrit 4-chloride heel/b5J resin,
Cl-pEFi post salt accumulation 1 stop ethylene elastomer.
Acrytic及び/又はM B S &、tアクリツ
ク・エラストマー及びMBS・エラストマーよりなる群
がらえらばれたエラストマーを意味する。Acrytic and/or MBS&, t refers to elastomers selected from the group consisting of acrylic elastomers and MBS elastomers.
本発明の後塩累化塙化ビニル糸成ノ1多用樹脂414成
物における上記童割合け1本如明多成分系組成物を構成
する複数成分出]で相互に影響し全うので。This is because the multiple components constituting the multi-component composition for children in the multi-use resin 414 composition of the present invention influence each other.
早−成分の量について一餞的にその技術的4器を述べる
ことはできないが、その川向について以下に説明しよう
。Although it is not possible to describe the four technical aspects of the amount of the early component, we will explain the various aspects below.
本発明組成物に−にいて、(1)Cl −P VCト(
ii)PVCから成る被合樹脂成分中、(−□L P
VCの量が上記問罪を越えて過剰νJC−fきると、っ
まシPVCの亀が上記範囲を越えて過少量にすぎると。In the composition of the present invention, (1) Cl-P VC (
ii) In the resin component to be bonded consisting of PVC, (-□L P
If the amount of VC exceeds the above range and exceeds νJC-f, then the amount of PVC exceeds the above range and becomes too small.
本発明組成物の曖ノした低温落錘耐衝撃性、優れた耐候
性、優れた成形7J11件、優れた2次加エイ111(
曲げ加工性、接)滑性、一層性)などを1己の優れた諸
性質と共にバランスよ< SkE備させることが困難と
なり、父、c t −pvcの童が上記範囲を越えて過
少量にすぎると、つまりP V Crb);rが上記範
囲を超えて過剰扉Vζすぎると1本発明組成物の優れた
尚温時のnl内水圧性、後れた耐〆ん性、優れた耐薬品
性などを11)ルの優れた時性質と共にバランスよく兼
備させることが困難となる傾向がめる。従って、本屁明
においては、前記<H>ct−pvcと(11)PVC
Q量範囲全範囲することが必要である。The composition of the present invention has vague low-temperature falling weight impact resistance, excellent weather resistance, 11 cases of excellent molding 7J, and excellent secondary processing rays 111 (
It became difficult to maintain a balance of bending workability, adhesion, lubricity, layering properties, etc., along with various other excellent properties, and the father and son of CT-PVC exceeded the above range and produced too little. If r exceeds the above range and the excess door Vζ exceeds 1, the composition of the present invention will have excellent internal water pressure resistance at still temperature, delayed oxidation resistance, and excellent chemical resistance. There is a tendency for it to be difficult to combine properties such as 11) with the excellent timing properties in a well-balanced manner. Therefore, in this clarification, the above <H>ct-pvc and (11) PVC
It is necessary to cover the entire Q quantity range.
又、本発明1.−11成物において−(iii)C1−
PEとGv)Acrylic 及び/又はMBSから
成る複合エラストマー成分中、C1−PEの賞が6重重
部以上過剰すさ゛ると、本発明組成物の折れた両温時の
耐水圧強度、優れた機械的強度、優れた融層性、優れた
耐熱性などを他の優れた諸性質と共にバランスよく兼備
させることが難かしく、父、 ac l −PEの訊が
1重毎部未満で過少量にすぎると1本句明組成物の優れ
た耐薬品性、耐候性などを他の代れた諸性質と共にバラ
ンスよ〈兼備さぞることが困難となる。一方、Acry
lic 及び/又はMBSの創が7重鐘部以上過剰叛に
すぎると1本発明組成物の優れた耐薬品性、優れた機械
的強度、優れた耐候性、潰れた耐熱性などを曲の1(れ
た諸性質と共にバランスよく兼備させることは困難でぽ
・・す。Moreover, the present invention 1. -(iii)C1- in the -11 composition
In the composite elastomer component consisting of PE and Gv) acrylic and/or MBS, if the amount of C1-PE is in excess of 6 parts or more, the composition of the present invention has excellent mechanical strength and water pressure resistance at both temperatures when broken. It is difficult to combine strength, excellent melting properties, excellent heat resistance, etc. with other excellent properties in a well-balanced manner. It is difficult to balance the excellent chemical resistance, weather resistance, etc. of the composition according to the present invention with other properties. On the other hand, Acry
If the wound of lic and/or MBS is excessively resistant to 7 or more bells, the excellent chemical resistance, mechanical strength, weather resistance, heat resistance, etc. of the composition of the present invention can be improved. (It is difficult to combine these properties in a well-balanced manner.)
