JPH04348163A - Thermoplastic resin composition little in elution of ion - Google Patents
Thermoplastic resin composition little in elution of ionInfo
- Publication number
- JPH04348163A JPH04348163A JP12124291A JP12124291A JPH04348163A JP H04348163 A JPH04348163 A JP H04348163A JP 12124291 A JP12124291 A JP 12124291A JP 12124291 A JP12124291 A JP 12124291A JP H04348163 A JPH04348163 A JP H04348163A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- resin composition
- elution
- manufactured
- chelating agent
- 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
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 38
- 238000010828 elution Methods 0.000 title claims abstract description 37
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- 239000002738 chelating agent Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 230000009477 glass transition Effects 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 5
- 229920006127 amorphous resin Polymers 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 5
- 229920002530 polyetherether ketone Polymers 0.000 claims description 5
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000012498 ultrapure water Substances 0.000 abstract description 35
- 229910021642 ultra pure water Inorganic materials 0.000 abstract description 34
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 abstract description 27
- 229910021645 metal ion Inorganic materials 0.000 abstract description 16
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013522 chelant Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 52
- 241000156978 Erebia Species 0.000 description 26
- 238000001746 injection moulding Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229920006367 Neoflon Polymers 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002492 poly(sulfone) Polymers 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001643 poly(ether ketone) Polymers 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 239000004801 Chlorinated PVC Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 2
- 229920006038 crystalline resin Polymers 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 229920013633 Fortron Polymers 0.000 description 1
- 239000004738 Fortron® Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920004747 ULTEM® 1000 Polymers 0.000 description 1
- 229920004710 VICTREX® PEEK 450G Polymers 0.000 description 1
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 1
- 229920004886 Victrex® PES Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008214 highly purified water Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、特に高純度の水（超純
水）を対象とする用途に好適に使用されるイオン溶出の
極めて少ない熱可塑性樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition with extremely low ionic elution, which is particularly suitable for applications involving highly purified water (ultrapure water).
【０００２】0002
【従来の技術】熱可塑性樹脂は溶融成形が可能で、パイ
プや容器などの形状に成形され、通常の用途のほか超純
水を対象とする特殊な用途にも使用されている。BACKGROUND OF THE INVENTION Thermoplastic resins can be melt-molded and molded into shapes such as pipes and containers, and are used not only for normal purposes but also for special purposes involving ultrapure water.
【０００３】例えば、半導体素子の製造において、半導
体素子表面の洗浄に使用される超純水の輸送配管材料と
して、ポリ塩化ビニル、塩素化ポリ塩化ビニル、ポリプ
ロピレン、ポリフッ化ビニリデン、ポリエーテルエーテ
ルケトン等の熱可塑性樹脂が使用ないしは提案されてい
る（例えば、配管技術 ’８７， １２． Ｐ ５２〜
５８参照）。For example, in the manufacture of semiconductor devices, polyvinyl chloride, chlorinated polyvinyl chloride, polypropylene, polyvinylidene fluoride, polyether ether ketone, etc. are used as pipe materials for transporting ultrapure water used for cleaning the surfaces of semiconductor devices. thermoplastic resins have been used or proposed (for example, Piping Technology '87, 12. P. 52~
58).
【０００４】ところが、このような熱可塑性樹脂からな
る超純水の輸送配管材料を使用する場合は、樹脂の種類
により程度の差はあるが、樹脂中の金属イオンのような
イオン性物質や有機物質が超純水中に溶出し、超純水の
純度が低下するという問題がある。However, when using ultrapure water transport piping materials made of such thermoplastic resins, the amount of ionic substances such as metal ions and organic substances in the resin varies depending on the type of resin. There is a problem that substances are eluted into the ultrapure water, reducing the purity of the ultrapure water.
【０００５】このように純度が低下した超純水で半導体
素子表面を洗浄すると、表面に付着した極くわずかの金
属イオンが素子の機能を阻害し、製品の歩留りが低下し
たり、その性能が低下したりする。また、溶出した有機
物質により超純水に微生物が繁殖してさらに水の純度が
低下する。When the surface of a semiconductor element is cleaned with ultrapure water of reduced purity, the very small amount of metal ions adhering to the surface inhibits the function of the element, reducing the yield of the product and impairing its performance. or decrease. Furthermore, the eluted organic substances cause microorganisms to grow in the ultrapure water, further reducing the purity of the water.
【０００６】[0006]
【発明が解決しようとする課題】超純水に繁殖する微生
物については、一般に、過酸化水素水を配管に通して洗
浄殺菌する方法や、８０〜１００ ℃近くまで加熱され
た超純水を配管に通して加熱殺菌する方法が行われてい
る。ところが、溶出したイオン性物質による汚染は防止
できず、半導体素子の集積度が高度化するに伴って、イ
オン性物質の溶出が極めて少ない超純水輸送配管材料が
要求されている。[Problems to be Solved by the Invention] Regarding microorganisms that breed in ultrapure water, there are generally methods for cleaning and sterilizing them by passing hydrogen peroxide solution through the pipes, or by washing and sterilizing the microorganisms by passing the pipes with ultrapure water heated to around 80 to 100 degrees Celsius. A method of heat sterilization is used. However, contamination due to eluted ionic substances cannot be prevented, and as the degree of integration of semiconductor devices becomes more sophisticated, there is a need for ultrapure water transport piping materials with extremely low levels of ionic substance elution.
【０００７】本発明は、このような要求に応えるもので
あり、本発明の目的とするところは、金属イオンの溶出
が極めて少ない熱可塑性樹脂組成物を提供することにあ
る。また、本発明の他の目的は、耐熱性及び耐熱水性に
優れ、しかも金属イオンの溶出が極めて少ない熱可塑性
樹脂組成物を提供することにある。The present invention meets these demands, and an object of the present invention is to provide a thermoplastic resin composition in which the elution of metal ions is extremely low. Another object of the present invention is to provide a thermoplastic resin composition that has excellent heat resistance and hot water resistance, and in which elution of metal ions is extremely low.
