JPH1045961A - Resin composition for container for high-purity hydrogen peroxide water - Google Patents
Resin composition for container for high-purity hydrogen peroxide waterInfo
- Publication number
- JPH1045961A JPH1045961A JP20998196A JP20998196A JPH1045961A JP H1045961 A JPH1045961 A JP H1045961A JP 20998196 A JP20998196 A JP 20998196A JP 20998196 A JP20998196 A JP 20998196A JP H1045961 A JPH1045961 A JP H1045961A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- resin composition
- container
- weight
- peroxide water
- 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
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は過酸化水素水用樹脂
組成物に関する。更に詳しくは含有不純物濃度が極めて
低い高純度な品質が要求される半導体製造分野、医療品
分野等に使用される、過酸化水素水による劣化が抑制さ
れた高純度過酸化水素水容器用樹脂組成物に関する。The present invention relates to a resin composition for aqueous hydrogen peroxide. More specifically, a resin composition for a high-purity hydrogen peroxide container, which is used in a semiconductor manufacturing field or a medical product field, which requires extremely low impurity concentration and high purity quality, and is suppressed from being deteriorated by hydrogen peroxide water. About things.
【０００２】[0002]
【従来の技術】半導体製造分野では半導体を形成するシ
リコンウエハの処理を始め多くの工程で、過酸化水素
水、硫酸、ふっ酸、アンモニア水等、種々の高純度薬品
が使用されている。これらの薬品には半導体の歩留まり
低下を引き起こす不純物、微粒子が極めて少ない高純度
な品質が要求される。例えば要求される品質は各金属不
純物の含有量は１．０重量ｐｐｂ未満、０．２μｍ以上
の微粒子が１００個／ｍｌ以下と厳しい。さらには、金
属不純物０．１重量ｐｐｂ未満、０．１μｍ以上の微粒
子が１００個／ｍｌ以下という極めて高い品質が近年要
求されつつある。したがって、これら高純度薬品の品質
を保持し輸送、保存するためには不純物、微粒子の発生
がない容器が要求される。2. Description of the Related Art In the field of semiconductor production, various high-purity chemicals such as aqueous hydrogen peroxide, sulfuric acid, hydrofluoric acid, and aqueous ammonia are used in many processes including the processing of silicon wafers for forming semiconductors. These chemicals are required to be of high purity with a very small amount of impurities and fine particles that cause a decrease in semiconductor yield. For example, the required quality is severe such that the content of each metal impurity is less than 1.0 ppb by weight and the number of fine particles of 0.2 μm or more is 100 particles / ml or less. In addition, extremely high quality, in which the number of fine particles having a metal impurity content of less than 0.1 ppb by weight and 0.1 μm or more is 100 particles / ml or less has been recently required. Therefore, in order to maintain, transport, and preserve the quality of these high-purity chemicals, containers that do not generate impurities and fine particles are required.
【０００３】高純度過酸化水素水の容器材質としては成
形性、価格等の面からポリオレフィンが多く使用されて
おり、中でも特に高密度ポリエチレンもしくはエチレン
・α−オレフィン共重合体が多く使用されている。しか
しながら、従来のポリエチレンもしくはエチレン・α−
オレフィン共重合体を使用する場合、樹脂中の低分子量
のオリゴマー溶出による微粒子発生、添加剤に起因する
微粒子、不純物溶出等が起こり、高純度薬品用容器材質
としては使用に耐えない。このため、これらの問題を解
決するために本発明者らは特開平７−６２１６１号公報
で、ポリオレフィン中のオリゴマー含有量の目安となる
沸騰ｎ−ヘキサンによる抽出した際の抽出量が０．２重
量％以下、ポリオレフィンに対する添加剤の量が全体で
１００重量ｐｐｍ以下であることを特徴とする高品質な
ポリエチレン樹脂組成物からなる過酸化水素水容器を開
示した。[0003] Polyolefin is often used as a container material of high-purity hydrogen peroxide solution from the viewpoint of moldability, cost, etc., and especially high-density polyethylene or ethylene / α-olefin copolymer is particularly used. . However, conventional polyethylene or ethylene α-
When an olefin copolymer is used, the generation of fine particles due to the elution of low molecular weight oligomers in the resin, the generation of fine particles and impurities due to additives, and the like occur, and cannot be used as a high-purity chemical container material. Therefore, in order to solve these problems, the present inventors disclosed in Japanese Patent Application Laid-Open No. 7-62161 that the amount of extraction when boiling n-hexane, which is a measure of the oligomer content in polyolefin, was 0.2%. A hydrogen peroxide water container comprising a high-quality polyethylene resin composition characterized by being not more than 100% by weight and not more than 100% by weight of an additive based on polyolefin is disclosed.
