JP2000002697A - Column for liquid chromatography and production thereof - Google Patents

Column for liquid chromatography and production thereof

Info

Publication number
JP2000002697A
JP2000002697A JP8027547A JP2754796A JP2000002697A JP 2000002697 A JP2000002697 A JP 2000002697A JP 8027547 A JP8027547 A JP 8027547A JP 2754796 A JP2754796 A JP 2754796A JP 2000002697 A JP2000002697 A JP 2000002697A
Authority
JP
Japan
Prior art keywords
porous glass
glass support
paint
liquid chromatography
column
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP8027547A
Other languages
Japanese (ja)
Inventor
Kumiko Maekawa
久美子 前川
Akira Tamaoki
彰 玉置
Tomoaki Nakanishi
智昭 中西
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Fusso Co Ltd
Original Assignee
Nippon Fusso Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Fusso Co Ltd filed Critical Nippon Fusso Co Ltd
Priority to JP8027547A priority Critical patent/JP2000002697A/en
Priority to PCT/JP1997/000339 priority patent/WO1997030349A1/en
Publication of JP2000002697A publication Critical patent/JP2000002697A/en
Pending legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/60—Construction of the column
    • G01N30/6047—Construction of the column with supporting means; Holders
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/60—Construction of the column
    • G01N30/6052—Construction of the column body

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a column for liquid chromatography having conditions for utilizing a porous glass support effectively in an HPLC, and a production method thereof. SOLUTION: A coating 2 composed of a particle group where particles having a particle size slightly larger than the diameter of pores of a porous glass support 1 and having such a composition that polyether ether ketone resin and glycol based organic solvent are dispersed at a ratio of 20/80-24/76 and admixed with 1-5% of a heat resistant and chemical resistant whisker as a film reinforcing agent is formed at a thickness of 100-500 μm around the porous glass support 1 formed into a rod by a dipping means and a part of the film is formed to permeate homogeneously on the the surface of the porous glass support 1 thus producing the column for liquid chromatography.

Description

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

【０００１】[0001]

【発明の属する技術分野】本発明は、複数の溶質が溶け
た移動相を、固定相を詰めたカラムに複数の溶質が溶け
た移動相を通すことにより、移動相と固定相との物理的
または化学的な相互作用により溶質を分解分析する液体
クロマトグラフィに使用する液体クロマトグラフィ用カ
ラムとその製造方法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a method for physically transferring a mobile phase in which a plurality of solutes are dissolved through a mobile phase in which a plurality of solutes is dissolved through a column packed with the stationary phase. The present invention also relates to a column for liquid chromatography used in liquid chromatography for decomposing and analyzing a solute by chemical interaction, and a method for producing the same.

【０００２】[0002]

【従来の技術】液体クロマトグラフィ（Liquid Chromat
ography,ＬＣ）は、固定相を詰めたカラムに複数の溶質
が溶けた移動相を通すことにより、移動相と固定相との
物理的または化学的な相互作用により溶質を分解分析す
る方法であり、専ら医薬品、合成高分子の領域で力を発
揮してきたが、さらに近年に入り、遺伝子組替えを含む
バイオテクノロジーや、医療の診断を含む生体情報把握
のための手段として広く使用されている。2. Description of the Related Art Liquid Chromat
ography, LC) is a method in which a solute is dissolved and analyzed by physical or chemical interaction between the mobile phase and the stationary phase by passing a mobile phase in which a plurality of solutes are dissolved through a column packed with the stationary phase. Although it has been exerting its power exclusively in the fields of pharmaceuticals and synthetic polymers, in recent years, it has been widely used as a means for grasping biological information including genetic modification and medical diagnosis.