【０００８】[0008]
【課題を解決するための手段】上記の目的は、熱可塑性
樹脂に、融点が１００ ℃以上で且つ水に不溶のキレー
ト化剤を含有させることにより達成することができる。[Means for Solving the Problems] The above object can be achieved by incorporating a chelating agent having a melting point of 100° C. or higher and insoluble in water into a thermoplastic resin.
【０００９】本発明に用いる熱可塑性樹脂樹脂は、例え
ば、射出成形法、押出成形法、ブロー成形法、圧縮成形
法等の方法による溶融成形が可能な樹脂である。なお、
本発明の熱可塑性樹脂組成物は、特に超純水を対象とす
る用途に使用されるものであるから、耐水性を有する樹
脂でなければならない。この場合、一般に、ＪＩＳ Ｋ
７２０９による吸水率が０．５ 重量％以下の樹脂が
使用される。The thermoplastic resin used in the present invention is a resin that can be melt-molded by methods such as injection molding, extrusion molding, blow molding, and compression molding. In addition,
Since the thermoplastic resin composition of the present invention is used particularly for applications involving ultrapure water, it must be a resin that has water resistance. In this case, generally JIS K
7209 water absorption of 0.5% by weight or less is used.
【００１０】このような熱可塑性樹脂としては、ポリ塩
化ビニル、塩素化ポリ塩化ビニル、ポリプロピレン、ポ
リエーテルケトン、ポリエーテルエーテルケトン、ポリ
フェニレンサルファイド、ポリスルホン、ポリアリール
スルホン、ポリエーテルスルホン、ポリエーテルイミド
、フッ素樹脂、例えばテトラフルオロエチレン−パーフ
ルオロアルキルビニルエーテル共重合体、テトラフルオ
ロエチレン−ヘキサフルオロプロピレン共重合体、ポリ
クロロトリフルオロエチレン、テトラフルオロエチレン
−エチレン共重合体、クロロトリフルオロエチレン−エ
チレン共重合体、ポリフッ化ビニリデン等が挙げられる
。Examples of such thermoplastic resins include polyvinyl chloride, chlorinated polyvinyl chloride, polypropylene, polyetherketone, polyetheretherketone, polyphenylene sulfide, polysulfone, polyarylsulfone, polyethersulfone, polyetherimide, Fluororesins, such as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer Examples include coalescence, polyvinylidene fluoride, and the like.
【００１１】特に、組成物がパイプや容器などに成形さ
れて、例えば、超純水を対象とする用途に使用される場
合は、８０〜１００ ℃近くの超純水による加熱殺菌が
行われる場合が多い。それゆえ、本発明に用いる熱可塑
性樹脂樹脂は、耐熱性及び耐熱水性が良好な樹脂が好ま
しい。[0011] In particular, when the composition is molded into a pipe or container and used for purposes involving ultrapure water, heat sterilization with ultrapure water at a temperature of about 80 to 100°C is performed. There are many. Therefore, the thermoplastic resin used in the present invention is preferably a resin having good heat resistance and hot water resistance.
【００１２】このような熱可塑性樹脂としては、フッ素
樹脂、ポリフェニレンサルファイド、ポリエーテルケト
ン、ポリエーテルエーテルケトンから選ばれる樹脂が好
適である。この樹脂は、その殆どが結晶性の樹脂であり
、いずれも特に耐熱性及び耐熱水性に優れ、しかも剛性
が高いという利点がある。なお、上記の樹脂は単独或い
は二種以上を混合して用いられる。[0012] As such a thermoplastic resin, a resin selected from fluororesin, polyphenylene sulfide, polyetherketone, and polyetheretherketone is suitable. Most of these resins are crystalline resins, and both have the advantage of being particularly excellent in heat resistance and hot water resistance, as well as being high in rigidity. The above resins may be used alone or in combination of two or more.
【００１３】また、ガラス転移温度（示差走査熱量計で
測定）が１００ ℃以上の無定形の樹脂も好適である。
このような無定形熱可塑樹脂としては、ポリスルホン、
ポリアリールスルホン、ポリエーテルスルホン、ポリエ
ーテルイミド等が挙げられる。この種の樹脂は、ガラス
転移温度が１００ ℃以上であるので、相当の耐熱性及
び耐熱水性を有する。また、無定形であるので、結晶性
の樹脂に比べて、パイプなどに成形する際に球晶の生成
する恐れがない。それゆえ、製品の内面がより平滑とな
りやすく、微生物や微粒子が付着しにくくなるという利
点がある。なお、上記の樹脂は単独或いは二種以上を混
合して用いられる。[0013] Also suitable are amorphous resins having a glass transition temperature (measured with a differential scanning calorimeter) of 100°C or higher. Such amorphous thermoplastic resins include polysulfone,
Examples include polyarylsulfone, polyethersulfone, polyetherimide, and the like. This type of resin has a glass transition temperature of 100° C. or higher, so it has considerable heat resistance and hot water resistance. Furthermore, since it is amorphous, there is no risk of spherulite formation when molding it into a pipe or the like, compared to crystalline resins. Therefore, there is an advantage that the inner surface of the product becomes smoother, making it difficult for microorganisms and fine particles to adhere to it. The above resins may be used alone or in combination of two or more.
【００１４】本発明においては、このような熱可塑性樹
脂に、融点が１００ ℃以上で且つ水に不溶のキレート
化剤が含有される。このようなキレート化剤としては、
デカメチレンジカルボン酸ジサリチロイルヒドラジド、
Ｎ，Ｎ’−ビス〔３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオニル〕ヒドラジン、Ｎ，
Ｎ’−ジ−２−ナフチル−ｐ−フェニレンジアミン、３
−（Ｎ−サリチロイル）アミノ−１，２，４−トリアゾ
ール、２，２’−メチレンビス（４−エチル−６−ｔ−
フェノール）、２，２’−メチレンビス（４−メチル−
６−ｔ−ブチルフェノール）等が挙げられる。In the present invention, such a thermoplastic resin contains a chelating agent having a melting point of 100° C. or higher and insoluble in water. Such chelating agents include
decamethylene dicarboxylic acid disalicyloyl hydrazide,
N,N'-bis[3-(3,5-di-t-butyl-4-
Hydroxyphenyl)propionyl]hydrazine, N,
N'-di-2-naphthyl-p-phenylenediamine, 3
-(N-salicyloyl)amino-1,2,4-triazole, 2,2'-methylenebis(4-ethyl-6-t-
phenol), 2,2'-methylenebis(4-methyl-
6-t-butylphenol) and the like.
