JPH1180449A - Polyethylene resin for large-sized vessel for highly pure chemical and vessel - Google Patents

Polyethylene resin for large-sized vessel for highly pure chemical and vessel

Info

Publication number
JPH1180449A
JPH1180449A JP24521697A JP24521697A JPH1180449A JP H1180449 A JPH1180449 A JP H1180449A JP 24521697 A JP24521697 A JP 24521697A JP 24521697 A JP24521697 A JP 24521697A JP H1180449 A JPH1180449 A JP H1180449A
Authority
JP
Japan
Prior art keywords
polyethylene resin
less
ppm
container
vessel
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
JP24521697A
Other languages
Japanese (ja)
Inventor
Tatsuhiko Ogusu
達彦 小楠
Hideki Kanazawa
秀樹 金澤
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.)
Tosoh Corp
Original Assignee
Tosoh Corp
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 Tosoh Corp filed Critical Tosoh Corp
Priority to JP24521697A priority Critical patent/JPH1180449A/en
Publication of JPH1180449A publication Critical patent/JPH1180449A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/12—Cans, casks, barrels, or drums

Landscapes

  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene resin for a large-sized vessel for highly pure chemicals and a vessel with minimized elution therefrom of contaminating substances such as resins extracted or deteriorated, etc., by chemicals, the vessel being excellent in impact resistance and can be repeatedly used for a long period of time. SOLUTION: This polyethylene resin for a large-sized vessel for highly pure chemicals with an internal volume of 50 liter or more has the following properties (1)-(6): (1) a density (JIS K-6760-1981) of 0.94-0.97 g/cm<3> , (2) a melt flow rate (JIS K7210-1976, condition 7), at 190 deg.C and 21.6 kg load, of 1-15 g/10 min, (3) a wt. average mol.wt. (Mw)/number average mol.wt. (Mn) ratio (Mw/Mn), obtained by the gel permeation chromatography, of 8-15, (4) a melt tension at 190 deg.C of 15-65 g, (5) an extract content by boiling n-hexane of 0.1 wt.% or less, and (6) an ash content of 50 ppm less.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、半導体装置産業分
野、精密工業部品分野及び医薬品等に使用される大型高
純度薬品用容器の製造に好適で、高純度薬品を充填した
場合に、薬品への微粒子の発生および金属溶出の極めて
少なく、かつ、落下強度の優れたポリエチレン樹脂及び
容器に関するものである。BACKGROUND OF THE INVENTION The present invention is suitable for manufacturing large-sized high-purity chemical containers used in the semiconductor device industry, precision industrial parts, pharmaceuticals, and the like. The present invention relates to a polyethylene resin and a container having extremely low generation of fine particles and elution of metal and excellent drop strength.

【０００２】[0002]

【従来の技術】近年、電子工業分野の著しい発達に伴っ
て、高純度薬品の需要が高まっている。高純度薬品は、
例えば、大規模化、集積化されたＬＳＩ等の電子回路の
製造に不可欠の薬品として使用されている。具体的に
は、ウエハー洗浄・エッチング用、配線・絶縁膜エッチ
ング用、治具洗浄用、現像液、レジスト希釈液、レジス
ト剥離液、乾燥用等の用途として、硫酸、塩酸、硝酸、
フッ化水素酸、フッ化アンモニウム、過酸化水素水、イ
ソプロピルアルコール、キシレン、ＴＭＡＨ、メタノー
ル、酢酸、リン酸、アンモニア水、ＰＧＭＥＡ、ＤＭＳ
Ｏ、ＮＭＰ、ＥＣＡ、乳酸エチル等が用いられている。
従来、これらの高純度薬品用容器用材料として、耐薬品
性、耐衝撃性、価格等の点から、ポリエチレン樹脂が使
用されている。しかしながら、従来のポリエチレン樹脂
製の容器では、薬品による該樹脂の溶出物や劣化物等の
汚染物質による内容物への汚染問題があり、高純度薬品
容器用として限界があった。すなわち、超ＬＳＩの微細
化に伴い、従来では金属不純物濃度が１ＰＰＢであった
ものが、現在では０．１ＰＰＢ以下が要求されている。
また、従来、０．５μｍ以上の微粒子が問題であったも
のが、０．２μｍ以上の微粒子が１００個／ｍｌ以下と
厳しい品質が要求されるようになり、より厳しい品質が
要求されている。さらに、小型容器では高純度薬品の充
填が煩雑であり、また、小型容器は一回の薬品充填のみ
の使用であるため、繰り返し使用できる大型容器用のポ
リエチレン樹脂の開発が待たれている。2. Description of the Related Art In recent years, demand for high-purity chemicals has been increasing with the remarkable development of the electronics industry. High purity chemicals
For example, it is used as an indispensable chemical for manufacturing electronic circuits such as large-scale integrated LSIs. Specifically, for use in cleaning and etching of wafers, etching of wiring and insulating films, cleaning of jigs, developing solutions, resist diluting solutions, resist stripping solutions, drying, etc., sulfuric acid, hydrochloric acid, nitric acid,
Hydrofluoric acid, ammonium fluoride, aqueous hydrogen peroxide, isopropyl alcohol, xylene, TMAH, methanol, acetic acid, phosphoric acid, aqueous ammonia, PGMEA, DMS
O, NMP, ECA, ethyl lactate and the like are used.
Conventionally, polyethylene resins have been used as materials for containers of these high-purity chemicals from the viewpoint of chemical resistance, impact resistance, price, and the like. However, conventional polyethylene resin containers have a problem of contamination of the contents by contaminants such as eluted and degraded products of the resin due to chemicals, and have been limited for use as high-purity chemical containers. That is, with the miniaturization of the VLSI, the metal impurity concentration was conventionally 1 PPB, but now it is required to be 0.1 PPB or less.
Conventionally, fine particles having a size of 0.5 μm or more have been a problem, but strict quality has been demanded, such as 100 particles / ml or less, having a size of 0.2 μm or more. Furthermore, the filling of high-purity chemicals in small containers is complicated, and the small containers are used only once for filling the chemicals. Therefore, the development of polyethylene resins for large containers that can be used repeatedly is awaited.

【０００３】大型になると流動性と溶融張力等の成形性
のバランスが取り難くなる。すなわち、流動性を良くす
るための分子量分布の拡大や分子量を低下させると、溶
融張力が低下する。更に、大型になると分子量分布の拡
大が必要となるが、溶出成分の増加によるクリーン性の
低下が問題になる。When the size is large, it is difficult to balance the fluidity and the moldability such as melt tension. That is, when the molecular weight distribution is increased or the molecular weight is reduced to improve the fluidity, the melt tension is reduced. Further, when the size becomes large, the molecular weight distribution needs to be expanded, but there is a problem in that the cleanliness is deteriorated due to an increase in elution components.

