WO2001002483A1 - Blooming-free polyolefin resin composition and molded article - Google Patents

Blooming-free polyolefin resin composition and molded article Download PDF

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Publication number
WO2001002483A1
WO2001002483A1 PCT/JP2000/004487 JP0004487W WO0102483A1 WO 2001002483 A1 WO2001002483 A1 WO 2001002483A1 JP 0004487 W JP0004487 W JP 0004487W WO 0102483 A1 WO0102483 A1 WO 0102483A1
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polyolefin
blooming
weight
parts
resin
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PCT/JP2000/004487
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French (fr)
Japanese (ja)
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Yoichi Kawasaki
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Nippon Unicar Company Limited
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Publication of WO2001002483A1 publication Critical patent/WO2001002483A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings

Definitions

  • the present invention relates to a non-blooming polyolefin-based resin thread product and a product thereof. More specifically, despite the large amount of a thiobisphenol-based antioxidant compound, blooming did not occur and was not observed. Polyolefin resin which has high aging resistance and durability, and retains excellent workability and scorch resistance when it is rolled over, etc., and is obtained by using the same. Related to goods. Background art
  • and a crosslinked polyolefin resin is used in special industrial fields such as the nuclear power generation field.
  • durability is required to be reliable.
  • the outside houses used for cables are exposed to high temperatures in the nuclear reactor for a long period of time.
  • heat aging and durability for a long period of time, for example, over 10 years, are required.
  • ⁇ obisphenol-based ⁇ has been most frequently used as an anti-oxidant for cables, but its solubility in polyolefin-based resin is low. For example, in polyethylene-based resin, 0.07 Sfi%.
  • a thiobisphenol-based antioxidant is In general, it is necessary to add 0.1% or more of 3 ⁇ 4 ⁇ used in the elimination. In the case of ⁇ fi, the solubility exceeds the above-mentioned solubility in the polyolefin resin. As a result, if only the thiobisphenol-based antioxidant thinner is turned over in the war, it means that the antioxidant is deposited on the surface by oil or powder.
  • t3 ⁇ 4-like ones are, for example, ⁇ (% & No. 6 2-9 1 7 3 ⁇ No. 6 2-3 6 0 6 1
  • a crosslinked polyethylene fiber blended with the antioxidant of the formula ⁇ is disclosed in Japanese Unexamined Patent Publication (Kokai) No. Heisei 3-247640.
  • a polyolefin is prepared by preliminarily adding a thiobisphenol-based antioxidant It ⁇ with a small amount of an oxide. It is a method of chemically dissociating and crosslinking the resin, such as by grafting, etc.
  • all of these methods have problems not only in that they are costly or require special operations, but also However, in applications such as cables in a nuclear reactor requiring high aging properties, there was a problem that sufficient durability was not achieved.
  • the present invention does not cause blooming even if a large amount of thiobisphenol-based antioxidant thinner is added from Agata, and is excellent in scorch resistance and addition resistance.
  • the objective is to produce a polyolefin resin yarn that is stable even when exposed to high temperatures for a long time. Disclosure of the invention
  • the present inventors have been eager to carry out the above-mentioned I ⁇ ! ⁇
  • Alkylene glycols have been found to enhance thiophene-based antioxidants and polyolefin-based compounds, and in particular, to increase the compatibility and compatibility with polyethylene-based resins, and have a high effect on preventing blooming. This has led to the present invention.
  • the polyolefin resin (A) 100 parts by weight of the polyolefin resin (A), 0.25 to 1.0 parts by weight of the thiobisphenol-based antioxidant thinner (B), and polyalkylene Glycol (C) 0.1 to 3.0 parts by weight is blended to form a non-blue mincable polyolefin resin.
  • a crosslinking agent (D) of 0.5 to 3.0 parts by weight is further added.
  • a non-blooming polyolefin-based fine-grained thread is created.
  • the polyolefin resin (A) is a polyethylene resin, and the non-blooming polyolefin resin yarn is used. Things are done.
  • the alkylene glycol (C) a non-blue mink 'type polyolefin resin thread material having a molecular weight of 1000 to 2000 and having a value of ⁇ 1 is used.
  • a non-blooming method comprising: using the non-blooming polyolefin-based shelf obtained by any one of the first to fourth aspects. Being able to produce one-migration polyolefin resin ⁇ 3 ⁇ 43 ⁇ 4.
  • the present invention relates to a non-blooming property obtained by blending a component (B) to (C) or a component ( ⁇ ) to (D) ( ⁇ ⁇ ⁇ l) with a polyolefin-based paste ( ⁇ ).
  • the present invention relates to a polyolefin-based resin composition and an article obtained therefrom, and preferred embodiments thereof include the following.
  • the crosslinking agent (D) is di-t-butylpropyloxide 1,1,1-bis-t-butylpropyloxybenzoate, 2,2-bis-t-butylpropyloxybutane, t-butylperoxybenzoate, dicumylpathone.
  • Polyolefin resin (A) has a density of 0.910 to 0.935 g / cm 3 and a melt mass flow rate of 0.5 to 1 Og / 10 minutes. That is The above-mentioned non-blooming polyolefin-based resin thread material and a product obtained therefrom.
  • the polyolefin-based purifier used in the present invention includes a polyolefin selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-11-pentene, 1-hexene, 1-octene and the like.
  • Warworm weight ⁇ The formation of these two or more types of monoolefins, amorphous block copolymers or random copolymers, and the copolymerization of these monoolefins with vinyl acetate diacrylate ⁇ : etc.
  • these polyolefin resins may be used in insects or as a mixture of two or more.
  • polyethylene-based resins are preferably used.
  • Ingredients Wl are prepared by high-pressure radical method, such as ⁇ polyethylene, ethylene-vinyl acetate-co-weight ⁇ fe and ethylene-ethyl acrylate-weight ⁇ k, or alumina or silica-alumina Filibus method by bandits such as mouths, Alumina: Standard method by molybdenum oxide, etc.
  • a polypropylene-based resin can also be suitably used.
  • Polypropylene-based features include, for example, random copolymerization of propylene with propylene and other polyolefins ⁇ :, block copolymers, etc., as well as these propylene-based features such as maleic acid3 ⁇ 4 * maleic acid.
  • the thiobisphenol-based antioxidant ( ⁇ ) used in the present invention can be any compound as long as it can be used as an antioxidant for polyolefin resin ⁇ / 4,4'-thiobis ( 3-Methyl-6-t-butylphenol, 4,4,1-thiobis (6-t-butyl-1 o-cresol), 2,2,1-thiobis (4-methyl-1-6-t-butylphenol), etc. Can be mentioned.
  • the thiobisphenol-based antioxidant resin is used in an amount of 0.25 to 1.0 part by weight, preferably 0.3 to 0.5 part by weight, and more preferably, 100 to 100 parts by weight of the polyolefin resin. Is blended in a ratio of 0.35 to 0.5 part by weight.
  • the polyalkylene glycol (C) is used in combination with the polyalkylene glycol (C), although the solubility is clearly higher than the solubility of the thiobisphenol-based antioxidant thinner in the polyolefin system.
  • the ⁇ of the tensile strength of the finely divided material of the present invention stored at 180 ° C for 4 days was thiobisphenol-based oxidation. Even if 0.25 parts by weight of fines were mixed, 70%, 0.3% by weight, 75%, and 0.35 parts by weight, 80%, 0.5% by weight Then, 83%, and for 1.0 part by weight, 84% fiber. On the other hand, if the distribution exceeds 1.0 parts by weight, the effect corresponding to the improvement will be reduced, and economically, it will become unhealthy.
  • the gravitational force of alkylene oxide having 2 to 4 carbon atoms can be used, and the alkylene oxide may be a polymerization of warworms or a mixed polymerization.
  • the weight due to the mixture of alkylene oxides may be a protein weight or a random weight ⁇ :.