【００１５】これ等の中でも、特に融点が加工温度より
も極端に高くなく分散性が良いこと、適度の分子量と樹
脂中での適度の易動性を有していること、加工温度で殆
ど分解しないこと、揮発性が小さく樹脂中での保留性が
あること、樹脂の機械的強度、耐熱性、加工性などに悪
影響を与えないこと等の条件を満足できるキレート化剤
が好ましい。Among these, in particular, the melting point is not extremely higher than the processing temperature, it has good dispersibility, it has an appropriate molecular weight and appropriate mobility in the resin, and it hardly decomposes at the processing temperature. It is preferable to use a chelating agent that satisfies the following conditions: chelating agent does not contain any additives, has low volatility and retention in the resin, and does not adversely affect the mechanical strength, heat resistance, processability, etc. of the resin.
【００１６】この観点から、デカメチレンジカルボン酸
ジサリチロイルヒドラジド、Ｎ，Ｎ’−ビス〔３−（３
，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロ
ピオニル〕ヒドラジン、Ｎ，Ｎ’−ジ−２−ナフチル−
ｐ−フェニレンジアミンが好適に用いられる。From this point of view, decamethylene dicarboxylic acid disalicyloyl hydrazide, N,N'-bis[3-(3
,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, N,N'-di-2-naphthyl-
p-phenylenediamine is preferably used.
【００１７】これ等のキレート化剤は、熱可塑性樹脂１
００ 重量部に対して、一般に０．００１ 〜４０重量
部の範囲で含有される。キレート化剤の含有量が０．０
０１ 重量部以下では、樹脂に残留されている金属イオ
ンのキレート化が充分でない。逆に、キレート化剤の含
有量が４０重量部以上では、樹脂の機械的強度や耐熱性
などが低下する。These chelating agents are suitable for thermoplastic resin 1
It is generally contained in a range of 0.001 to 40 parts by weight per 0.00 parts by weight. Chelating agent content is 0.0
If the amount is less than 0.01 parts by weight, the metal ions remaining in the resin will not be sufficiently chelated. On the other hand, if the content of the chelating agent is 40 parts by weight or more, the mechanical strength and heat resistance of the resin will decrease.
【００１８】本発明の熱可塑性樹脂組成物は、例えば、
熱可塑性樹脂を粉末状に粉砕し、これに適量のキレート
化剤を混合し、これをパイプや容器などの各種製品に成
形することにより得ることができる。また、ペレット状
の熱可塑性樹脂に適量のキレート化剤を混練し、これを
パイプや容器など各種製品に成形することにより得るこ
とができる。The thermoplastic resin composition of the present invention includes, for example,
It can be obtained by pulverizing a thermoplastic resin into a powder, mixing an appropriate amount of a chelating agent therein, and molding this into various products such as pipes and containers. Alternatively, it can be obtained by kneading an appropriate amount of a chelating agent into a pelletized thermoplastic resin and molding the mixture into various products such as pipes and containers.
【００１９】なお、本発明の熱可塑性樹脂組成物には、
その目的を損なわない範囲で、安定剤、滑剤、可塑剤、
加工助剤、着色剤、補強剤、充填剤等の添加剤が少量添
加されていてもよい。[0019] The thermoplastic resin composition of the present invention includes:
Stabilizers, lubricants, plasticizers,
Additives such as processing aids, colorants, reinforcing agents, fillers, etc. may be added in small amounts.
【００２０】[0020]
【作用】通常、熱可塑性樹脂中には、金属イオン等のイ
オン性物質を含む重合触媒やその他の添加剤が、少なか
らず残留している。本発明の組成物のように、熱可塑性
樹脂に融点が１００ ℃以上で且つ水に不溶のキレート
化剤が適量含有されていると、樹脂中に残留している金
属イオンに対してこのキレート化剤が配位してキレート
を形成し、不純物としての金属イオンは、キレート化剤
に補足されて樹脂からの溶出が防止される。[Operation] Usually, a considerable amount of polymerization catalysts and other additives containing ionic substances such as metal ions remain in thermoplastic resins. When a thermoplastic resin contains an appropriate amount of a water-insoluble chelating agent having a melting point of 100°C or higher, as in the composition of the present invention, this chelating agent is effective against the metal ions remaining in the resin. The agent coordinates to form a chelate, and metal ions as impurities are captured by the chelating agent and prevented from being eluted from the resin.
【００２１】しかも、上記のキレート化剤は、融点が１
００ ℃以上で且つ水に不溶であるので、使用される熱
可塑性樹脂の耐熱性や耐熱水性と相まって、通常の条件
下での使用は勿論のこと、この組成物がパイプや容器な
どに成形されて超純水を対象とする用途に使用される際
には、８０〜１００ ℃近くまで超純水を加熱して殺菌
処理を行うことが可能である。この場合、キレート化剤
が組成物から超純水中に溶出することはない。Moreover, the above chelating agent has a melting point of 1
Since it is insoluble in water at temperatures above 00°C, combined with the heat resistance and hot water resistance of the thermoplastic resin used, this composition can be used not only under normal conditions, but also when molded into pipes, containers, etc. When ultrapure water is used in applications where ultrapure water is targeted, it is possible to sterilize the ultrapure water by heating it to nearly 80 to 100°C. In this case, the chelating agent will not be eluted from the composition into the ultrapure water.