【０００３】一方、高速液体クロマトグラフィ（ＨＰＬ
Ｃ）は、機器やシステムの発展の他にカラム強化剤の発
展も重要であり、最近ではＨＰＬＣの固定相の高性能化
が期待されている多孔質ガラス支持体（ポーラスガラ
ス）に着眼され、パイプ（SUSまたはPEEK樹脂）に多孔
質ガラス支持体の粉末を充填した液体クロマトグラフィ
用カラムや、棒状に形成された支持体、例えば、特開昭
６３−２０００６０号公報に開示されているように、シ
リカゲルまたは多孔質ガラス支持体からなる担体と、該
担体に対して化学結合を有するポリ〔Ｎ−（ベンジル−
２−ヒドロキシエトキシカルボニルメチル）アクリルア
ミド〕、及びエチル２−アクリルアミド−３−フェニル
ブロバナートと２−ヒドロキシエチルアクリレートとの
共重合体からなる群より選ばれた高分子物質からなる支
持体（株式会社島津製作所製）に、熱収縮チューブを利
用した皮膜を形成し、さらに周りから水圧をかけて密着
させた液体クロマトグラフィ用カラムが使用されてい
る。On the other hand, high performance liquid chromatography (HPL)
In C), the development of column strengthening agents is also important in addition to the development of instruments and systems. Recently, attention has been focused on a porous glass support (porous glass), which is expected to improve the performance of HPLC stationary phases. A column for liquid chromatography in which a pipe (SUS or PEEK resin) is filled with a powder of a porous glass support, or a support formed in a rod shape, for example, as disclosed in JP-A-63-200060, A carrier composed of silica gel or a porous glass support, and a poly [N- (benzyl-
2-hydroxyethoxycarbonylmethyl) acrylamide], and a support made of a polymer substance selected from the group consisting of a copolymer of ethyl 2-acrylamido-3-phenylbrobanate and 2-hydroxyethyl acrylate (Co., Ltd. (Manufactured by Shimadzu Corporation), a column for liquid chromatography is used in which a film is formed using a heat-shrinkable tube, and water pressure is applied from the surroundings to bring the film into close contact.

【０００４】[0004]

【発明が解決しようとする課題】これら液体クロマトグ
ラフィ用カラムは、200kgf/cm2程度の加圧下において破
損して分析液が漏れたり、隙間が発生してリークしない
こと、分析液が溶出イオン・パーティクルで汚染されな
いこと、分析液によって侵されない耐薬品性を具備する
こと等の条件を備えた皮膜をカラムの周囲に形成する必
要があり、これが充足されて初めて、多孔質ガラス支持
体のＨＰＬＣへの有効利用が可能となるのである。These liquid chromatography columns are broken under a pressure of about 200 kgf / cm 2, so that the analytical solution does not leak due to gaps or gaps are generated. It is necessary to form a film around the column under conditions such as not being contaminated by the sample, having chemical resistance not to be attacked by the analysis solution, and the like. Effective use becomes possible.

【０００５】しかし、前者のパイプへの多孔質ガラス支
持体の粉末を充填手段では、粉末の間にできる間隙の安
定性が悪く、また粉末充填によっては高圧をかけると粉
末が移動する場合があって安定性に欠け優れた分解能が
得られない点、及びきわめて厄介な充填作業や高価な充
填装置を必要とすることからコスト高となる点に解決す
べき課題があった。However, in the former method of filling the powder of the porous glass support into the pipe, the stability of the gap formed between the powders is poor, and depending on the powder filling, the powder may move when a high pressure is applied. There is a problem to be solved in that a high resolution is not obtained due to lack of stability and that an extremely troublesome filling operation and an expensive filling device are required, resulting in an increase in cost.

【０００６】また後者の棒状に形成された多孔質ガラス
（非粉末）の支持体に、熱収縮チューブを利用した皮膜
を形成する手段では、安定して均一な孔を利用すること
ができることから、分解能力を向上（目標理論段数6000
段）させることができるとともに、分析液を200kgf/cm2
の圧力下において通すこともできる等の利点があるにも
関わらず、PFA 熱収縮チューブとの間に間隙が生じてリ
ークを生じるだけでなく、残留触媒、未反応分子の溶出
があることから、前者と同様、優れた分解能が得られな
い点に解決すべき課題があった。In the latter means of forming a film using a heat-shrinkable tube on a porous glass (non-powder) support formed in the shape of a rod, stable and uniform pores can be used. Improved decomposition capacity (target theoretical plate number 6000)
Step) and the analysis solution is 200kgf / cm 2
Despite the advantages such as being able to pass under pressure, not only does a leak occur due to the formation of a gap with the PFA heat-shrinkable tube, but also residual catalyst and unreacted molecules elute, As with the former, there is a problem to be solved in that excellent resolution cannot be obtained.