又、該AcryLsc及び/又けIVI B Sの量が
taxi:miS禾満で過少量にすぎると、本発明組成
物の捩れた低温落錘衝撃性、優れた機械119狩性など
を他の優れた諸性質と共にバランスよく兼備した組成物
が得難い。In addition, if the amount of AcryLsc and/or IVIBS is too small, the twisted low-temperature drop weight impact resistance, excellent mechanical 119 hunting properties, etc. of the composition of the present invention may be affected by other advantages. It is difficult to obtain a composition that has all these properties in a well-balanced manner.
更に、上記(iii)ct−pp:と(iy) Ac
ry l i c 及び/又はMBSから成る複合エ
ラストマー成分は、前記<1)C1−PEと(ii)
P V Cから成る複合樹脂成分100−Jg 京都に
対して、(ii)iv)の合計tで25重足部〜12i
iji部の量軛囲で用いる。これら合計瞼か上記順回f
越えて多すぎると、本発明組成物の優i1.た、筒部に
於ける耐水圧性、優れた耐薬品性、優れた耐熱性、優れ
た耐候性、優れた機械的強度、優れた2次加工性(接層
性、融眉性曲げ加工性)などを他の優れた時性質と共に
バランスよく兼備させることは困難でるり、また、上記
範囲を越えて過少量にすぎると1本発明組成物の優れた
低温に於り−る落′4(Ifi撃性、優れた機械的強度
、曖れた2次加工性などを他の優れた諸性質と共にバラ
ンスよく兼備させることが難〃・しい。Furthermore, the above (iii) ct-pp: and (iy) Ac
The composite elastomer component consisting of ry l i c and/or MBS is composed of the above <1) C1-PE and (ii)
Composite resin component consisting of P V C 100-Jg Kyoto, total of (ii) and iv) t is 25 to 12i
It is used in the yokukei of the iji part. These total eyelids or the above order f
If the amount exceeds 1. In addition, water pressure resistance in the cylindrical part, excellent chemical resistance, excellent heat resistance, excellent weather resistance, excellent mechanical strength, and excellent secondary processability (layer contact, fusion and bending processability) It is difficult to combine these properties with other excellent thermal properties in a well-balanced manner, and if the amount exceeds the above range and is too small, the excellent low temperature properties of the composition of the present invention may be reduced. It is difficult to achieve a well-balanced combination of other excellent properties such as impact resistance, excellent mechanical strength, and vague secondary processability.
従って、上記(iii)Cl −PR及び(iy) A
cryl ic及び/又(dMBsは、夫々、上記童頓
囲及び合計対範囲を満足する麓で使用される。Therefore, the above (iii) Cl-PR and (iy) A
Crylic and/or (dMBs) are used at the foot satisfying the above doton range and total pair range, respectively.
本発明組成物の経通態様に於ては、さらに前記(イ)及
び(ロ)の好′si瀘条件をも充足することが好ましい
。これら好適亜条件ヶも1両足ぜしめることによって、
仮も優れた各時性を蔵も好t t、いバランスで兼備し
た不〜E明組成物を提供することができる。In the oral mode of the composition of the present invention, it is preferable that the preferable Si filtering conditions of (a) and (b) above are also satisfied. By combining both of these favorable subconditions,
It is possible to provide a composition that has both excellent temporal properties and a good balance.
本発明の咬J温素化垣化ビニル系成形用・IM(力汀す
目成吻は、前記例示の如き(i)Ct −P V C,
(li)PV (、’、(iii)(1’ l −PE
及び(iy) Acry l i c及び/又はMES
、更にノツr望によシ他の硝加剤金、同時にもしくは任
意の1獣序で混合することにより製造することができる
。該混合手段も適宜に選択料ハ」でき、できるだけ上記
各成分を均一に混合できるr、I4s4重段ケ選択する
のがよい。The bite-resistant vinyl-based molding/IM of the present invention (the force-reducing eye formation is as exemplified above (i) Ct-P V C,
(li) PV (,', (iii) (1' l -PE
and (iy) Acrylic and/or MES
Furthermore, it can be produced by mixing with other nitrifying agents simultaneously or in any one order. The mixing means can be selected as appropriate, and it is preferable to select a multi-stage method that can mix the above-mentioned components as uniformly as possible.
混合は、例えば、混合機としてヘンシェルミキサーやス
・9−ミキサーのような筒速ミキザー、リゼングレンダ
ー、パンパ’J −ミ*−1+−−1連続ニーダ−、ミ
キシングロール、ライカイキなどを例示できる。For mixing, for example, a cylinder speed mixer such as a Henschel mixer or a S.9-mixer, a Rizenglander, a Pampa'J-Mi*-1+--1 continuous kneader, a mixing roll, a Raikaiki, etc. can be used as a mixer. .