【００２２】[0022]
【実施例】以下、本発明の実施例及び比較例を示す。
実施例１
テトラフルオロエチレン−パーフルロエチレン共重合体
（ネオフロンＰＦＡ ＡＰ−２１０：ダイキン社製）１
００ 重量部と、融点が２１２ ℃で且つ水に不溶のデ
カメチレンジカルボン酸ジサリチロイルヒドラジド（Ｍ
ＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）２重量
部とを混合し、これを３５０ ℃で溶融混練し射出成形
機により、厚さ１ｍｍの樹脂組成物の板を成形した。[Examples] Examples and comparative examples of the present invention will be shown below. Example 1 Tetrafluoroethylene-perfluoroethylene copolymer (Neoflon PFA AP-210: manufactured by Daikin Corporation) 1
00 parts by weight and decamethylene dicarboxylic acid disalicyloyl hydrazide (M
ARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) in an amount of 2 parts by weight, and the mixture was melt-kneaded at 350° C. and molded into a resin composition plate with a thickness of 1 mm using an injection molding machine.
【００２３】この板をトリクレン、メタノール、超純水
でこの順に洗浄して試験板（縦４ｃｍ×横２ｃｍ×２０
枚及び縦４ｃｍ×横１ｃｍ×１２枚）とし、この試験板
について、次の方法により金属イオン等のイオン性物質
の溶出性及び有機物質の溶出性を評価した。その結果を
表１に示す。[0023] This plate was washed with trichlene, methanol, and ultrapure water in this order, and a test plate (4 cm long x 2 cm wide x 20
The test plates were used to evaluate the elution properties of ionic substances such as metal ions and the elution properties of organic substances using the following method. The results are shown in Table 1.
【００２４】（１）イオン性物質の溶出性テフロン製容
器に超純水（１５０ ｍｌ）を入れこの超純水に上記の
試験板（縦４ｃｍ×横２ｃｍ×２０枚）を浸漬して密閉
し、これを８０℃のギヤーオーブンに入れて７日間放置
する。その後、テフロン製容器内の超純水の電気伝導度
を測定することにより、金属イオン等のイオン性物質の
溶出性を評価する。(1) Elution of ionic substances Pour ultrapure water (150 ml) into a Teflon container, immerse the above test plates (4 cm long x 2 cm wide x 20 sheets) in this ultra pure water, and seal. , and leave it in a gear oven at 80°C for 7 days. Thereafter, the elution of ionic substances such as metal ions is evaluated by measuring the electrical conductivity of the ultrapure water in the Teflon container.
【００２５】なお、この測定に用いた超純水の電気伝導
度は、０．５ μＳ／ｃｍであった。また、テフロン製
容器からの金属イオン等のイオン性物質の溶出量を知る
ために、上記の板を浸漬しない場合について、超純水の
電気伝導度を測定した（ブランク測定値）。この電気伝
導度は１５．５μＳ／ｃｍであった。[0025] The electrical conductivity of the ultrapure water used in this measurement was 0.5 μS/cm. Furthermore, in order to find out the amount of ionic substances such as metal ions eluted from the Teflon container, the electrical conductivity of ultrapure water was measured when the plate was not immersed (blank measurement value). This electrical conductivity was 15.5 μS/cm.
【００２６】（２）有機物質の溶出性
パイレックス製容器に超純水（７０ ｍｌ）を入れこの
超純水に上記の試験板（縦４ｃｍ×横１ｃｍ×１２枚）
を浸漬して密閉し、これを８０℃のギヤーオーブンに入
れて７日間放置する。その後、パイレックス製容器内の
超純水の全有機物炭素量（ＴＯＣ）を測定することによ
り、有機物質の溶出性を評価する。(2) Elution of organic substances Pour ultrapure water (70 ml) into a Pyrex container and place the above test plates (4 cm long x 1 cm wide x 12 sheets) in this ultra pure water.
Soak it, seal it, and leave it in a gear oven at 80°C for 7 days. Thereafter, the elution of organic substances is evaluated by measuring the total organic carbon content (TOC) of the ultrapure water in the Pyrex container.
【００２７】なお、この測定に用いた超純水の全有機物
炭素量は、１２０ ｐｐｂ であった。また、パイレッ
クス製容器からの有機物質の溶出量を知るために、上記
の板を浸漬しない場合について、超純水の全有機物炭素
量を測定した（ブランク測定値） 。この全有機物炭素
量（ＴＯＣ）は、５４０ ｐｐｂ であった。The total organic carbon content of the ultrapure water used in this measurement was 120 ppb. In addition, in order to find out the amount of organic substances eluted from the Pyrex container, the total organic carbon content of the ultrapure water was measured (blank measurement) when the plate was not immersed. The total organic carbon content (TOC) was 540 ppb.
【００２８】実施例２
テトラフルオロエチレン−ヘキサフルオロプロピレン共
重合（ネオフロンＦＥＰＮＰ−２０ ：ダイキン社製）
１００ 重量部と、デカメチレンジカルボン酸ジサリチ
ロイルヒドラジド（ＭＡＲＫ ＣＤＡ−６：アデカアー
ガス化学社製）２重量部とを混合し、これを３２０ ℃
で溶融混練し射出成形機により、厚さ１ｍｍの樹脂組成
物の板を成形した。Example 2 Tetrafluoroethylene-hexafluoropropylene copolymerization (Neoflon FEPNP-20: manufactured by Daikin)
100 parts by weight and 2 parts by weight of decamethylene dicarboxylic acid disalicyloyl hydrazide (MARK CDA-6: manufactured by Adeka Argus Chemical Co., Ltd.) were mixed, and the mixture was heated at 320°C.
The mixture was melt-kneaded and molded into a plate of the resin composition with a thickness of 1 mm using an injection molding machine.