【０００４】０．２μｍ以上の微粒子の発生が５００個
／ｍｌ以下である、クリーンなポリエチレン樹脂製の容
器として、特開平７−２５７５４０号公報に提案されて
いる容器がある。しかし、該特開平７−２５７５４０号
公報に提案されている容器は、０．２μｍ以上の微粒子
の発生数が十分に満足できるものではなく、また、該特
開平７−２５７５４０号公報に提案されているポリエチ
レン樹脂は、大型容器を得るために必要な大きな溶融張
力を有していないので、大型高純度薬品容器用のポリエ
チレン樹脂とは言えない。大型高純度薬品容器として
は、特公平４−２０７７３号公報に、ＦＲＰ等の補強用
の外筒と、これに内挿されているポリエチレン製の内筒
からなる提案がある。該ポリエチレンはメルトインデッ
クス０．０１〜０．０４ｇ／１０分、密度０．９５３〜
０．９５７ｇ／ｃｍ3であり、金属成分を含有する添加
剤を実質的に含まないものであるが、０．５μｍ以上の
微粒子が１０〜２０個／ｍｌ程度ある。金属成分を含有
する添加剤を実質的に含まないこと、及び、ヒンダード
フェノール系の酸化防止剤のみとしただけでは、０．２
μｍ以上の微粒子の発生が１００個／ｍｌ以下であるク
リーンな容器は得られない。なお、特公平４−２０７７
３号公報の提案は、補強する外筒を必要とするため工程
が複雑であり、補強しなくても、強度の優れた大型高純
度薬品容器用のポリエチレン樹脂の開発が必要である。As a container made of a clean polyethylene resin in which the generation of fine particles having a particle size of 0.2 μm or more is 500 particles / ml or less, there is a container proposed in JP-A-7-257540. However, the container proposed in Japanese Patent Application Laid-Open No. 7-257540 does not sufficiently satisfy the generation number of fine particles of 0.2 μm or more. Some polyethylene resins do not have the high melt tension necessary to obtain large containers, and therefore cannot be said to be polyethylene resins for large high-purity chemical containers. As a large-sized high-purity chemical container, Japanese Patent Publication No. 4-20773 discloses a proposal comprising an outer cylinder for reinforcement such as FRP and an inner cylinder made of polyethylene inserted therein. The polyethylene has a melt index of 0.01 to 0.04 g / 10 min and a density of 0.953 to
0.957 g / cm 3, which is substantially free of an additive containing a metal component, but has about 10 to 20 microparticles / ml of 0.5 μm or more. If the additive containing a metal component is not substantially contained, and only the hindered phenol-based antioxidant is used alone, 0.2
A clean container in which the generation of fine particles of μm or more is 100 particles / ml or less cannot be obtained. In addition, Japanese Patent Publication 4-2077
The proposal of Japanese Patent Publication No. 3 requires an outer cylinder to be reinforced, which complicates the process. Even without reinforcement, it is necessary to develop a polyethylene resin for a large, high-purity chemical container having excellent strength.

【０００５】[0005]

【発明が解決しようとする課題】本発明は、大型高純度
薬品容器用ポリエチレン樹脂であって、該ポリエチレン
樹脂を大型高純度薬品容器として使用した場合に、薬品
による該樹脂の溶出物や劣化物等の汚染物質の溶出を極
力抑え、かつ、耐衝撃性に優れ、長期間の繰り返し使用
可能な大型高純度薬品容器用ポリエチレン樹脂及び容器
の提供を目的とするものである。DISCLOSURE OF THE INVENTION The present invention relates to a polyethylene resin for a large-sized high-purity chemical container, and when the polyethylene resin is used as a large-sized high-purity chemical container, the resin is eluted or degraded by the chemical. It is an object of the present invention to provide a polyethylene resin for a large high-purity chemical container and a container which can minimize elution of contaminants and the like, have excellent impact resistance, and can be used repeatedly for a long time.

【０００６】[0006]

【課題を解決するための手段】本発明者らは、鋭意検討
した結果、特定の性状を有するポリエチレン樹脂を使用
することによって上記の問題を解決できることを見い出
し、本発明に到達した。Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by using a polyethylene resin having a specific property, and have reached the present invention.

【０００７】即ち、以下の（１）〜（６）の特性を有す
る、内容積が５０リットル以上の大型高純度薬品容器用
ポリエチレン樹脂である。That is, it is a polyethylene resin for a large high-purity chemical container having the following characteristics (1) to (6) and having an inner volume of 50 liters or more.

【０００８】（１）密度（ＪＩＳ Ｋ６７６０−１９８
１）が０．９４〜０．９７ｇ／ｃｍ3、（２）１９０
℃、２１．６Ｋｇ荷重のメルトフローレート（ＪＩＳ
Ｋ７２１０−１９７６、条件７、ＨＬＭＦＲ）が１〜１
５ｇ／１０分、（３）ゲルパーミエーション・クロマト
グラフィー（ＧＰＣ）より求められる重量平均分子量
（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が
８〜１５、（４）１９０℃における溶融張力（ＭＴ）が
１５〜６５ｇ、（５）沸騰ノルマルヘキサン抽出量が
０．１重量％以下、（６）灰分量が５０ＰＰＭ以下であ
る本発明のポリエチレン樹脂は含有塩素量が１５ＰＰＭ
以下であることが好ましい。また、溶融張力（ＭＴ）は
ＨＬＭＦＲと特定の関係を有すことが好ましい。さら
に、該ポリエチレン樹脂は、該ポリエチレン樹脂に添加
する添加物と添加量を特定することが好ましい。即ち、
該樹脂に対して（Ａ）中和剤として脂肪酸金属塩類を１
５０ＰＰＭ以下として添加してなること、および／又は
（Ｂ）酸化防止剤としてフェノール系酸化防止剤を８０
０ＰＰＭ以下として添加してなることが好ましい。以下
に、本発明の大型高純度薬品容器用ポリエチレン樹脂に
ついて、更に詳細に説明する。(1) Density (JIS K6760-198)
1) is 0.94 to 0.97 g / cm 3 , (2) 190
° C, melt flow rate at 21.6 Kg load (JIS
K7210-1976, condition 7, HLMFR) 1-1
5 g / 10 min, (3) a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) determined by gel permeation chromatography (GPC) of 8 to 15, (4) 190 ° C. The polyethylene resin of the present invention having a melt tension (MT) of 15 to 65 g, a boiling normal hexane extraction amount of 0.1% by weight or less, and an ash content of 50 PPM or less has a chlorine content of 15 PPM.
The following is preferred. Further, the melt tension (MT) preferably has a specific relationship with HLMFR. Further, it is preferable that the polyethylene resin specifies the additive to be added to the polyethylene resin and the amount of the additive. That is,
(A) a fatty acid metal salt as a neutralizing agent with respect to the resin;
And / or (B) a phenolic antioxidant as an antioxidant.
It is preferable to add it as 0 PPM or less. Hereinafter, the polyethylene resin for a large high-purity chemical container of the present invention will be described in more detail.

【０００９】本発明に用いられる高純度薬品容器用ポリ
エチレン樹脂は、チタン、ジルコニウム等の遷移金属化
合物、マグネシウムの化合物、及び有機アルミニウム化
合物から成る高活性チーグラー系触媒を重合用触媒とし
て用い、エチレンもしくは、エチレンと炭素数３〜２０
のα−オレフィンを所望の密度となる割合にして共重合
することにより、好適に製造することができる。The polyethylene resin for a high-purity chemical container used in the present invention uses a highly active Ziegler-based catalyst comprising a transition metal compound such as titanium or zirconium, a compound of magnesium, and an organoaluminum compound as a catalyst for polymerization. , Ethylene and carbon number 3-20
Can be suitably produced by copolymerizing the α-olefin having a desired density.

【００１０】炭素数３〜２０のα−オレフィンとして
は、プロピレン、１−ブテン、４−メチル−１−ペンテ
ン、３−メチル−１−ブテン、１−ペンテン、１−ヘキ
セン、１−ヘプテン、１−オクテン、１−ノネン、１−
デセン、１−ウンデセン、１−ドデセン、１−トリデセ
ン、１−テトラデセン、１−ペンタデセン、１−ヘキサ
デセン、１−ヘプタデセン、１−オクタデセン、１−ノ
ナデセン、１−エイコセンなどを挙げることが出来る。As the α-olefin having 3 to 20 carbon atoms, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-pentene, 1-hexene, 1-heptene, -Octene, 1-nonene, 1-
Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, and the like can be given.

