JP2004018735A - Tubular formed article of polypropylene resin - Google Patents

Tubular formed article of polypropylene resin Download PDF

Info

Publication number
JP2004018735A
JP2004018735A JP2002177359A JP2002177359A JP2004018735A JP 2004018735 A JP2004018735 A JP 2004018735A JP 2002177359 A JP2002177359 A JP 2002177359A JP 2002177359 A JP2002177359 A JP 2002177359A JP 2004018735 A JP2004018735 A JP 2004018735A
Authority
JP
Japan
Prior art keywords
stabilizer
polypropylene
weight
polypropylene resin
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2002177359A
Other languages
Japanese (ja)
Inventor
Hirotsugu Yoshida
吉田 博次
Junichi Yokoyama
横山 順一
Koji Ichihara
市原 幸治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority to JP2002177359A priority Critical patent/JP2004018735A/en
Publication of JP2004018735A publication Critical patent/JP2004018735A/en
Pending legal-status Critical Current

Links

Abstract

<P>PROBLEM TO BE SOLVED: To provide a formed article of a polypropylene resin having improved durability and attaining sufficient suppressing effect against oxidative deterioration in a pipe for hot water flowing. <P>SOLUTION: The tubular formed article of a polypropylene resin is produced by forming a polypropylene resin composition composed of a polypropylene resin, a phenolic stabilizer (a) expressed by a specific structural formula, another phenolic stabilizer (b) and a sulfur-based stabilizer (c) [preferably further a phosphorus-based stabilizer (d)] in the form of a tube. The sum of the phenolic stabilizer (a) and the phenolic stabilizer (b) is 0.2-1.0 pt. wt. based on 100 pts. wt. of the polypropylene resin, the weight ratio of the phenolic stabilizer (a) to the phenolic stabilizer (b) [(a)/(b)] is 0.01-0.5, the content of the sulfur-based stabilizer is 0.2-1.0 pt. wt., and preferably further the content of the phosphorus-based stabilizer (d) is 0.2-0.5 pt. wt. <P>COPYRIGHT: (C)2004,JPO

Description

【0001】
【発明の属する技術分野】
本発明は、ポリプロピレン系樹脂管状成形体に関し、詳しくは排水、給水、給湯、消火等の用途に好適に使用されるポリプロピレン系樹脂管状成形体に関する。
【0002】
【従来の技術】
従来、排水、給水、給湯、消火等の用途に用いられる管や継手などの管状成形体においては硬質塩化ビニルやポリオレフィン系樹脂などの材料が多用されているが、特に高温水が流れる管路においては、耐熱クリープ性等の高温物性の点でポリプロピレン系樹脂管状成形体が適している。
しかし、ポリプロピレン系樹脂は通常3級炭素を多く含むため化学的には酸化劣化を起こしやすいという問題があり、高温水が流れる管路に用いる場合に解決すべき重要な問題となっている。
【0003】
この問題に対し、特開平8−59913号公報には、ポリプロピレン樹脂に、下記(A)、(B)、及び(C)成分を、該樹脂100重量部に対して各々0.05〜3重量部で、かつ、(B)成分の配合量に対する(A)成分の配合量の比を1.0以下となるように配合したポリプロピレン樹脂組成物から成形されてなることを特徴とするポリプロピレン樹脂製給排水用管状成形体[(A)1,3,5−トリス(2,6−ジメチル−3−ヒドロキシ−4−t−ブチルベンジル)イソシアヌレート、及び、3,9−ビス{2−〔3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ〕−1,1−ジメチルエチル}−2,4,8,10−テトラオキサスピロ〔5.5〕ウンデカンからなる群より選ばれた少なくとも一種の化合物;(B)ペンタエリスリット−テトラ(β−アルキル−チオプロピオネート)(ここで、アルキル基の炭素数は4〜20である。);(C)ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、及び、ベンゾエート系化合物からなる群より選ばれた少なくとも一種の化合物]が提案されているが、必ずしも酸化劣化に対する充分な抑制効果が得られるものではなく、長期の使用に耐え得る程度の改良には到っていないのが現状である。
【0004】
【発明が解決しようとする課題】
本発明の目的は、上記従来のポリプロピレン系樹脂管状成形体の問題点に鑑み、高温水が流れる管路においても酸化劣化に対する充分な抑制効果が得られ、耐久性の改良されたポリプロピレン系樹脂管状成形体を提供することにある。
【0005】
【課題を解決するための手段】
請求項1記載のポリプロピレン系樹脂管状成形体は、ポリプロピレン系樹脂、下記一般式(1)で表されるフェノール系安定剤(a)、下記一般式(2)で表されるフェノール系安定剤(b)及び下記一般式(3)で表されるイオウ系安定剤(c)からなるポリプロピレン系樹脂組成物が管状に成形されてなるポリプロピレン系樹脂管状成形体であって、ポリプロピレン系樹脂100重量部に対してフェノール系安定剤(a)とフェノール系安定剤(b)との合計の含有量が0.2〜1.0重量部であり、フェノール系安定剤(a)とフェノール系安定剤(b)との重量比[(a)/(b)]が0.01〜0.5であり、且つ、ポリプロピレン系樹脂100重量部に対してイオウ系安定剤(c)の含有量が0.2〜1.0重量部であることを特徴とする。
【化5】