【０００４】また、ポリエチレンもしくはエチレン・α
−オレフィン共重合体は通常、チーグラー触媒もしくは
フィリップス触媒により製造されるが、高純度過酸化水
素水用材質としては特にチーグラー触媒で重合されたポ
リエチレンもしくはエチレン・α−オレフィン共重合体
もしくはそれに改質のために必要な最小限の量の添加剤
を添加した樹脂組成物が好ましい。これはフィリップス
触媒に比べチーグラー触媒で重合されたポリエチレンも
しくはエチレン・α−オレフィン共重合体の方が、樹脂
中に残存している金属触媒の過酸化水素水への溶出が少
ないためである。一方、フィリップス触媒で重合された
ポリエチレンもしくはエチレン・α−オレフィン共重合
体からなる樹脂組成物は樹脂中に残存する金属触媒の過
酸化水素水への溶出が多く、高純度に過酸化水素水を保
持できない。Also, polyethylene or ethylene α
-Olefin copolymers are usually produced with Ziegler catalysts or Phillips catalysts, but as materials for high-purity hydrogen peroxide water, in particular, polyethylene or ethylene / α-olefin copolymers polymerized with Ziegler catalysts or modifications thereof The resin composition to which the minimum amount of additives necessary for the above is added is preferred. This is because polyethylene or ethylene / α-olefin copolymer polymerized with the Ziegler catalyst has less elution of the metal catalyst remaining in the resin into the hydrogen peroxide solution than the Phillips catalyst. On the other hand, a resin composition composed of polyethylene or an ethylene / α-olefin copolymer polymerized with a Phillips catalyst has a large amount of metal catalyst remaining in the resin eluted into aqueous hydrogen peroxide, and the aqueous hydrogen peroxide is highly purified. I can't keep it.
【０００５】しかしながら、チーグラー触媒で重合され
たポリエチレンもしくはエチレン・α−オレフィン共重
合体、あるいはこれによる樹脂組成物を容器材質として
用いる場合でも、過酸化水素水との接触により残存する
触媒が原因で容器が劣化する現象があり、その結果、輸
送、貯蔵中における容器の破損、それに伴う過酸化水素
水の漏洩、更には漏洩した過酸化水素水の急激な分解等
の問題が起こることがあった。[0005] However, even when polyethylene or ethylene / α-olefin copolymer polymerized with a Ziegler catalyst or a resin composition based on the same is used as a container material, the catalyst remaining due to the contact with hydrogen peroxide solution causes a problem. There is a phenomenon that the container deteriorates, and as a result, problems such as breakage of the container during transportation and storage, leakage of the hydrogen peroxide solution accompanying it, and rapid decomposition of the leaked hydrogen peroxide solution may occur. .
【０００６】チーグラー触媒によるポリエチレンもしく
はエチレン・α−オレフィン共重合体あるいはこれによ
る樹脂組成物のこの現象は過酸化水素水を用いたときに
極めて顕著である。例えば薬液としてアンモニア水、ふ
っ酸等を用いた場合はこのような劣化はほとんど起こら
ない。This phenomenon of a Ziegler-catalyzed polyethylene or ethylene / α-olefin copolymer or a resin composition based on the same is extremely remarkable when hydrogen peroxide is used. For example, when ammonia water, hydrofluoric acid or the like is used as a chemical, such deterioration hardly occurs.
【０００７】チーグラー触媒による上記の問題に対して
は、例えばステアリン酸カルシウム等金属石鹸を添加し
た樹脂組成物とすることで解決できるが、このような樹
脂組成物を高純度過酸化水素水用容器に使用した場合、
金属石鹸に由来する金属不純物が過酸化水素水中へ溶出
してしまう。さらに、微粒子も多く発生する。その結
果、これら樹脂組成物は高純度過酸化水素水容器用材質
としては使用できなくなるという問題があった。The above problem caused by the Ziegler catalyst can be solved by using a resin composition to which a metal soap such as calcium stearate is added. However, such a resin composition is used in a container for high-purity hydrogen peroxide. If used,
Metal impurities derived from the metal soap elute into the hydrogen peroxide solution. Further, many fine particles are generated. As a result, there is a problem that these resin compositions cannot be used as a material for a high-purity hydrogen peroxide water container.
【０００８】以上のことから、高純度過酸化水素水の品
質を低下させずかつ過酸化水素水による劣化がないポリ
エチレンもしくはエチレン・α−オレフィン共重合体あ
るいはそれによる樹脂組成物からなる高純度過酸化水素
水容器用樹脂組成物を提供することは困難であった。[0008] From the above, a high-purity peroxide made of polyethylene or an ethylene / α-olefin copolymer or a resin composition thereof without deteriorating the quality of the high-purity hydrogen peroxide solution and not deteriorating due to the hydrogen peroxide solution. It has been difficult to provide a resin composition for a hydrogen oxide water container.
【０００９】[0009]
【発明が解決しようとする課題】本発明は半導体製造用
等極めて高純度な品質を要求される高純度過酸化水素水
を高度に保持し、過酸化水素水による劣化を生じない過
酸化水素水容器用樹脂組成物を提供することにある。SUMMARY OF THE INVENTION The present invention relates to a hydrogen peroxide solution which is capable of maintaining high purity hydrogen peroxide solution which is required to have extremely high purity, such as for semiconductor production, and which is not deteriorated by the hydrogen peroxide solution. It is to provide a resin composition for containers.
【００１０】[0010]
【課題を解決するための手段】本発明者らは鋭意努力の
結果、微粒子の発生、不純物の溶出無しに過酸化水素水
による劣化が防止されたポリエチレンまたはエチレン・
α−オレフィン共重合体による樹脂組成物からなる高純
度過酸化水素水容器用樹脂組成物を見いだした。Means for Solving the Problems As a result of intensive efforts, the present inventors have made polyethylene or ethylene polyethylene which is prevented from being deteriorated by hydrogen peroxide without generating fine particles and eluting impurities.
A resin composition for a high-purity hydrogen peroxide water container comprising a resin composition of an α-olefin copolymer was found.