混合方式は、上記混合機に各成分を投入し、例えば、2
10℃以下の温度でそれぞれの混合機に見合った時間、
均一にブレンドするのが好ましい。The mixing method is to put each component into the mixer, for example, 2
At a temperature below 10℃, the time appropriate for each mixer,
Preferably, it is blended uniformly.
本発明の後塩素化塩化ビニル系成形用1剥脂廻成物は、
(1)Cl −PVC,(ii)PVG、 QH)C
l −PE及びQy)Acrylic及び/又はMBS
の必須4成分のほかに、純々の他の雄刃l剤を含有する
ことができる。The post-chlorinated vinyl chloride-based molding degreasing composition of the present invention is:
(1) Cl-PVC, (ii) PVG, QH)C
l -PE and Qy) Acrylic and/or MBS
In addition to the four essential ingredients, it may contain other pure agents.
このような硝加剤の例としては、たとえば、安定剤、滑
剤、酸化防止剤、充填剤、紫外線吸収剤、着色剤などの
添加剤を例示することができる。Examples of such nitrifying agents include additives such as stabilizers, lubricants, antioxidants, fillers, ultraviolet absorbers, and colorants.
こ′i′+、らの添加剤の具体例としては、たとえば、
三塩基性硫酸鉛、二塩漬性亜リン酸鉛などの無機塩系、
鉛安定剤、fチル錫マレート、ブチル錫うウレ−)、
ブチル錫メルカゾタイド、オクチル錫マレート、オクチ
ル錫メルカプタイト、メチル錫メルカプタイドの如き錫
系ヅ定剤などの如き安だ剤墨たとえばステアリン酸鉛、
ステアリン酸カドミウム、ステアリン&!&亜鉛、ステ
アリン酸カルシウムのような金属石鹸、パラフィンワッ
クス、マイクロクリスタルワックス、ポリエチレンワッ
クス、脂肪酸、脂肪暇アミド、脂肪暇エステル、脂肪酸
ケトン、脂肪アルコール、脂肪酸の部分エステルワック
スの如き滑剤;たとえばフェニル−α−ナフチルアミン
、フェニル−β−ナフチルアミン、アルドール−α−ナ
フチルアミンなどのナフチルアミン系、P−イソゾロボ
キシーヅフェニルアミン、# 、 #’−ジフェニルー
プロピレンジアミンなどのソフェニルアミン系、2,2
.4−トリメチル−1、2−?/ヒドロキノンのW合物
、6−ニトキシー2,2.4−トリメチル−1,2−ジ
ヒドロキノリンなどのキノリン系、l−オキシ−3−メ
チル−4−イソプロピルベンゼン、2,6−ノー第三−
プチル−4−メチルフェノールなどのモノフェノール系
、B11−vヒドロキシジフェニル、ヒンダード、ビス
フェノール、トリス−(2−メチル−4−ヒドロキシ−
5−第三−ブチルフェニル)ブタンなどのポリフェノー
ル系、4−41−チオビス−(6−第三−プチル−3−
メチルフェノール)72:どのチオビスフェノール系な
どの如き酸化防止剤tたとえば炭ばカルシウム、けイ敵
アルミニウム、水酸化アルミニウム、炭はマグネシウム
、水酸化マグネシウム、けいそう土、木粉、タルク、シ
リカ、マイカなどの如き充填剤;たとえばフェニル・サ
リシレート、p−オクチルフェニルサシレートのような
サルチルMu導体2゜4−ソヒドロキシ・ベンゾフェノ
ン、2−ヒドロキシ−4−メトキシ嗜ベンゾフェノンの
ようなベンゾフェノン系、2−(2′−ヒドロキシ−5
′−メチル−フェニル)ペンツトリアゾール、’2−(
2’−ヒドロキシ−al、r、?−ジー第三−プチルー
フェニル)ベンゾトリアゾールなどのようなトリアゾー
ル系、レゾルシノール・モノベンゾエート% 2゜4−
ジー第三−プチルフェニル−3,5−ソー第三−ブチル
−4−ヒドロキシベンゾエート、O−ペンゾイル安息香
咳メチルの如き紫外線吸収剤Hたとえば酸化チタン、鉛
白、リトポン、パライト。Specific examples of these additives include, for example,
Inorganic salts such as tribasic lead sulfate and dichlorinated lead phosphite,
lead stabilizer, f-thyl tin malate, butyl tin urea),
Tin-based fixatives such as butyltin mercazotide, octyltin malate, octyltin mercaptite, methyltin mercaptide, stabilizers such as lead stearate,
Cadmium stearate, stearin &! & lubricants such as zinc, metallic soaps such as calcium stearate, paraffin wax, microcrystalline wax, polyethylene wax, fatty acids, fatty acid amides, fatty acid esters, fatty acid ketones, fatty alcohols, partial ester ester waxes of fatty acids; e.g. phenyl-α - Naphthylamine series such as naphthylamine, phenyl-β-naphthylamine, aldol-α-naphthylamine, sophenylamine series such as P-isozoloboxyduphenylamine, #, #'-diphenyl-propylene diamine, 2,2
.. 4-trimethyl-1,2-? /W compound of hydroquinone, quinoline series such as 6-nitoxy-2,2.4-trimethyl-1,2-dihydroquinoline, l-oxy-3-methyl-4-isopropylbenzene, 2,6-no-tertiary-
Monophenols such as butyl-4-methylphenol, B11-v hydroxydiphenyl, hindered, bisphenol, tris-(2-methyl-4-hydroxy-
Polyphenols such as 5-tert-butylphenyl)butane, 4-41-thiobis-(6-tert-butyl-3-
