JPH1017729A - Container for high-purity chemical - Google Patents
Container for high-purity chemicalInfo
- Publication number
- JPH1017729A JPH1017729A JP17459796A JP17459796A JPH1017729A JP H1017729 A JPH1017729 A JP H1017729A JP 17459796 A JP17459796 A JP 17459796A JP 17459796 A JP17459796 A JP 17459796A JP H1017729 A JPH1017729 A JP H1017729A
- Authority
- JP
- Japan
- Prior art keywords
- container
- polyethylene
- density
- purity
- copolymer
- 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.)
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- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体装置産業分
野や精密工業部品分野等において、例えば、部品の洗浄
用用途に使用される高純度薬品用容器に好適で、特に、
高純度薬品を充填した場合、その機械強度の経時低下が
少なく、薬品中への微粒子の発生が少ないポリエチレン
容器に関するものである。The present invention is suitable for use in high purity chemical containers used for cleaning components in the semiconductor device industry, precision industrial parts, and the like.
The present invention relates to a polyethylene container which, when filled with a high-purity chemical, has little decrease in mechanical strength with time and little generation of fine particles in the chemical.
【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急速に高まっている。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
路の製造に必要不可欠の薬品として使用されている。例
えば、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、乾燥用等用途として、硫酸、塩酸、硝酸、
弗化水素酸、弗化アンモニウム、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、ＤＭＳＯ、
ＮＭＰ、ＥＣＡ、乳酸エチルなどが用いられている。従
来、これらの高純度薬品用容器材料としては、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、高純度薬品を充填する
と、従来のポリエチレン樹脂製容器では、経時で容器の
機械強度が低下し、長期間の使用が困難であった。2. Description of the Related Art In recent years, demand for high-purity chemicals has been rapidly increasing with the remarkable development of the field of electronics industry. High-purity chemicals are used as indispensable chemicals for manufacturing electronic circuits such as large-scale integrated LSIs. For example, for cleaning / etching wafers, etching wiring / insulating films, cleaning jigs, developing solutions, resist diluents, resist stripping solutions, and drying applications, such as sulfuric acid, hydrochloric acid, and nitric acid.
Hydrofluoric acid, ammonium fluoride, aqueous hydrogen peroxide, isopropyl alcohol, xylene, TMAH, methanol,
Acetic acid, phosphoric acid, aqueous ammonia, PGMEA, DMSO,
NMP, ECA, ethyl lactate and the like are used. Conventionally, polyethylene resin has been used as a container material for these high-purity chemicals in terms of chemical resistance, impact resistance, price, and the like. However, when filled with a high-purity chemical, in a conventional polyethylene resin container, the mechanical strength of the container decreases over time, and it has been difficult to use the container for a long time.
【０００３】ポリエチレン樹脂製容器の耐薬品性を増加
させる方法としては、ポリエチレン樹脂を製造する際
に、重合反応に使用する触媒の活性効率を向上させ、触
媒系から発生する金属残さ等を減少させる方法や、重合
の際、低分子量成分の副生を低減させる方法が考えられ
るが、従来の技術では困難であった。また、酸化防止剤
等を添加する方法が知られているが、薬品中への微粒子
の発生原因となるため、好ましくない。[0003] As a method of increasing the chemical resistance of a polyethylene resin container, when producing a polyethylene resin, the activity efficiency of a catalyst used in a polymerization reaction is improved, and a metal residue or the like generated from the catalyst system is reduced. Although a method and a method of reducing by-products of low molecular weight components during polymerization are conceivable, conventional techniques have been difficult. In addition, a method of adding an antioxidant or the like is known, but this is not preferable because it causes generation of fine particles in the chemical.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、高純度薬品
の容器として使用して、耐薬品性が良好な、すなわち、
機械強度の長期安定性に優れ、薬品中への微粒子の発生
の少ない容器の提供を目的とするものである。DISCLOSURE OF THE INVENTION The present invention is used as a container for high purity chemicals and has good chemical resistance,
It is an object of the present invention to provide a container having excellent long-term stability of mechanical strength and having less generation of fine particles in a medicine.