【００１１】すなわち、本発明はチーグラー触媒により
重合したポリエチレンまたはエチレン・α−オレフィン
共重合体からなる樹脂組成物において、分子量が４００
以下のヒンダードフェノール系化合物から選択された少
なくとも１種の化合物を１００〜１０００重量ｐｐｍ含
有する樹脂からなる高純度過酸化水素水容器用樹脂組成
物に係わる。That is, the present invention relates to a resin composition comprising polyethylene or an ethylene / α-olefin copolymer polymerized by a Ziegler catalyst and having a molecular weight of 400
The present invention relates to a resin composition for a high-purity hydrogen peroxide water container comprising a resin containing 100 to 1000 ppm by weight of at least one compound selected from the following hindered phenol compounds.
【００１２】[0012]
【発明の実施の形態】チーグラー触媒により重合したポ
リエチレンまたはエチレン・α−オレフィン共重合体と
は、マグネシウム化合物、チタン等の遷移金属化合物、
及び有機アルミニウム化合物からなる触媒を使用し、エ
チレン、もしくは少なくとも一種類の炭素数３〜２０の
α−オレフィンとを所望密度になるような割合で重合さ
せることにより得られる。重合はスラリー重合、気相重
合、溶液重合など種々の方法により行ないうる。BEST MODE FOR CARRYING OUT THE INVENTION A polyethylene or an ethylene / α-olefin copolymer polymerized by a Ziegler catalyst refers to a transition metal compound such as a magnesium compound and titanium,
And a catalyst comprising an organoaluminum compound, and polymerized with ethylene or at least one α-olefin having 3 to 20 carbon atoms in such a ratio as to obtain a desired density. The polymerization can be performed by various methods such as slurry polymerization, gas phase polymerization, and solution polymerization.
【００１３】また、密度が０．９３０〜０．９８０ｇ／
ｃｍ3 、ＭＩ（メルトインデックス）が０．０１〜１．
０ｇ／１０ｍｉｎのポリエチレンまたはエチレン・α−
オレフィン共重合体が本発明で使用される。ここで、密
度が０．９３０ｇ／ｃｍ3 未満では溶出成分が増加し微
粒子の原因となってしまい、０．９８０ｇ／ｃｍ3 より
大きいと耐衝撃強度が劣る。またＭＩが０．０１ｇ／１
０ｍｉｎ未満では成形流動性が劣り、１．０ｇ／１０ｍ
ｉｎより大きいと衝撃強度や溶融張力が劣ってしまい適
当ではない。Further, the density is 0.930 to 0.980 g /
cm 3 , MI (melt index) 0.01 to 1.
0 g / 10 min polyethylene or ethylene α-
Olefin copolymers are used in the present invention. Here, if the density is less than 0.930 g / cm 3 , the eluted components increase and cause fine particles, and if the density is more than 0.980 g / cm 3 , the impact strength is poor. In addition, MI is 0.01 g / 1.
If it is less than 0 min, the molding fluidity is inferior, and 1.0 g / 10 m
If it is larger than in, the impact strength and the melt tension are inferior and are not suitable.
【００１４】本発明におけるヒンダードフェノール系化
合物は分子量が４００以下の化合物が使用される。ここ
でヒンダードフェノール系化合物とは、第三級ブチル基
を少なくとも一つ有するフェノール系化合物である。ま
た、分子内に第三級ブチル化ヒドロキシフェニル基を複
数含有しても良い。具体的には、２，６−ジ−ｔ−ブチ
ルフェノール（分子量２０６）、２，６−ジ−ｔ−ブチ
ル−４−メチルフェノール（分子量２２０）、２，６−
ジ−ｔ−ブチル−４−エチルフェノール（分子量２３
４）、２，６−ジ−ｔ−ブチル−４−ヒドロキシメチル
フェノール（分子量２３６）、２−ｔ−ブチル−４−メ
トキシフェノール（分子量１８０）、３−ｔ−ブチル−
４−メトキシフェノール（分子量１８０）、２，４−ジ
メチル−６−ｔ−ブチルフェノール（分子量１７８）、
２，２’−メチレン−ビス−（４−メチル−６−ｔ−ブ
チルフェノール）（分子量３４０）、２，２’−メチレ
ン−ビス−（４−エチル−６−ｔ−ブチルフェノール）
（分子量３６８）、４，４’−ブチリデン−ビス−（３
−メチル−６−ｔ−ブチルフェノール）（分子量３８
２）等が挙げられる。The hindered phenol compound used in the present invention has a molecular weight of 400 or less. Here, the hindered phenol compound is a phenol compound having at least one tertiary butyl group. Further, a plurality of tertiary butylated hydroxyphenyl groups may be contained in the molecule. Specifically, 2,6-di-t-butylphenol (molecular weight 206), 2,6-di-t-butyl-4-methylphenol (molecular weight 220), 2,6-di-t-butyl-4-methylphenol
Di-t-butyl-4-ethylphenol (molecular weight 23
4), 2,6-di-t-butyl-4-hydroxymethylphenol (molecular weight 236), 2-t-butyl-4-methoxyphenol (molecular weight 180), 3-t-butyl-
4-methoxyphenol (molecular weight 180), 2,4-dimethyl-6-t-butylphenol (molecular weight 178),
2,2'-methylene-bis- (4-methyl-6-t-butylphenol) (molecular weight 340), 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol)
(Molecular weight 368), 4,4'-butylidene-bis- (3
-Methyl-6-t-butylphenol) (molecular weight 38)
2) and the like.