  • one or both terminals of the alkylene glycol terminal group may be either ether-terminated or ester-terminated.
  • Specific examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol. Among them, polyethylene glycol is preferably used, and those having an amount of 1000 to 2000 are preferable.
  • the distribution of polyalkylene glycol ⁇ M is based on 100 parts by weight of polyolefin resin, 0.1 to 3.0 parts by weight, preferably 0.3 to 2.5 parts by weight. If the amount of polyalkylene glycol cornole is less than 0.1 part, bunoreming will occur! On the other hand, if the distribution ft exceeds 3.0 parts, the effect corresponding to the distribution M cannot be improved, and instead, the scorch property may be degraded. (Invited SIE contact, operative responsibilities » ⁇ ) are also undesirable because they also have an adverse effect.
  • the polyolefin-based resin composition of the present invention is desirably cross-linked with a cross-linking agent to increase heat resistance.
  • the frame (D) used in the present invention may be any type as long as it is a compound usually used in this field. Specifically, di-t-butyl peroxide, 1,1-bis-t-butyl butoxybenzoate, 2,2-bis-t-butyl peroxybutane, t-butyl peroxy butane Benzoate, dicumylbaoxide, 2,5-dimethyl-1,2,5-di-t-butylpropyloxyhexane, t-butylcumylperoxide, 2,5-dimethyl-2,5-di-t —Alkali dioxide power such as butyl veroxyhexane is shown, and among these, those having a decomposition temperature of 150 to 200 ° C.
  • the distribution M of the cross-linking agent is usually 0.5 to 3.0 parts by weight based on 10 polyolefin olefins. If the distribution of the crosslinking agent is less than 0.5 part by weight, good crosslinking cannot be obtained. As a result, for example, sufficient heatability cannot be obtained. On the other hand, if it exceeds 3 parts by weight, the scorch resistance becomes poor. The effect comes out.
  • the polyolefin sealant of the present invention may have a range that does not impair the growth of the tree, if desired.
  • other components (E) such as other resin components, additives, and auxiliary materials may be blended.
  • the working agent and auxiliary materials may be any of those normally used, such as a violet ray absorbing agent, other antioxidant _M, 3 ⁇ 4S agent, Obi S (anchoring agent, workability Materials, difficult agents, agents, dispersing agents, copper damage prevention, crosslinking aids, neutralizers, foaming agents, fine particles, colorants, pigments, scorch prevention such as bonbon black, H-methylstyrene dimer, etc. No.
  • the polyolefin-based resin fiber of the present invention includes the above-mentioned polyolefin-based resin (A), thiobisphenol-based antioxidant thinner (B), and polyalkylene glycol (C), and optionally a crosslinking agent (D). It is prepared from other components (E) that are required depending on the application.
  • the resin fiber is usually made into fibers such as pellets, granules, granules, powders, etc., but it is particularly preferable that it is in the form of pellets because of its strict youngness.
  • Various known methods can be applied for pelletizing, but in the present invention, the following method (a) or (b) is particularly preferable.
  • a polyolefin-based resin (A) is mixed with a thiobisphenol-based antioxidant (B), a polyalkylene glycol (C), a bridge (D), and other materials (E).
  • B thiobisphenol-based antioxidant
  • C polyalkylene glycol
  • D bridge
  • E other materials
  • a mixer such as a Banbury mixer, a continuous mixer, a knee, a mouth, or an extruder
  • the melting point of the polyolefin resin is higher than the melting point of the polyolefin resin and lower than the decomposition temperature of the crosslinking agent. After uniform kneading, granulate konjac.
  • a mixture of a polyolefin (A) and a thiobisphenol compound (i.e., ih3 ⁇ 4 (B), polyalkylene glycol (C), and ⁇ (E) of fe) was mixed using a kneading machine. Granulated by heating uniformly above the melting point of the polyolefin-based resin, and decomposing on 3 ⁇ 4 ⁇ into pellets containing the crosslinking agent (D) Soak.
  • D crosslinking agent
  • Example was measured by the evaluation method shown below.
  • the blooming resistance was as follows: 10 g of the cross-linked sheet was left in a thermo-hygrostat at 50 ° C, 50% release, and 50% for 1 month. By using liquid gas chromatography, the amount of antioxidant that had bloomed in the free solution was calculated and divided by the shelf arrangement S, and the amount of blooming was calculated as a percentage. The blue mink's resistance was judged to be acceptable when the amount of calming was 50% or less.
  • the scorch resistance was determined by measuring the torque value for 30 minutes at 140 ° C using a vertical mouthless rheometer according to ISO 6502. Those with a difference between the minimum torque value and the torque value after 30 minutes of 0.5 or less were judged as acceptable ( ⁇ ), and those with a difference of more than 0.5 as unacceptable (X).
  • the aging property was determined by ffl according to JIS C3005, paragraph 19. Heating was performed at 180 ° C for 4 days, and judgment was made based on the values of tensile strength »and elongation». These »mean that the larger the value, the less the deterioration has progressed, that is, it has aging resistance.
  • Bell column 1
  • High pressure 3 ⁇ 4 ⁇ polyethylene (melt muff mouth liquid is 2 g / l for 0 min, density is 0.922 g / cm, manufactured by Nippon Rikiichi Co., Ltd.) 100 parts by weight, 4, 4, 1 thiobis (3-methinole 1 6-t-butyl phenol) 0.25 parts and 0.1 parts by weight of polyethylene glycol having a molecular weight of 20000 were blended, and the mixture was kneaded with a Banbury mixer at 180 ° C for 10 minutes, and then 2.5 mm in diameter, Granulated into a 2.5 mm long beret.
  • Molecule M 6000 1.0 2.0 3.0 3.0 3.0
  • the male examples 2 to 6 and the comparative examples 1 to 3 were the same as in the sickle example 1 except that the molecular weight and the distribution of the oxidized anti-sickness ⁇ S and / or polyethylene glycol were changed to those shown in Table 1.
  • an impregnated polyethylene pellet and a crosslinked sheet were prepared and prepared. Table 1 also shows these fffi results.
  • the blooming resistance was 50% or less in percentage terms, and the scorch resistance was also reduced to Wejira.
  • the aging property is 1-5, and the aging property is good, and the resin is very strong.
  • Example 1 In Example 1, 0.2 parts by weight of a thiobisphenol-based antioxidant used from ⁇ ⁇ ⁇ was used. Due to the effect of polyethylene glycol, anti-blooming resistance was good. However, at 180 ° C used in the present invention, the so-called 180 ° C was used.
  • the resin thread material of the present invention can be suitably used for applications requiring long-term durability, such as electrode coverings for nuclear reactors and automobile parts.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

A blooming-free polyolefin resin composition comprising 100 parts by weight of a polyolefin resin (A), 0.25 to 1.0 part by weight of a thiobisphenol antioxidant (B), and 0.1 to 3.0 parts by weight of a polyalkylene glycol (C).