【００１１】該ポリエチレン樹脂の製造における重合方
法はスラリー重合、気相重合、溶液重合など例示するこ
とが出来る。なかでも、薬品に溶出する金属不純物濃度
を低く抑え、また、微粒子の発生の原因となる低分子重
合体の樹脂への取り込みを制限するため、炭素数が６以
上かつ１０以下の飽和炭化水素系の重合媒体、例えば、
ノルマルヘキサン、ノルマルヘプタン等を用いるスラリ
ー重合において、多段重合法を採用すると良い。この多
段重合法として、密度が０．９４〜０．９８ｇ／ｃｍ3
の低分子量成分と、密度が０．９２〜０．９５ｇ／ｃｍ
3で該低分子量より密度の低い高分子量成分の二成分と
からなり、該二成分の重合生成量比が、低分子量成分：
高分子量成分＝２０：８０〜８０：２０である、二段重
合法が例示できる。The polymerization method in the production of the polyethylene resin can be exemplified by slurry polymerization, gas phase polymerization, solution polymerization and the like. Above all, saturated hydrocarbons having 6 or more and 10 or less carbon atoms in order to keep the concentration of metal impurities eluted in chemicals low and to limit the incorporation of low molecular weight polymers that cause fine particles into resin. Polymerization medium, for example,
In a slurry polymerization using normal hexane, normal heptane, or the like, a multi-stage polymerization method is preferably employed. As the multi-stage polymerization method, the density is 0.94 to 0.98 g / cm 3.
And a low molecular weight component having a density of 0.92 to 0.95 g / cm
In 3 it is composed of two components of a high molecular weight component having a lower density than the low molecular weight, and the ratio of polymerization amount of the two components is as follows:
A two-stage polymerization method in which the high molecular weight component is 20:80 to 80:20 can be exemplified.

【００１２】また、該ポリエチレン樹脂は以下に示すよ
うに密度、メルトフローレート、分子量分布（Ｍｗ／Ｍ
ｎ）、溶融張力、沸騰ノルマルヘキサン抽出量および灰
分量を特定するものである。The polyethylene resin has a density, a melt flow rate and a molecular weight distribution (Mw / M
n), the melt tension, the amount of boiling normal hexane extracted, and the amount of ash are specified.

【００１３】即ち、該ポリエチレン樹脂の密度（ＪＩＳ
Ｋ６７６０−１９８１）は０．９４〜０．９７ｇ／ｃ
ｍ3であり、０．９４ｇ／ｃｍ3未満では容器内の高純度
薬品への溶出ポリマー成分が増加し、微粒子の発生原因
となる。また、密度が０．９７ｇ／ｃｍ3を超えると耐
薬品性の低下により容器の強度が低下する。That is, the density of the polyethylene resin (JIS
K6760-1981) is 0.94 to 0.97 g / c.
m 3 , and if it is less than 0.94 g / cm 3 , the amount of the polymer component eluted into the high-purity chemical in the container increases, which causes the generation of fine particles. On the other hand, when the density exceeds 0.97 g / cm 3 , the strength of the container is reduced due to a decrease in chemical resistance.

【００１４】該ポリエチレン樹脂の１９０℃、２１．６
Ｋｇ荷重のメルトフローレート（ＪＩＳ Ｋ７２１０−
１９７６、条件７、ＨＬＭＦＲと記す）は１〜１５ｇ／
１０分であり、ＨＬＭＦＲが１ｇ／１０分未満では流動
性が低下する。また、ＨＬＭＦＲが１５ｇ／１０分を超
えると、落下強度が低下する。The polyethylene resin has a temperature of 190.degree.
Melt flow rate of Kg load (JIS K7210-
1976, condition 7, HLMFR) is 1 to 15 g /
When the HLMFR is less than 1 g / 10 minutes, the fluidity is reduced. If the HLMFR exceeds 15 g / 10 minutes, the drop strength decreases.

【００１５】該ポリエチレン樹脂のゲルパーミエーショ
ン・クロマトグラフィー（ＧＰＣ）より求められる重量
平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比Ｍｗ／
Ｍｎは８〜１５であり、８未満では分子量分布が狭くて
流動性が劣り、また、樹脂の劣化を促進させる。該Ｍｗ
／Ｍｎが１５を超えると、分子量分布が拡大して微粒子
の発生原因となる低分子量成分が増加する。また、該Ｍ
ｗ／Ｍｎが１５を超えると、パリソン結合部のピンチオ
フ部の形状が劣るようになり、落下強度が低下する。The ratio Mw / weight average molecular weight (Mw) to number average molecular weight (Mn) of the polyethylene resin determined by gel permeation chromatography (GPC).
Mn is from 8 to 15, and when it is less than 8, the molecular weight distribution is narrow and the fluidity is poor, and the deterioration of the resin is promoted. The Mw
When / Mn is more than 15, the molecular weight distribution is widened, and low molecular weight components causing fine particles are increased. In addition, the M
If w / Mn exceeds 15, the shape of the pinch-off portion of the parison joint becomes inferior, and the drop strength decreases.

【００１６】該ポリエチレン樹脂の１９０℃における溶
融張力（ＭＴ、単位ｇ）は１５〜６５ｇ、好ましくは１
５〜６０ｇであり、６５ｇを越えると流動性が低下す
る。また１５ｇ未満では、パリソンの自重を支える溶融
張力が低下し、大型ブロー成形し難くなる。また、ＭＴ
が１５ｇ未満では偏肉が生じ落下強度が低下する。The polyethylene resin has a melt tension (MT, unit: g) at 190 ° C. of 15 to 65 g, preferably 1 to 65 g.
The amount is 5 to 60 g, and if it exceeds 65 g, the fluidity decreases. If the weight is less than 15 g, the melt tension that supports the weight of the parison decreases, and it becomes difficult to perform large-size blow molding. Also, MT
If it is less than 15 g, uneven wall thickness occurs and the drop strength decreases.

【００１７】該ポリエチレン樹脂の沸騰ノルマルヘキサ
ン抽出量は０．１重量％以下であり、０．１重量％を超
えると、薬品への溶出ポリマー成分が増加し、微粒子の
発生原因となる。The amount of boiling normal hexane extracted from the polyethylene resin is 0.1% by weight or less. If the amount exceeds 0.1% by weight, the amount of polymer components eluted into the chemical increases, which causes the generation of fine particles.

【００１８】また、該ポリエチレン樹脂に含有する灰分
量は該樹脂に対して５０ＰＰＭ以下である。該ポリエチ
レン樹脂に含有する灰分量が５０ＰＰＭを超えると、薬
品に灰分が溶出するため、薬品中の金属不純物濃度を増
加させる。灰分量は、全樹脂に対する完全灰化物の割合
を重量ＰＰＭで示すものである。完全灰化物は電気炉で
完全灰化して得られるもので、Ａｌ，Ｍｇ，Ｔｉ，Ｓｉ
等の重合触媒の残存物、中和剤等の金属含有の添加物及
びポリエチレン樹脂の製造時の不純物・付着物の金属酸
化物である。The amount of ash contained in the polyethylene resin is 50 PPM or less with respect to the resin. If the amount of ash contained in the polyethylene resin exceeds 50 PPM, ash is eluted in the chemical, so that the concentration of metal impurities in the chemical is increased. The ash content indicates the ratio of complete ash to the total resin by weight PPM. Completely incinerated is obtained by complete incineration in an electric furnace, and includes Al, Mg, Ti, Si
And the like, metal-containing additives such as neutralizing agents, and metal oxides of impurities and deposits during the production of polyethylene resins.

【００１９】該ポリエチレン樹脂の、蛍光Ｘ線装置で測
定される含有塩素量は、全ポリエチレン樹脂に対して１
５ＰＰＭ以下であることが好ましい。全ポリエチレン樹
脂に対して１５ＰＰＭを超えると、塩素が成形機及び金
型の金属を腐食させ、また、成形品の変色の原因となる
ため塩素を補足する中和剤が必要となり、止むを得ず使
用した中和剤が金属不純物の原因となる。The content of chlorine in the polyethylene resin measured by a fluorescent X-ray apparatus is 1 to the total polyethylene resin.
It is preferably at most 5 PPM. If the total polyethylene resin exceeds 15 PPM, chlorine will corrode the metal of the molding machine and the mold, and cause discoloration of the molded product. The used neutralizing agent causes metal impurities.