Methylphenol) 72: Antioxidants such as thiobisphenols, etc. For example, charcoal calcium, aluminum hydroxide, aluminum hydroxide, charcoal magnesium, magnesium hydroxide, diatomaceous earth, wood powder, talc, silica, mica Fillers such as phenyl salicylate, saltyl Mu conductors such as p-octylphenyl sacylate; 2'-hydroxy-5
'-Methyl-phenyl)penztriazole, '2-(
2'-Hydroxy-al,r,? - Triazoles such as di-tertiary-butylphenyl) benzotriazole, resorcinol monobenzoate% 2゜4-
Ultraviolet absorbers such as di-tert-butylphenyl-3,5-so-tert-butyl-4-hydroxybenzoate, O-penzoylbenzoin, cough methyl, etc., such as titanium oxide, lead white, lithopon, palite.
カーボンブラック、カドミウムレッド、べんがら、銀朱
、カドミウムイエローのような無機系顔料、アゾ系顔料
、ニトロソ顔料、ニトロ顔料、塩基性染料レーキ、フタ
ロシアニン顔料、などの如き着色剤等を例示することが
できる。Examples include inorganic pigments such as carbon black, cadmium red, red rose, silver vermilion, and cadmium yellow, and colorants such as azo pigments, nitroso pigments, nitro pigments, basic dye lakes, and phthalocyanine pigments.
これら添加剤の使用量は、本発明組成物の前述の諸物件
に実質的な低下を伴わないかぎり任意に選択できるが1
例えば、前記必須4成分の合計型−1dK基いて、約0
〜約5重量%の安冗剤、約0.5〜約5重重チの滑剤、
約0〜約2重蓋チの#枝化防止剤、約θ〜約10重量%
Q−芯填剤、約θ〜約2ffi i!if:%の紫外線
吸収剤、約0〜約3玉倉%の着色剤の如き使用ii:f
例示することができる。The amount of these additives to be used can be arbitrarily selected as long as the above-mentioned properties of the composition of the present invention are not substantially deteriorated.
For example, based on the sum of the four essential components -1dK, approximately 0
- about 5% by weight of a cheap agent, about 0.5 to about 5% by weight of a lubricant,
About 0 to about 2 layers of anti-branching agent, about θ to about 10% by weight
Q-core filler, about θ to about 2ffi i! If:% ultraviolet absorber, about 0 to about 3% colorant, etc. ii:f
I can give an example.
本発明の彼塩累化塩化ビニル系成形用(イ・1脂組成物
は、既述の如き優れた改4吋性質を示し且つこれらの優
れた諸性質をバランスよく兼備したユニークな特性全発
揮するため、後)詰素化垣化ビニル樹脂/塩化ビニル樹
脂/エラストマー系の従来組成物の利用分野において有
利に利用できるほかに、従来組成物が実用的に利用困難
であったような比較的苛酷な1更用条件にさらされる用
途に於ても有オIJに利用できる。斯くて1例えば、工
業用の畠温薬液配管、タンク、地下埋設配管、温廃水用
下水配眉・、高温画用する桑欣容播、などの如き利用分
野に加えて、史に、例えば、亀カケープルの保穫管、メ
ッキ槽、塩累ガス配管の如き用途においても好イr11
合にオIJ用することができる。The polyvinyl chloride-based molding composition of the present invention exhibits the excellent modified properties as described above, and exhibits unique properties that combine these excellent properties in a well-balanced manner. Therefore, it can be used advantageously in the field of application of conventional compositions such as (later) packed vinyl resin/vinyl chloride resin/elastomer system, and can also be used in comparative areas where conventional compositions have been difficult to use practically. It can be used effectively even in applications where it is exposed to severe single-use conditions. Thus, in addition to fields of application such as industrial chemical piping, tanks, underground piping, sewage pipes for hot waste water, and Kuwa Xinyong distributing for high temperature painting, etc., in history, for example, R11 is also suitable for applications such as storage pipes for turtle caples, plating tanks, and salt accumulation gas piping.