Figure 2004018735
[式中、R、Rはメチル基またはt−ブチル基であり、少なくとも一方はt−ブチル基であって、R、Rはそれぞれ独立に炭素原子数1〜3のアルキレン基である。]
【化6】
Figure 2004018735
[式中、R、Rはメチル基またはt−ブチル基であり、少なくとも一方はt−ブチル基である。]
【化7】
Figure 2004018735
[式中、Rはそれぞれ独立に炭素原子数12〜18のアルキル基であり、Rはそれぞれ独立に炭素原子数1〜3のアルキレン基である。]
請求項2記載のポリプロピレン系樹脂管状成形体は、請求項1記載のポリプロピレン系樹脂管状成形体であって、ポリプロピレン系樹脂組成物は、更に下記一般式(4)で表されるリン系安定剤(d)が含有され、その含有量がポリプロピレン系樹脂100重量部に対して0.2〜0.5重量部であることを特徴とする。
【化8】
Figure 2004018735
[式中、R、Rはメチル基またはt−ブチル基であり、少なくとも一方はt−ブチル基である。]
【0006】
以下、本発明を詳細に説明する。
本発明におけるポリプロピレン系樹脂としては、特に限定されず、プロピレンの単独重合体、又は、プロピレンと、エチレン、ブテン−1、ペンテン−1、ヘキセン−1、4−メチル−ペンテン−1等のα−オレフィン等との、ブロック、ランダムもしくはグラフト共重合体等が挙げられる。なかでもプロピレン−エチレンブロック共重合体が低温耐衝撃性の点で好ましい。
【0007】
本発明におけるフェノール系安定剤(a)[以下、「成分(a)」ともいう]としては、上記一般式(1)で表されるものであれば特に限定されず、例えば、R、Rがt−ブチル基であり、Rがエチレン基、Rがメチレン基であるペンタエリスリトール テトラキス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]などが好適である。
上記成分(a)は、上記一般式(1)に表される化学構造を有することによって主として管状に成形する場合の成形温度に対する酸化劣化などを抑制する機能を発揮し、成形時の耐熱性を向上しうるものと考えられる。
【0008】
本発明におけるフェノール系安定剤(b)[以下、「成分(b)」ともいう]としては、上記一般式(2)で表されるものであれば特に限定されず、例えば、R、Rがt−ブチル基である3,3’,3”,5,5’,5”−ヘキサ−tert−ブチル−a,a’,a”−(メシチレン−2,4,6−トリイル)トリ−p−クレゾールなどが好適である。
上記成分(b)は、上記一般式(2)に表される化学構造を有することによって管状成形体に流される高温水による酸化劣化などを抑制する機能を発揮し、耐久性を向上し得るものと考えられる。
【0009】
上記成分(a)と成分(b)との合計の含有量は、ポリプロピレン系樹脂100重量部に対して0.2〜1.0重量部とされ、好ましくは0.4〜0.8重量部である。含有量が少なすぎるとポリプロピレン系樹脂に対する酸化劣化抑制効果が不充分となりやすく、含有量が多すぎると成分が成形体表面へブリードアウト(浸出)しやすくなる。
【0010】
また、本発明においては上記成分(a)と成分(b)との重量比[(a)/(b)]が0.01〜0.5であることが必要であり、好ましくは0.02〜0.4である。重量比が0.01未満では管状に成形する場合の成形温度による酸化劣化などが発生しやすくなり、重量比が0.5を越えると成形体に高温水等を流して使用する際の酸化劣化などの抑制が不充分になりやすい。
【0011】
本発明におけるイオウ系安定剤(c)[以下、「成分(c)」ともいう]としては、上記一般式(3)で表されるものであれば特に限定されない。上記一般式(3)におけるRとしては、例えば、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基などが挙げられ、Rとしては、例えば、メチレン基、エチレン基、プロピレン基などが挙げられる。中でもRがエチレン基であるジオクタデシル3,3’−チオジプロピオネートやジドデシル3,3’−チオジプロピオネートなどが好適である。
【0012】
上記成分(c)の含有量は、ポリプロピレン系樹脂100重量部に対して0.2〜1.0重量部とされ、好ましくは0.3〜0.8重量部である。含有量が少なすぎるとポリプロピレン系樹脂に対する酸化劣化抑制効果が不充分となりやすく、含有量が多すぎると成分が成形体表面へブリードアウト(浸出)するなどの問題が生じやすくなる。
【0013】
本発明における上記ポリプロピレン系樹脂組成物には、更にリン系安定剤(d)が含有されたものであることが好ましい。
上記リン系安定剤(d)[以下、「成分(d)」ともいう]としては、上記一般式(4)で表されるものであれば特に限定されず、例えば、R、Rがt−ブチル基であるトリス(2,4−ジ−tert−ブチルフェニル)フォスファイトなどが好適である。
【0014】
上記成分(c)の含有量は、ポリプロピレン系樹脂100重量部に対して0.2〜0.5重量部であることが好ましく、より好ましくは0.25〜0.4重量部である。含有量が少なすぎると管状に成形する場合の成形温度による酸化劣化に対する抑制効果が不充分となりやすく、含有量が多すぎると成分が成形体表面へブリードアウト(浸出)しやすくなる。
【0015】
本発明におけるポリプロピレン系樹脂組成物は、本発明の効果を阻害しない限り上記成分以外の付加的成分が含有されたものであってもよい。
上記付加的成分としては、例えば従来公知の酸化防止剤、光安定剤、中和剤、滑剤、帯電防止剤、金属不活性化剤、着色剤、分散剤、核剤、充填剤、及び上記ポリプロピレン系樹脂以外の樹脂やゴム等が挙げられる。
【0016】
上記充填剤としては、例えばタルク、マイカ、ガラス繊維等が挙げられ、これらの充填剤がポリプロピレン系樹脂100重量部に対して0.1〜30重量部含有されたものは成形体の剛性を向上し得る点で好ましい。
また、上記ポリプロピレン系樹脂以外の樹脂やゴムとしては、例えば、低・中・高密度ポリエチレン、ポリブテン、エチレン−プロピレン系共重合体ゴム、エチレン−ブテン系共重合体ゴム等が挙げられる。
【0017】
本発明のポリプロピレン系樹脂管状成形体の製造方法としては、特に限定されず、例えば、上記ポリプロピレン系樹脂組成物を用い、従来公知の押出成形法や射出成形法により管や継手などの管状成形体を得ることができる。
【0018】
(作用)
本発明のポリプロピレン系樹脂管状成形体においては、特定の化学構造を有するフェノール系安定剤(a)、フェノール系安定剤(b)及びイオウ系安定剤(c)が特定量含有され、特に成分(a)と成分(b)との重量比[(a)/(b)]が0.01〜0.5であるポリプロピレン系樹脂組成物を用いるので、その作用機構は必ずしも明らかではないが、成分(a)に対する成分(b)の比率が高いことによって、成分(a)の主として成形時における劣化抑制の働きと、成分(b)の主として高温水など使用時の劣化抑制の働きがバランスよく効果を発揮し、通常ポリプロピレン系樹脂に含まれる3級炭素等における化学的な酸化劣化を有効に抑制することができるものと推定される。
【0019】
上記ポリプロピレン系樹脂組成物が、更に特定の化学構造を有するリン系安定剤(d)を含有するものであると、上記効果は更に確実なものとなる。
【0020】
【実施例】
以下に実施例および比較例を示すことにより、本発明を具体的に説明する。
尚、本発明は下記実施例のみに限定されるものではない。
(実施例1〜4、比較例1〜3)
ポリプロピレン系樹脂としてプロピレン−エチレンブロック共重合体(メルトフローレート0.5g/10分)100重量部に対し、成分(a)〜(d)を表1に示す重量部数配合し、得られたポリプロピレン系樹脂組成物を下記の押出設備を用いて樹脂温度230℃にて押出成形し、ポリプロピレン系樹脂管状成形体(外径52mm、肉厚2mmの直管)を得た。
<押出設備>
押出機:スクリュー径65mm、L/D25、45Kwモータ搭載の単軸押出機金型 :マルチマニホールドタイプの2層パイプ金型
水槽 :バキューム式噴霧水槽(冷却水温:15℃)
【0021】
(比較例4)
成分(a)〜(c)に変えて、成分(e)〜(g)を表1に示す重量部数配合したこと以外は実施例1と同様にしてポリプロピレン系樹脂管状成形体(外径52mm、肉厚2mmの直管)を得た。
(評価)
得られたポリプロピレン系樹脂管状成形体を各々300mmの長さに切断し、この管内に95℃の熱水を連続的に通水し、5000時間経過後に通水を止め、通水後の各管について引張強度を測定し、各管の初期引張強度に対する比(5000h引張強度/初期引張強度)を求めた。これらの結果を表1に示す。
【0022】
【表1】
Figure 2004018735
なお、表1中の各成分(a)〜(g)は、それぞれ以下の化合物を示す。
(a);ペンタエリスリトール テトラキス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]