Description

明 細 書 非ブル一ミング性ポリオレフィン系樹脂糸誠物及び膨品 技術分野  Description Non-bleamable polyolefin resin yarns and expanded products
本発明は、 非ブルーミング性ポリオレフィン系樹脂糸誠物及びその 品に関し、 さらに詳しくは、 チォビスフエノール系酸化防細を多量配合したにもかかわらず、 ブ ルーミングの発生がなく、 かつ 导られなかった高い而撫老化性と耐久性を有し、 し かも鬈徹覆等に湖幼ロェする際に、 優れた加工性と耐スコーチ性を保持するポリオレ フィン系樹脂 «物及びそれを用いて得られた 品に関する。 背景技術  The present invention relates to a non-blooming polyolefin-based resin thread product and a product thereof. More specifically, despite the large amount of a thiobisphenol-based antioxidant compound, blooming did not occur and was not observed. Polyolefin resin which has high aging resistance and durability, and retains excellent workability and scorch resistance when it is rolled over, etc., and is obtained by using the same. Related to goods. Background art
近 «)1やシース層等の導体外部がポリオレフィン系樹 β| に架橋ポリオレフィ ン系樹脂で被覆された ®線ケ一ブルは、 原子力発電分野などの特殊な産業分野にまで利 用されるようになったが、 こうした産業分野においては、 耐久性^ f言頼性か 度に要求 されている。特に原子力発電分野においては、鬈镍ケ一ブルに用いられる外»廳は、 原子炉内で高温に長期間暴露されるため、 導体そのものからの発熱を考えると、 9 0°C 以上の高温においても、 長期、 例えば 1 0年以上にわたる耐熱老化 や耐久性が必要 とされている。  (1) A wire cable in which the outside of a conductor such as (1) or a sheath layer is coated with a polyolefin resin β | and a crosslinked polyolefin resin is used in special industrial fields such as the nuclear power generation field. However, in these industrial fields, durability is required to be reliable. Particularly in the field of nuclear power generation, the outside houses used for cables are exposed to high temperatures in the nuclear reactor for a long period of time. However, heat aging and durability for a long period of time, for example, over 10 years, are required.
ί¾*から、 鬈镍ケ一ブル絶籠用の酸化防細としては、 チォビスフエノール系 匕 が最も多く使われてきたが、 ポリオレフイン系樹脂に対する溶解度は、 低く、 例え ば、 ポリエチレン系樹脂の では、 0. 0 7 Sfi%程度である。 一方、 離ケーブル の謹 ¾老化性を確保するために、 かかるチォビスフエノール系酸化防止剤を電線ケープ ル絶 に使用する ¾ ^は、 通常 0. 1 %以上配合することが必要とさ その配 ^fiでは、上記のポリオレフィン系樹脂に対する溶解度を超えることとなる。その結果、 チォビスフエノール系酸化防細のみを戦で翻すると、 酸化防止剤の析出（樹脂に 配合した働！]剤が表面に油状又は粉末状などの开狱で滲みだし析出することを指し、 以 下、 「ブル一ミング」 という。 ） 力 生し、 析出した酸化防止剤が輸送 に付着した り、 装置を汚染したりするという問題が起こる。 さらに、 酸化防止剤のブルーミン グは、 こうした問題以外に、 樹脂の耐熱 にも影響を与え、 その結果、 必要な が 得られなかったり、 酸化防止剤の分散が不均一となったり、 或いは信頼性^ (氐下すると いった問題が生じる。 そのため、 これまでは、 棚旨材料の保管期間を制限したり、 β で保管したりするといったタ微が講じら 煩雑な管理が必要であった。 According to 、 *, 酸化 obisphenol-based 匕 has been most frequently used as an anti-oxidant for cables, but its solubility in polyolefin-based resin is low. For example, in polyethylene-based resin, 0.07 Sfi%. On the other hand, in order to secure the aging resistance of the detached cable, such a thiobisphenol-based antioxidant is In general, it is necessary to add 0.1% or more of ¾ ^ used in the elimination. In the case of ^ fi, the solubility exceeds the above-mentioned solubility in the polyolefin resin. As a result, if only the thiobisphenol-based antioxidant thinner is turned over in the war, it means that the antioxidant is deposited on the surface by oil or powder. This is referred to as “blooming.” The problem arises that the generated antioxidant adheres to the transportation and contaminates the equipment. In addition, blooming of the antioxidant, besides these problems, also affects the heat resistance of the resin, resulting in the inability to obtain the required amount, uneven dispersion of the antioxidant, or reliability. ^ (氐 There is a problem of lowering. For this reason, complicated management was required until now, such as restricting the storage period of shelf materials and storing them in β.
このような酸化防細のブルーミングに伴う問廳を抜: «に麟肖するため、 これま でいろいろの驗ゃ試みがなされてきた。その中でも t¾的なものとしては、 例えば、 ί(% &昭 6 2— 9 1 7 3号^^公昭 6 2— 3 6 0 6 1号では、 チォビスフエノール系酸化 防細と他の 1種の酸化防細を組^^配合した架橋ポリエチレン繊物が、 さらに、 特開平 3— 2 4 7 6 4 0号では、 チオビスフエノール系酸化防 It ^を予め少量の有 » 酸化物でもってポリオレフイン樹脂にグラフト化等の化学離合させ、 そ に架橋さ せる方法 されている。 しかし、 これらの方法には、 いずれも、 高コストであると か若しくは «な操作を要するという問題があるばかりでなく、 高ヽ碰老化性が 要 とされる原子炉内鬈镍ゃケーブル等の用途にあっては、 十分な耐久性力 られないとい う問題があった。  In order to excel at the problem associated with the blooming of such oxidation-resistant thin films, various experiments have been attempted so far. Among them, t¾-like ones are, for example, ί (% & No. 6 2-9 1 7 3 ^^ No. 6 2-3 6 0 6 1 A crosslinked polyethylene fiber blended with the antioxidant of the formula ^^ is disclosed in Japanese Unexamined Patent Publication (Kokai) No. Heisei 3-247640. A polyolefin is prepared by preliminarily adding a thiobisphenol-based antioxidant It ^ with a small amount of an oxide. It is a method of chemically dissociating and crosslinking the resin, such as by grafting, etc. However, all of these methods have problems not only in that they are costly or require special operations, but also However, in applications such as cables in a nuclear reactor requiring high aging properties, there was a problem that sufficient durability was not achieved.
このように、 酸化防 のブルーミングを抜 に解消するための方法には、 十分に 満足のレヽくものがなく、 高、碰老化性を得るためには、 チォビスフエノール系酸化防 細の配^ Mを単に増加させる方法以外に実用的な手段がなく、 その際には、 酸化防止 剤の配 を増加させると、 再びブル一ミングが発生するという問題があった。 As described above, there is no sufficiently satisfactory method for eliminating the blooming of oxidation prevention, and in order to obtain high aging resistance, it is necessary to use a thiobisphenol-based oxidation prevention method. There is no practical means other than simply increasing M, in which case antioxidant There was a problem that blooming occurred again when the distribution of the agent was increased.
従って、 本発明は、 上記のような状況に鑑み、 縣から問題であったチオビスフエノ ール系酸化防細を多く配合してもブルーミングの発生がなく、 かつ耐スコーチ性や加 ェ性にも優 tレ しかも高温に長期間暴露されても安定なポリオレフィン系樹脂糸 物を することを目的としている。 発明の開示  Therefore, in view of the above-mentioned situation, the present invention does not cause blooming even if a large amount of thiobisphenol-based antioxidant thinner is added from Agata, and is excellent in scorch resistance and addition resistance. The objective is to produce a polyolefin resin yarn that is stable even when exposed to high temperatures for a long time. Disclosure of the invention
本発明者らは、 上記の I ^を するために鋭意! ^寸した結果、 ポリオレフイン系樹 脂にチォビスフエノール系酸化防細を配合する際に、 さらにポリアルキレングリコー ルを配合すると、 そのポリアルキレングリコールがチォビスフエノール系酸化防止剤と ポリオレフイン系欄旨、 特にポリエチレン系樹脂との «†生や相溶'性を高め、 それに伴 いブル一ミング防止に対して高い効果を示すことを見出し、本発明を するに至った。 すなわち、 本発明の第 1の発明によれば、 ポリオレフイン系樹脂（A) 1 0 0重量部 に、 チオビスフエノ一ル系酸化防細 (B) 0. 2 5〜1 . 0重量部、 及びポリアルキ レングリコール （C) 0. 1〜3. 0重量部を配合してなる非ブルーミンク '性ポリオレ フィン系樹脂 «物か される。  The present inventors have been eager to carry out the above-mentioned I ^! ^ As a result of sizing, when blending a polyalkylene glycol with a polyolefin-based resin and a thiobisphenol-based oxidized thinner, Alkylene glycols have been found to enhance thiophene-based antioxidants and polyolefin-based compounds, and in particular, to increase the compatibility and compatibility with polyethylene-based resins, and have a high effect on preventing blooming. This has led to the present invention. That is, according to the first invention of the present invention, 100 parts by weight of the polyolefin resin (A), 0.25 to 1.0 parts by weight of the thiobisphenol-based antioxidant thinner (B), and polyalkylene Glycol (C) 0.1 to 3.0 parts by weight is blended to form a non-blue mincable polyolefin resin.