【００１５】この中でも２，６−ジ−ｔ−ブチル−４−
メチルフェノール（ＢＨＴ）が極めて好ましく、これを
用いた場合、少量の含有量で過酸化水素水による劣化を
抑制することができ、さらに樹脂からの不純物溶出、微
粒子発生も充分抑えることができる。それに対し、分子
量が４００を越えるヒンダードフェノール系化合物は、
過酸化水素水による劣化に対する防止効果が著しく低く
なるため使用に耐えない。Of these, 2,6-di-t-butyl-4-
Methyl phenol (BHT) is extremely preferable. When this is used, a small amount of the compound can suppress deterioration due to hydrogen peroxide solution, and can sufficiently suppress elution of impurities from the resin and generation of fine particles. On the other hand, hindered phenol compounds having a molecular weight exceeding 400 are
Since the effect of preventing deterioration due to the hydrogen peroxide solution is extremely low, it cannot be used.
【００１６】またこのヒンダードフェノール系化合物の
含有量はポリエチレンまたはエチレン・α−オレフィン
共重合体に対して１００〜１０００重量ｐｐｍが好まし
い。含有量が１００重量ｐｐｍ未満であると過酸化水素
水による樹脂組成物の劣化を充分抑えることはできな
く、一方、１０００重量ｐｐｍを超えると許容できない
量の微粒子発生、不純物溶出が起こることがある。The content of the hindered phenol compound is preferably 100 to 1000 ppm by weight based on polyethylene or ethylene / α-olefin copolymer. If the content is less than 100 ppm by weight, deterioration of the resin composition due to hydrogen peroxide water cannot be sufficiently suppressed, while if it exceeds 1000 ppm by weight, generation of unacceptable amounts of fine particles and impurity elution may occur. .
【００１７】なお、本発明に用いられるヒンダードフェ
ノール系化合物の等級に制限はない。ここで等級とはヒ
ンダードフェノール系化合物の純度をいう。但し、等級
によってはヒンダードフェノール系化合物の製造時、保
管時等に金属を代表とする不純物、微粒子の混入も否定
できず、これが問題となることもありうる。この場合は
必要に応じて公知の方法、すなわち洗浄、蒸留、再結晶
化等の方法でそれを精製して使用することが好ましい。There is no limitation on the grade of the hindered phenol compound used in the present invention. Here, the grade refers to the purity of the hindered phenol compound. However, depending on the grade, the contamination of impurities and fine particles typified by metal during the production and storage of the hindered phenolic compound cannot be denied, which may be a problem. In this case, if necessary, it is preferable to purify and use it by a known method, that is, a method such as washing, distillation, recrystallization and the like.
【００１８】ヒンダードフェノール系化合物の、ポリエ
チレンまたはエチレン・α−オレフィン共重合体からな
る樹脂組成物へ含有させる方法に制限はない。例とし
て、重合後のポリエチレンまたはエチレン・α−オレフ
ィン共重合体の粉体をペレット化する段階に添加する方
法、または予めバンバリーミキサー、ミキシングロー
ル、その他特殊ミキサーなどで製造されたヒンダードフ
ェノール系化合物を高濃度に含むマスターバッチと、ポ
リエチレンまたはエチレン・α−オレフィン共重合体と
を成形前、あるいは成形機内でブレンドする方法、もし
くはヒンダードフェノール系化合物を容器成形時に直接
添加する方法等が挙げられる。The method of incorporating the hindered phenolic compound into a resin composition comprising polyethylene or an ethylene / α-olefin copolymer is not limited. As an example, a method of adding to the stage of pelletizing polyethylene or ethylene-α-olefin copolymer powder after polymerization, or a hindered phenolic compound previously produced with a Banbury mixer, mixing roll, other special mixer, etc. A high-concentration master batch and a method of blending a polyethylene or ethylene / α-olefin copolymer before molding or in a molding machine, or a method of directly adding a hindered phenol compound during container molding. .
【００１９】本発明による樹脂組成物を用いて高純度過
酸化水素水用容器を成形する方法及び成形する環境に制
限はない。成形方法は例としてブロー成形、回転成形、
射出成形、押田成形等既知の成形方法が、環境としては
通常の室内環境下や、空気中の浮遊粒子を適切なフィル
ターで除去し得られた空気からなる清浄な空間、いわゆ
るクリーンルーム内等が挙げられる。中でもクリーンル
ーム内で、かつ微粒子を除去したガスを用いたブロー成
形による成形方法は、清浄度の高い高純度過酸化水素水
用容器を成形するためにより好ましい。There is no limitation on the method for molding a container for high-purity hydrogen peroxide water using the resin composition according to the present invention and the environment for molding. Molding methods are blow molding, rotational molding,
Known molding methods such as injection molding, Oshida molding, the environment is a normal indoor environment, or a clean space consisting of air obtained by removing airborne particles with an appropriate filter, so-called clean room etc. Can be Above all, a molding method by blow molding in a clean room using a gas from which fine particles have been removed is more preferable for molding a container for a high-purity hydrogen peroxide solution having high cleanliness.
【００２０】また、ヒンダードフェノール系化合物及び
有機、無機顔料を除き、その他の改質のための添加剤の
合計含有量が１００重量ｐｐｍ以下の樹脂組成物が、本
発明による高純度過酸化水素水用樹脂組成物として使用
される。その他の改質のための添加剤合計含有量が１０
０重量ｐｐｍを越えると微粒子が発生することがあり、
高純度過酸化水素水の容器材質として使用できないこと
が多々ある。このため、必要に応じそれらを用いる場合
は添加量を１００ｐｐｍ以下にする必要がある。さらに
は一切添加しないことが、より好ましい。The resin composition having a total content of additives of 100 ppm by weight or less, excluding the hindered phenolic compound and organic and inorganic pigments, may be a high-purity hydrogen peroxide according to the present invention. Used as a resin composition for water. 10 total additives for other modification
If it exceeds 0 ppm by weight, fine particles may be generated,
In many cases, it cannot be used as a container material for high-purity hydrogen peroxide. Therefore, when they are used as necessary, the amount of addition must be 100 ppm or less. Further, it is more preferable not to add at all.