(b);3,3’,3”,5,5’,5”−ヘキサ−tert−ブチル−a,a’,a”−(メシチレン−2,4,6−トリイル)トリ−p−−クレゾール
(c);ジオクタデシル 3,3’−チオジプロピオネート
(d);トリス(2,4−ジ−tert−ブチルフェニル)フォスファイト
(e);1,3,5−トリス(2,6−ジメチル−3−ヒドロキシ−4−t−ブチルベンジル)イソシアヌレート
(f);ペンタエリスリット−テトラ(β−ラウリル−チオプロピオネート)
(g);2−(2’−ヒドロキシ−3’,5’−ジ−t−ブチルフェニル)−5−クロロベンゾトリアゾール
【0023】
表1より明らかなように、本発明の実施例においては初期強度に対する5000時間経過後の引張強度の低下が極めて少なく、優れた耐久性を有することが判明した。
【0024】
【発明の効果】
本発明のポリプロピレン系樹脂管状成形体は、ポリプロピレン系樹脂、特定の化学構造を有する、フェノール系安定剤(a)、フェノール系安定剤(b)及びイオウ系安定剤(c)が特定量含有され、また、フェノール系安定剤(a)とフェノール系安定剤(b)との重量比が特定の範囲であるポリプロピレン系樹脂組成物が管状に成形されてなるポリプロピレン系樹脂管状成形体であるので、成形時や使用時の熱などによる材料の酸化劣化を効果的に抑制することができ、優れた耐久性を発揮することができる。
【0025】
上記ポリプロピレン系樹脂管状成形体において、ポリプロピレン系樹脂組成物が、更に特定の化学構造を有する特定量のリン系安定剤(d)を含有するものであると、上記効果は更に確実なものとなる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polypropylene-based resin tubular molded article, and more particularly to a polypropylene-based resin tubular molded article suitably used for applications such as drainage, water supply, hot water supply, and fire extinguishing.
[0002]
[Prior art]
Conventionally, materials such as hard vinyl chloride and polyolefin resin are often used in tubular molded bodies such as pipes and joints used for drainage, water supply, hot water supply, fire extinguishing, etc. Is suitable from the viewpoint of high temperature properties such as heat creep resistance.
However, polypropylene-based resins usually contain a large amount of tertiary carbon, and thus have a problem that they are chemically susceptible to oxidative deterioration. This is an important problem to be solved when used in a pipeline through which high-temperature water flows.
[0003]
To solve this problem, JP-A-8-59913 discloses that the following components (A), (B) and (C) are added to a polypropylene resin in an amount of 0.05 to 3 parts by weight based on 100 parts by weight of the resin. Part, and molded from a polypropylene resin composition blended so that the ratio of the blending amount of the component (A) to the blending amount of the component (B) is 1.0 or less. Tubular molded body for water supply and drainage [(A) 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate and 3,9-bis {2- [3- Selected from the group consisting of (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl {-2,4,8,10-tetraoxaspiro [5.5] undecane. At least (B) pentaerythrit-tetra (β-alkyl-thiopropionate) (where the alkyl group has 4 to 20 carbon atoms); (C) benzotriazole-based compound, benzophenone-based compound Compounds, and at least one compound selected from the group consisting of benzoate compounds] have not been proposed, but do not necessarily provide a sufficient inhibitory effect on oxidative degradation, and are improved to withstand long-term use. Has not reached the current state.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a polypropylene-based resin tube having an improved durability in which a sufficient effect of suppressing oxidative deterioration is obtained even in a pipe through which high-temperature water flows, in view of the above-mentioned problems of the conventional polypropylene-based resin molded tube. It is to provide a molded article.
[0005]
[Means for Solving the Problems]
The polypropylene resin tubular molded article according to claim 1 is a polypropylene resin, a phenolic stabilizer (a) represented by the following general formula (1), and a phenolic stabilizer represented by the following general formula (2) ( a polypropylene-based resin molded article obtained by molding a polypropylene-based resin composition comprising b) and a sulfur-based stabilizer (c) represented by the following general formula (3) into a tubular shape, wherein 100 parts by weight of the polypropylene-based resin is The total content of the phenol-based stabilizer (a) and the phenol-based stabilizer (b) is 0.2 to 1.0 part by weight, and the phenol-based stabilizer (a) and the phenol-based stabilizer ( b) is 0.01 to 0.5, and the content of the sulfur-based stabilizer (c) is 0.1 to 100 parts by weight of the polypropylene-based resin. 2 to 1.0 parts by weight And butterflies.