【００２０】また、大型ブロー成形において、吹込中の
溶融樹脂の肉まわりを良くすることにより、成形容器の
各部の肉厚を均一にし、落下強度を高めるためには、該
ポリエチレン樹脂の１９０℃における溶融張力（ＭＴ、
単位ｇ）は、１９０℃、２１．６Ｋｇ荷重のメルトフロ
ーレート（ＪＩＳ Ｋ７２１０−１９７６、条件７、Ｈ
ＬＭＦＲと記す）に対して下記の、 ＬｏｇＭＴ≧−０．４５５×ＬｏｇＨＬＭＦＲ＋１．６
４ なる関係を満たすことが好ましい。In large blow molding, the thickness of each part of the molding container is made uniform by improving the thickness of the molten resin being blown and the drop strength is increased. Melt tension (MT,
The unit g) is a melt flow rate (JIS K7210-1976, condition 7, H) at 190 ° C. under a load of 21.6 kg.
LogMT ≧ −0.455 × LogHLMFR + 1.6 with respect to LMFR).
4 is preferably satisfied.

【００２１】さらに、本発明に用いられる高純度薬品容
器用ポリエチレン樹脂は、酸化防止剤、耐光安定剤、及
び中和剤等の全ての添加剤及び添加物が無添加であるこ
とが好ましい。ここで、中和剤とはステアリン酸カルシ
ウム、ステアリン酸マグネシウム及びステアリン酸亜鉛
に代表される脂肪酸金属塩とハイドロタルサイト類であ
って、何れも薬品中に溶出して金属汚染物質となるもの
であり、無添加であることが好ましい。また、本来無添
加が好ましいが、内容物の薬品の種類によっては、
（Ａ）中和剤として１５０ＰＰＭ以下の脂肪酸金属塩類
および／又は（Ｂ）酸化防止剤として８００ＰＰＭ以下
のフェノール系酸化防止剤を添加することにより、樹脂
の薬品による酸化劣化を防止し、微粒子の発生及び容器
の変色を抑える。従って、本発明のポリエチレン樹脂に
対して、（Ａ）中和剤として１５０ＰＰＭ以下の脂肪酸
金属塩類を添加すること、および／又は（Ｂ）酸化防止
剤として８００ＰＰＭ以下のフェノール系酸化防止剤を
添加することも好ましい。中和剤としてはハイドロタル
サイト類よりも金属分が少ない脂肪酸金属塩類が好まし
い。脂肪酸金属塩類がポリエチレン樹脂に対し１５０Ｐ
ＰＭを超えて添加すると、薬品中に金属分が溶出して金
属不純物の発生原因となる。フェノール系酸化防止剤が
ポリエチレン樹脂に対し８００ＰＰＭを越えると、薬品
中に溶出して微粒子の発生原因となる。フェノール系酸
化防止剤としては、２，６−ジ−ｔ−ブチル−ｐ−クレ
ゾール、ブチル化ヒドロキシアニソール、２，６−ジ−
ｔ−ブチル−４−エチルフェノール、ステアリル−β−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）
プロピオネート等のモノフェノール系酸化防止剤と２，
２’−メチレンビス（４−メチル−６−ｔ−ブチルフェ
ノール）、２，２’−メチレンビス（４−エチル−６−
ｔ−ブチルフェノール）のビスフェノール系酸化防止剤
及びテトラキス−［メチレン−３−（３’，５’−ジ−
ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネー
ト］メタン、１，３，５−トリメチル−２，４，６−ト
リス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジ
ル）ベンゼン等の高分子量型フェノール系酸化防止剤の
ものが挙げられる。Further, the polyethylene resin for a high-purity chemical container used in the present invention is preferably free of all additives and additives such as an antioxidant, a light-resistant stabilizer and a neutralizing agent. Here, the neutralizing agent is a fatty acid metal salt represented by calcium stearate, magnesium stearate and zinc stearate and hydrotalcites, all of which elute into the chemical and become metal contaminants. , Is preferably not added. In addition, it is originally preferable that no additive is used, but depending on the type of chemicals in the contents,
By adding (A) a fatty acid metal salt of 150 PPM or less as a neutralizing agent and / or (B) a phenolic antioxidant of 800 PPM or less as an antioxidant, the resin is prevented from being oxidized and degraded by chemicals, and the generation of fine particles. And reduce discoloration of the container. Therefore, to the polyethylene resin of the present invention, (A) a fatty acid metal salt of 150 PPM or less is added as a neutralizing agent, and / or (B) a phenolic antioxidant of 800 PPM or less is added as an antioxidant. It is also preferred. As the neutralizing agent, fatty acid metal salts having a lower metal content than hydrotalcites are preferable. Fatty acid metal salts are 150P for polyethylene resin
If it is added in excess of PM, a metal component is eluted in the chemical and causes metal impurities. When the phenolic antioxidant exceeds 800 PPM with respect to the polyethylene resin, it elutes in the chemical and causes fine particles. Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-
t-butyl-4-ethylphenol, stearyl-β-
(3,5-di-t-butyl-4-hydroxyphenyl)
Monophenolic antioxidants such as propionate and 2,
2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-
t-butylphenol) bisphenol-based antioxidant and tetrakis- [methylene-3- (3 ′, 5′-di-
t-butyl-4'-hydroxyphenyl) propionate] high molecular weight such as methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene Type phenolic antioxidants.

【００２２】本発明の高純度薬品容器用ポリエチレン樹
脂はブロー成形、回転成形等既知の成形方法により容器
状に成形することにより高純度薬品容器となる。クリー
ンルーム内でこれらの成形を行うとダストによる汚染を
防止できる。ブロー成形に際しては、フィルターで微粒
子を取り除いたエアーをブローエアーに用いる方法はク
リーンな容器を製造するのに好ましい。大型容器の形状
は特定しないが、容器の容量は内容積が５０リットル以
上、好ましくは、１００リットル以上である。また、外
部をＦＲＰ及び金属等で囲った、１トン〜４トンのコン
テナ容器の内容器としての使用も可能である。The polyethylene resin for a high-purity medicine container of the present invention is formed into a container by a known molding method such as blow molding and rotational molding to obtain a high-purity medicine container. Performing these moldings in a clean room can prevent dust contamination. At the time of blow molding, a method of using air from which fine particles have been removed by a filter as blow air is preferable for producing a clean container. Although the shape of the large container is not specified, the capacity of the container is 50 liters or more, preferably 100 liters or more. Further, it can be used as an inner container of a 1 to 4 ton container container whose outside is surrounded by FRP and metal.

【００２３】薬品の種類によっては遮光性容器にする必
要があり、本発明のポリエチレン樹脂を内層とし、有機
顔料あるいは無機顔料等の遮光性材料を含む層を少なく
とも一層含む多層容器としても、また、クリーン度を保
てる範囲内で有機顔料あるいは無機顔料を本発明のポリ
エチレン樹脂に添加してもかまわない。Depending on the type of chemicals, it is necessary to form a light-shielding container. A multilayer container comprising the polyethylene resin of the present invention as an inner layer and at least one layer containing a light-shielding material such as an organic pigment or an inorganic pigment, Organic pigments or inorganic pigments may be added to the polyethylene resin of the present invention as long as the degree of cleanliness can be maintained.

【００２４】[0024]

【実施例】以下、本発明について実施例により説明する
が、これら実施例に限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but is not limited to these examples.

【００２５】試験方法は以下の方法に従った。The test method was as follows.

【００２６】密度：ＪＩＳ Ｋ６７６０−1981に従っ
て、１００℃の熱水に１時間浸漬した後、室温に徐冷し
た試験片を、２３℃に保った密度勾配管で測定した。Density: According to JIS K6760-1981, a test piece which was immersed in hot water at 100 ° C. for 1 hour and then cooled slowly to room temperature was measured with a density gradient tube kept at 23 ° C.

【００２７】Ｍｗ／Ｍｎ：ウオーターズ社製１５０Ｃ
ＡＬＣ／ＧＰＣ（カラム；東ソー製ＧＭＨＨＲ−Ｈ
（Ｓ）、溶媒；１，２，４−トリクロロベンゼン）を使
用して、ＧＰＣ法により、Ｍｗおよび、Ｍｗ／Ｍｎを算
出した。なお、東ソー製標準ポリスチレンを用いて、ユ
ニバーサルキャリブレーション法によりカラム溶出体積
は校正した。Mw / Mn: 150C manufactured by Waters
ALC / GPC (column: GMHHR-H manufactured by Tosoh)
(S), solvent; 1,2,4-trichlorobenzene), and Mw and Mw / Mn were calculated by GPC method. The column elution volume was calibrated by the universal calibration method using standard polystyrene manufactured by Tosoh Corporation.