【００２１】ここでいうその他の改質のための添加剤と
は例えばヒンダードアミン系化合物などの耐光安定剤、
ステアリン酸カルシウム、ステアリン酸亜鉛等の金属石
鹸、あるいはハイドロタルサイトなどの中和剤、滑剤等
が挙げられる。また、有機顔料として、フタロシアニン
系、キナクリドン系、アゾ系等が、無機顔料として、酸
化チタン、カーボンブラック、ベンガラ等が挙げられ
る。The other additives for modification include light stabilizers such as hindered amine compounds,
Examples include metal soaps such as calcium stearate and zinc stearate, and neutralizing agents such as hydrotalcite and lubricants. Examples of the organic pigment include phthalocyanine-based, quinacridone-based, and azo-based pigments, and examples of the inorganic pigment include titanium oxide, carbon black, and red bean.
【００２２】有機、無機顔料の本発明による高純度過酸
化水素水用樹脂組成物における含有量に制限はない。し
かしながら、含有量が少ない場合は充分な遮光効果、着
色効果が得られず、また極めて含有量が多いと許容でき
ない微粒子発生が懸念されることがある。このため、好
ましい含有量の例として０．０１重量％〜５重量％が挙
げられる。これらの有機、無機顔料、あるいはその他の
改質のための添加剤の、本発明における高純度過酸化水
素水用樹脂組成物への含有させる方法に制限はない。例
としてこれらを高濃度に含有するマスターバッチを使用
する方法等が挙げられる。さらには樹脂中のオリゴマー
含有量の指針となる沸騰ｎ−ヘキサンによる抽出した際
の抽出量が０．２重量％以下であるポリエチレンまたは
エチレン・α−オレフィン共重合体を用いることが好ま
しい。The content of the organic and inorganic pigments in the high-purity aqueous hydrogen peroxide resin composition of the present invention is not limited. However, when the content is small, a sufficient light-shielding effect and coloring effect cannot be obtained, and when the content is extremely large, generation of unacceptable fine particles may be concerned. For this reason, an example of a preferable content is 0.01% by weight to 5% by weight. There is no limitation on the method of incorporating these organic or inorganic pigments or other additives for modification into the high-purity aqueous hydrogen peroxide resin composition of the present invention. As an example, a method using a masterbatch containing these at a high concentration can be mentioned. Further, it is preferable to use polyethylene or an ethylene / α-olefin copolymer whose extraction amount at the time of extraction with boiling n-hexane, which serves as a guide for the oligomer content in the resin, is 0.2% by weight or less.
【００２３】抽出操作はソックスレー抽出装置を用いて
充分な時間、例えば２０時間沸騰ｎ−ヘキサンにより抽
出することで行なわれる。これにより、微粒子発生原因
の一つである樹脂中のオリゴマー含有量の指針が求めら
れる。抽出量が０．２重量％を超えるポリエチレンまた
はエチレン・α−オレフィン共重合体を用いた場合は微
粒子発生が著しくなり、高純度過酸化水素水容器用樹脂
として使用に耐えなくなる。このため、本発明にこれら
を使用することはできない。The extraction operation is carried out by extraction with boiling n-hexane for a sufficient time, for example, 20 hours using a Soxhlet extraction apparatus. Accordingly, a guideline for the oligomer content in the resin, which is one of the causes of generation of fine particles, is required. When a polyethylene or an ethylene / α-olefin copolymer having an extraction amount exceeding 0.2% by weight is used, the generation of fine particles becomes remarkable, and the resin cannot be used as a resin for a high-purity hydrogen peroxide water container. Therefore, they cannot be used in the present invention.
【００２４】以上のことから、チーグラー触媒によるポ
リエチレンまたはエチレン・α−オレフィン共重合体の
劣化を防止する従来の添加剤、例えばステアリン酸カル
シウム等金属石鹸などが添加された従来の樹脂組成物と
は異なり、本発明によれば、高純度過酸化水素水を充填
しても微粒子増加、不純物特に金属類溶出が起こらず、
かつ過酸化水素水による劣化が充分抑えられた優れた高
純度過酸化水素水容器用樹脂組成物を提供することがで
きる。なお、本発明における容器に充填される過酸化水
素水の濃度に制限はないが通常５〜６０重量％のものが
用いられる。From the above, unlike the conventional resin composition to which a conventional additive for preventing the degradation of polyethylene or ethylene / α-olefin copolymer by Ziegler catalyst, for example, a metal soap such as calcium stearate is added. According to the present invention, even when filled with a high-purity hydrogen peroxide solution, the increase in fine particles, impurities particularly metals do not elute,
Further, it is possible to provide an excellent resin composition for a high-purity hydrogen peroxide water container, in which deterioration due to hydrogen peroxide water is sufficiently suppressed. The concentration of the hydrogen peroxide solution filled in the container in the present invention is not limited, but usually 5 to 60% by weight is used.