Embedded image
Figure 2004018735
[Wherein, R 1 and R 2 are a methyl group or a t-butyl group, at least one of them is a t-butyl group, and R 3 and R 4 are each independently an alkylene group having 1 to 3 carbon atoms. is there. ]
Embedded image
Figure 2004018735
[Wherein, R 1 and R 2 are a methyl group or a t-butyl group, and at least one of them is a t-butyl group. ]
Embedded image
Figure 2004018735
[Wherein, R 5 is each independently an alkyl group having 12 to 18 carbon atoms, and R 6 is each independently an alkylene group having 1 to 3 carbon atoms. ]
The polypropylene-based resin tubular molded product according to claim 2 is the polypropylene-based resin tubular molded product according to claim 1, wherein the polypropylene-based resin composition further comprises a phosphorus-based stabilizer represented by the following general formula (4). (D) is contained, and its content is 0.2 to 0.5 part by weight based on 100 parts by weight of the polypropylene resin.
Embedded image
Figure 2004018735
[Wherein, R 7 and R 8 are a methyl group or a t-butyl group, and at least one of them is a t-butyl group. ]
[0006]
Hereinafter, the present invention will be described in detail.
The polypropylene resin in the present invention is not particularly limited, and may be a homopolymer of propylene or propylene and α- such as ethylene, butene-1, pentene-1, hexene-1, and 4-methyl-pentene-1. Examples include block, random or graft copolymers with olefins and the like. Among them, a propylene-ethylene block copolymer is preferred in view of low-temperature impact resistance.
[0007]
Phenolic stabilizers in the present invention (a) [hereinafter referred to as "component (a)"] as is not particularly limited as long as it is represented by the above general formula (1), for example, R 1, R Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] wherein 2 is a t-butyl group, R 3 is an ethylene group, and R 4 is a methylene group; is there.
The component (a) has a chemical structure represented by the general formula (1), and mainly exhibits a function of suppressing oxidative deterioration with respect to a molding temperature when molding into a tube, and has a heat resistance during molding. It is thought that it can be improved.
[0008]
Phenolic stabilizers in the present invention (b) [hereinafter referred to as "component (b)"] as is not particularly limited as long as it is represented by the above general formula (2), for example, R 1, R 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri, wherein 2 is a t-butyl group -P-cresol and the like are preferred.
The component (b) has a chemical structure represented by the general formula (2), thereby exhibiting a function of suppressing oxidative deterioration and the like due to high-temperature water flowing through the tubular molded body, and improving durability. it is conceivable that.
[0009]
The total content of the above components (a) and (b) is 0.2 to 1.0 part by weight, preferably 0.4 to 0.8 part by weight, per 100 parts by weight of the polypropylene resin. It is. If the content is too small, the effect of suppressing the oxidative deterioration of the polypropylene-based resin tends to be insufficient, and if the content is too large, the components tend to bleed out to the surface of the molded article.
[0010]
In the present invention, the weight ratio [(a) / (b)] of the component (a) to the component (b) needs to be 0.01 to 0.5, and preferably 0.02. ~ 0.4. If the weight ratio is less than 0.01, oxidative deterioration due to the molding temperature when forming into a tube tends to occur, and if the weight ratio exceeds 0.5, oxidative deterioration when high temperature water or the like is flowed through the molded body for use. Etc. are likely to be insufficiently suppressed.