【００２８】溶融張力（ＭＴ）：東洋精機（株）製の
メルトテンションテスターを使用し、樹脂温度１９０℃
で測定した。Melt tension (MT): Using a melt tension tester manufactured by Toyo Seiki Co., Ltd., resin temperature 190 ° C.
Was measured.

【００２９】沸騰ノルマルヘキサン抽出量（ｎ−
Ｃ6）：ソックスレー抽出器を用い、樹脂２ｇをノルマ
ルヘキサン溶媒４００ｍｌで２時間抽出した。全樹脂に
対する抽出分の重量％で示す。The amount of boiling normal hexane extracted (n-
C 6 ): Using a Soxhlet extractor, 2 g of the resin was extracted with 400 ml of normal hexane solvent for 2 hours. It is shown as a percentage by weight of the extractables relative to the total resin.

【００３０】灰分量：ＪＩＳ Ｋ２２７２−１９８５
に準拠し、秤量した白金蒸発皿上にポリエチレン樹脂２
５ｇを置き、ガラス蓋で上部を覆いバーナーで徐々に灰
化し、次いで７７５±２５℃の電気炉で完全灰化し、灰
化後に重量測定した。全樹脂に対する完全灰化物の割合
を重量ＰＰＭで示す。Ash content: JIS K2272-1985
Polyethylene resin 2 on a weighed platinum evaporation dish according to
5 g was placed, the top was covered with a glass lid, and gradually incinerated with a burner, then completely incinerated in an electric furnace at 775 ± 25 ° C., and weighed after incineration. The ratio of complete ash to total resin is indicated by weight PPM.

【００３１】含有塩素量：約１０ｇのポリエチレン樹
脂を加熱プレスを使用して試験片とし、蛍光Ｘ線装置で
定性定量した。全樹脂に対する塩素の割合を重量ＰＰＭ
で示す。Chlorine content: Approximately 10 g of a polyethylene resin was used as a test piece using a heating press, and qualitatively quantified using a fluorescent X-ray apparatus. The ratio of chlorine to total resin is expressed in weight PPM
Indicated by

【００３２】微粒子数：ポリエチレン樹脂を大型ブロ
ー成形することで得られた内容積１００リットルの容器
を使用した。クリーンルーム内で、容器に５０リットル
の超純水を入れ１５秒間振とうする洗浄を５回繰り返し
た後、容器に１００リットルの超純水を入れ３０分間静
置して、０．２μｍ以上の微粒子の数をリヨン株式会社
製ＫＬ−２２型液体微粒子カウンターで測定した。ま
た、同様に超純水で５回洗浄後、容器に１００リットル
の超純水を入れ５０℃にて１ヶ月間静置した後、０．２
μｍ以上の微粒子の数を同液体微粒子カウンターで測定
した。水中の微粒子数は個／ｍｌで示す。Number of fine particles: A container having an inner volume of 100 liters obtained by subjecting a polyethylene resin to large blow molding was used. In a clean room, washing was repeated 5 times by placing 50 liters of ultrapure water in a container and shaking for 15 seconds. Then, 100 liters of ultrapure water was placed in the container and allowed to stand for 30 minutes. Was measured with a KL-22 type liquid fine particle counter manufactured by Lyon Co., Ltd. Similarly, after washing five times with ultrapure water, 100 liter of ultrapure water was put into a container, and allowed to stand at 50 ° C. for one month.
The number of fine particles having a size of μm or more was measured by the same liquid fine particle counter. The number of fine particles in water is indicated by the number of particles / ml.

【００３３】金属不純物濃度：ポリエチレン樹脂を大
型ブロー成形することで得られた内容積１００リットル
の容器を５０リットルの超純水で５回洗浄後、容器に１
００リットルの超純水を充填し、５０℃で１ヶ月間静置
した後、ＩＣＰ−ＭＳ装置又はフレームレス原子吸光光
度計（検出下限界０．０１ＰＰＢ）で測定した。測定金
属はＡｌ，Ｃａ，Ｃｒ，Ｍｇ，Ｔｉ，Ｚｒ，Ｎａ，Ｋ，
Ｆｅ，Ｍｎ，Ｚｎ、Ｎｉの１２種類。Metallic impurity concentration: A container having an inner volume of 100 liters obtained by subjecting a polyethylene resin to large-size blow molding is washed with 50 liters of ultrapure water five times, and then added to the container.
After filling with 100 liters of ultrapure water and leaving it to stand at 50 ° C. for one month, measurement was performed with an ICP-MS device or a flameless atomic absorption spectrophotometer (lower detection limit: 0.01 PPB). Measurement metals are Al, Ca, Cr, Mg, Ti, Zr, Na, K,
12 types of Fe, Mn, Zn and Ni.

【００３４】低温落下試験：［状態調整］大型容器に
１００リットルのエチレングリコール５０％水溶液を入
れ、−１８℃の低恒温室に２４時間以上放置する。［落
下試験］内容液が−１８℃になった後、容器の胴部がコ
ンクリート製の地面に水平に当たるようにして、高さ１
ｍより落下させて、大型容器の破損状況を確認する。破
損しない場合は、２０ｃｍ間隔で最高３．２ｍを限度
に、落下高さを増加させ、破損させる。容器が破損した
高さを落下強度（ｍ）とする。Low temperature drop test: [condition adjustment] 100 liters of a 50% aqueous solution of ethylene glycol is placed in a large container and left in a low temperature room at -18 ° C for 24 hours or more. [Drop test] After the liquid content reaches -18 ° C, the height of the container is set to 1 so that the body of the container hits the concrete ground horizontally.
Check the damage of the large container. If it does not break, increase the drop height up to a maximum of 3.2 m at 20 cm intervals and break it. The height at which the container is broken is defined as the drop strength (m).

【００３５】実施例１ （１）固体触媒成分（Ａ）の調製 特開平７−４１５１３号公報に従い、Ａｌ，Ｔｉ，Ｍｇ
及びＣｌを主成分とするチーグラー系触媒（固体触媒成
分（Ａ））を調製した。すなわち、窒素で充分置換した
３リットルガラスフラスコに、金属マグネシウム粉末４
０ｇ（１．６５モル）およびチタンテトラブトキシド２
２５ｇ（０．６６モル）を入れ、ヨウ素２．０ｇを溶解
したｎ−ブタノール２５６ｇ（３．５モル）を９０℃で
２時間かけて加え、さらに発生する水素ガスを排除しな
がら窒素シール下で１４０℃で２時間撹拌した。これを
１１０℃とした後に、テトラエトキシシラン３７ｇ
（０．１８モル）とテトラメトキシシラン２５ｇ（０．
１７モル）を加え、さらに１４０℃で２時間撹拌した。
次いで、ヘキサン２．１リットルを加えて均一溶液を得
た。この均一溶液を撹拌装置を備えた１０リットルのス
テンレス製オートクレーブに入れ、内温を４５℃に保ち
ジエチルアルミニウムクロライド１．４モルとｉ−ブチ
ルアルミニウムジクロライド０．５６モルを含むヘキサ
ン溶液０．７４ｋｇを１時間かけて加え、さらに６０℃
で１時間撹拌した。次いでｉ−ブチルアルミニウムジク
ロライドの１０．４モルを含むヘキサン溶液３．２ｋｇ
を加え６０℃で１時間撹拌を行い固体触媒成分を得た。
得られた固体触媒成分（Ａ）はヘキサンを用いて残存す
る未反応物および副生成物を除去した後、ヘキサンスラ
リーとして用いた。Example 1 (1) Preparation of solid catalyst component (A) According to JP-A-7-41513, Al, Ti, Mg
And a Ziegler catalyst (solid catalyst component (A)) containing Cl as a main component. That is, a metal magnesium powder 4 was placed in a 3-liter glass flask sufficiently purged with nitrogen.
0 g (1.65 mol) and titanium tetrabutoxide 2
25 g (0.66 mol) were added, and 256 g (3.5 mol) of n-butanol in which 2.0 g of iodine had been dissolved was added at 90 ° C. over 2 hours. Stirred at 140 ° C. for 2 hours. After raising the temperature to 110 ° C., 37 g of tetraethoxysilane
(0.18 mol) and 25 g of tetramethoxysilane (0.
17 mol), and the mixture was further stirred at 140 ° C. for 2 hours.
Next, 2.1 liters of hexane was added to obtain a homogeneous solution. This homogeneous solution was placed in a 10-liter stainless steel autoclave equipped with a stirrer, and while keeping the internal temperature at 45 ° C, 0.74 kg of a hexane solution containing 1.4 mol of diethyl aluminum chloride and 0.56 mol of i-butyl aluminum dichloride was added. Add over 1 hour and add 60 ° C
For 1 hour. Then 3.2 kg of a hexane solution containing 10.4 mol of i-butylaluminum dichloride
And stirred at 60 ° C. for 1 hour to obtain a solid catalyst component.
The obtained solid catalyst component (A) was used as a hexane slurry after removing remaining unreacted substances and by-products using hexane.