In some cases, it can be used for OIJ.
以下、比較例をまじえ実施例により本発明組成物の数例
について更に詳しく例示する。Hereinafter, several examples of the compositions of the present invention will be illustrated in more detail by way of examples along with comparative examples.
尚、低温落錘耐衝撃性、尚温時耐内水圧破壊性。In addition, it has low-temperature falling weight impact resistance and internal water pressure rupture resistance when still hot.
耐薬品性、耐熱性−耐候性、実用耐久性のテスト及び評
価は、下記のとおりである。Tests and evaluations of chemical resistance, heat resistance-weather resistance, and practical durability are as follows.
試験方法及び評価2−
試験片の調製!−
後記実施例及び比較例に示した量割合の下記成分組成
(1)C1−PVCにカテンプ7’−781+塩素含量
68wtチ、平均重合度1000i日本カーバイド工業
株式会社製品)
(II) P V Cにカビニル、S’G−1100
1平均重合度1000+玉菱化成工某株式会社製品)(
iIi) C1−PE(エラスレン3017 j塩素
含量wt% +昭和電工株式会社製品)
(iy) Acrylic(HI A 28 r呉羽
化学工業体式会社製品)
MBS(BTAmNX+ 同上
#
(v) 安定剤CTVS MA−300Asブチル
錫系安定剤;日東化成株式会社製品)
(vD 滑剤(ハイワックス200Pi4リエチレン
・ワックス系滑斎り三井石油化学工業株式会社製品)
を、751ヘンシル・ミキサーを用いて室温で材料を投
入し間遠回転により120℃まで昇温混合し、50℃ま
で冷却して混合組成物(コンパウンド)を形成する。Test method and evaluation 2- Preparation of test piece! - The following component composition (1) C1-PVC with Katemp 7'-781 + chlorine content 68wt, average degree of polymerization 1000i Nippon Carbide Industries Co., Ltd. product) in the amounts shown in the Examples and Comparative Examples below (II) P V C Kabinir, S'G-1100
1 Average degree of polymerization 1000 + Tamabishi Kasei Co., Ltd. product) (
iIi) C1-PE (Elastrene 3017j chlorine content wt% + Showa Denko K.K. product) (iy) Acrylic (HI A 28 r Kureha Chemical Industry Co., Ltd. product) MBS (BTAmNX+ Same as above # (v) Stabilizer CTVS MA-300As Butyltin stabilizer; Nitto Kasei Co., Ltd. product) (vD lubricant (Hiwax 200Pi4 polyethylene wax based lubricant Mitsui Petrochemical Industries Co., Ltd. product) was added to the mixer at room temperature using a 751 Henshil mixer. The mixture is heated to 120° C. by centrifugal rotation, and then cooled to 50° C. to form a mixed composition (compound).
上記コンパウンドを、押出機(池具鉄工株式会社製RC
−100■型)を用いて、樹脂温度が160℃〜220
℃の蝿囲で押出成形して、外径32闘、内径25m5.
平均厚み3關の試験用パイプを成形する。The above compound was processed using an extruder (RC manufactured by Ikegu Iron Works Co., Ltd.).
-100 ■ type), the resin temperature is 160℃ to 220℃.
Extrusion molded at a temperature of 32°C, outer diameter 32m, inner diameter 25m5.
A test pipe with an average thickness of 3 mm is formed.
テスト及び評価;− (α)低温落錘耐衝撃性テスト。Testing and evaluation;- (α) Low temperature falling weight impact resistance test.
試験用/eイブをパイプ長20儂に切断した試、験片3
0ケをW4製し、これらを0℃の恒温槽中で4時間冷却
する。Test specimen 3: Test by cutting e-ve into a pipe length of 20 degrees
0 pieces were made of W4 and cooled for 4 hours in a constant temperature bath at 0°C.
この0°Cに冷却した試験片の管側面へ5 kgの重錘
を自然落下させ、試験片が破壊しない場合はl水準高く
、試験片が破壊した場合け1水準低くシ。A 5 kg weight is dropped naturally onto the side of the tube of the test piece cooled to 0°C, and if the test piece does not break, the level is raised one level, and if the test piece breaks, the level is lowered by one level.
これを30ケのサンプルについてくり返し、破壊しなか
った高さの合計の平均値より試験片が50チの確率で破
壊する商さ、すなわち50チ破壊高さを求める( cm
)。数値が犬であるほど低温落錘耐衝撃性が優れてい
ることを示す。Repeat this for 30 samples, and calculate the quotient of the probability that the test piece will break at 50 inches, that is, the 50-inch failure height, from the average value of the total height that did not break (cm
). The higher the value, the better the low-temperature falling weight impact resistance.