【０００５】[0005]
【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、特定のポリエチレンまたはエチレン・α−オ
レフィン共重合体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。As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific polyethylene or ethylene / α-olefin copolymer, and have reached the present invention. did.
【０００６】即ち、本発明は、（ａ）密度が０．９１５
〜０．９８０ｇ／ｃｍ3、（ｂ）ＪＩＳ Ｋ６７６０
（１９８１年）に従って、１９０℃、２１６０ｇの荷重
下で測定されたメルトフローレート（ＭＦＲ）が０．０
３〜５０ｇ／１０分の範囲であり、（ｃ）重量平均分子
量（Ｍw）と数平均分子量（Ｍn）の比（Ｍw／Ｍn）が３
以下、（ｄ）示差走査型熱量計（以下ＤＳＣと言う）に
より測定される融点が一つであるポリエチレンまたはエ
チレンと炭素数３〜２０のα−オレフィンとの共重合体
からなることを特徴とする高純度薬品用容器に関するも
のである。That is, according to the present invention, (a) the density is 0.915
０．９0.980 g / cm 3 , (b) JIS K6760
(1981), the melt flow rate (MFR) measured at 190 ° C under a load of 2160 g is 0.0
(C) the ratio ( Mw / Mn ) of the weight average molecular weight ( Mw ) to the number average molecular weight ( Mn ) is 3
Hereinafter, (d) it is characterized by comprising polyethylene or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, the melting point of which is one measured by a differential scanning calorimeter (hereinafter, referred to as DSC). The present invention relates to a container for high-purity chemicals.
【０００７】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【０００８】本発明において、上記ポリエチレンないし
エチレン・α−オレフィン共重合体の密度が０．９１５
ｇ／ｃｍ3未満では、薬品に溶出し易い分岐が多い成分
が増加するため、耐薬品性が低下する。ＭＦＲが０．０
３ｇ／１０分未満では、押出時の負荷が大きく成形性が
低下し、５０ｇ／１０分を超えると製品の強度が低下す
る。Ｍw／Ｍnが３を超えると組成分布が広くなるため耐
薬品性が低下する。さらに、ＤＳＣで測定される融点が
複数になると組成分布が広くなり、薬品に溶出し易い分
岐が多い成分が増加して耐薬品性が低下する。In the present invention, the polyethylene or ethylene / α-olefin copolymer has a density of 0.915
If it is less than g / cm 3 , components having many branches that are easily eluted with the chemical will increase, and the chemical resistance will decrease. MFR is 0.0
If the amount is less than 3 g / 10 minutes, the load at the time of extrusion is large and the moldability is reduced. If the amount exceeds 50 g / 10 minutes, the strength of the product is reduced. When M w / M n exceeds 3, the composition distribution is widened and the chemical resistance is reduced. Further, when the melting point measured by DSC becomes plural, the composition distribution becomes wide, and the components having many branches which are easily eluted with the chemical increase, and the chemical resistance decreases.
【０００９】このようなポリエチレンないしエチレン・
α−オレフィン共重合体は、１個または２個のシクロペ
ンタジエニル骨格を有する配位子が周期律表４〜６族の
遷移金属、好ましくは、チタン、ジルコニウムまたはハ
フニウムに配位した公知のメタロセン化合物とアルモキ
サンとを組み合わせた触媒、または、上記メタロセン化
合物とこれと反応してイオン性の錯体を形成するイオン
性化合物および有機金属化合物を組み合わせた触媒を用
いて、ポリエチレンないしエチレン・α−オレフィンを
製造することができる。[0009] Such polyethylene or ethylene.
The α-olefin copolymer is a known one in which a ligand having one or two cyclopentadienyl skeletons is coordinated to a transition metal of Groups 4 to 6 of the periodic table, preferably titanium, zirconium or hafnium. Using a catalyst in which a metallocene compound and an alumoxane are combined, or a catalyst in which an ionic compound and an organometallic compound which form an ionic complex by reacting with the metallocene compound are combined with polyethylene, ethylene or α-olefin Can be manufactured.