【００２５】[0025]
【実施例】以下に実施例を挙げて本発明を詳細に説明す
るが、本発明はこれらの実施例により何ら限定されるも
のでない。なお、測定した金属系不純物の種類は「Book
of SEMI Standards 1995 Process Chemical Volume」に
おける「SEMI C 8.5-95Standard for hydrogen peroxid
e, grade 3 」中の「Specification 」に記載されてい
る金属であった。また、これらの金属系不純物の測定
は、ＩＣＰ−ＭＳ（Inductive Coupling-Mass spectrom
etry）法もしくは原子吸光法によった。また、微粒子測
定はレーザー光散乱を利用する測定方法によった。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The type of metal impurities measured is "Book
of SEMI C 8.5-95 Standard for hydrogen peroxid in the SEMI Standards 1995 Process Chemical Volume.
e, grade 3 "in" Specification ". The measurement of these metallic impurities is performed by ICP-MS (Inductive Coupling-Mass spectrom
etry) method or atomic absorption method. The measurement of the fine particles was performed by a measuring method using laser light scattering.
【００２６】実施例１ チーグラー触媒で重合し、かつヒンダードフェノール系
化合物を添加する前の密度が０．９５６ｇ／ｃｍ3 、Ｍ
Ｉが０．３５ｇ／10min であり、また沸騰ｎ−ヘキサン
による抽出した際の抽出量が０．０８重量％以下のポリ
エチレンからなる高密度ポリエチレン樹脂組成物（東ソ
ー製、商品名ニポロンハード８０２２）に２，６−ジ−
ｔ−ブチル−４−メチルフェノール（ＢＨＴ）のみを所
定量添加し、その樹脂組成物を用いて約２６ｃｍ×２６
ｃｍ×３５ｃｍのほぼ直方体の容器を成形した。これに
３１重量％過酸化水素水を２０ｋｇ充填し、６０℃で４
ヶ月放置した。その後内容物を２０ｋｇの水に代え、底
面を下にし垂直方向から落下させ、破損の有無を求め
た。なお、最初の落下高さは１．０ｍとし、破損しない
場合は高さを各０．５ｍ加え、５．０ｍまで落下を継続
し、落下試験を行なった。Example 1 The polymer was polymerized with a Ziegler catalyst and had a density before addition of a hindered phenol compound of 0.956 g / cm 3 , M
I was 0.35 g / 10 min, and the amount of extraction was 0.08% by weight or less when extracted with boiling n-hexane. A high-density polyethylene resin composition (Nipolon Hard 8022, manufactured by Tosoh Corporation) was used. , 6-di-
A predetermined amount of only t-butyl-4-methylphenol (BHT) was added, and about 26 cm × 26
A substantially rectangular parallelepiped container of cm × 35 cm was formed. This is filled with 20 kg of 31% by weight hydrogen peroxide solution,
Left for months. Thereafter, the contents were replaced with 20 kg of water, and the contents were dropped from the vertical direction with the bottom face down to determine whether there was damage. In addition, the initial drop height was 1.0 m, and in the case where there was no damage, the height was added to each of 0.5 m and the drop was continued to 5.0 m, and a drop test was performed.
【００２７】また、落下試験を行なっていない、同じ種
類の容器を用い、３１％重量％過酸化水素水を２０ｋｇ
充填した。その後、５０℃で１ヶ月放置し、放置により
樹脂からの過酸化水素水への不純物溶出濃度を求める溶
出試験を行なった。なお、溶出金属濃度の定量下限は
０．０１ｐｐｂであった。さらに、落下試験、溶出試験
を行なっていない、同じ種類の容器を用い、３１重量％
過酸化水素水を２０ｋｇ充填した。続いてリオン社製
０．１μｍ対応パーティクルカウンター（ＫＬ−２４）
を用い、過酸化水素水中の微粒子量を測定した。その
後、トラック積載により３００ｋｍの輸送を行なった
後、再度同様に微粒子量を測定し、輸送による微粒子増
加量を求める微粒子発生試験を行なった。試験で得られ
た結果を表１に示す。これらすべての種類の容器は高純
度過酸化水素水用容器として適当であった。In addition, using a container of the same type which has not been subjected to a drop test, 20 kg of a 31% by weight hydrogen peroxide solution was used.
Filled. Thereafter, the resin was allowed to stand at 50 ° C. for one month, and an elution test was performed to determine the concentration of impurities eluted from the resin into the aqueous hydrogen peroxide solution. The lower limit of quantification of the eluting metal concentration was 0.01 ppb. Further, using a container of the same type, which has not been subjected to a drop test and a dissolution test, is used in an amount of 31% by weight.
20 kg of hydrogen peroxide solution was charged. Next, a particle counter for 0.1 μm made by Rion (KL-24)
Was used to measure the amount of fine particles in the hydrogen peroxide solution. Then, after transporting 300 km by truck loading, the amount of fine particles was measured again in the same manner, and a fine particle generation test was performed to determine the amount of increase in fine particles due to transportation. Table 1 shows the results obtained in the test. All these types of vessels were suitable as vessels for high purity aqueous hydrogen peroxide.
【００２８】 [0028]
【００２９】比較例１ ＢＨＴの添加量を変えた以外は実施例１と同様に行ない
各種試験を行なった。得られた結果を表２に示す。これ
らすべての容器は高純度過酸化水素水用容器としては不
適当であった。Comparative Example 1 Various tests were performed in the same manner as in Example 1 except that the amount of BHT added was changed. Table 2 shows the obtained results. All these containers were unsuitable as containers for high-purity aqueous hydrogen peroxide.
【００３０】 [0030]
【００３１】実施例２ ＢＨＴの代わりに表３に示すヒンダードフェノール系化
合物、添加量にした以外は実施例１と同様に行なった。
得られた結果を表３に示す。これらすべての容器は高純
度過酸化水素水用容器として適当であった。Example 2 The procedure of Example 1 was repeated, except that the hindered phenol compound shown in Table 3 was used instead of BHT, and the amount of addition was changed.