[0011]
The sulfur-based stabilizer (c) [hereinafter, also referred to as “component (c)”] in the present invention is not particularly limited as long as it is represented by the general formula (3). Examples of R 5 in the general formula (3) include a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. As R 6 , for example, a methylene group, ethylene Group, propylene group and the like. Among them, dioctadecyl 3,3'-thiodipropionate and didodecyl 3,3'-thiodipropionate in which R 6 is an ethylene group are preferred.
[0012]
The content of the component (c) is 0.2 to 1.0 part by weight, preferably 0.3 to 0.8 part by weight, based on 100 parts by weight of the polypropylene resin. If the content is too small, the effect of suppressing oxidative deterioration of the polypropylene resin tends to be insufficient, and if the content is too large, problems such as bleeding out (leaching) of the components to the surface of the molded article tend to occur.
[0013]
It is preferable that the polypropylene-based resin composition of the present invention further contains a phosphorus-based stabilizer (d).
The phosphorus-based stabilizer (d) [hereinafter, also referred to as “component (d)”] is not particularly limited as long as it is represented by the general formula (4), and for example, R 7 and R 8 are Tris (2,4-di-tert-butylphenyl) phosphite, which is a t-butyl group, and the like are preferable.
[0014]
The content of the component (c) is preferably 0.2 to 0.5 part by weight, more preferably 0.25 to 0.4 part by weight, based on 100 parts by weight of the polypropylene resin. If the content is too small, the effect of suppressing the oxidative deterioration due to the molding temperature when forming into a tube tends to be insufficient, and if the content is too large, the components tend to bleed out (leach) to the surface of the molded body.
[0015]
The polypropylene-based resin composition of the present invention may contain additional components other than the above components as long as the effects of the present invention are not impaired.
Examples of the additional component include a conventionally known antioxidant, light stabilizer, neutralizer, lubricant, antistatic agent, metal deactivator, colorant, dispersant, nucleating agent, filler, and the polypropylene. Resins and rubbers other than the base resin are exemplified.
[0016]
Examples of the filler include talc, mica, glass fiber and the like. Those containing 0.1 to 30 parts by weight of these fillers with respect to 100 parts by weight of the polypropylene resin improve the rigidity of the molded article. It is preferable in that it can be performed.
Examples of the resin or rubber other than the polypropylene resin include low, medium and high density polyethylene, polybutene, ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, and the like.
[0017]
The method for producing the polypropylene-based resin tubular molded article of the present invention is not particularly limited. For example, a tubular molded article such as a pipe or a joint may be produced by using the above-mentioned polypropylene-based resin composition by a conventionally known extrusion molding method or injection molding method. Can be obtained.
[0018]
(Action)
In the polypropylene-based resin tubular molded article of the present invention, a phenol-based stabilizer (a), a phenol-based stabilizer (b), and a sulfur-based stabilizer (c) having a specific chemical structure are contained in specific amounts, and in particular, the component ( Since a polypropylene resin composition having a weight ratio [(a) / (b)] of a) to component (b) of 0.01 to 0.5 is used, its mechanism of action is not necessarily clear, but the When the ratio of the component (b) to the component (a) is high, the effect of suppressing the deterioration of the component (a) mainly at the time of molding and the function of suppressing the deterioration of the component (b) mainly at the time of use such as high-temperature water are balanced. It is presumed that the chemical oxidation degradation of tertiary carbon and the like usually contained in a polypropylene resin can be effectively suppressed.