【００１０】上記触媒を用いたポリエチレンないしエチ
レン・α−オレフィン共重合体の製造方法としては、気
相法、スラリ−法、溶液法、高圧法などを挙げることが
できる。The method for producing a polyethylene or ethylene / α-olefin copolymer using the above catalyst includes a gas phase method, a slurry method, a solution method and a high pressure method.
【００１１】溶液法としては、重合条件は以下のように
挙げられる。重合温度は共重合体が溶液状態であること
及び生産性を上げることを考慮して１２０℃以上である
ことが必要である。重合温度の上限は特に限定されない
が、分子量低下の原因となる連鎖反応を抑え、かつ触媒
効率を低下させないために３００℃以下が好ましい。ま
た、重合時の圧力については特に限定されないが、生産
性をあげるために大気圧以上が好ましい。In the solution method, the polymerization conditions are as follows. The polymerization temperature needs to be 120 ° C. or higher in consideration of the fact that the copolymer is in a solution state and that productivity is increased. The upper limit of the polymerization temperature is not particularly limited, but is preferably 300 ° C. or lower in order to suppress a chain reaction that causes a decrease in molecular weight and not to lower the catalyst efficiency. The pressure during the polymerization is not particularly limited, but is preferably at least atmospheric pressure in order to increase the productivity.
【００１２】高圧法としては、重合条件は以下のように
挙げられる。重合温度は共重合体が溶液状態であること
及び生産性を上げることを考慮して１２０℃以上である
ことが必要である。重合温度の上限は特に限定されない
が、分子量低下の原因となる連鎖移動反応を抑え、かつ
触媒効率を低下させないために３００℃以下が好まし
い。また、重合時の圧力についは、特に限定されないが
高圧法プロセスにおいて安定的に重合条件が得られる５
００ｋｇｆ／ｃｍ2以上が好ましい。In the high-pressure method, the polymerization conditions are as follows. The polymerization temperature needs to be 120 ° C. or higher in consideration of the fact that the copolymer is in a solution state and that productivity is increased. Although the upper limit of the polymerization temperature is not particularly limited, it is preferably 300 ° C. or lower in order to suppress a chain transfer reaction that causes a decrease in molecular weight and not to lower catalyst efficiency. The pressure during the polymerization is not particularly limited, but the polymerization conditions can be stably obtained in the high-pressure process.
It is preferably at least 00 kgf / cm 2 .
【００１３】また、気相法としては、共重合体が粉体状
態であることから高温は好ましくなく、１００℃以下で
あることが必要である。重合温度の下限は特に限定され
ないが、生産性を上げるために５０℃以上が好ましい。In the gas phase method, high temperatures are not preferred because the copolymer is in a powder state, and it is necessary that the temperature be 100 ° C. or less. The lower limit of the polymerization temperature is not particularly limited, but is preferably 50 ° C. or higher in order to increase productivity.
【００１４】また、スラリー法としては、重合条件は以
下のように挙げられる。重合温度は生産性を上げること
を考慮して１００℃以下であることが必要である。ま
た、重合圧力については、特に限定されないが、生産性
を上げるために大気圧以上が好ましい。The polymerization conditions for the slurry method are as follows. The polymerization temperature needs to be 100 ° C. or lower in consideration of increasing productivity. The polymerization pressure is not particularly limited, but is preferably atmospheric pressure or higher in order to increase productivity.
【００１５】炭素数３〜２０のα−オレフィンとして
は、プロピレン、ブテン−１、４−メチル−ペンテン−
１、３−メチル−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−１などを挙げることが出来る。As the α-olefin having 3 to 20 carbon atoms, propylene, butene-1,4-methyl-pentene-
1,3-methyl-butene-1, pentene-1, hexene-1, heptene-1, 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-1 and the like.