また、 本発明の第 2の発明によれば、 第 1の発明において、 上記の成分 (A)〜（C) に加え、 更に、 架橋剤 (D) 0. 5〜3. 0重量部を配合してなる非ブル一ミング性ポ リオレフィン系ネ細旨糸誠物が艱される。  Further, according to the second invention of the present invention, in the first invention, in addition to the above components (A) to (C), a crosslinking agent (D) of 0.5 to 3.0 parts by weight is further added. A non-blooming polyolefin-based fine-grained thread is created.
さらに、 本発明の第 3の発明によれば、 第 1又は第 2の発明において、 ポリオレフィ ン系樹脂 (A) は、 ポリエチレン系樹脂であることを舰とする非ブルーミング性ポリ ォレフィン系樹脂糸誠物が される。  Further, according to the third invention of the present invention, in the first or second invention, the polyolefin resin (A) is a polyethylene resin, and the non-blooming polyolefin resin yarn is used. Things are done.
さらに、 本発明の第 4の発明によれば、 第 1乃至第 3のいずれかの発明において、 ポ リアルキレングリコール （C) は、 分子量が 1 0 0 0〜2 0 0 0 0のポリエチレングリ コールであることを^1とする非ブルーミンク'性ポリオレフィン系樹脂糸誠物が さ れる。 Further, according to the fourth invention of the present invention, in any one of the first to third inventions, As the alkylene glycol (C), a non-blue mink 'type polyolefin resin thread material having a molecular weight of 1000 to 2000 and having a value of ^ 1 is used.
さらにまた、 本発明の第 5の発明によれば、 第 1乃至第 4のいずれかの発明により得 られた非ブルーミング性ポリオレフィン系棚旨 物を用いて i»してなることを とする非ブル一ミング性ポリオレフイン系樹脂 β¾¾品が される。  Furthermore, according to a fifth aspect of the present invention, there is provided a non-blooming method comprising: using the non-blooming polyolefin-based shelf obtained by any one of the first to fourth aspects. Being able to produce one-migration polyolefin resin β¾¾.
本発明は、 上記した如く、 ポリオレフイン系糊旨 (Α) に、 成分 (B) ~ ( C)若し くは成分 (Β)〜（D) (^匕^ lを配合した非ブル一ミング性ポリオレフイン系樹脂組 成物及びそれから得られる 品に係るものであるが、 その好ましい態様としては、 次 のものが包含される。  As described above, the present invention relates to a non-blooming property obtained by blending a component (B) to (C) or a component (Β) to (D) (^ 匕 ^^ l) with a polyolefin-based paste (Α). The present invention relates to a polyolefin-based resin composition and an article obtained therefrom, and preferred embodiments thereof include the following.
①ポリオレフイン系ネ細旨（A) l o o 部に、 チォビスフエノール系酸化防 ( ①Polyolefin-based grit (A) In the loo part, thiobisphenol-based antioxidant (
B) 0. 2 5 ~ 1. 0重量部、 ポリアルキレングリコール （C) 0. 1〜3. 0重量部B) 0.25 to 1.0 parts by weight, polyalkylene glycol (C) 0.1 to 3.0 parts by weight
、 及ひ" ¾讓 (D) 0. 5〜3. 0重量部に加え、 さらに各種添加剤や補助資材から選 ばれる少なくとも 1種の化^ (E) を配合してなる非ブルーミング性ポリオレフイン 系樹脂糸誠物及びそれから得られる β ^品。 Non-blooming polyolefin based on 0.5 to 3.0 parts by weight and at least one compound selected from various additives and auxiliary materials ^ (E) Resin thread material and β ^ product obtained from it.
橋剤 (D) は、 ジ— t—プチルパ一ォキシドヽ 1， 1—ビス— t—プチルバ一ォ キシベンゾエー卜、 2 , 2—ビス一 t—プチルパ一ォキシブタン、 t—ブチルパーォキ シベンゾェ一ト、 ジクミルパ一ォキシド、 2， 5—ジメチル一 2， 5—ジ一 t—プチル パーォキシへキサン、 t—プチルクミルパーォキシド、 2， 5—ジメチル一 2， 5—ジ —t—ブチルパーォキシへキサンから選ばれる少なくとも 1種であることを »とする 、 上記の非ブルーミング性ポリオレフイン系樹脂糸誠物及びそれから得られる舰品。 The crosslinking agent (D) is di-t-butylpropyloxide 1,1,1-bis-t-butylpropyloxybenzoate, 2,2-bis-t-butylpropyloxybutane, t-butylperoxybenzoate, dicumylpathone. Oxide, 2,5-dimethyl-1,2,5-di-t-butylperoxyhexane, t-butylcumylperoxide, 2,5-dimethyl-1,2,5-di-t-butylperoxyhexane The non-blooming polyolefin resin thread described above, which is at least one kind, and a product obtained therefrom.
③ポリオレフイン系樹脂 (A) は、 密度が 0. 9 1 0~ 0 . 9 3 5 g/cm3、 メル トマスフローレ一卜が 0. 5〜1 O g/ 1 0分であるポリエチレン系翻旨であることを とする、 上記の非ブルーミング性ポリオレフィン系樹脂糸誠物及びそれから得られ る 品。 発明を実施するための最良の形態 ③ Polyolefin resin (A) has a density of 0.910 to 0.935 g / cm 3 and a melt mass flow rate of 0.5 to 1 Og / 10 minutes. That is The above-mentioned non-blooming polyolefin-based resin thread material and a product obtained therefrom. BEST MODE FOR CARRYING OUT THE INVENTION
以下、 本発明について詳細に説明する。  Hereinafter, the present invention will be described in detail.
1 . ポリオレフイン系 ί鋤旨 (Α)  1. Polyolefin type spade (Α)
本発明で用いられるポリオレフイン系擺旨としては、 エチレン、 プロピレン、 1—ブ テン、 1—ペンテン、 4—メチル一 1—ペンテン、 1—へキセン、 1—ォクテンなどか ら選ばれるひ一ォレフィンの戦虫重^^ これら 2種以上のひ一ォレフィンの結 生あ るいは非晶性ブロック共重合体又はランダム共重合 並びにこれらひ一ォレフィンと 酢酸ビニルゃァクリル酸エステルとの共重^:などが挙げられるが、 これらのポリオレ フィン系樹脂は、 ί虫で用いても又は 2種以上を混合して用いてもよい。  The polyolefin-based purifier used in the present invention includes a polyolefin selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-11-pentene, 1-hexene, 1-octene and the like. Warworm weight ^^ The formation of these two or more types of monoolefins, amorphous block copolymers or random copolymers, and the copolymerization of these monoolefins with vinyl acetate diacrylate ^: etc. However, these polyolefin resins may be used in insects or as a mixture of two or more.