(6) 高温時耐内水圧破壊性テスト。(6) Internal water pressure rupture resistance test at high temperatures.
試験用ノクイデをノにイブ長50cmに切断した試験片
を用いる。パイプ試験片の片嬬全鋸性治具でシールし、
他方の端から水圧機を用いて、昇圧速度10に9/Cr
l・分、測足温度60℃の条件で水圧を負荷し、試験片
が破壊する圧力を測定する(kl?/d、於60℃)。A test piece is used, which is obtained by cutting a test piece into a length of 50 cm. Seal the pipe test piece with a fully sawn jig,
From the other end, use a water pressure machine to increase the pressure to 9/Cr at a rate of 10.
Water pressure is applied under conditions of 1 min and foot measurement temperature of 60°C, and the pressure at which the test piece breaks is measured (kl?/d, at 60°C).
その測定値で示す。60℃の水槽にパイプを1時間状態
調整し、60℃水槽中で試験する。数値が犬であるほど
^温時耐内水圧破壊性が優′iしていることを示す。It is shown as the measured value. Condition the pipe for 1 hour in a 60°C water bath and test in the 60°C water bath. The higher the value, the better the resistance to internal water pressure rupture at high temperatures.
(C) 耐薬品性テスト。(C) Chemical resistance test.
試験用パイプ會パイプ長5αに切断した試験片を秤量(
,9) t、、この試験片をオイル・パス上60′Cに
加温した93チIi、SO,中に浸漬する。Test pipe: Weigh the test piece cut to a pipe length of 5α (
, 9) t, This test piece is immersed in 93mm Ii, SO, heated to 60'C above an oil path.
この条件で2週間連続浸漬したのち敗り出して、赤洗浄
し乾いた布で表面の水分をふきとった後すみやかに市>
l’、 (Ji’ )を秤と膚し、浸漬前の試触片東爪
に対する浸漬処理陵の試験片咽卵の増加分を葬出し百分
率で示す。数イlの大であるはど耐薬品性が悪く、小で
あるほど耐薬品性が榎れていることを示す。After 2 weeks of continuous soaking under these conditions, it begins to rot, and after washing the red and wiping off the moisture on the surface with a dry cloth, immediately put it in the market.>
l' and (Ji') are weighed on a scale, and the increase in the number of ova on the test piece from the immersion treatment compared to the test piece before immersion is shown in percentage. A value of several liters indicates poor chemical resistance, and a value of several liters indicates poor chemical resistance.
更に、浸頂処、I!I!後の試験片について、その外観
を肉眼で観桜し、外観変化を下記評随基準に従って判定
する。In addition, I! I! The appearance of the subsequent test piece is inspected with the naked eye, and changes in appearance are judged according to the following evaluation criteria.
li+浸漬処理前に比しで認め得る変化なし。li+No discernible change compared to before immersion treatment.
2級!軽度の変色が認められる。2nd class! Slight discoloration is observed.
3級g茶色調に変色する。Grade 3: Discolors to brown.
4級8黒褐色調に変色する。Grade 4 8 Discolors to blackish brown.
5級2黒色調に変色し、発汗現象が認められる。Grade 5 2 Discoloration to blackish tone and sweating phenomenon observed.
級値の小であるほど耐薬品性/)柚、とれていることを
示す。The lower the grade value, the better the chemical resistance.
(力 耐M(性テスト。(Force resistance M (ability test).
パイプより1cWLX2cmに切り出した試験片を5ゆ
・f(5kl?fとは力で馳/cr&と同穫)の荷重で
。A test piece cut out from the pipe to a size of 1cWL x 2cm was subjected to a load of 5ft.
JIS KT206C熱可塑性プラスチックのビカッ
ト軟化点試験方法)に従ってテストし、ビカット軟化点
(℃)を測定して示す。数値の大であるほど耐熱性の優
れていることを示す。Tested according to JIS KT206C (Vicat Softening Point Test Method for Thermoplastic Plastics), and the Vicat softening point (°C) is measured and shown. The larger the value, the better the heat resistance.
(6)耐候性テスト。(6) Weather resistance test.
(e −1) W−0−MCウェザオメーター)10
0時間後シャルピー・テスト。(e-1) W-0-MC Weatherometer) 10
Charpy test after 0 hours.