【００１６】本発明におけるポリエチレンないしエチレ
ン・α−オレフィン共重合体は、無添加、または、必要
に応じて酸化防止剤、耐候安定剤、帯電防止剤、滑剤、
ブロッキング防止剤、有機・無機顔料等、通常ポリオレ
フィンに使用される添加剤を添加してもかまわない。樹
脂中に上記の添加剤を混合する方法は特に制限されるも
のではないが、例えば、重合後のペレットの造粒工程で
直接添加する方法、また、予め高濃度のマスターバッチ
を作成し、これを成形時にドライブレンドする方法等が
挙げられる。The polyethylene or ethylene / α-olefin copolymer in the present invention is free of additives or, if necessary, an antioxidant, a weather stabilizer, an antistatic agent, a lubricant,
Additives usually used for polyolefins, such as anti-blocking agents and organic / inorganic pigments, may be added. The method of mixing the above-mentioned additives in the resin is not particularly limited, for example, a method of directly adding in a granulation step of pellets after polymerization, or a method of preparing a high-concentration master batch in advance, And dry blending at the time of molding.
【００１７】また、加工性、製品強度をさらに高めるた
めに、本発明のポリエチレンないしエチレン・α−オレ
フィン共重合体は、ポリオレフィン樹脂等とブレンドし
て用いてもよく、内層に本ポリエチレンないしエチレン
・α−オレフィン共重合体を使用し、外層にポリオレフ
ィン樹脂等を用いて多層容器としてもよい。In order to further enhance processability and product strength, the polyethylene or ethylene / α-olefin copolymer of the present invention may be used by blending with a polyolefin resin or the like. A multi-layer container may be formed by using an α-olefin copolymer and using a polyolefin resin or the like for the outer layer.
【００１８】ブレンドして用いる場合には、加工性、耐
薬品性を考えると、本発明のポリエチレンないしエチレ
ン・α−オレフィン共重合体のブレンド量は５０重量％
以上が好ましい。When used as a blend, the blending amount of the polyethylene or ethylene / α-olefin copolymer of the present invention is 50% by weight in consideration of processability and chemical resistance.
The above is preferred.
【００１９】外層に使用される材料は、容器の形状にで
きるものなら特に限定されないが、成形性、製品強度を
考えるとＪＩＳ Ｋ７１０６（１９８２年）で規定され
た曲げこわさが６０００ｋｇｆ／ｃｍ2以上、ＪＩＳ
Ｋ７１１０（１９８４年）で規定されたアイゾット衝撃
値が１０ｋｇｆ／ｃｍ3以上であるポリオレフィン樹脂
が好ましく、特に、強度、加工性の面から高密度ポリエ
チレンが好適である。本発明のポリエチレンないしエチ
レン・α−オレフィン共重合体と高密度ポリエチレンと
のブレンド方法については、特に限定されるものではな
いが、具体的には、押出機、ブレベンダー、バンバリー
ミキサー等を用いて製造できる。The material used for the outer layer is not particularly limited as long as it can be formed into the shape of a container. Considering formability and product strength, the bending stiffness specified by JIS K7106 (1982) is 6000 kgf / cm 2 or more. JIS
Polyolefin resins having an Izod impact value specified by K7110 (1984) of 10 kgf / cm 3 or more are preferable, and high-density polyethylene is particularly preferable in terms of strength and workability. The method for blending the polyethylene or ethylene / α-olefin copolymer of the present invention with a high-density polyethylene is not particularly limited, but specifically, using an extruder, a Brebender, a Banbury mixer, or the like. Can be manufactured.