本発明では、 これらポリオレフイン系樹脂の中でもポリエチレン系樹脂が好適に用い られる。具 W lには、 高圧ラジカル法で Mされる {£¾度ポリエチレン、 エチレン一酢 酸ビニル共重^ feよびエチレン—アクリル酸ェチル共重^ k 又は、 アルミナ又はシ リカ一アルミナ ί¾寺酸化ク口ム等の匪によるフィリツブス法、 アルミナ ίΐί寺酸化モリ ブデン等の触 f某によるスタンダード法、 遷移金属と有^ g化合物によるチグラー系触 媒によるチグラ一法、 若しくはメタ口セン嫩某系などのシングルサイト膽某によって重 合されるエチレン戦虫重^あるいはエチレンと炭素数 3〜 1 0の 1—ブテン、 1—ぺ ンテン、 1一へキセン、 1ーォクテン、 1—デセン、 1—ドデセン、 4—メチル一 1— ペンテン等のひ一ォレフィンとの共重合体などカ举げられる。 これらポリエチレン系樹 脂には、 高密度ポリェチレス 中密度ポリエチレン、 直鎖状 度エチレン一ひ一ォレ フィン共重合 直鎖^ ί«度ェチレン一ひ一ォレフィン共重^:等も含まれる。 そして、 ポリエチレン系樹脂は、 藤性、 »t生、 柔軟性、 低温特性の点から、 密度 が 0. 9 1 0〜0. 9 3 5 g/cm3、 メルトマスフローレートが 0 . 5 ~ 1 0 g/ l 0分程度であることが好ましレ In the present invention, among these polyolefin-based resins, polyethylene-based resins are preferably used. Ingredients Wl are prepared by high-pressure radical method, such as {polyethylene, ethylene-vinyl acetate-co-weight ^ fe and ethylene-ethyl acrylate-weight ^ k, or alumina or silica-alumina Filibus method by bandits such as mouths, Alumina: Standard method by molybdenum oxide, etc. f: Standard method by transition metal, Zigler method by transition metal and ^ g compound, Zigler method by catalyst, or Meta method: 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-ethylene with 1 to 10 carbon atoms and 3 to 10 carbon atoms combined by single-site bunching —Methyl-1—Copolymers with monoolefins such as pentene. These polyethylene resins also include high-density polyethylene, medium-density polyethylene, linear ethylene copolymer, linear ethylene copolymer, and the like. Then, the polyethylene resin, Fuji resistance, »t raw, flexibility, in terms of low-temperature characteristics, density 0. 9 1 0~0. 9 3 5 g / cm 3, melt mass flow rate is from 0.5 to 1 0 g / l 0 minutes is preferable.
さらに、 本発明では、 ポリプロピレン系樹脂も好適に用いることができる。 ポリプロ ピレン系機旨としては、 プロピレンの對 プロピレンと他のひ一ォレフィンと のランダム共重^:やプロック共重合体などのほかに、 これらのプロピレン系 ί細旨をマ レイン酸¾*マレイン酸などのカルボン酸ゃ»冰物、 或いはメ夕クリル酸グリシジ ルなどのエポキシ基を有する化合物ゃビニルトリメトキシシランなどの不飽和シラン化 合吻などによりグラフト変性した変性プロピレン系樹脂が挙げられる。  Further, in the present invention, a polypropylene-based resin can also be suitably used. Polypropylene-based features include, for example, random copolymerization of propylene with propylene and other polyolefins ^ :, block copolymers, etc., as well as these propylene-based features such as maleic acid¾ * maleic acid. And a modified propylene-based resin graft-modified with a compound having an epoxy group such as glycidyl methacrylate or an unsaturated silane such as vinyltrimethoxysilane.
2. チォビスフエノール系酸化防止剤 (Β) 2. Thiobisphenol-based antioxidant (Β)
本発明で用いられるチォビスフエノール系酸化防 (Β) は、 ポリオレフイン系樹 脂用の酸化防細として の化 ^ /であれば何であってもよ 具鹏には、 4， 4 ' —チォビス （3—メチルー 6— t—ブチルフエノール） 、 4 , 4， 一チォビス （6— t —プチル一 o—クレゾ一ル） 、 2 , 2， 一チォビス （4—メチル一6— t—ブチルフエ ノール） 等を挙げることができる。  The thiobisphenol-based antioxidant (Β) used in the present invention can be any compound as long as it can be used as an antioxidant for polyolefin resin ^ / 4,4'-thiobis ( 3-Methyl-6-t-butylphenol, 4,4,1-thiobis (6-t-butyl-1 o-cresol), 2,2,1-thiobis (4-methyl-1-6-t-butylphenol), etc. Can be mentioned.
本発明では、 チォビスフエノール系酸化防細は、 ポリオレフィン系樹脂 l O O Sfi 部に対して、 0. 2 5〜1 . 0重量部、 好ましくは 0. 3〜0. 5重量部、 さらに好ま しくは 0. 3 5 ~0. 5重量部の割合で配合される。  In the present invention, the thiobisphenol-based antioxidant resin is used in an amount of 0.25 to 1.0 part by weight, preferably 0.3 to 0.5 part by weight, and more preferably, 100 to 100 parts by weight of the polyolefin resin. Is blended in a ratio of 0.35 to 0.5 part by weight.
この配^ *は、 前述のように、 明らかにチォビスフエノーノレ系酸化防細のポリオレ フィン系棚旨に対する溶解度を超えるものであるにもかかわらず、 ポリアルキレングリ コール （C) を併用することにより、 ブルーミングを抑制することが可能となる。 すな わち、 ポリオレフイン系綳旨 1 0 0重量部に対して、 チォビスフエノール系酸化防細 を 0. 2 5重量部配合しても、 所定の耐ブルーミング性試験に合格する。 麵老化性を 高めるために、 0. 3重量部以上、 さらには、 より高い 老化性を得るために、 0. 3 5重量部以上用いても、 更に驚くべきことには、 1 . 0 部を用いても、 酸化防止 剤が樹脂の表面に析出するブルーミングは認められな 、。 As described above, the polyalkylene glycol (C) is used in combination with the polyalkylene glycol (C), although the solubility is clearly higher than the solubility of the thiobisphenol-based antioxidant thinner in the polyolefin system. This makes it possible to suppress blooming. That is, with respect to 100 parts by weight of polyolefin, the thiobisphenol-based antioxidant thinner Even if 0.25 parts by weight is blended, it passes the prescribed blooming resistance test.て も 0.3 parts by weight or more to enhance aging, and even 0.35 parts by weight or more to obtain higher aging, more surprisingly, 1.0 part by weight Even when used, blooming in which the antioxidant is deposited on the surface of the resin is not observed.
そして、 この配 ^の範囲では、 酸化防 の配 を増加すれば、 配 に伴って 老化性も向上することが認められている。 本発明の ffiに用いた i ^の 老化性 試験によると、 1 8 0°C、 4日間の条件下で保存した本発明の f細旨 物の引張強さの 辦は、チオビスフエノ一ル系酸化防細を 0. 2 5重量部配合した でも、 7 0%、 0. 3重量部の場合では、 7 5 %、 0. 3 5重量部の場合では、 8 0 %、 0. 5重量部 の では、 8 3 %、 さらに、 1 . 0重量部の では、 8 4 %を纖する。 一方、 配 ^が 1 . 0重量部を超えると、 それに見合う効果の向上が少なくなり、 経済的にも不 禾 |Jとなる。  In this range, it is recognized that the aging property is improved with the increase of the oxidation resistance. According to the aging test of i ^ used in the ffi of the present invention, the 強 of the tensile strength of the finely divided material of the present invention stored at 180 ° C for 4 days was thiobisphenol-based oxidation. Even if 0.25 parts by weight of fines were mixed, 70%, 0.3% by weight, 75%, and 0.35 parts by weight, 80%, 0.5% by weight Then, 83%, and for 1.0 part by weight, 84% fiber. On the other hand, if the distribution exceeds 1.0 parts by weight, the effect corresponding to the improvement will be reduced, and economically, it will become unhealthy.