Table 3 shows the obtained results. All of these vessels were suitable as vessels for high purity aqueous hydrogen peroxide.
【００３２】 [0032]
【００３３】比較例２ ＢＨＴの代わりに表４に示す化合物、添加量にした以外
は実施例１と同様に行なった。得られた結果を表４に示
す。これらすべての容器は高純度過酸化水素水用容器と
しては不適当であった。Comparative Example 2 The procedure of Example 1 was repeated, except that the compounds shown in Table 4 were used instead of BHT, and the amounts of addition were changed. Table 4 shows the obtained results. All these containers were unsuitable as containers for high-purity aqueous hydrogen peroxide.
【００３４】 [0034]
【００３５】比較例３ フィリップス触媒で製造され、またＢＨＴ等ヒンダード
フェノール系化合物を添加せず、さらにその他の添加さ
れた添加剤の総量が１００重量ｐｐｍ以下、及び沸騰ｎ
−ヘキサンによる抽出した際の抽出量が０．０７重量％
以下である高密度ポリエチレン樹脂組成物（東燃製、商
品名ＲＳ１０００）を用いた以外は実施例１と同様に行
なった。得られた結果を表５に示す。この容器は高純度
過酸化水素水用容器としては不適当であった。COMPARATIVE EXAMPLE 3 A hindered phenolic compound such as BHT was prepared without adding a hindered phenol compound, and the total amount of other additives was 100 ppm by weight or less.
-Extraction amount by hexane is 0.07% by weight
The procedure was performed in the same manner as in Example 1 except that the following high-density polyethylene resin composition (trade name: RS1000, manufactured by Tonen) was used. Table 5 shows the obtained results. This container was not suitable as a container for high-purity hydrogen peroxide solution.
【００３６】 [0036]
【００３７】[0037]
【発明の効果】本発明によれば、高純度過酸化水素水を
充填しても微粒子増加、不純物特に金属類溶出が起こら
ず、かつ過酸化水素水による劣化が充分抑えられた優れ
た高純度過酸化水素水容器用樹脂組成物を提供すること
ができる。According to the present invention, even when filled with high-purity hydrogen peroxide solution, fine particles are not increased, impurities and particularly metals are not eluted, and deterioration due to hydrogen peroxide solution is sufficiently suppressed. A resin composition for a hydrogen peroxide water container can be provided.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成９年２月２８日[Submission date] February 28, 1997
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３２[Correction target item name] 0032
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３２】[0032]
【表１】 [Table 1]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３４[Correction target item name] 0034
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３４】[0034]
【表２】 [Table 2]
Claims (4)
レンまたはエチレン・α−オレフィン共重合体からなる
樹脂組成物において、第三級ブチル基を少なくとも一つ
有するフェノール系化合物からなる分子量４００以下の
ヒンダードフェノール系化合物の中から選択された少な
くとも１種の化合物を１００〜１０００重量ｐｐｍ含有
する樹脂からなる高純度過酸化水素水容器用樹脂組成物1. A resin composition comprising polyethylene or an ethylene / α-olefin copolymer polymerized by a Ziegler catalyst, comprising a phenolic compound having at least one tertiary butyl group and having a molecular weight of 400 or less. High purity hydrogen peroxide water container resin composition comprising a resin containing 100 to 1000 ppm by weight of at least one compound selected from the compounds
フィン共重合体において、沸騰ｎ−ヘキサンによる抽出
量が０．２重量％以下であることを特徴とする請求項１
記載の高純度過酸化水素水容器用樹脂組成物2. The polyethylene or ethylene / α-olefin copolymer, wherein an extraction amount by boiling n-hexane is 0.2% by weight or less.
Resin composition for a high-purity hydrogen peroxide water container according to the description
顔料、有機顔料を除く、他の含有添加剤の総量が１００
重量ｐｐｍ以下の樹脂組成物であることを特徴とする請
求項１又は２記載の高純度過酸化水素水容器用樹脂組成
物3. The total amount of other additives, excluding the hindered phenol compound and the inorganic and organic pigments, is 100.
The resin composition for a high-purity hydrogen peroxide water container according to claim 1 or 2, wherein the resin composition is a resin composition having a weight of not more than ppm.