【００２０】また、本発明の高純度薬品用容器の製造方
法は、特に限定されるものではないが、例えば、吹込み
成形や回転成形等によって製造できる。吹込み成形で
は、押出機により樹脂を溶融して単層または多層構造の
筒状のパリソンに押出し、押出されたパリソンを金型で
挟んで、ブローピンより加圧ガスを吹き込み、冷却し、
成形できる。また、回転成形では、樹脂粉末を金型内に
投入し、その金型を回転させながら外部より加熱し、樹
脂を溶融させて金型内部に付着させ、冷却後、成形品を
取り出すことによって成形できる。The method for producing the high-purity chemical container of the present invention is not particularly limited, but it can be produced by, for example, blow molding or rotational molding. In blow molding, the resin is melted by an extruder and extruded into a single-layer or multi-layer cylindrical parison, the extruded parison is sandwiched by a mold, a pressurized gas is blown from a blow pin, and cooled.
Can be molded. In the case of rotational molding, the resin powder is put into a mold, heated from the outside while rotating the mold, the resin is melted and adhered inside the mold, and after cooling, the molded product is taken out. it can.
【００２１】[0021]
【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.
【００２２】Ｍw／Ｍn、融点、密度、耐薬品性（落下強
度、引張強度、微粒子数）の測定は、以下の方法によっ
て測定した。Measurements of M w / M n , melting point, density, and chemical resistance (drop strength, tensile strength, number of fine particles) were measured by the following methods.
【００２３】Ｍw／Ｍnは、ウオーターズ社製１５０Ｃ
ＡＬＣ／ＧＰＣ（カラム：東ソー社製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Ｍnを測定し、Ｍw
／Ｍnを算出した。なお、東ソー社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。M w / M n is 150C manufactured by Waters.
ALC / GPC (column: GMHHR-H manufactured by Tosoh Corporation)
(S), solvent: 1,2,4-trichlorobenzene) using, by the GPC method, was measured M w and M n, M w
/ Mn was calculated. The column elution volume was calibrated by universal calibration using standard polystyrene manufactured by Tosoh Corporation.
【００２４】融点（℃）は、示差走査型熱量計、パーキ
ンエルマー社製「ＤＳＣ−７」を用いて測定した。装置
内で試料を２００℃で５分間溶融させた後に、１０℃／
分の冷却速度で３０℃まで冷却したものについて、再度
１０℃／分の昇温速度で昇温させたときに得られる吸熱
曲線の最大ピークの位置の温度を融点とした。The melting point (° C.) was measured using a differential scanning calorimeter, “DSC-7” manufactured by PerkinElmer. After the sample was melted at 200 ° C for 5 minutes in the apparatus, 10 ° C /
The temperature at the position of the maximum peak of the endothermic curve obtained when the material cooled to 30 ° C. at a cooling rate of 10 minutes per minute was taken as the melting point.
【００２５】密度は、ＪＩＳ Ｋ６７６０（１９８１
年）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。耐薬品性については、引張強度と落下強度および
微粒子数によって評価した。 引張強度 成形した内容積５００ｍｌの容器に下記の薬品を各々充
填後、５０℃で一定期間放置した後、薬品を取り出し、
水で洗浄した後、ＪＩＳ Ｋ７１１３（１９８１年）
２号ダンベルを使用して同容器より試験片を作成し、Ｊ
ＩＳ Ｋ７１１３（１９８１年）に準拠して引張試験を
行った。The density is determined according to JIS K6760 (1981)
After immersion in hot water at 100 ° C. for 1 hour, the test piece cooled slowly to room temperature was measured with a density gradient tube kept at 23 ° C. The chemical resistance was evaluated based on tensile strength, drop strength, and the number of fine particles. Tensile strength After filling each of the following chemicals into a molded container with a capacity of 500 ml, leave at 50 ° C. for a certain period, take out the chemicals,
After washing with water, JIS K7113 (1981)
Prepare a test piece from the same container using No. 2 dumbbell,
A tensile test was performed according to IS K7113 (1981).