【００３６】（２）ポリエチレン樹脂の製造 内容積３７０リットルの連続式重合器に、水分量２ＰＰ
Ｍ以下の脱水精製したヘキサン１１０リットル／時間、
有機アルミニウム化合物（Ｂ）としてトリイソブチルア
ルミニウムを１６４ミリモル／時間、上記固体触媒成分
（Ａ）を０．９５ｇ／時間、エチレン２０．０ｋｇ／時
間、水素を対エチレン濃度比０．６モル／モルになるよ
うにそれぞれを供給しながら、８５℃、全圧３０ｋｇ／
ｃｍ2、平均滞留時間を１．８時間の条件下で連続的に
第１段目の重合を行った。第１段目のエチレン単独重合
体（低分子量成分）は、１９０℃、２．１６Ｋｇ荷重の
メルトフローレート（ＪＩＳ Ｋ７２１０−1976、条件
４、ＭＦＲと記す）は１８ｇ／１０分で密度０．９７４
ｇ／ｃｍ3であった。(2) Production of polyethylene resin A continuous polymerization vessel having an inner volume of 370 liters was charged with a water content of 2 PP.
110 liters / hour of dehydrated and purified hexane of M or less,
As the organoaluminum compound (B), triisobutylaluminum was 164 mmol / hr, the solid catalyst component (A) was 0.95 g / hr, ethylene was 20.0 kg / hr, and hydrogen was adjusted to an ethylene concentration ratio of 0.6 mol / mol. 85 ° C, total pressure 30kg /
The first-stage polymerization was carried out continuously under the conditions of cm 2 and an average residence time of 1.8 hours. The first stage ethylene homopolymer (low molecular weight component) has a melt flow rate (JIS K7210-1976, condition 4, described as MFR) of 190 g at a load of 2.16 kg and a density of 0.974 at 18 g / 10 min.
g / cm 3 .

【００３７】第１段目の重合体を含むヘキサンスラリー
は、フラッシュタンクにて未反応の水素およびエチレン
を除去した後、内容積５４５リットルの別の連続式重合
器に導入した。この重合器に追加のヘキサンを１２１リ
ットル／時間供給しながら、エチレン２０．０ｋｇ／時
間、１−ブテンを０．７ｋｇ／時間、水素を対エチレン
濃度比０．０３モル／モル、８０℃、全圧２０ｋｇ／ｃ
ｍ2、平均滞留時間を１．４時間の条件下に第２段目の
重合（高分子量成分）を行った。第２段重合器からの排
出物はフラッシュタンクにて未反応の水素、エチレン、
１−ブテンを除去した後、ヘキサン５０リットル／時間
を追加供給した後、乾燥工程を経てエチレン系共重合体
の混合物パウダーを得た。低分子量成分の重合割合は５
０重量％で、高分子量成分の重合割合は５０重量％であ
った。以上の二つの分子量成分を連続重合する二段重合
法により得た重合パウダーを、酸化防止剤、中和剤、紫
外線吸収剤等一切使用せずに無添加で５０ｍｍφ押出機
にて造粒し、ポリエチレン樹脂を得た。該ポリエチレン
樹脂は、密度が０．９５４ｇ／ｃｍ3であり、１９０
℃、２１．６Ｋｇ荷重のメルトフローレートが５．６ｇ
／１０分であり、ＧＰＣより求められるＭｗ／Ｍｎが１
０．３であり、１９０℃の溶融張力が２２ｇ、沸騰ノル
マルヘキサン抽出量が０．０８％であり、灰分量が３３
ＰＰＭであり、含有塩素量が８ＰＰＭであった。After removing unreacted hydrogen and ethylene in a flash tank, the hexane slurry containing the first-stage polymer was introduced into another continuous polymerization vessel having an internal volume of 545 liters. While feeding additional 121 liters / hour of hexane to the polymerization vessel, ethylene 20.0 kg / hour, 1-butene 0.7 kg / hour, hydrogen were added at a concentration ratio of ethylene to 0.03 mol / mol at 80 ° C. Pressure 20kg / c
The second stage polymerization (high molecular weight component) was performed under the conditions of m 2 and an average residence time of 1.4 hours. The effluent from the second-stage polymerization vessel is passed through a flash tank to unreacted hydrogen, ethylene,
After removing 1-butene, 50 liter / hour of hexane was additionally supplied, followed by a drying step to obtain a mixture powder of an ethylene-based copolymer. The polymerization ratio of the low molecular weight component is 5
At 0% by weight, the polymerization ratio of the high molecular weight component was 50% by weight. The polymerization powder obtained by the two-stage polymerization method of continuously polymerizing the above two molecular weight components is granulated with a 50 mmφ extruder without any addition without using any antioxidant, neutralizing agent, ultraviolet absorber or the like, A polyethylene resin was obtained. The polyethylene resin has a density of 0.954 g / cm 3 ,
Melt flow rate of 5.6 g at 21.6 kg load at ℃
/ 10 minutes, and Mw / Mn determined by GPC is 1
0.3, the melt tension at 190 ° C. was 22 g, the boiling normal hexane extraction amount was 0.08%, and the ash content was 33
It was PPM and the chlorine content was 8 PPM.

【００３８】（２）大型ブロー成形及び該成形品の評価 大型ブロー成形は日本製鋼所製ＭＢ８０／Ｐ１１５型中
空成形機を使用し、成形温度２１０℃にて行い、直径４
４０ｍｍφ、高さ８００ｍｍの円筒形状、平均肉厚４ｍ
ｍ、内容積１００リットル、容器重量７．０Ｋｇの大型
容器を作製した。得られた大型容器を用いて、上記した
低温落下試験、金属不純物濃度及び微粒子数の測定を行
った。(2) Large-size blow molding and evaluation of the molded product The large-size blow molding was performed at a molding temperature of 210 ° C. using a MB80 / P115 type hollow molding machine manufactured by Nippon Steel Works.
40mmφ, 800mm height cylindrical shape, average thickness 4m
m, a large container having an inner volume of 100 liters and a container weight of 7.0 kg. Using the obtained large container, the above-mentioned low-temperature drop test, the measurement of the metal impurity concentration and the number of fine particles were performed.

【００３９】表１に示すように、落下強度は３．２ｍ以
上であり、また、金属不純物濃度は０．０１ＰＰＢ以上
の濃度となる金属がなく、保存中の微粒子の増加も少な
かった。As shown in Table 1, the metal had a drop strength of 3.2 m or more, a metal impurity concentration of 0.01 PPB or more, and little increase in fine particles during storage.