[0019]
When the polypropylene-based resin composition further contains a phosphorus-based stabilizer (d) having a specific chemical structure, the above-mentioned effect is further ensured.
[0020]
【Example】
Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples.
The present invention is not limited only to the following examples.
(Examples 1-4, Comparative Examples 1-3)
Components (a) to (d) were mixed with 100 parts by weight of a propylene-ethylene block copolymer (melt flow rate: 0.5 g / 10 min) as a polypropylene-based resin to obtain a polypropylene obtained by blending the parts by weight shown in Table 1. The resin composition was extruded at a resin temperature of 230 ° C. using the following extrusion equipment to obtain a polypropylene resin tubular molded product (a straight pipe having an outer diameter of 52 mm and a wall thickness of 2 mm).
<Extrusion equipment>
Extruder: Single-screw extruder with 65 mm screw diameter, L / D 25, 45 Kw motor Die: Multi-manifold type two-layer pipe Die tank: Vacuum spray water tank (cooling water temperature: 15 ° C)
[0021]
(Comparative Example 4)
Except that components (e) to (g) were blended in parts by weight as shown in Table 1 in place of components (a) to (c), a polypropylene resin tubular molded product (outer diameter 52 mm, A straight pipe having a thickness of 2 mm) was obtained.
(Evaluation)
Each of the obtained polypropylene-based resin tubular molded products was cut into a length of 300 mm, hot water at 95 ° C. was continuously passed through the tubes, and after 5000 hours, the water flow was stopped. , The tensile strength was measured, and the ratio of each tube to the initial tensile strength (5000 h tensile strength / initial tensile strength) was determined. Table 1 shows the results.
[0022]
[Table 1]
Figure 2004018735
In addition, each component (a)-(g) in Table 1 shows the following compounds, respectively.
(A); pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
(B); 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-- Cresol (c); dioctadecyl 3,3'-thiodipropionate (d); tris (2,4-di-tert-butylphenyl) phosphite (e); 1,3,5-tris (2,6 -Dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate (f); pentaerythritol-tetra (β-lauryl-thiopropionate)
(G); 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole
As is evident from Table 1, in Examples of the present invention, the decrease in tensile strength after lapse of 5000 hours from the initial strength was extremely small, and it was found to have excellent durability.
[0024]
【The invention's effect】
The polypropylene-based resin tubular molded article of the present invention contains a polypropylene-based resin, a phenol-based stabilizer (a), a phenol-based stabilizer (b) and a sulfur-based stabilizer (c) having a specific chemical structure in a specific amount. Further, since the polypropylene resin composition in which the weight ratio of the phenolic stabilizer (a) to the phenolic stabilizer (b) is in a specific range is a polypropylene-based resin tubular molded article, Oxidation degradation of the material due to heat during molding or use can be effectively suppressed, and excellent durability can be exhibited.
[0025]
In the above-mentioned polypropylene-based resin tubular molded article, when the polypropylene-based resin composition further contains a specific amount of the phosphorus-based stabilizer (d) having a specific chemical structure, the above-described effect is further ensured. .