【００２６】 過酸化水素水：三菱瓦斯化学社製 特級過酸化水素水（３１％） 硝酸 ：和光純薬社製 特級試薬硝酸（６１％） 硫酸 ：和光純薬社製 特級試薬硫酸（９８％） 落下強度 成形した内容積５００ｍｌの容器に各々薬品を充填後、
５０℃で一定期間放置した後、薬品を取り出し、水で洗
浄した後、同容器に水を満液まで充填して、密栓をした
後、３ｍの高さより容器の底面を下にして垂直に落下さ
せ、１０個の容器の落下試験を行い、その内の割れた数
を求めた。薬品は、上記の引張試験と同様のものを用い
た。Hydrogen peroxide: Special grade hydrogen peroxide (31%) manufactured by Mitsubishi Gas Chemical Company Nitric acid: Special grade nitric acid (61%) manufactured by Wako Pure Chemical Co. Sulfuric acid: Special grade reagent sulfuric acid (98%) manufactured by Wako Pure Chemical Industries Drop strength After filling each of the molded 500ml containers with chemicals,
After leaving at 50 ° C for a certain period of time, take out the medicine, wash it with water, fill the container with water until it is full, seal it, and drop it vertically with the bottom of the container down from a height of 3 m. Then, a drop test was performed on 10 containers, and the number of cracks was determined. The same chemicals as used in the above tensile test were used.
【００２７】微粒子数の測定 ０．１μｍのフィルターで濾過した純水で容器を十分洗
浄した後、容器内に純水を充填した。これを４０℃で一
定期間静置した後、ＨＩＡＣ／ＲＯＹＣＯ液体微粒子カ
ウンター・シリーズ４１００で、０．５μｍ以上の微粒
子の数を測定した。全ての操作は、クラス１０００のク
リーンルーム内で行った。Measurement of Number of Fine Particles After the container was sufficiently washed with pure water filtered through a 0.1 μm filter, the container was filled with pure water. This was allowed to stand at 40 ° C. for a certain period, and the number of fine particles having a size of 0.5 μm or more was measured with a HIAC / ROYCO liquid fine particle counter series 4100. All operations were performed in a class 1000 clean room.
【００２８】実施例１ メタロセン触媒を用いて重合された、密度が０．９４４
ｇ／ｃｍ3、ＭＦＲが０．１９ｇ／１０分、Ｍw／Ｍ
n１．９であるエチレン・ヘキセン−１共重合体を使用
し、吹込み空気口に０．２μｍのフィルターを装着し
て、下記の条件で厚み１．５ｍｍ、容器容積５００ｍｌ
の容器を成形した。この容器を用いて耐薬品性の評価と
して引張試験、落下試験および微粒子数の測定を行い、
その結果を表１、表２、および表４に示した。Example 1 A polymer having a density of 0.944 polymerized using a metallocene catalyst
g / cm 3 , MFR 0.19 g / 10 min, M w / M
n 1.9 ethylene hexene-1 copolymer was used, a 0.2 μm filter was attached to the blowing air port, the thickness was 1.5 mm, and the container volume was 500 ml under the following conditions.
Was molded. Using this container, a tensile test, a drop test and a measurement of the number of fine particles were performed as evaluation of chemical resistance,
The results are shown in Tables 1, 2 and 4.
【００２９】 比較例１ チーグラー型触媒を用いて重合された、高密度ポリエチ
レン（ＭＦＲ０．３５ｇ／１０分、密度０．９５６ｇ／
ｃｍ3、Ｍw／Ｍn１１．７）を使用した以外は実施例１
と同様にして容器を成形し耐薬品性の評価を行った。そ
の結果を表１、表２および表４に示した。[0029] Comparative Example 1 High-density polyethylene (MFR 0.35 g / 10 min, density 0.956 g /
Example 1 except that cm 3 , M w / M n 11.7) was used.
A container was formed in the same manner as described above, and the chemical resistance was evaluated. The results are shown in Tables 1, 2 and 4.
【００３０】比較例２ フィリップス型触媒を用いて重合された、高密度ポリエ
チレン（ＭＦＲ０．１１ｇ／１０分、密度０．９５３ｇ
／ｃｍ3、Ｍw／Ｍn５．５）を使用した以外は実施例１
と同様にして容器を成形し耐薬品性の評価を行った。そ
の結果を表１、表２、表４に示した。Comparative Example 2 High-density polyethylene (MFR 0.11 g / 10 min, density 0.953 g) polymerized using a Philips type catalyst
/ Cm 3 , M w / M n 5.5)
A container was formed in the same manner as described above, and the chemical resistance was evaluated. The results are shown in Tables 1, 2 and 4.