3. ポリアノレキレングリコール （C) 3. Polyanoalkylene glycol (C)
本発明で用いられるポリアルキレングリコール （C) としては、 炭素数 2~4のアル キレンォキサイドの重^力 用でき、 アルキレンォキサイドは、 戦虫の重合でも、 混 の重合でもよい。 またアルキレンォキサイドの混^による重^は、 プロヅク重 でも、 ランダム重^:でもよい。 またアルキレングリコールの末端基は、 片 又 は両末端が、 ェ一テルま權されていてもよく、 エステルま棚されていてもよい。 ポリア ルキレングリコールの具体例として、 ポリエチレングリコール、 ポリプロピレングリコ ールなどを挙げることができる。 このうち、 ポリエチレングリコールが好ましく用いら t また、 量が 1 0 0 0〜2 0 0 0 0のものが好ましい。  As the polyalkylene glycol (C) used in the present invention, the gravitational force of alkylene oxide having 2 to 4 carbon atoms can be used, and the alkylene oxide may be a polymerization of warworms or a mixed polymerization. The weight due to the mixture of alkylene oxides may be a protein weight or a random weight ^ :. In addition, one or both terminals of the alkylene glycol terminal group may be either ether-terminated or ester-terminated. Specific examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol. Among them, polyethylene glycol is preferably used, and those having an amount of 1000 to 2000 are preferable.
ポリアルキレングリコールの配^ Mは、ポリオレフイン系樹脂 1 0 0重量部に対して、 0. 1〜3. 0 部、 好ましくは 0. 3〜2 . 5重量部である。 ポリアルキレングリ コーノレの配^!が 0. 1 部未満では、 ブノレ一ミングが！ ^する恐れがあり、 一方、 配^ ftが 3. 0 部を超えると、 配^ Mに見合う効果の向上が得られず、 かえってス コーチ性^ «色力^匕することがあり、
Figure imgf000009_0001
(誘 SIE接、 術責固有 »ί) にも悪影 響が出るため、 望ましくない。 The distribution of polyalkylene glycol ^ M is based on 100 parts by weight of polyolefin resin, 0.1 to 3.0 parts by weight, preferably 0.3 to 2.5 parts by weight. If the amount of polyalkylene glycol cornole is less than 0.1 part, bunoreming will occur! On the other hand, if the distribution ft exceeds 3.0 parts, the effect corresponding to the distribution M cannot be improved, and instead, the scorch property may be degraded.
Figure imgf000009_0001
(Invited SIE contact, operative responsibilities »ί) are also undesirable because they also have an adverse effect.
4. 架橋剤 (D) 4. Crosslinking agent (D)
本発明のポリオレフイン系樹脂組成物は、 耐熱性を上げるために、 架橋剤で架橋する ことが望ましい。  The polyolefin-based resin composition of the present invention is desirably cross-linked with a cross-linking agent to increase heat resistance.
本発明に用いられる架 (D) としては、 通常この分野で使用されている化^)で あれば何でもよい。 具体的には、 ジ一 t—プチルパーォキシド、 1 , 1—ビス一 t—ブ チルバ一ォキシベンゾェート、 2 , 2—ビス一 t—ブチルパーォキシブタン、 t—プチ ルパーォキシベンゾェ一ト、 ジクミルバ一ォキシド、 2， 5—ジメチル一 2， 5—ジ一 t—プチルパ一ォキシへキサン、 t—プチルクミルパーォキシド、 2， 5—ジメチルー 2， 5—ジ一 t—ブチルバーォキシへキサン等の有^ ¾化物力 示されるが、 これら の中で、 1分間半減期を得るまでの分解温度が 1 5 0〜2 0 0°Cのものが好ましい。 架橋剤の配^ Mは、通常、ポリオレフイン系翻旨 1 0 Ofifi部に対して、 0. 5〜3. 0重量部である。架橋剤の配^ *が 0. 5重量部未満であると、良好な架橋が得られず、 その結果、 例えば加熱 性が十分得られず、 一方、 3重量部を超えると、 耐スコーチ 性に影響が出てくる。  The frame (D) used in the present invention may be any type as long as it is a compound usually used in this field. Specifically, di-t-butyl peroxide, 1,1-bis-t-butyl butoxybenzoate, 2,2-bis-t-butyl peroxybutane, t-butyl peroxy butane Benzoate, dicumylbaoxide, 2,5-dimethyl-1,2,5-di-t-butylpropyloxyhexane, t-butylcumylperoxide, 2,5-dimethyl-2,5-di-t —Alkali dioxide power such as butyl veroxyhexane is shown, and among these, those having a decomposition temperature of 150 to 200 ° C. until a half-life of 1 minute is obtained are preferable. The distribution M of the cross-linking agent is usually 0.5 to 3.0 parts by weight based on 10 polyolefin olefins. If the distribution of the crosslinking agent is less than 0.5 part by weight, good crosslinking cannot be obtained. As a result, for example, sufficient heatability cannot be obtained. On the other hand, if it exceeds 3 parts by weight, the scorch resistance becomes poor. The effect comes out.
5 . 他の成分 (E) 5. Other ingredients (E)
本発明のポリオレフイン 封脂 物には、 所望に応じてその樹生を損なわない範囲 で、 他の樹脂成分や添加剤、 補助資材等の他の成分 (E) を配合してもよい。 The polyolefin sealant of the present invention may have a range that does not impair the growth of the tree, if desired. In addition, other components (E) such as other resin components, additives, and auxiliary materials may be blended.
働 Π剤や補助資材としては、 通常配合される^ Πのものなら何でもよいが、 例えば、 紫 線吸収剤、 他の酸化防 _M、 ¾S定剤、 帯 S(¾止剤、 加工性己娘材、 難剤、 剤、 分散剤、 銅害防細、 架橋助剤、 中和剤、 発泡剤、 気碰細、 着色剤、 顔料、 力 一ボンブラヅク、 ひ一メチルスチレンダイマー等のスコーチ防 などが挙げられる。  The working agent and auxiliary materials may be any of those normally used, such as a violet ray absorbing agent, other antioxidant _M, ¾S agent, Obi S (anchoring agent, workability Materials, difficult agents, agents, dispersing agents, copper damage prevention, crosslinking aids, neutralizers, foaming agents, fine particles, colorants, pigments, scorch prevention such as bonbon black, H-methylstyrene dimer, etc. No.
6. ポリオレフィン系^ f旨糸誠物及び 品 6. Polyolefin-based products
本発明のポリオレフィン系樹脂繊物は、 上記のポリオレフィン系樹脂 (A) 、 チォ ビスフエノール系酸化防細 （B) 、 及びポリアルキレングリコール （C)、 さらに'必 要に応じて架橋剤 (D)、 また用途によって 要となる他の成分（E)から調製される。 樹脂繊物は、 通常、 ペレツト、 グラニュール、 粒、 粉末等の繊にされるが、 厳幼口 ェ ®{g利さからペレツト状であることが特に好ましい。ペレツト状に造粒するためには、 種々の公知の方法を適用することができるが、 本発明では、 次の （a) 又は （b) の方 法が特に好ましい。  The polyolefin-based resin fiber of the present invention includes the above-mentioned polyolefin-based resin (A), thiobisphenol-based antioxidant thinner (B), and polyalkylene glycol (C), and optionally a crosslinking agent (D). It is prepared from other components (E) that are required depending on the application. The resin fiber is usually made into fibers such as pellets, granules, granules, powders, etc., but it is particularly preferable that it is in the form of pellets because of its strict youngness. Various known methods can be applied for pelletizing, but in the present invention, the following method (a) or (b) is particularly preferable.