Claims (2)

ポリプロピレン系樹脂、下記一般式(1)で表されるフェノール系安定剤(a)、下記一般式(2)で表されるフェノール系安定剤(b)及び下記一般式(3)で表されるイオウ系安定剤(c)からなるポリプロピレン系樹脂組成物が管状に成形されてなるポリプロピレン系樹脂管状成形体であって、ポリプロピレン系樹脂100重量部に対してフェノール系安定剤(a)とフェノール系安定剤(b)との合計の含有量が0.2〜1.0重量部であり、フェノール系安定剤(a)とフェノール系安定剤(b)との重量比[(a)/(b)]が0.01〜0.5であり、且つ、ポリプロピレン系樹脂100重量部に対してイオウ系安定剤(c)の含有量が0.2〜1.0重量部であることを特徴とするポリプロピレン系樹脂管状成形体。
Figure 2004018735
[式中、R、Rはメチル基またはt−ブチル基であり、少なくとも一方はt−ブチル基であって、R、Rはそれぞれ独立に炭素原子数1〜3のアルキレン基である。]
Figure 2004018735
[式中、R、Rはメチル基またはt−ブチル基であり、少なくとも一方はt−ブチル基である。]
Figure 2004018735
[式中、Rはそれぞれ独立に炭素原子数12〜18のアルキル基であり、Rはそれぞれ独立に炭素原子数1〜3のアルキレン基である。]
Polypropylene resin, phenolic stabilizer (a) represented by the following general formula (1), phenolic stabilizer (b) represented by the following general formula (2) and represented by the following general formula (3) A polypropylene-based resin tubular molded article obtained by forming a polypropylene-based resin composition comprising a sulfur-based stabilizer (c) into a tubular shape, wherein a phenol-based stabilizer (a) and a phenol-based The total content with the stabilizer (b) is 0.2 to 1.0 part by weight, and the weight ratio of the phenol-based stabilizer (a) to the phenol-based stabilizer (b) [(a) / (b) )] Is from 0.01 to 0.5, and the content of the sulfur-based stabilizer (c) is from 0.2 to 1.0 part by weight based on 100 parts by weight of the polypropylene-based resin. Polypropylene-based resin tubular molded article.
Figure 2004018735
[Wherein, R 1 and R 2 are a methyl group or a t-butyl group, at least one of them is a t-butyl group, and R 3 and R 4 are each independently an alkylene group having 1 to 3 carbon atoms. is there. ]
Figure 2004018735
[Wherein, R 1 and R 2 are a methyl group or a t-butyl group, and at least one of them is a t-butyl group. ]
Figure 2004018735
[Wherein, R 5 is each independently an alkyl group having 12 to 18 carbon atoms, and R 6 is each independently an alkylene group having 1 to 3 carbon atoms. ]
ポリプロピレン系樹脂組成物は、更に下記一般式(4)で表されるリン系安定剤(d)が含有され、その含有量がポリプロピレン系樹脂100重量部に対して0.2〜0.5重量部であることを特徴とする請求項1記載のポリプロピレン系樹脂管状成形体。
Figure 2004018735
[式中、R、Rはメチル基またはt−ブチル基であり、少なくとも一方はt−ブチル基である。]
The polypropylene-based resin composition further contains a phosphorus-based stabilizer (d) represented by the following general formula (4), and the content thereof is 0.2 to 0.5 parts by weight based on 100 parts by weight of the polypropylene-based resin. The polypropylene-based resin tubular molded article according to claim 1, wherein the tubular molded article is a part.
Figure 2004018735
[Wherein, R 7 and R 8 are a methyl group or a t-butyl group, and at least one of them is a t-butyl group. ]
JP2002177359A 2002-06-18 2002-06-18 Tubular formed article of polypropylene resin Pending JP2004018735A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002177359A JP2004018735A (en) 2002-06-18 2002-06-18 Tubular formed article of polypropylene resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2002177359A JP2004018735A (en) 2002-06-18 2002-06-18 Tubular formed article of polypropylene resin