【０００７】本発明は、市販（三井東圧化学株式会社、
住友化学工業株式会社等）されているポリエーテルエー
テルケトン樹脂（ＰＥＥＫ樹脂）が、機械的強靭性、高
純度性、耐薬品性に優れ、分析分野において実績がある
点に着眼し、多孔質ガラス支持体のＨＰＬＣへの有効利
用条件を具備する液体クロマトグラフィ用カラムとその
製造方法の提供を目的としている。The present invention is commercially available (Mitsui Toatsu Chemical Co., Ltd.,
Focusing on the fact that polyetheretherketone resin (PEEK resin) manufactured by Sumitomo Chemical Co., Ltd.) has excellent mechanical toughness, high purity, and chemical resistance and has a proven track record in the analytical field. It is an object of the present invention to provide a column for liquid chromatography having a condition for effectively using a support for HPLC and a method for producing the same.

【０００８】[0008]

【課題を解決するための手段】本発明の液体クロマトグ
ラフィ用カラムは、ポリエーテルエーテルケトン樹脂を
グリコール系有機溶剤に分散させ、これに耐熱性、耐薬
品性等を備えたウィスカー等の膜強化剤を添加混合した
組成であって、後記多孔質ガラス支持体に形成されてい
る微細な孔径よりも僅かに大きい粒径の粒子が分布され
た粒子群から構成される皮膜を、棒状に成形された多孔
質ガラス支持体の周囲に、ディッピング手段により薄く
とも 100μm 以上であってクラック等によるリークの生
じない範囲の膜厚とし且つ多孔質ガラス支持体の表面に
前記組成の皮膜の一部が浸透状に均質に形成されている
ことを特徴とする液体クロマトグラフィ用カラム。According to the liquid chromatography column of the present invention, a polyether ether ketone resin is dispersed in a glycol-based organic solvent, and a film strengthening agent such as a whisker having heat resistance and chemical resistance is added thereto. Was added and mixed, and a coating composed of particles in which particles having a particle diameter slightly larger than the fine pore diameter formed on the porous glass support described later were formed into a rod shape. A film having a thickness of at least 100 μm or more is formed around the porous glass support by dipping means so that leakage due to cracks or the like does not occur, and a part of the film having the composition described above penetrates the surface of the porous glass support. A liquid chromatography column, which is formed homogeneously in a liquid chromatography column.

【０００９】なお、ポリエーテルエーテルケトン樹脂／
グリコール系有機溶剤、例えばプロピレングリコールと
の比率は、20/80 〜24/76 とし、これに対する膜強化剤
としてのウィスカーの添加量は１〜５％とすることが、
液体クロマトグラフィ用カラムとしてＨＰＬＣへの有効
利用条件を具備させる上で最適である。The polyether ether ketone resin /
The ratio with a glycol-based organic solvent, for example, propylene glycol, is 20/80 to 24/76, and the addition amount of whiskers as a film strengthening agent is 1 to 5%.
It is most suitable as a column for liquid chromatography in providing effective use conditions for HPLC.