【００３１】実施例２ メタロセン型触媒を用いて重合された、密度が０．９４
６ｇ／ｃｍ3、ＭＦＲが３．６４ｇ／１０分、Ｍw／Ｍn
１．８であるエチレン・ヘキセン−１共重合体を内層と
し、外層として高密度ポリエチレン（東ソー株式会社
製、商品名『ニポロンハード』８３００Ａ、ＭＦＲ０．
３５ｇ／１０分、密度０．９５４ｇ／ｃｍ3）を使用
し、吹き込み空気口に０．２μｍのフィルターを装着し
て、下記の条件で内層厚み０．５ｍｍ、外層厚み１．０
ｍｍ、容器容量５００ｍｌの容器を成形した。この容器
を用いて落下試験および微粒子数の測定を行った。その
結果を表３、表４に示した。Example 2 Polymerized with a metallocene type catalyst and having a density of 0.94
6 g / cm 3 , MFR 3.64 g / 10 min, M w / M n
The ethylene / hexene-1 copolymer of 1.8 is used as the inner layer and the outer layer is made of high density polyethylene (manufactured by Tosoh Corporation, trade name "Nipolon Hard" 8300A, MFR0.
35 g / 10 min, density 0.954 g / cm 3 ), a filter of 0.2 μm was attached to the blowing air port, and the inner layer thickness was 0.5 mm and the outer layer thickness was 1.0 under the following conditions.
mm, a container having a container capacity of 500 ml was molded. Using this container, a drop test and measurement of the number of fine particles were performed. The results are shown in Tables 3 and 4.
【００３２】 実施例３ メタロセン型触媒を用いて重合された共重合体を、密度
が０．９２０ｇ／ｃｍ3、ＭＦＲが２．３０ｇ／１０
分、Ｍw／Ｍn１．９であるエチレン・ヘキセン−１共重
合体とした以外は、実施例２と同様にして容器を成形し
て落下試験および微粒子数の測定を行った。その結果を
表３および表４に示した。[0032] Example 3 A copolymer polymerized using a metallocene catalyst was prepared to have a density of 0.920 g / cm 3 and an MFR of 2.30 g / 10.
A container was molded in the same manner as in Example 2 except that an ethylene / hexene-1 copolymer having Mw / Mn of 1.9 was used, and a drop test and the number of fine particles were measured. The results are shown in Tables 3 and 4.
【００３３】比較例３ 実施例２のメタロセン型触媒を用いて重合されたエチレ
ン・ヘキセン−１共重合体の代わりに、チーグラー型触
媒を用いて重合された、高密度ポリエチレン（ＭＦＲ
０．３５ｇ／１０分、密度０．９５６ｇ／ｃｍ3、Ｍw／
Ｍn１１．７）を使用した以外は実施例２と同様にして
容器を成形し落下試験および微粒子数の測定を行った。
その結果を表３および表４に示した。Comparative Example 3 A high-density polyethylene (MFR) polymerized using a Ziegler-type catalyst instead of the ethylene-hexene-1 copolymer polymerized using the metallocene-type catalyst of Example 2
0.35 g / 10 min, density 0.956 g / cm 3 , M w /
A container was formed in the same manner as in Example 2 except that Mn 11.7) was used, and a drop test and the number of fine particles were measured.
The results are shown in Tables 3 and 4.