a. ポリオレフイン系翻 (A) に チオビスフエノ一ル系酸化防細 (B) 、 ポリ アルキレングリコール （C) 、 架翻 (D)及びその他の戯 （E) を配合し、 得られ た配^/を、 例えば、 バンバリ一ミキサー、 コンティニユアスミキサー、 ニー ー、 口 ール又は押出機のような混 ^楝機を用いて、 ポリオレフイン系樹脂の溶融 以上で、 か つ架橋剤の分解温度以下の で均一に混練した後、 昆铼物を造粒する。  a. A polyolefin-based resin (A) is mixed with a thiobisphenol-based antioxidant (B), a polyalkylene glycol (C), a bridge (D), and other materials (E). For example, using a mixer such as a Banbury mixer, a continuous mixer, a knee, a mouth, or an extruder, the melting point of the polyolefin resin is higher than the melting point of the polyolefin resin and lower than the decomposition temperature of the crosslinking agent. After uniform kneading, granulate konjac.
b. ポリオレフイン系 (A) にチオビスフエノーノレ系酸ィ匕防 ih¾ (B) 、 ポリア ルキレングリコール （C) 及びそ © feの^ (E) を配合した配^を、 練機を用い てポリオレフィン系樹脂の溶 以上で均一に温铼することにより造粒し、 ヽで造 粒されたペレットに、 ¾^上で分解 以下に加熱して献とした架橋剤 (D) を含 浸させる。 纖例および比翻 b. A mixture of a polyolefin (A) and a thiobisphenol compound (i.e., ih¾ (B), polyalkylene glycol (C), and ^ (E) of fe) was mixed using a kneading machine. Granulated by heating uniformly above the melting point of the polyolefin-based resin, and decomposing on ¾ ^ into pellets containing the crosslinking agent (D) Soak. Fiber examples
以下に、 本発明について鍾例及び比樹列を挙げて詳細に説明するが、 本発明は、 こ れらによって限定されるものではない。 なお、 実施例及び]： 例における各物性は、 次 に示す評価方法で測定した。  Hereinafter, the present invention will be described in detail with reference to examples and specific examples, but the present invention is not limited thereto. In addition, each physical property in an Example and]: Example was measured by the evaluation method shown below.
評価方法 Evaluation method
(1)耐ブルーミンク'性  (1) Blue mink resistance
耐ブルーミング性は、 藤し架橋したシート 10gを、 離が 50°C、 相タ 驢が 5 0 %の恒温恒湿器に、 1ヶ月静置した後、 これを 25mlのクロ口ホルムで洗浄し、 液 体ガスクロマトグラフィ一を用いことにより、 游液中のブルーミングしてきた酸化防 細の量を し、 棚の配^ Sで除算して、 ブル一ミング量を百分率で算出し、 謹 した。耐ブル一ミンク'性は、 カレ一ミング量が 50%以下を合格とした。  The blooming resistance was as follows: 10 g of the cross-linked sheet was left in a thermo-hygrostat at 50 ° C, 50% release, and 50% for 1 month. By using liquid gas chromatography, the amount of antioxidant that had bloomed in the free solution was calculated and divided by the shelf arrangement S, and the amount of blooming was calculated as a percentage. The blue mink's resistance was judged to be acceptable when the amount of calming was 50% or less.
(2)耐スコーチ性  (2) Scorch resistance
耐スコーチ性は、 ISO 6502に縦の口一夕一レスレオメーターを使用し、 試 を 140°Cとして、 30分間のトルク値を測定し、 謹した。最小トルク値と 3 0分後のトルク値との差が、 0. 5以下のものを合格（〇） とし、 0. 5を超えるのも のを不合格 (X) とした。  The scorch resistance was determined by measuring the torque value for 30 minutes at 140 ° C using a vertical mouthless rheometer according to ISO 6502. Those with a difference between the minimum torque value and the torque value after 30 minutes of 0.5 or less were judged as acceptable (〇), and those with a difference of more than 0.5 as unacceptable (X).
(3)隱老化性  (3) Oki aging
謹 ¾老化性は、 J I S C3005の 19項に準じて fflした。 180°Cで 4日間加 熱を行い、 その引張強さ »及び伸び »の値により判断した。 これらの »は、 大き 、値ほど劣化が進んでいな 、こと、 すなわち應老化性があることを意味する。 鐘列 1 The aging property was determined by ffl according to JIS C3005, paragraph 19. Heating was performed at 180 ° C for 4 days, and judgment was made based on the values of tensile strength »and elongation». These »mean that the larger the value, the less the deterioration has progressed, that is, it has aging resistance. Bell column 1
高圧 ¾{驢度ポリエチレン （メルトマスフ口一レートが 2g/l 0分、 密度が 0. 9 22 g/cm 日本ュニ力一製） 100重量部に、 4， 4， 一チォビス （3—メチノレ 一 6— t—プチルフエノール） 0. 25 部、 及び分子量 20000のポリエチレン グリコール 0. 1重量部を配合し、 バンバリ一ミキサーにより 180°Cの で 10分 間温練した後、 直径 2. 5 mm、 長さ 2. 5 mmのべレットに造粒した。  High pressure ¾ {polyethylene (melt muff mouth liquid is 2 g / l for 0 min, density is 0.922 g / cm, manufactured by Nippon Rikiichi Co., Ltd.) 100 parts by weight, 4, 4, 1 thiobis (3-methinole 1 6-t-butyl phenol) 0.25 parts and 0.1 parts by weight of polyethylene glycol having a molecular weight of 20000 were blended, and the mixture was kneaded with a Banbury mixer at 180 ° C for 10 minutes, and then 2.5 mm in diameter, Granulated into a 2.5 mm long beret.
次いで、 このペレットに、 60°Cにカロ熱して液化したジクミルパーォキシドを加え、 プレンダ一で 30分間混合し、 ポリエチレンペレツトにジクミルバ一ォキサイドを含浸 させた。 この含浸ポリエチレンペレットを用いて、 耐スコーチ性の評価を行った。 また、 上記 曼ポリエチレンペレットを、 プレス β¾Β ^を用いて 120 °Cでシ一 卜に ¾fi ^し、 次いで 180°Cで架橋させた。 この架橋シートを所定のダンベル 型に打ち抜きし、 これを として、 耐ブルーミング性、 am老化性を上記の方法で評 価した。 謹結果は、 表 1に示す。 Next, dicumyl peroxide liquefied by heating to 60 ° C. was added to the pellets, mixed with a blender for 30 minutes, and polyethylene pellets were impregnated with dicumyl peroxide. Using this impregnated polyethylene pellet, scorch resistance was evaluated. In addition, the man polyethylene pellets were subjected to に fi ^ at 120 ° C using a press β ^^ and then crosslinked at 180 ° C. This crosslinked sheet was punched out into a predetermined dumbbell mold, and the blooming resistance and am aging resistance were evaluated using the above method as described above. The results are shown in Table 1.