【００１０】また、本発明の液体クロマトグラフィ用カ
ラムの製造方法は、ポリエーテルエーテルケトン樹脂を
グリコール系有機溶剤に分散させ、これにウィスカー等
の膜強化剤を添加混合した組成であって、粒径分布が3.
17〜61.00 μm の粒子群から構成される塗料を、上端開
口の塗料槽に収容し、該塗料槽を、棒状に成形された孔
径 2μm 程度の多孔質ガラス支持体が気密状態で上下移
動でき且つ真空圧から常圧に戻すことができるようにし
た真空形成室内に配設し、該真空形成室内を真空状態と
した状態で、前記多孔質ガラス支持体を塗料槽内の塗料
にディッピングした後、真空形成室内を常圧に戻して塗
料槽から前記多孔質ガラス支持体を引き上げて真空形成
室内から取り出し、これに焼成処理を加えることを特徴
とする方法であり、焼成処理としては、およそ、150 〜
200 ℃までを１時間、200 〜350℃までを30分、350 〜4
00 ℃までを１時間、400 〜350 ℃までを１時間とする
焼成条件において実施することが、品質保持、製作能率
上において最適である。The method for producing a column for liquid chromatography according to the present invention has a composition in which a polyetheretherketone resin is dispersed in a glycol-based organic solvent, and a film-reinforcing agent such as whisker is added thereto and mixed. Distribution is 3.
A paint composed of particles having a particle size of 17 to 61.00 μm is accommodated in a paint tank having an upper end opening, and a porous glass support having a pore diameter of about 2 μm, which is formed in a rod shape, can be moved up and down in an airtight state, and It is arranged in a vacuum forming chamber capable of returning to normal pressure from vacuum pressure, and after the porous glass support is dipped in paint in a paint tank while the vacuum forming chamber is in a vacuum state, The vacuum forming chamber is returned to normal pressure, the porous glass support is pulled up from the paint tank and taken out of the vacuum forming chamber, and a baking treatment is added thereto. ~
1 hour to 200 ° C, 30 minutes from 200 to 350 ° C, 350 to 4
It is best to carry out the calcination under the conditions of sintering up to 00 ° C. for 1 hour and 400-350 ° C. for 1 hour in terms of quality maintenance and production efficiency.

【００１１】[0011]

【発明の実施の形態】及びDETAILED DESCRIPTION OF THE INVENTION AND

【実施例】（実施例１）図１は本発明に係る液体クロマ
トグラフィ用カラムの軸方向の拡大断面図、図２は軸直
角拡大断面図であり、直径4.7mm 、長さ30mmの断面円形
の棒状に成形された平均孔径 2μm 程度の多孔質ガラス
支持体１の周囲に、以下に説明する組成の皮膜をディッ
ピング手段により、膜厚100 〜500 μm に形成したもの
である。(Example 1) FIG. 1 is an enlarged sectional view in the axial direction of a column for liquid chromatography according to the present invention, and FIG. 2 is an enlarged sectional view perpendicular to the axis, having a circular cross section having a diameter of 4.7 mm and a length of 30 mm. A film having a composition described below is formed around a porous glass support 1 having a mean pore diameter of about 2 μm formed into a rod shape and having a film thickness of 100 to 500 μm by dipping means.

【００１２】前記皮膜の組成については、ポリエーテル
エーテルケトン樹脂（ＰＥＥＫ樹脂）の粉砕品（150PF
13M ）と、グリコール系有機溶剤の一種であるプロピレ
ングリコールとの比率を、約0.15〜0.45の範囲（12/88
、15/85 、20/80 、22/78 、24/76 、25/75 、30/70
）のそれぞれに、これに対する膜強化剤としてウィス
カー（大塚化学株式会社製チタン酸カリウィスカー「テ
ィスモ−Ｎ（商標）」）を使用し、その添加量を０〜10
％の範囲で混合した皮膜組成サンプルを調剤し、これら
を対象として粒度分布測定を行った。Regarding the composition of the film, a pulverized product of polyetheretherketone resin (PEEK resin) (150PF
13M) and propylene glycol, a kind of glycol-based organic solvent, in the range of about 0.15 to 0.45 (12/88
, 15/85, 20/80, 22/78, 24/76, 25/75, 30/70
), A whisker (Kari Whisker “Tismo-N (trademark)” manufactured by Otsuka Chemical Co., Ltd.) was used as a film-strengthening agent, and the added amount was 0 to 10
%, And a film composition sample mixed in the range of% was prepared, and the particle size distribution was measured for these samples.