【００２９】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例３
ポリクロロトリフルオロエチレン（ネオフロンＣＴＦＥ
Ｍ−３００：ダイキン社製）１００ 重量部と、デカ
メチレンジカルボン酸ジサリチロイルヒドラジド（ＭＡ
ＲＫ ＣＤＡ−６：アデカアーガス化学社製）２重量部
とを混合し、これを２６０ ℃で溶融混練し射出成形機
により、厚さ１ｍｍの樹脂組成物の板を成形した。Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 3 Polychlorotrifluoroethylene (Neoflon CTFE
100 parts by weight of M-300 (manufactured by Daikin) and 100 parts by weight of decamethylene dicarboxylic acid disalicyloyl hydrazide (MA
2 parts by weight of RK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) were melted and kneaded at 260° C., and a plate of the resin composition with a thickness of 1 mm was molded using an injection molding machine.
【００３０】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例４
テトラフルオロエチレン−エチレン共重合体（ネオフロ
ンＥＴＦＥ ＥＰ−５２０ ：ダイキン社製）１００
重量部と、デカメチレンジカルボン酸ジサリチロイルヒ
ドラジド（ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学
社製）２重量部とを混合し、これを３１０ ℃で溶融混
練し射出成形機により、厚さ１ｍｍの樹脂組成物の板を
成形した。[0030] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 4 Tetrafluoroethylene-ethylene copolymer (Neoflon ETFE EP-520: manufactured by Daikin Corporation) 100
parts by weight and 2 parts by weight of decamethylene dicarboxylic acid disalicyloyl hydrazide (MARK CDA-6: manufactured by Adeka Argus Chemical Co., Ltd.), melted and kneaded at 310°C, and molded into a 1 mm thick molded product using an injection molding machine. A plate of the resin composition was molded.
【００３１】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例５
ポリフッ化ビニリデン（ネオフロンＶＤＦ ＶＰ−８１
０：ダイキン社製）１００ 重量部と、デカメチレンジ
カルボン酸ジサリチロイルヒドラジド（ＭＡＲＫ ＣＤ
Ａ−６：アデカアーガス化学社製）２重量部とを混合し
、これを２２０ ℃で溶融混練し射出成形機により、厚
さ１ｍｍの樹脂組成物の板を成形した。[0031] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 5 Polyvinylidene fluoride (Neoflon VDF VP-81
0: manufactured by Daikin Corporation) 100 parts by weight and decamethylene dicarboxylic acid disalicyloyl hydrazide (MARK CD
A-6: 2 parts by weight (manufactured by Adeka Argus Chemical Co., Ltd.) were mixed, the mixture was melt-kneaded at 220°C, and a plate of the resin composition with a thickness of 1 mm was molded using an injection molding machine.
【００３２】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例６
ポリフッ化ビニリデン（ネオフロンＶＤＦ ＶＰ−８１
０：ダイキン社製）１００ 重量部と、融点が３２５
℃で且つ水に不溶の３−（Ｎ−サリチロイル）アミノ−
１，２，４−トリアゾール（ＭＡＲＫ ＣＤＡ−１：ア
デカアーガス化学社製）２重量部とを混合し、これを２
２０ ℃で溶融混練し射出成形機により厚さ１ｍｍの樹
脂組成物の板を成形した。[0032] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 6 Polyvinylidene fluoride (Neoflon VDF VP-81
0: manufactured by Daikin Corporation) 100 parts by weight and melting point of 325
℃ and insoluble in water 3-(N-salicyloyl)amino-
2 parts by weight of 1,2,4-triazole (MARK CDA-1: manufactured by Adeka Argus Chemical Co., Ltd.)
The resin composition was melt-kneaded at 20° C. and molded into a plate of the resin composition with a thickness of 1 mm using an injection molding machine.
【００３３】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例７
ポリフッ化ビニリデン（ネオフロンＶＤＦ ＶＰ−８１
０：ダイキン社製）１００ 重量部と、融点が２２４
〜２２９ ℃で且つ水に不溶のＮ，Ｎ’−ビス〔３−（
３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プ
ロピオニル〕ヒドラジン（ＩＲＧＡＮＯＸ ＭＤ１０２
４：日本チバガイギー社製）２重量部とを混合し、これ
を２２０ ℃で溶融混練し射出成形機により、厚さ１ｍ
ｍの樹脂組成物の板を成形した。[0033] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 7 Polyvinylidene fluoride (Neoflon VDF VP-81
0: manufactured by Daikin Corporation) 100 parts by weight and a melting point of 224
~229 °C and insoluble in water N,N'-bis[3-(
3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine (IRGANOX MD102
4: Nippon Ciba Geigy Co., Ltd.)), melted and kneaded the mixture at 220°C, and molded it to a thickness of 1 m using an injection molding machine.
A plate of the resin composition of m was molded.
【００３４】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例８
ポリフッ化ビニリデン（ネオフロンＶＤＦ ＶＰ−８１
０：ダイキン社製）１００ 重量部と、融点が２３８
℃で且つ水に不溶のＮ，Ｎ’−ジ−２−ナフチル−ｐ−
フェニレンジアミン（ノクラック Ｗｈｉｔｅ：大内新
興化学社製）２重量部とを混合し、これを２２０℃で溶
融混練し射出成形機により、厚さ１ｍｍの樹脂組成物の
板を成形した。[0034] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 8 Polyvinylidene fluoride (Neoflon VDF VP-81
0: manufactured by Daikin Corporation) 100 parts by weight, and the melting point is 238
℃ and insoluble in water, N,N'-di-2-naphthyl-p-
The mixture was mixed with 2 parts by weight of phenylenediamine (Nocrac White, manufactured by Ouchi Shinko Kagaku Co., Ltd.), melted and kneaded at 220° C., and molded into a resin composition plate with a thickness of 1 mm using an injection molding machine.
【００３５】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例９
ポリフェニレンサルファイド（フォートロンＫＳＰ Ｔ
−３００ ：呉羽化学社製）１００重量部と、デカメチ
レンジカルボン酸ジサリチロイルヒドラジド（ＭＡＲＫ
ＣＤＡ−６：アデカアーガス化学社製）２重量部とを
混合し、これを３１０ ℃で溶融混練し射出成形機によ
り、厚さ１ｍｍの樹脂組成物の板を成形した。[0035] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 9 Polyphenylene sulfide (Fortron KSP T
-300: manufactured by Kureha Chemical Co., Ltd.) 100 parts by weight and decamethylene dicarboxylic acid disalicyloyl hydrazide (MARK
2 parts by weight of CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) were mixed, and the mixture was melt-kneaded at 310° C. and molded into a plate of the resin composition with a thickness of 1 mm using an injection molding machine.