【００４０】実施例２ 実施例１で得られた重合パウダーに、酸化防止剤として
テトラキス−［メチレン−３−（３’，５’−ジ−ｔ−
ブチル−４’−ヒドロキシフェニル）プロピオネート］
メタンを５００ＰＰＭ加えて、５０ｍｍφ押出機にて造
粒し、ポリエチレン樹脂を得た。実施例１と同様に大型
ブロー成形し、得られた大型容器を用いて上記した、低
温落下試験、金属不純物濃度及び微粒子数の測定を行っ
た。Example 2 The polymerized powder obtained in Example 1 was added to tetrakis- [methylene-3- (3 ′, 5′-di-t-) as an antioxidant.
Butyl-4'-hydroxyphenyl) propionate]
Methane was added at 500 PPM and granulated with a 50 mmφ extruder to obtain a polyethylene resin. The large-size blow molding was performed in the same manner as in Example 1, and the low-temperature drop test, the metal impurity concentration, and the number of fine particles were measured using the obtained large container.

【００４１】表１に示すように、落下強度は３．２ｍ以
上であり、また、金属不純物濃度は０．０１ＰＰＢ以上
の濃度となる金属がなく、保存中の微粒子の増加も少な
かった。As shown in Table 1, the metal had a drop strength of not less than 3.2 m, a metal impurity concentration of not less than 0.01 PPB, and little increase in fine particles during storage.

【００４２】比較例１ Ｃｒ及びＳｉＯ2を主成分とするフィリップス系触媒を
用いて製造した重合パウダーに、酸化防止剤として、テ
トラキス−［メチレン−３−（３’，５’−ジ−ｔ−ブ
チル−４’−ヒドロキシフェニル）プロピオネート］メ
タンを５００ＰＰＭ加えて５０ｍｍφ押出機にて造粒
し、ポリエチレン樹脂を得た。該ポリエチレン樹脂は密
度が０．９４６ｇ／ｃｍ3であり、１９０℃、２１．６
Ｋｇ荷重のメルトフローレートが５．２ｇ／１０分であ
り、ＧＰＣより求められるＭｗ／Ｍｎが９．２であり、
１９０℃の溶融張力が３３ｇ、沸騰ノルマルヘキサン抽
出量が０．１１％であり、灰分量が１７０ＰＰＭあり、
含有塩素量が１ＰＰＭ未満である。実施例１と同様に大
型ブロー成形し、得られた大型容器を用いて、上記した
低温落下試験、金属不純物濃度及び微粒子数の測定を行
った。Comparative Example 1 Tetrakis- [methylene-3- (3 ', 5'-di-t-) was added as an antioxidant to a polymerized powder produced using a Phillips catalyst containing Cr and SiO 2 as main components. [Butyl-4'-hydroxyphenyl) propionate] methane was added at 500 PPM and granulated with a 50 mmφ extruder to obtain a polyethylene resin. The polyethylene resin has a density of 0.946 g / cm 3 , 190 ° C., 21.6
The melt flow rate under a Kg load is 5.2 g / 10 min, Mw / Mn determined by GPC is 9.2,
The melt tension at 190 ° C. is 33 g, the boiling normal hexane extraction amount is 0.11%, the ash content is 170 PPM,
The chlorine content is less than 1 PPM. The large-size blow molding was performed in the same manner as in Example 1, and the above-described low-temperature drop test, the measurement of the metal impurity concentration, and the number of the fine particles were performed using the obtained large container.

【００４３】表１に示すように、落下強度は３．２ｍ以
上であった。しかし、金属不純物濃度はクロム（Ｃｒ）
が０．０３ＰＰＢと増加し、０．２μｍ以上の微粒子が
１００個／ｍｌ以下を満足していない。As shown in Table 1, the drop strength was 3.2 m or more. However, the metal impurity concentration is chromium (Cr)
Increased to 0.03 PPB, and the number of fine particles having a size of 0.2 μm or more did not satisfy 100 particles / ml or less.

【００４４】比較例２ 実施例１と同じ、Ａｌ，Ｔｉ，Ｍｇ及びＣｌを主成分と
するチーグラー系触媒（固体触媒成分（Ａ））を用い、
第２目の重合器の水素を対エチレン濃度比０．０５モル
／モルとした以外は実施例１と同様に、ヘキサン中でエ
チレンとブテン−１を連続重合する二段重合法により、
重合パウダーを得た。重合パウダーを、酸化防止剤、中
和剤、紫外線吸収剤等一切使用せずに無添加で５０ｍｍ
φ押出機にて造粒し、ポリエチレン樹脂を得た。該ポリ
エチレン樹脂は密度が０．９５５ｇ／ｃｍ3であり、１
９０℃、２１．６Ｋｇ荷重のメルトフローレートが８．
５ｇ／１０分であり、ＧＰＣより求められるＭｗ／Ｍｎ
が１３．５であり、１９０℃の溶融張力が１４ｇ、沸騰
ノルマルヘキサン抽出量が０．０８％であり、灰分量が
２０ＰＰＭであり、含有塩素量が９ＰＰＭであった。該
ポリエチレン樹脂を実施例１と同様に大型ブロー成形し
た。得られた容器を用いて、上記した低温落下試験、金
属不純物濃度及び微粒子数の測定を行った。Comparative Example 2 A Ziegler catalyst (solid catalyst component (A)) containing Al, Ti, Mg and Cl as main components was used in the same manner as in Example 1.
A two-stage polymerization method of continuously polymerizing ethylene and butene-1 in hexane in the same manner as in Example 1 except that the hydrogen in the second polymerization reactor was set to a concentration ratio of ethylene to 0.05 mol / mol.
A polymerization powder was obtained. 50mm without addition of polymerized powder without using any antioxidant, neutralizer, UV absorber, etc.
Granulation was performed using a φ extruder to obtain a polyethylene resin. The polyethylene resin has a density of 0.955 g / cm 3 ,
The melt flow rate at 90 ° C. under a load of 21.6 Kg is 8.
5 g / 10 min, Mw / Mn determined by GPC
Was 13.5, the melt tension at 190 ° C. was 14 g, the amount of boiling normal hexane extracted was 0.08%, the ash content was 20 PPM, and the chlorine content was 9 PPM. The polyethylene resin was subjected to large blow molding in the same manner as in Example 1. Using the obtained container, the above-mentioned low-temperature drop test, the measurement of the metal impurity concentration and the number of fine particles were performed.

【００４５】表１に示すように、落下強度は２．０ｍと
低いものであった。金属不純物濃度は０．０１ＰＰＢ以
上の濃度となる金属がなく、保存中の微粒子の増加も少
なかった。As shown in Table 1, the drop strength was as low as 2.0 m. There was no metal having a metal impurity concentration of 0.01 PPB or more, and there was little increase in fine particles during storage.

【００４６】比較例３ 実施例１と同じ、Ａｌ，Ｔｉ，Ｍｇ及びＣｌを主成分と
するチーグラー系触媒（固体触媒成分（Ａ））を用い、
ただし、ヘキサン中の水分を１５ＰＰＭに調節した以外
は実施例１と同様に、ヘキサン中でエチレンとブテン−
１を連続重合する二段重合法により、ポリエチレン樹脂
を得た。該ポリエチレン樹脂は密度が０．９５５ｇ／ｃ
ｍ3であり、１９０℃、２１．６Ｋｇ荷重のメルトフロ
ーレートが４．６ｇ／１０分であり、ＧＰＣより求めら
れるＭｗ／Ｍｎが１２．７であり、１９０℃の溶融張力
が２６ｇ、沸騰ノルマルヘキサン抽出量が０．０９％で
あり、灰分量が６８ＰＰＭであり、含有塩素量が１９Ｐ
ＰＭであった。該ポリエチレン樹脂を中和剤及び酸化防
止剤等を一切使用せずに、実施例１と同様に大型ブロー
成形した。得られた容器を用いて、上記した低温落下試
験、金属不純物濃度及び微粒子数の測定を行った。Comparative Example 3 A Ziegler catalyst (solid catalyst component (A)) containing Al, Ti, Mg and Cl as main components was used in the same manner as in Example 1.
However, in the same manner as in Example 1 except that the water content in hexane was adjusted to 15 PPM, ethylene and butene-
A polyethylene resin was obtained by a two-stage polymerization method in which 1 was continuously polymerized. The polyethylene resin has a density of 0.955 g / c.
m 3 , melt flow rate at 190 ° C. under a load of 21.6 kg was 4.6 g / 10 min, Mw / Mn determined by GPC was 12.7, melt tension at 190 ° C. was 26 g, boiling normal Hexane extraction amount is 0.09%, ash content is 68PPM, chlorine content is 19P
PM. The polyethylene resin was subjected to large blow molding in the same manner as in Example 1 without using any neutralizing agent, antioxidant or the like. Using the obtained container, the above-mentioned low-temperature drop test, the measurement of the metal impurity concentration and the number of fine particles were performed.