【００１３】 粒度分布測定 粒度測定器 コールターカウンター ＴＡ−１１型（セイシン興業 株式会社製） 電解液 ＩＳＯＴＯＮ アパーチャー径 ２００μｍ サンプル塗料容量 １ ｍｌ 希釈倍率 １Particle size distribution measurement Particle size analyzer Coulter counter TA-11 type (manufactured by Seishin Kogyo Co., Ltd.) Electrolyte ISOTON Aperture diameter 200 μm Sample paint volume 1 ml Dilution ratio 1

【００１４】 計算値（体積分布） 平均値 ：12.76 μm 中位径 ：13.08 μm 歪 度：-0.146 標準偏差： 3.81 μm 20% 以下径：18.98 μm 尖 度： 3.146 変動係数：29.8％ 80% 以上径： 8.59 μm その結果は、下記、表１に示す通りであり、またその粒
度分布図は図４、図５に示す通りである。Calculated value (volume distribution) Average value: 12.76 μm Median diameter: 13.08 μm Skewness: -0.146 Standard deviation: 3.81 μm 20% or less Diameter: 18.98 μm Kurtosis: 3.146 Variation coefficient: 29.8% 80% or more diameter : 8.59 μm The results are as shown in Table 1 below, and the particle size distribution diagrams are as shown in FIGS. 4 and 5.

【００１５】[0015]

【表１】 [Table 1]

【００１６】（液体クロマトグラフィ用カラムの製造方
法）そして、上記各組成の塗料を使用して以下の方法に
より液体クロマトグラフィ用カラムを製作した。すなわ
ち、棒状に成形された多孔質ガラス支持体を軸方向に気
密状態で上下移動させるようにした真空形成室内に、前
記組成の一種の塗料を収容した上端開口の塗料槽を配設
し、前記真空形成室内を510mmHg の真空状態とした状態
で、前記多孔質ガラス支持体に塗料槽内の塗料をディッ
ピングし、真空形成室内を常圧に戻すと同時に塗料槽か
ら多孔質ガラス支持体を引き上げ、焼成処理を実施し、
多孔質ガラス支持体の周面に膜厚100 〜500 μm の皮膜
を形成した。(Production Method of Liquid Chromatography Column) Then, a liquid chromatography column was manufactured by the following method using the paints having the above-mentioned compositions. That is, in a vacuum forming chamber in which a porous glass support formed in a rod shape is vertically moved in an airtight state in an axial direction, a paint tank having an upper end opening containing a kind of paint of the above composition is arranged, In a state where the vacuum forming chamber was in a vacuum state of 510 mmHg, the paint in the paint tank was dipped on the porous glass support, and the vacuum forming chamber was returned to normal pressure, and at the same time, the porous glass support was pulled out of the paint tank, Carry out baking treatment,
A film having a thickness of 100 to 500 μm was formed on the peripheral surface of the porous glass support.

【００１７】上記焼成処理については、皮膜厚が均一に
形成できれば特に限定するものではないが、上記の方法
の実施例においては、バッチ式の小型電気炉を使用し、
およそ150 〜200 ℃まで１時間、200 〜350 ℃まで30
分、350 〜400 ℃まで１時間、400 〜350 ℃まで１時間
の焼成条件において実施した。The baking treatment is not particularly limited as long as the film thickness can be formed uniformly, but in the embodiment of the above method, a batch type small electric furnace is used.
Approx. 1 hour from 150 to 200 ° C, 30 from 200 to 350 ° C
The firing was carried out under the conditions of 1 minute to 350-400 ° C. and 1 hour to 400-350 ° C.

【００１８】なお、多孔質ガラス支持体１は、公知の、
シリカゲルまたは多孔質ガラス支持体からなる担体と、
該担体に対して化学結合を有するポリ〔Ｎ−（ベンジル
−２−ヒドロキシエトキシカルボニルメチル）アクリル
アミド〕、及びエチル２−アクリルアミド−３−フェニ
ルブロバナートと２−ヒドロキシエチルアクリレートと
の共重合体からなる群より選ばれた高分子物質からなる
もの（株式会社島津製作所製）を使用した（以下の実施
例において同じ）。The porous glass support 1 is made of a known material,
A carrier comprising silica gel or a porous glass support;
Poly [N- (benzyl-2-hydroxyethoxycarbonylmethyl) acrylamide] having a chemical bond to the carrier, and a copolymer of ethyl 2-acrylamido-3-phenylbrobanate and 2-hydroxyethyl acrylate A polymer consisting of a polymer substance selected from the following group (manufactured by Shimadzu Corporation) was used (the same applies to the following examples).