【００３６】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例１０
ガラス転移温度１６２ ℃のポリエーテルケトン（ビク
トレックス ＰＥＫ ２２０Ｇ ：アイ・シー・アイ・
ジャパン社製）１００重量部と、デカメチレンジカルボ
ン酸ジサリチロイルヒドラジド（ＭＡＲＫ ＣＤＡ−６
：アデカアーガス化学社製）２重量部とを混合し、これ
を４００ ℃で溶融混練し射出成形機により、厚さ１ｍ
ｍの樹脂組成物の板を成形した。[0036] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 10 Polyetherketone (Victrex PEK 220G: I.C.I.
Japan Co., Ltd.) and 100 parts by weight of decamethylene dicarboxylic acid disalicyloyl hydrazide (MARK CDA-6
2 parts by weight (manufactured by Adeka Argus Chemical Co., Ltd.), melted and kneaded at 400°C, and molded with an injection molding machine to a thickness of 1 m.
A plate of the resin composition of m was molded.
【００３７】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例１１
ガラス転移温度１４３ ℃のポリエーテルエーテルケト
ン（ビクトレックス ＰＥＥＫ４５０Ｇ：アイ・シー・
アイ・ジャパン社製）１００重量部と、デカメチレンジ
カルボン酸ジサリチロイルヒドラジド（ＭＡＲＫＣＤＡ
−６：アデカアーガス化学社製）２重量部とを混合し、
これを３８０℃で溶融混練し射出成形機により、厚さ１
ｍｍの樹脂組成物の板を成形した。[0037] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 11 Polyetheretherketone with a glass transition temperature of 143°C (Victrex PEEK450G: I.C.
100 parts by weight of decamethylene dicarboxylic acid disalicyloyl hydrazide (MARKCDA)
-6: manufactured by Adeka Argus Chemical Co., Ltd.) 2 parts by weight,
This was melted and kneaded at 380°C and molded using an injection molding machine to a thickness of 1.
A plate of the resin composition of mm was molded.
【００３８】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表１に示す。
実施例１２
ガラス転移温度１９０ ℃のポリスルホン（ユーデル
Ｐ−１７００：アモコジャパン社製）１００重量部と、
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）２重
量部とを混合し、これを３６０ ℃で溶融混練し射出成
形機により、厚さ１ｍｍの樹脂組成物の板を成形した。[0038] Regarding this plate, the elution properties of ionic substances and the elution properties of organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 12 Polysulfone (Udel) with a glass transition temperature of 190 °C
P-1700: manufactured by Amoco Japan) 100 parts by weight,
Decamethylene dicarboxylic acid disalicyloyl hydrazide (
2 parts by weight of MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) were mixed, and the mixture was melt-kneaded at 360° C. and molded into a plate of the resin composition with a thickness of 1 mm using an injection molding machine.
【００３９】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表２に示す。
実施例１３
ガラス転移温度１９０ ℃のポリスルホン（ユーデル
Ｐ−１７００：アモコジャパン社製）１００重量部と、
３−（Ｎ−サリチロイル）アミノ−１，２，４−トリア
ゾール（ＭＡＲＫＣＤＡ−１：アデカアーガス化学社製
）２重量部とを混合し、これを３６０ ℃で溶融混練し
射出成形機により、厚さ１ｍｍの樹脂組成物の板を成形
した。[0039] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 13 Polysulfone (Udel) with a glass transition temperature of 190 °C
P-1700: manufactured by Amoco Japan) 100 parts by weight,
2 parts by weight of 3-(N-salicyloyl)amino-1,2,4-triazole (MARKCDA-1: manufactured by Adeka Argus Chemical Co., Ltd.), melted and kneaded at 360°C, and molded using an injection molding machine to give a thickness of A 1 mm plate of the resin composition was molded.
【００４０】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表２に示す。
実施例１４
ガラス転移温度１９０ ℃のポリスルホン（ユーデル
Ｐ−１７００：アモコジャパン社製）１００重量部と、
Ｎ，Ｎ’−ビス〔３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオニル〕ヒドラジン（ＩＲ
ＧＡＮＯＸ ＭＤ１０２４：日本チバガイギー社製）２
重量部とを混合し、これを３６０ ℃で溶融混練し射出
成形機により、厚さ１ｍｍの樹脂組成物の板を成形した
。[0040] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 14 Polysulfone (Udel) with a glass transition temperature of 190°C
P-1700: manufactured by Amoco Japan) 100 parts by weight,
N,N'-bis[3-(3,5-di-t-butyl-4-
Hydroxyphenyl)propionyl]hydrazine (IR
GANOX MD1024: Manufactured by Ciba Geigy, Japan) 2
parts by weight were mixed, the mixture was melt-kneaded at 360°C, and a plate of the resin composition with a thickness of 1 mm was molded using an injection molding machine.
【００４１】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表２に示す。
実施例１５
ガラス転移温度１９０ ℃のポリスルホン（ユーデル
Ｐ−１７００：アモコジャパン社製） １００ 重量部
と、Ｎ，Ｎ’−ジ−２−ナフチル−ｐ−フェニレンジア
ミン（ノクラック Ｗｈｉｔｅ：大内新興化学社製）２
重量部とを混合し、これを３６０ ℃で溶融混練し射出
成形機により、厚さ１ｍｍの樹脂組成物の板を成形した
。[0041] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 15 Polysulfone (Udel) with a glass transition temperature of 190°C
P-1700: manufactured by Amoco Japan Co., Ltd.) 100 parts by weight, and N,N'-di-2-naphthyl-p-phenylenediamine (Nocrac White: manufactured by Ouchi Shinko Chemical Co., Ltd.) 2
parts by weight were mixed, the mixture was melt-kneaded at 360°C, and a plate of the resin composition with a thickness of 1 mm was molded using an injection molding machine.