Publications (1)

Publication Number Publication Date
JP2004018735A true JP2004018735A (en) 2004-01-22

Family

ID=31175416

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2002177359A Pending JP2004018735A (en) 2002-06-18 2002-06-18 Tubular formed article of polypropylene resin

Country Status (1)

Country Link
JP (1) JP2004018735A (en)

Similar Documents

Publication Publication Date Title
JPH0270737A (en) Extrudable thermoplastic hydrocarbon polymer composition
JP2007500283A (en) Polyphenylene ether and / or polystyrene-containing compositions having excellent tribological properties and methods for improving the tribological properties of polyphenylene ether and / or polystyrene compositions
KR980009369A (en) Polytetrafluoroethylene-containing powder mixture, thermoplastic resin composition containing the same and molded article made therefrom
JP4436753B2 (en) Extrudable thermoplastic composition
PT1254184E (en) Crosslinkable polyethylene composition, process for the production of a pipe and pipe
JP4567001B2 (en) Melt processable composition
US6852921B1 (en) Wire-protective tube
JP2001200154A (en) Polyketone-based resin composition, and film, sheet and tube all made of the same composition
WO2015133315A1 (en) Method for melt molding of vinylidene fluoride resin, and melt molded product of vinylidene fluoride resin
JP5241111B2 (en) Propylene-based resin composition and piping member molded using the same
JP6181465B2 (en) Water-foamed thermoplastic elastomer composition for composite molding
JP2004018735A (en) Tubular formed article of polypropylene resin
JPS59113059A (en) Thermoplastic resin composition
KR100891705B1 (en) Polypropylene Resin Composition for Pipe and Heat Water Pipe Device
JP3967507B2 (en) Pipe made of polyethylene resin composition
JPH09324081A (en) Crosslinked polyethylene pipe
JP5220058B2 (en) Polyolefin resin foam molding
WO2015064394A1 (en) Olefin-based resin composition, molded body and method for suppressing deterioration thereof
JPH05170932A (en) Tubular polypropylene resin molding for watersupply and drainage
JP2012067257A (en) Polyvinyl chloride resin composition and flexible cable protecting tube
KR100566861B1 (en) Polypropylene resin composition for pipe and heat water pipe device
JP2019044111A (en) Dynamic crosslinking type thermoplastic elastomer composition and molded body thereof
JP3494497B2 (en) Polyethylene resin composition for hollow molding
JP6838439B2 (en) Thermoplastic elastomer composition
JP2004035756A (en) Method for preventing deposit of ethylene-vinyl acetate copolymer and low deposit ethylene-vinyl acetate copolymer composition