【００３４】比較例４ 比較例３のチーグラー型触媒を用いて重合された高密度
ポリエチレンの代わりにフィリップス型触媒を用いて重
合された、高密度ポリエチレン（ＭＦＲ０．１１ｇ／１
０分、密度０．９５３ｇ／ｃｍ3、Ｍw／Ｍn５．５）を
使用した以外は比較例３と同様にして容器を成形し落下
試験および微粒子数の測定を行った。その結果を表３お
よび表４に示した。Comparative Example 4 A high-density polyethylene (MFR 0.11 g / 1) polymerized using a Phillips catalyst instead of the high-density polyethylene polymerized using the Ziegler catalyst of Comparative Example 3
A container was molded in the same manner as in Comparative Example 3 except that 0 minutes, a density of 0.953 g / cm 3 and M w / M n 5.5) were used, and a drop test and a measurement of the number of fine particles were performed. The results are shown in Tables 3 and 4.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】[0037]
【表３】 [Table 3]
【００３８】[0038]
【表４】 [Table 4]
【００３９】[0039]
【発明の効果】本発明によって得られる容器は、従来の
ポリエチレン容器に比べ、高純度薬品を充填した場合、
耐薬品性に優れ、その機械強度を長期間安定して保持す
ることが可能であり、半導体装置分野や精密工業部品分
野等に於いて部品の洗浄、エッチング等また、医療用、
食品用に要求される純度の高い溶剤の容器に好適に利用
される。According to the present invention, the container obtained by the present invention, when filled with a high-purity chemical as compared with a conventional polyethylene container,
It has excellent chemical resistance and can maintain its mechanical strength stably for a long time. Cleaning and etching of parts in the field of semiconductor devices and precision industrial parts, etc.
It is suitably used for containers of high-purity solvents required for foods.
【００４０】[0040]
Claims (1)
ｃｍ3、（ｂ）ＪＩＳ Ｋ６７６０（１９８１年）に従
って、１９０℃，２１６０ｇの荷重下で測定されたメル
トフローレート（ＭＦＲ）が０．０３〜５０ｇ／１０
分、（ｃ）重量平均分子量（Ｍw）と数平均分子量
（Ｍn）の比（Ｍw／Ｍn）が３以下、（ｄ）示差走査型
熱量計により測定される融点が一つであるポリエチレン
またはエチレンと炭素数３〜２０のα−オレフィンとの
共重合体からなる高純度薬品用容器。(A) a density of 0.915 to 0.980 g /
cm 3 , (b) a melt flow rate (MFR) measured at 190 ° C. under a load of 2160 g according to JIS K6760 (1981) is 0.03 to 50 g / 10
(C) the ratio ( Mw / Mn ) of the weight average molecular weight ( Mw ) to the number average molecular weight ( Mn ) is 3 or less, and (d) the melting point measured by a differential scanning calorimeter is one. A container for high-purity chemicals comprising a certain polyethylene or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17459796A JP3750200B2 (en) | 1996-07-04 | 1996-07-04 | Container for high-purity chemicals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17459796A JP3750200B2 (en) | 1996-07-04 | 1996-07-04 | Container for high-purity chemicals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1017729A true JPH1017729A (en) | 1998-01-20 |
| JP3750200B2 JP3750200B2 (en) | 2006-03-01 |
Family
ID=15981360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17459796A Expired - Fee Related JP3750200B2 (en) | 1996-07-04 | 1996-07-04 | Container for high-purity chemicals |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3750200B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001122239A (en) * | 1999-10-29 | 2001-05-08 | Mitsubishi Gas Chem Co Inc | Transportation container for high purity ammonia water |
| JP2008144180A (en) * | 1998-03-25 | 2008-06-26 | Daikin Ind Ltd | Fluorine-containing elastomer |
-
1996
- 1996-07-04 JP JP17459796A patent/JP3750200B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008144180A (en) * | 1998-03-25 | 2008-06-26 | Daikin Ind Ltd | Fluorine-containing elastomer |
| JP2012211347A (en) * | 1998-03-25 | 2012-11-01 | Daikin Industries Ltd | Method of producing fluorine-containing elastomer |
| JP2001122239A (en) * | 1999-10-29 | 2001-05-08 | Mitsubishi Gas Chem Co Inc | Transportation container for high purity ammonia water |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3750200B2 (en) | 2006-03-01 |
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