【００４２】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表２に示す。
実施例１６
ガラス転移温度２１９ ℃のポリアリールスルホン（レ
ーデル Ａ−１００：アモコジャパン社製） １００
重量部と、デカメチレンジカルボン酸ジサリチロイルヒ
ドラジド（ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学
社製）２重量部とを混合し、これを３５０ ℃で溶融混
練し射出成形機により、厚さ１ｍｍの樹脂組成物の板を
成形した。[0042] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 16 Polyaryl sulfone with a glass transition temperature of 219°C (Radel A-100: manufactured by Amoco Japan) 100
parts by weight and 2 parts by weight of decamethylene dicarboxylic acid disalicyloyl hydrazide (MARK CDA-6: manufactured by Adeka Argus Chemical Co., Ltd.), melted and kneaded at 350 °C, and molded into a 1 mm thick molded product using an injection molding machine. A plate of the resin composition was molded.
【００４３】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表２に示す。
実施例１７
ガラス転移温度２２５ ℃のポリエーテルスルホン（ビ
クトレックスＰＥＳ ４８００Ｇ ：ＩＣＩジャパン社
製）１００重量部と、デカメチレンジカルボン酸ジサリ
チロイルヒドラジド（ＭＡＲＫ ＣＤＡ−６：アデカア
ーガス化学社製）２重量部とを混合し、これを３５０
℃で溶融混練し射出成形機により厚さ１ｍｍの樹脂組成
物の板を成形した。[0043] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 17 100 parts by weight of polyether sulfone (Victrex PES 4800G, manufactured by ICI Japan Co., Ltd.) with a glass transition temperature of 225°C and 2 parts of decamethylene dicarboxylic acid disalicyloyl hydrazide (MARK CDA-6, manufactured by Adeka Argus Chemical Co., Ltd.) 350 parts by weight.
The resin composition was melt-kneaded at 0.degree. C. and molded into a plate of the resin composition with a thickness of 1 mm using an injection molding machine.
【００４４】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表２に示す。
実施例１８
ガラス転移温度２１５ ℃のポリエーテルイミド（ウル
テム １０００ ：ＧＥプラスチック社製）１００ 重
量部と、デカメチレンジカルボン酸ジサリチロイルヒド
ラジド（ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社
製）２重量部とを混合し、これを３８０ ℃で溶融混練
し射出成形機により、厚さ１ｍｍの樹脂組成物の板を成
形した。[0044] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 18 100 parts by weight of polyetherimide with a glass transition temperature of 215°C (Ultem 1000, manufactured by GE Plastics) and 2 parts by weight of decamethylene dicarboxylic acid disalicyloyl hydrazide (MARK CDA-6, manufactured by Adeka Argus Chemical) The mixture was melt-kneaded at 380° C. and molded into a resin composition plate with a thickness of 1 mm using an injection molding machine.
【００４５】この板について、実施例１と同様にしてイ
オン性物質の溶出性及び有機物質の溶出性を評価した。
その結果を表２に示す。
比較例１
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例１と同様に行った。そ
の結果を表３に示す。[0045] Regarding this plate, the elution properties of ionic substances and organic substances were evaluated in the same manner as in Example 1. The results are shown in Table 2. Comparative Example 1 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 1 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 3.
【００４６】比較例２
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例２と同様に行った。そ
の結果を表３に示す。Comparative Example 2 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 2 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 3.
【００４７】比較例３
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例３と同様に行った。そ
の結果を表３に示す。Comparative Example 3 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 3 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 3.
【００４８】比較例４
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例４と同様に行った。そ
の結果を表３に示す。Comparative Example 4 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 4 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 3.
【００４９】比較例５
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例５と同様に行った。そ
の結果を表３に示す。Comparative Example 5 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 5 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 3.
【００５０】比較例６
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例９と同様に行った。そ
の結果を表３に示す。Comparative Example 6 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 9 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 3.
【００５１】比較例７
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例１０と同様に行った。
その結果を表３に示す。Comparative Example 7 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 10 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 3.
【００５２】比較例８
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例１１と同様に行った。
その結果を表３に示す。Comparative Example 8 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 11 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 3.
【００５３】比較例９
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例１２と同様に行った。
その結果を表４に示す。Comparative Example 9 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 12 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 4.
【００５４】比較例１０
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例１６と同様に行った。
その結果を表４に示す。Comparative Example 10 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 16 was conducted except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 4.
【００５５】比較例１１
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例１７と同様に行った。
その結果を表４に示す。Comparative Example 11 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 17 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 4.
【００５６】比較例１２
デカメチレンジカルボン酸ジサリチロイルヒドラジド（
ＭＡＲＫ ＣＤＡ−６：アデカアーガス化学社製）を全
く混合しないこと以外は、実施例１８と同様に行った。
その結果を表４に示す。Comparative Example 12 Decamethylene dicarboxylic acid disalicyloyl hydrazide (
The same procedure as in Example 18 was carried out except that MARK CDA-6 (manufactured by Adeka Argus Chemical Co., Ltd.) was not mixed at all. The results are shown in Table 4.
【００５７】以上の実施例及び比較例において、測定さ
れた超純水の電気伝導度の値から試験板を浸漬しない場
合の超純水の電気伝導度１５．５μＳ／ｃｍ（ブランク
測定値）を差引き、その値から試験板からの金属イオン
等のイオン性物質の溶出性が判断される。それによると
、キレート化剤を含有する本発明の実施例が、これと対
応するキレート化剤を含有しない従来の比較例に較べ、
金属イオン等のイオン性物質の溶出が極めて少ないこと
がわかる。In the above Examples and Comparative Examples, the electrical conductivity of ultrapure water when the test plate is not immersed is 15.5 μS/cm (blank measurement value) from the value of the electrical conductivity of ultrapure water measured. After subtraction, the elution of ionic substances such as metal ions from the test plate is determined from the value. According to this, the examples of the present invention containing a chelating agent compared with the corresponding conventional comparative examples not containing a chelating agent,
It can be seen that the elution of ionic substances such as metal ions is extremely small.