物が２，６−ジ−ｔ−ブチル−４−メチルフェノールで
あることを特徴とする請求項１〜３記載の高純度過酸化
水素水容器用樹脂組成物4. The high purity hydrogen peroxide water container according to claim 1, wherein the selected hindered phenol compound is 2,6-di-t-butyl-4-methylphenol. Resin composition
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20998196A JPH1045961A (en) | 1996-08-08 | 1996-08-08 | Resin composition for container for high-purity hydrogen peroxide water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20998196A JPH1045961A (en) | 1996-08-08 | 1996-08-08 | Resin composition for container for high-purity hydrogen peroxide water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1045961A true JPH1045961A (en) | 1998-02-17 |
Family
ID=16581890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20998196A Pending JPH1045961A (en) | 1996-08-08 | 1996-08-08 | Resin composition for container for high-purity hydrogen peroxide water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1045961A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1097899A1 (en) * | 1998-05-08 | 2001-05-09 | Aicello Chemical Co., Ltd. | Container for high purity liquid chemicals |
| WO2017163922A1 (en) | 2016-03-24 | 2017-09-28 | 富士フイルム株式会社 | Active ray-sensitive or radiation-sensitive composition, method for purifying active ray-sensitive or radiation-sensitive composition, pattern-forming method, and method for producing electronic device |
| WO2017163816A1 (en) | 2016-03-24 | 2017-09-28 | 富士フイルム株式会社 | Active light sensitive or radiation sensitive composition, method for producing active light sensitive or radiation sensitive composition, pattern forming method, and electronic device producing method |
| WO2018061944A1 (en) | 2016-09-29 | 2018-04-05 | 富士フイルム株式会社 | Active light sensitive or radiation sensitive resin composition, pattern forming method and method for producing electronic device |
| WO2021065450A1 (en) | 2019-09-30 | 2021-04-08 | 富士フイルム株式会社 | Active light sensitive or radiation sensitive resin composition, active light sensitive or radiation sensitive film, pattern forming method, and method for producing electronic device |
| WO2021200056A1 (en) | 2020-03-30 | 2021-10-07 | 富士フイルム株式会社 | Active-light-sensitive or radiation-sensitive resin composition, active-light-sensitive or radiation-sensitive film, pattern formation method, method for manufacturing electronic device, active-light-sensitive or radiation-sensitive resin composition for manufacturing photomask, and method for manufacturing photomask |
| WO2021200179A1 (en) | 2020-03-31 | 2021-10-07 | 富士フイルム株式会社 | Actinic-ray-sensitive or radiation-sensitive resin composition, actinic-ray-sensitive or radiation-sensitive film, method for forming pattern, and method for producing electronic device |
-
1996
- 1996-08-08 JP JP20998196A patent/JPH1045961A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1097899A1 (en) * | 1998-05-08 | 2001-05-09 | Aicello Chemical Co., Ltd. | Container for high purity liquid chemicals |
| US6237809B1 (en) | 1998-05-08 | 2001-05-29 | Aicello Chemical Co., Ltd. | Container for high purity liquid chemicals |
| WO2017163922A1 (en) | 2016-03-24 | 2017-09-28 | 富士フイルム株式会社 | Active ray-sensitive or radiation-sensitive composition, method for purifying active ray-sensitive or radiation-sensitive composition, pattern-forming method, and method for producing electronic device |
| WO2017163816A1 (en) | 2016-03-24 | 2017-09-28 | 富士フイルム株式会社 | Active light sensitive or radiation sensitive composition, method for producing active light sensitive or radiation sensitive composition, pattern forming method, and electronic device producing method |
| WO2018061944A1 (en) | 2016-09-29 | 2018-04-05 | 富士フイルム株式会社 | Active light sensitive or radiation sensitive resin composition, pattern forming method and method for producing electronic device |
| WO2021065450A1 (en) | 2019-09-30 | 2021-04-08 | 富士フイルム株式会社 | Active light sensitive or radiation sensitive resin composition, active light sensitive or radiation sensitive film, pattern forming method, and method for producing electronic device |
| WO2021200056A1 (en) | 2020-03-30 | 2021-10-07 | 富士フイルム株式会社 | Active-light-sensitive or radiation-sensitive resin composition, active-light-sensitive or radiation-sensitive film, pattern formation method, method for manufacturing electronic device, active-light-sensitive or radiation-sensitive resin composition for manufacturing photomask, and method for manufacturing photomask |
| WO2021200179A1 (en) | 2020-03-31 | 2021-10-07 | 富士フイルム株式会社 | Actinic-ray-sensitive or radiation-sensitive resin composition, actinic-ray-sensitive or radiation-sensitive film, method for forming pattern, and method for producing electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1190692A (en) | Polyethylene compositions for rotational moulding processes | |
| AU614942B2 (en) | Compositions to improve properties of olefin polymers containing such compositions | |
| US5846656A (en) | Stabilization systems for polymeric material in pellet form | |
| JPH1045961A (en) | Resin composition for container for high-purity hydrogen peroxide water | |
| JPH1180257A (en) | Polyethylene resin for highly pure reagent container and highly pure reagent container comprising same | |
| JP2004331706A (en) | High-density polyethylene resin and container using the same resin | |
| JPH06322193A (en) | Radiation-resistant polypropylene resin composition | |
| JPH1121393A (en) | Resin composition for high-purity aqueous hydrogen peroxide container | |
| JP3743788B2 (en) | Polyethylene resin for high-purity chemical containers, composition and high-purity chemical container comprising the same | |
| KR101494964B1 (en) | Polypropylene resin composition with good impact strength, transparency, and hinge resistance, and process for their manufacture | |
| JP2005075847A (en) | Polyproylene resin composition | |
| EP0213788B1 (en) | Method for improving the clarity of propylene polymers | |
| EP0446801B1 (en) | Solid catalyst component for use in polymerization of alpha-olefins | |
| JP2009545655A (en) | High density polyethylene composition, method for producing the same, article produced therefrom, and method for producing such article | |
| FR2478654A1 (en) | COMPOSITIONS OF ANTISTATIC POLYOLEFIN RESINS | |
| JPH02163143A (en) | Polyolefin-based resin composition | |
| JP2000129045A (en) | Clean vessel made of polyethylene | |
| JP2005171169A (en) | Polypropylene resin composition | |
| JP5283891B2 (en) | Polyethylene resin composition for clean container packaging | |
| JPH1180449A (en) | Polyethylene resin for large-sized vessel for highly pure chemical and vessel | |
| US5468792A (en) | Clarifying compositions, process for making and polyolefin compositions containing them | |
| JPH0986587A (en) | Container for hydrogen peroxide water | |
| KR200236334Y1 (en) | Hollow Bodies To Fill High Pure Chemicals | |
| JP7145168B2 (en) | Method for producing olefinic resin composition | |
| JP2864207B2 (en) | Method for producing modified polyethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050418 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20050427 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20050817 |