試験用・ぐイブをパイプ長1ocr/Lに切断した試験
片を用いる。試験片をブラックパネル63±2℃の温度
で180分間隔で18分間スプレーするウエザオメータ
ーで100時間照射処理した後、処理後の試験片からシ
ャルピー衝撃強度試験片を切す出シ、ASTM D−
256に示されるシャルピー試験法に従って%20”C
でシャルピー衝撃強度(ゆ・crrr / crl )
を測定して示す。数値が犬であるほどW−0−Ml 0
0 hr後シャルピー・テストによる耐候性が優れてい
ることを示す。A test piece made by cutting a test tube into a pipe length of 1 ocr/L is used. After the test piece was irradiated for 100 hours with a weatherometer that sprayed the black panel at a temperature of 63 ± 2 ° C for 18 minutes at 180 minute intervals, a Charpy impact strength test piece was cut from the treated test piece. ASTM D −
%20”C according to the Charpy test method set forth in 256
Charpy impact strength (yu・crrr/crl)
Measure and show. The higher the number, the more W-0-Ml 0
Shows excellent weather resistance by Charpy test after 0 hr.
(g −2) W−0−M400時間後落錘テスト。(g-2) W-0-M Drop weight test after 400 hours.
?
る。処理後の試験片の各1raiについて、前記((Z
)と同様にして落錘耐衝袈性テストヲイ1つて、破壊高
さく crn )を実測し、30ケの試験片の破壊筒さ
のA術平均値(tx )で示す。数値が大であるほどW
−0−M400hr後落→テストによる耐候性が優れて
いることを示す。? Ru. For each rai of the test piece after treatment, the above ((Z
) In a falling weight impact resistance test, the fracture height (crn) was actually measured and expressed as the average value (tx) of the fracture height of 30 test pieces. The larger the number, the W
-0-M Dropped after 400 hours → Indicates excellent weather resistance by test.
(イ)実用耐久性テスト。(a) Practical durability test.
長さ5tnの試験用パイプを介して40℃〜60℃の塩
素ガスを供給する。試験用・にイブは戸外に配管し、8
月中旬から翌年の8月中旬まで1ケ年間、上記廖累ガス
供給配管として夾用銅久テストに供した。テスト終了恢
、テストすみ試験用ieイブの中央部付近より、ノにイ
ブ艮5儒のテスト用パイプを切υ取り、測尾温度25°
Cに於て、パイプの周方向から10 yap / mi
nの速度で圧縮して破壊したときのパイプの変形量(
crn )を実測した。Chlorine gas at 40°C to 60°C is supplied through a test pipe with a length of 5 tn. For testing, pipes are installed outdoors, and
The pipe was used as the above-mentioned gas supply pipe for the long-term test of copper for one year from mid-August to mid-August of the following year. After the test was completed, a 5-meter test pipe was cut from near the center of the test tube, and the tail temperature was 25°.
At C, 10 yap/mi from the circumferential direction of the pipe
The amount of deformation of the pipe when it is compressed and destroyed at a speed of n (
crn) was actually measured.
圧縮テスト前のパイプ長と破壊時の、eイブ長との差か
らパイプの変形量(cm )を求め、圧縮テスト前のパ
イプ長に対する変形量を回分率で示す。変形量が50%
以上の場合には破壊せずに評価する。The amount of deformation (cm 2 ) of the pipe is determined from the difference between the length of the pipe before the compression test and the e-beam length at the time of failure, and the amount of deformation with respect to the length of the pipe before the compression test is expressed as a batch rate. Deformation amount is 50%
In the above cases, evaluate without destroying.
変形値が大きいほど実用耐久性が優れていることを示す
。The larger the deformation value, the better the practical durability.
実施例1〜3及び比較例1〜5
後掲第1表に示した成分組成及び童の前記試験片の、A
判の項に述べたc t−pvc、”P V C。Examples 1 to 3 and Comparative Examples 1 to 5 A
ct-pvc, "PVC" mentioned in the judgment section.
Cl −PE、 Acrylic又はMBS、f定酌及
び滑剤を用いた組成物をi(+4製し、前記試験方法及
び評価に従ってテストした。その結呆を下掲第1表に示
した。Compositions using Cl-PE, Acrylic or MBS, f-stable and lubricant were prepared as i(+4) and tested according to the test method and evaluation described above. The results are shown in Table 1 below.
実施例4〜7
CL −PVC,P VC,CL −PE、 A1B5
゜Acrylicの種類、量などを第2表に示すとおり
にf更したほかは、実施例1〜3と同様に行って組成物
を得た。その結果を下掲第2表に示した。Examples 4 to 7 CL-PVC, PVC, CL-PE, A1B5
Compositions were obtained in the same manner as in Examples 1 to 3, except that the type and amount of Acrylic were changed as shown in Table 2. The results are shown in Table 2 below.