表 1 灾施例 1 実施 12 実施例 3 実施例 4 実施例 5 実施例 6 比較伊 11 比較 12 比較例 3 原材料 （重量部） Table 1 Example 1 Example 12 Example 3 Example 4 Example 5 Example 6 Comparative example 11 Comparative 12 Comparative example 3 Raw material (parts by weight)
(A) 卨圧法低密度ボリエチレン ¾ 1 100 100 100 100 100 100 100 100 100 (A) Low pressure method low density polyethylene ¾ 1 100 100 100 100 100 100 100 100 100
(B) チオビスフ ノール系酸化防 剤 注 2 0.25 0.3 0.35 0.5 1.0 0.35 0.2 0.25 0.5(B) Thiobisphenol-based antioxidant Note 2 0.25 0.3 0.35 0.5 1.0 0.35 0.2 0.25 0.5
(C) ポリエチレングリコール (C) Polyethylene glycol
分了 fi 1000 5.0  Fi 1000 fi 5.0
分子 M 6000 1.0 2.0 3.0 3.0 3.0  Molecule M 6000 1.0 2.0 3.0 3.0 3.0
分子 tt 20000 0.1  Molecule tt 20000 0.1
2.0 2.0 2.0 2.0 2.5 2.0  2.0 2.0 2.0 2.0 2.5 2.0
CO 2.0 2.0 2.0 耐ブルーミング性 （o ) 50 44 26 28 45 30 35 85 98 耐スコーチ性 O O O O 〇 O O X X 耐熱老化性  CO 2.0 2.0 2.0 Blooming resistance (o) 50 44 26 28 45 30 35 85 98 Scorch resistance O O O O 〇 O O X X Heat aging resistance
引¾強さ残^ ( ) 70 75 81 83 84 80 58 く 10 く 10 仲び残率 (%) 73 80 84 89 91 82 65 <10 く 10 注 2 : 4 , 4 ' ーチォビス （3—メチルー 6— t—ブチルフエノール）  Remaining tensile strength ^ () 70 75 81 83 84 80 58 10 10 Remaining rate (%) 73 80 84 89 91 82 65 <10 10 Note 2: 4, 4'-Thoobis (3-methyl-6 — T-butylphenol)
注 3 ：ジクミルパーォキシド Note 3: Dicumyl peroxide
鐘列 2〜6、 比較例 1〜3 Bell row 2-6, Comparative examples 1-3
雄例 2〜6及び比較例 1〜3は、 鎌例 1において、 酸化防細の酉己^ S、 及び/ 又はポリエチレングリコールの分子量と配^ fiを表 1に示したものに変えた以外は、 実 施例 1と同様に、 含浸ポリエチレンペレット及び架橋シートを作製し、 した。 これ らの fffi結果も、 表 1に示した。  The male examples 2 to 6 and the comparative examples 1 to 3 were the same as in the sickle example 1 except that the molecular weight and the distribution of the oxidized anti-sickness ^ S and / or polyethylene glycol were changed to those shown in Table 1. In the same manner as in Example 1, an impregnated polyethylene pellet and a crosslinked sheet were prepared and prepared. Table 1 also shows these fffi results.
以上の結果から明らかなように、 鎌例 1〜6では、 耐ブルーミング性は、 百分率表 示で 5 0%以下であり、 また、 耐スコーチ性も維寺さ 引張強さ辭及 申び残率で 1¾5した碰老化性も良好であり、 非常に強い ¾W匕性及び J B性の良好な樹脂誠物 である。  As is evident from the above results, in Sickle Examples 1 to 6, the blooming resistance was 50% or less in percentage terms, and the scorch resistance was also reduced to Wejira. The aging property is 1-5, and the aging property is good, and the resin is very strong.
一方、 ！： 例 1は、 チォビスフエノール系酸化防止剤を ί ^から用いられている量で ある 0. 2重量部を配合したものである。 ポリエチレングリコールの効果により、 耐ブ ルーミング tt¾ひ面スコ一チ性は、 良好であつたが、 本発明の謂で用いた 1 8 0°Cで on the other hand, ! Example 1: In Example 1, 0.2 parts by weight of a thiobisphenol-based antioxidant used from か ら ^ was used. Due to the effect of polyethylene glycol, anti-blooming resistance was good. However, at 180 ° C used in the present invention, the so-called 180 ° C was used.
4日間という過酷な条件下では、瞧老化性が、 mと比較して明らかに劣つていた。 比翻 2及び 3は、 ポリエチレングリコールを配合しない誠 rr'あるが、 耐ブルー ミング性及ひ スコーチ性の謹結果は、 鎌例と比べて悪く、 また、 瞧老化性も、 ほとんどの酸化防細がブル一ミングしたことにより、 測定不能に近い値を示した。 産業上の利用可謝生 Under the harsh conditions of 4 days, 瞧 aging was clearly inferior to m. In Comparative Examples 2 and 3, although polyethylene glycol is not blended, there is no rr ', but the results of blooming resistance and scorch resistance are worse than those of sickle cases. Showed a value close to impossible to measure due to blooming. Industrial use
本発明では、 特定量のポリアルキレングリコールを、 ポリオレフイン系棚旨組成物に 配合することにより、 ブル一ミングカ 生し不可能と考えられていた該ポリオレフ イン系 ί綳旨 1 0 0重量部に対し 0. 2 5〜1 . 0重量部の、 «から最も良く使われて いるチォビスフエノール系酸化防細を配合することができ、 碰姥化性を改善し、 ま た、 耐スコーチ性も良好に維持できた。 この配^ βの範囲では、 チォビスフエノール系 酸化防細の配^ *を増加させれば、 それだけ^繊物の隱老化性が高まるので、 これまで得られなかった高い耐久性力 られた。 したがって、 本発明の樹脂糸誠物は、 長期の耐久性が必要とされる原子炉内用電«覆材ゃ自動車部品などの用途に好適に利 用することができる。 In the present invention, by blending a specific amount of polyalkylene glycol into a polyolefin-based composition, 100 parts by weight of the polyolefin-based composition, which was considered impossible to bloom, was considered. 0.25 to 1.0 parts by weight of thiobisphenol-based oxidation thinner, which is most commonly used from «, can be blended to improve 碰 ubanization and good scorch resistance Could be maintained. In this range of ^ β, thiobisphenol-based Increasing the distribution of oxidized thinners increases the aging resistance of the textiles, resulting in a higher durability than previously obtained. Therefore, the resin thread material of the present invention can be suitably used for applications requiring long-term durability, such as electrode coverings for nuclear reactors and automobile parts.

Claims

請 求 の 範 囲 The scope of the claims
1. ポリオレフィン系綳旨 (A) 100重量部に、 チォビスフエノール系酸化防細 (B) 0. 25〜： I. OS*部、 及びポリアルキレングリコール （C) 0. 1〜3. 0 重量部を配合してなる非ブル一ミング性ポリオレフイン系樹脂«物。 1. Polyolefin-based (A) 100 parts by weight, thiobisphenol-based oxidation-resistant (B) 0.25-: I. OS * part, and polyalkylene glycol (C) 0.1-3.0 parts by weight A non-blooming polyolefin-based resin with a blended part.
2. 更に、 架翻 (D) 0. 5-3. 0重量部を配合してなる請求項 1に記載の非ブ ルーミング性ポリオレフィン系樹脂 «物。  2. The non-blooming polyolefin-based resin according to claim 1, further comprising 0.5-3.0 parts by weight of the reversion (D).
3. ポリオレフイン系測旨 (A)は、 ポリエチレン系樹脂であることを ¾とする、 請求項 1又は 2に記載の非ブル一ミング性ポリオレフィン系樹脂糸誠物。  3. The non-blooming polyolefin-based resin thread according to claim 1, wherein the polyolefin-based measurement (A) is a polyethylene-based resin.
4. ポリアルキレングリコール （C) は、 分子量が 1000~20000のポリェチ レングリコールであることを特徴とする、 請求項 1乃至 3の ヽずれか 1項に記載の非ブ ル一ミング性ポリオレフィン系樹脂糸誠物。  4. The non-blueming polyolefin resin according to any one of claims 1 to 3, wherein the polyalkylene glycol (C) is a polyethylene glycol having a molecular weight of 1,000 to 20,000. Itoshimono.
5. 請細 1乃至 4の Lヽずれか 1項に言 3¾の非ブルーミング性ポリオレフィン系キ聽 «物を用いて してなることを とする、 非ブル一ミング性ポリオレフイン系樹 脂赚品。  5. A non-blooming polyolefin resin product, which is obtained by using the non-blooming polyolefin-based listening material described in the item 3 in the paragraph 1 or 4 of the sub-claims.
PCT/JP2000/004487 1999-07-06 2000-07-06 Blooming-free polyolefin resin composition and molded article WO2001002483A1 (en)

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EP2516544B1 (en) * 2009-12-21 2016-12-21 Union Carbide Chemicals & Plastics Technology LLC Medium voltage cable insulation
US8691904B2 (en) * 2010-06-10 2014-04-08 Union Carbide Chemicals & Plastics Technology Llc Thiobis phenolic antioxidant/polyethylene glycol blends
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