【００５８】[0058]
【表１】[Table 1]
【００５９】[0059]
【表２】[Table 2]
【００６０】[0060]
【表３】[Table 3]
【００６１】[0061]
【表４】[Table 4]
【００６２】[0062]
【発明の効果】上述の通り、本発明の熱可塑性樹脂組成
物は、熱可塑性樹脂に、融点が１００℃以上で且つ水に
不溶のキレート化剤が含有されているので、樹脂に残留
している金属イオンに対してこのキレート化剤が配位し
てキレートを形成し、不純物となる金属イオンはキレー
ト化剤に補足されて樹脂からの溶出が防止される。Effects of the Invention As mentioned above, the thermoplastic resin composition of the present invention contains a chelating agent having a melting point of 100°C or higher and insoluble in water, so that it does not remain in the resin. The chelating agent coordinates with the metal ions present to form a chelate, and the metal ions that become impurities are captured by the chelating agent and prevented from being eluted from the resin.
【００６３】しかも、上記のキレート化剤は、融点が１
００ ℃以上で且つ水に不溶であるので、使用される熱
可塑性樹脂の耐熱性や耐熱水性と相まって、耐熱性や耐
熱水性に優れた樹脂組成物が得られる。Moreover, the above chelating agent has a melting point of 1
Since it is insoluble in water at a temperature of 00° C. or higher, in combination with the heat resistance and hot water resistance of the thermoplastic resin used, a resin composition with excellent heat resistance and hot water resistance can be obtained.
【００６４】したがって、本発明の熱可塑性樹脂組成物
は、パイプ、継ぎ手、バルブ、タンク、容器などの各種
製品に成形され、半導体表面の洗浄に使用される超純水
の輸送配管材料やシリコンウエハ処理用の耐熱性容器、
加熱殺菌や蒸気殺菌が行われる培養器、高純度水処理用
ビーカーなど、特に超純水を対象とする用途に好適に使
用することができる。Therefore, the thermoplastic resin composition of the present invention can be molded into various products such as pipes, joints, valves, tanks, and containers, and can be used as piping materials for transporting ultrapure water used for cleaning semiconductor surfaces and silicon wafers. heat-resistant containers for processing,
It can be suitably used particularly in applications that target ultrapure water, such as culture vessels in which heat sterilization or steam sterilization is performed, and beakers for high-purity water treatment.
Claims (4)
上で且つ水に不溶のキレート化剤が含有されていること
を特徴とするイオン溶出の少ない熱可塑性樹脂組成物。1. A thermoplastic resin composition with little ionic elution, characterized in that the thermoplastic resin contains a chelating agent having a melting point of 100° C. or more and which is insoluble in water.
リフェニレンサルファイド、ポリエーテルケトン、ポリ
エーテルエーテルケトンから選ばれる少なくとも一種の
樹脂を用いることを特徴とする請求項１記載のイオン溶
出の少ない熱可塑性樹脂組成物。2. The thermoplastic resin with low ionic elution according to claim 1, wherein at least one resin selected from fluororesin, polyphenylene sulfide, polyetherketone, and polyetheretherketone is used as the thermoplastic resin. Composition.
が１００ ℃以上の無定形樹脂を用いることを特徴とす
る請求項１記載のイオン溶出の少ない熱可塑性樹脂組成
物。3. The thermoplastic resin composition with low ion elution according to claim 1, wherein an amorphous resin having a glass transition temperature of 100° C. or higher is used as the thermoplastic resin.
ボン酸ジサリチロイルヒドラジド、Ｎ，Ｎ’−ビス〔３
−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル
）プロピオニル〕ヒドラジン、Ｎ，Ｎ’−ジ−２−ナフ
チル−ｐ−フェニレンジアミンから選ばれる少なくとも
一種を用いることを特徴とする請求項１から３のいずれ
か１項に記載のイオン溶出の少ない熱可塑性樹脂組成物
。4. As a chelating agent, methylene dicarboxylic acid disalicyloyl hydrazide, N,N'-bis[3
A claim characterized in that at least one selected from -(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine and N,N'-di-2-naphthyl-p-phenylenediamine is used. 4. The thermoplastic resin composition with low ion elution according to any one of 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12124291A JPH04348163A (en) | 1991-05-27 | 1991-05-27 | Thermoplastic resin composition little in elution of ion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12124291A JPH04348163A (en) | 1991-05-27 | 1991-05-27 | Thermoplastic resin composition little in elution of ion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04348163A true JPH04348163A (en) | 1992-12-03 |
Family
ID=14806424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12124291A Pending JPH04348163A (en) | 1991-05-27 | 1991-05-27 | Thermoplastic resin composition little in elution of ion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04348163A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019009079A1 (en) * | 2017-07-03 | 2019-01-10 | 日立化成株式会社 | Polyketone composition containing hydrazide compound, polyketone cured product, optical element and image display device |
| JP2020105287A (en) * | 2018-12-26 | 2020-07-09 | 日立化成株式会社 | Polyketone composition containing hydrazide compound, polyketone cured product, optical element and image display device |
-
1991
- 1991-05-27 JP JP12124291A patent/JPH04348163A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019009079A1 (en) * | 2017-07-03 | 2019-01-10 | 日立化成株式会社 | Polyketone composition containing hydrazide compound, polyketone cured product, optical element and image display device |
| CN110785466A (en) * | 2017-07-03 | 2020-02-11 | 日立化成株式会社 | Hydrazide compound-containing polyketone composition, polyketone cured product, optical element, and image display device |
| JP2020105287A (en) * | 2018-12-26 | 2020-07-09 | 日立化成株式会社 | Polyketone composition containing hydrazide compound, polyketone cured product, optical element and image display device |
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