【００４７】表１に示すように、落下強度は３．２ｍ以
上であった。しかし、金属不純物濃度はＡｌが０．２５
ＰＰＢとなった。保存中の微粒子の増加は少なかった。As shown in Table 1, the drop strength was 3.2 m or more. However, the metal impurity concentration was 0.25 for Al.
It became PPB. The increase in fine particles during storage was small.

【００４８】[0048]

【表１】 [Table 1]

【００４９】[0049]

【発明の効果】大型高純度薬品容器として本発明のポリ
エチレン樹脂を使用した場合に、薬品による該樹脂の溶
出物や劣化物及び金属不純物等の汚染物質を極力抑える
ため、超ＬＳＩの微細化に対応できるクリーンな容器を
提供できる。さらに、落下強度に優れるため、繰り返し
の使用ができる。As described above, when the polyethylene resin of the present invention is used as a large-sized high-purity chemical container, contaminants such as leaching, deterioration and metal impurities of the resin due to the chemical are suppressed as much as possible. A clean container that can be provided can be provided. Furthermore, since it has excellent drop strength, it can be used repeatedly.

【００５０】[0050]

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 以下の（１）〜（６）の特性を有する、
内容積が５０リットル以上の大型高純度薬品容器用ポリ
エチレン樹脂。 （１）密度（ＪＩＳ Ｋ６７６０−１９８１）が０．９
４〜０．９７ｇ／ｃｍ3、（２）１９０℃、２１．６Ｋ
ｇ荷重のメルトフローレート（ＪＩＳ Ｋ７２１０−１
９７６、条件７）が１〜１５ｇ／１０分、（３）ゲルパ
ーミエーション・クロマトグラフィー（ＧＰＣ）より求
められる重量平均分子量（Ｍｗ）と数平均分子量（Ｍ
ｎ）の比（Ｍｗ／Ｍｎ）が８〜１５、（４）１９０℃に
おける溶融張力が１５〜６５ｇ、（５）沸騰ノルマルヘ
キサン抽出量が０．１重量％以下、（６）灰分量が５０
ＰＰＭ以下である1. It has the following characteristics (1) to (6):
Polyethylene resin for large high-purity chemical containers with an inner volume of 50 liters or more. (1) Density (JIS K6760-1981) is 0.9
4-0.97 g / cm 3 , (2) 190 ° C., 21.6K
Melt flow rate of g load (JIS K7210-1)
976, condition 7) is 1 to 15 g / 10 min, (3) weight average molecular weight (Mw) and number average molecular weight (M) determined by gel permeation chromatography (GPC).
n) the ratio (Mw / Mn) is 8 to 15, (4) the melt tension at 190 ° C. is 15 to 65 g, (5) the amount of boiling normal hexane extracted is 0.1% by weight or less, and (6) the ash content is 50%.
Less than or equal to PPM 【請求項２】 含有塩素量が１５ＰＰＭ以下である請求
項第１項に記載の大型高純度薬品容器用ポリエチレン樹
脂。2. The polyethylene resin for a large high-purity chemical container according to claim 1, wherein the chlorine content is 15 PPM or less. 【請求項３】 １９０℃、２１．６Ｋｇ荷重のメルトフ
ローレート（ＪＩＳ Ｋ７２１０−１９７６、条件７、
ＨＬＭＦＲと記す、単位ｇ／１０分）と１９０℃におけ
る溶融張力（ＭＴと記す、単位ｇ）が下記の、 ＬｏｇＭＴ≧−０．４５５×ＬｏｇＨＬＭＦＲ＋１．６
４ なる関係を満たすことを特徴とする請求項第１項または
第２項に記載の大型高純度薬品容器用ポリエチレン樹
脂。3. A melt flow rate at 190 ° C. under a load of 21.6 kg (JIS K7210-1976, condition 7,
The melt tension at 190 ° C. (unit: g, expressed as MT) is as follows: Log MT ≧ −0.455 × Log HLMFR + 1.6.
4. The polyethylene resin for a large-scale high-purity chemical container according to claim 1, wherein the following relationship is satisfied. 【請求項４】 （Ａ）中和剤として１５０ＰＰＭ以下の
脂肪酸金属塩類および／又は（Ｂ）酸化防止剤として８
００ＰＰＭ以下のフェノール系酸化防止剤を添加してな
ることを特徴とする請求項第１項から第３項に記載の大
型高純度薬品容器用ポリエチレン樹脂。4. A metal salt of a fatty acid of 150 PPM or less (A) as a neutralizing agent and / or (B) 8 as an antioxidant.
The polyethylene resin for a large high-purity chemical container according to any one of claims 1 to 3, wherein a phenolic antioxidant of 00 PPM or less is added. 【請求項５】 請求項第１項から第４項に記載のポリエ
チレン樹脂からなる内容積５０リットル以上の大型高純
度薬品容器。5. A large-sized high-purity chemical container comprising the polyethylene resin according to claim 1 and having an inner volume of 50 liter or more.
JP24521697A 1997-09-10 1997-09-10 Polyethylene resin for large-sized vessel for highly pure chemical and vessel Pending JPH1180449A (en)

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JP24521697A JPH1180449A (en) 1997-09-10 1997-09-10 Polyethylene resin for large-sized vessel for highly pure chemical and vessel

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JPH1180449A true JPH1180449A (en) 1999-03-26

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007022610A (en) * 2005-07-20 2007-02-01 Aicello Chemical Co Ltd Low foaming polyethylene container
JP2009138122A (en) * 2007-12-07 2009-06-25 Tosoh Corp Polyethylene-based resin composition and blow-molded container comprising the same
JP2015183130A (en) * 2014-03-25 2015-10-22 日本ポリエチレン株式会社 Polyethylene for large-sized high purity chemical container
JP2020117615A (en) * 2019-01-23 2020-08-06 東洋紡株式会社 Polyimide acid composition, method for producing polyimide acid composition and method for producing polyimide
US11693321B2 (en) 2016-03-31 2023-07-04 Fujifilm Corporation Treatment liquid for manufacturing semiconductor, storage container storing treatment liquid for manufacturing semiconductor, pattern forming method, and method of manufacturing electronic device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007022610A (en) * 2005-07-20 2007-02-01 Aicello Chemical Co Ltd Low foaming polyethylene container
JP2009138122A (en) * 2007-12-07 2009-06-25 Tosoh Corp Polyethylene-based resin composition and blow-molded container comprising the same
JP2015183130A (en) * 2014-03-25 2015-10-22 日本ポリエチレン株式会社 Polyethylene for large-sized high purity chemical container
US11693321B2 (en) 2016-03-31 2023-07-04 Fujifilm Corporation Treatment liquid for manufacturing semiconductor, storage container storing treatment liquid for manufacturing semiconductor, pattern forming method, and method of manufacturing electronic device
US11892775B2 (en) 2016-03-31 2024-02-06 Fujifilm Corporation Storage container storing treatment liquid for manufacturing semiconductor
JP2020117615A (en) * 2019-01-23 2020-08-06 東洋紡株式会社 Polyimide acid composition, method for producing polyimide acid composition and method for producing polyimide

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