Claims (1)
)(iiD i&塩素化ポリエチレン・エラストマ−
1道魚都〜6車針部未満 (IV) アクリツク・エラストマー及びMBs・エ
ラストマーよりなる群からえらはレタエラストマー IM気部〜8重般部 但し、上記(ii)及びGv)の合計が25軍量部〜1
2乗掬都である、 を含有して成ることをLl、F減とするmJA−n化J
盆化ビニル系成形用佃脂岨成物。 2 該(iii) r (IV)の嵐鍵比がI+1〜2
である’i)許請求の範囲第1項記載の組成刀。 3、該(in)の量が(1)後塩素化塩化ビニル慨脂1
00厘銚暴f対して11軍量部以下である′11許請求
の範囲第1項もしくは第2項記11&の組成物。[Claims] 1. The following (+) and (ii) (1) After J, 4-carbon vinyl chloride rut resin 55: ii removal to less than 70 parts by weight (11) 30 parts by weight of vinyl chloride hatsumode The following (iii) and (iv) are applied to a total of 100g of 45-point support parts.
) (iiD i & chlorinated polyethylene elastomer
1 road fish capital - less than 6 needle parts (IV) From the group consisting of Acrylic elastomer and MBs elastomer, gills are Reta elastomer IM air part - 8 heavy general part However, the total of (ii) and Gv) above is 25 parts Volume ~1
mJA-n conversion J with Ll and F reduced as containing
Tsukujia composite material for vinyl molding. 2 The Arashi key ratio of (iii) r (IV) is I+1~2
'i) The composition sword according to claim 1. 3. The amount of (in) is (1) after chlorinated vinyl chloride fat 1
The composition according to claim 1 or 2, 11&, which has an amount of not more than 11 parts by weight per 00000000000 ml.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21706482A JPS59108055A (en) | 1982-12-13 | 1982-12-13 | Postchlorinated vinyl chloride molding resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21706482A JPS59108055A (en) | 1982-12-13 | 1982-12-13 | Postchlorinated vinyl chloride molding resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59108055A true JPS59108055A (en) | 1984-06-22 |
JPH0221418B2 JPH0221418B2 (en) | 1990-05-14 |
Family
ID=16698262
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21706482A Granted JPS59108055A (en) | 1982-12-13 | 1982-12-13 | Postchlorinated vinyl chloride molding resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59108055A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6225147A (en) * | 1985-07-24 | 1987-02-03 | Osaka Soda Co Ltd | Post-chlorinated vinyl chloride resin composition |
WO2004096908A1 (en) * | 2003-04-25 | 2004-11-11 | Kaneka Corporation | Chlorinated vinyl chloride resin composition |
CN102964721A (en) * | 2012-11-28 | 2013-03-13 | 安徽玉发塑业有限公司 | Chlorinated polyvinyl chloride tubular product |
JP2015511248A (en) * | 2012-01-13 | 2015-04-16 | ゲオルク フィッシャー デカ ゲゼルシャフト ミット ベシュレンクテル ハフツングGeorg Fischer DEKA GmbH | Polyvinyl chloride compositions, tubes, ducts or containers, use of PVC compositions, and uses of tubes, ducts or containers |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4832941A (en) * | 1971-09-01 | 1973-05-04 | ||
JPS4834228A (en) * | 1971-09-06 | 1973-05-17 | ||
JPS5033094A (en) * | 1973-07-30 | 1975-03-31 |
-
1982
- 1982-12-13 JP JP21706482A patent/JPS59108055A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4832941A (en) * | 1971-09-01 | 1973-05-04 | ||
JPS4834228A (en) * | 1971-09-06 | 1973-05-17 | ||
JPS5033094A (en) * | 1973-07-30 | 1975-03-31 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6225147A (en) * | 1985-07-24 | 1987-02-03 | Osaka Soda Co Ltd | Post-chlorinated vinyl chloride resin composition |
JPH0312582B2 (en) * | 1985-07-24 | 1991-02-20 | Daisow Co Ltd | |
WO2004096908A1 (en) * | 2003-04-25 | 2004-11-11 | Kaneka Corporation | Chlorinated vinyl chloride resin composition |
US7332544B2 (en) | 2003-04-25 | 2008-02-19 | Kaneka Corporation | Chlorinated vinyl chloride resin composition |
JP2015511248A (en) * | 2012-01-13 | 2015-04-16 | ゲオルク フィッシャー デカ ゲゼルシャフト ミット ベシュレンクテル ハフツングGeorg Fischer DEKA GmbH | Polyvinyl chloride compositions, tubes, ducts or containers, use of PVC compositions, and uses of tubes, ducts or containers |
CN102964721A (en) * | 2012-11-28 | 2013-03-13 | 安徽玉发塑业有限公司 | Chlorinated polyvinyl chloride tubular product |
CN102964721B (en) * | 2012-11-28 | 2015-08-05 | 安徽玉发塑业有限公司 | A kind of chlorinated polyvinyl chloride tubes |
Also Published As
Publication number | Publication date |
---|---|
JPH0221418B2 (en) | 1990-05-14 |
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