【００１９】上記方法により製作した液体クロマトグラ
フィ用カラムをそれぞれＨＩＬＣに使用して、分析液を
200kgf/cm2の圧力下において通したところ、配合比率及
びウィスカー添加量及び膜厚によって、ＰＥＥＫ樹脂の
特性（機械的強靭性、不純物がなく高純度、耐薬品性
等）が生かされ、圧力によるクラックも分析液のリーク
によるショートパスも、不純物の溶出もない優れた分解
能を具備した発明目的が達成できたものと、皮膜がポー
ラス状になったり、ピンホールができたり、膜厚のばら
つきが大きく、焼成後に皮膜にクラックが発生する等を
原因とする、分析液のリークによるショートパス現象や
不純物溶出を起こし、分解能を得ることができないもの
とが判明した。その結果は以下の通りである。Using the columns for liquid chromatography produced by the above method for HILC, the analytical solution was
When passed under a pressure of 200 kgf / cm 2 , the characteristics (mechanical toughness, high purity without impurities, high chemical resistance, etc.) of the PEEK resin are utilized depending on the compounding ratio, the amount of whisker added, and the film thickness. In addition to the achievement of the object of the invention having excellent resolution without cracks, short paths due to leaks of the analysis solution, and elution of impurities, the film becomes porous, pinholes are formed, and the film thickness varies. It was found that the resolution could not be obtained due to the short path phenomenon and the elution of impurities due to the leakage of the analysis solution, which were caused by cracks in the film after baking. The results are as follows.

【００２０】[0020]

【表２】 なお、膜厚は100 〜500 μm の範囲において略同一結果
であり、500 μm 以上になるとポーラス状となり好まし
くなかった。[Table 2] The results were almost the same when the film thickness was in the range of 100 to 500 µm. When the film thickness was 500 µm or more, the film became porous and was not preferable.

【００２１】そこで、配合比率 20/80 、22/78 、24/7
6 であって、粒径3.17〜61.00 μm、ウィスカー添加量
１〜５％のサンプル（Ａグループ）と、それ以外のサン
プル（Ｂグループ）について、断面の顕微鏡でその組織
を確認したところ、Ａ、Ｂの各グループについて、図
１、図２、図３に示すように、多孔質ガラス支持体支持
体１と皮膜２との境界部に、FRP 状の傾斜組織部３（Ｐ
ＥＥＫ樹脂と多孔質ガラス支持体が混じった層組織）が
形成されていたが、Ｂグループについては、膜厚にバラ
ツキがあり、焼成後に温度変化によるクラック、溶剤の
蒸発によるポーラス状化、ピンホール等が認められた。Therefore, the mixing ratio of 20/80, 22/78, 24/7
6 and a sample having a particle size of 3.17 to 61.00 μm and a whisker addition amount of 1 to 5% (Group A), and the other samples (Group B), the microstructures of the cross sections were examined. For each group B, as shown in FIGS. 1, 2 and 3, the FRP-like inclined texture 3 (P) was formed at the boundary between the porous glass support 1 and the coating 2.
A layer structure in which the EEK resin and the porous glass support were mixed) was formed. However, in the group B, there was variation in film thickness, cracks due to temperature changes after firing, porous formation due to evaporation of the solvent, and pinholes. And so on.

【００２２】（実施例２）ＰＥＥＫ樹脂に、プロピレン
グリコールに代えてフッソ樹脂ＰＦＡ塗料（500CL）を
８／２の比率で混合することによりエナメル塗料化し
て、多孔質ガラス支持体（三井デュポンクロロケミカル
製）の周面に皮膜を一度に均一な100 μm 以上の皮膜を
形成する目的でディツピング塗装した結果、膜厚300 μ
m の均一で強固な皮膜が形成された。しかし、液体クロ
マトグラフィ用カラムとして利用した場合には、液体流
出の始めに異物が流出し、安定するまでに１時間を必要
としたが、この時間的経済性を許容すれば、多孔質ガラ
ス支持体のＨＰＬＣへの有効利用条件を具備する液体ク
ロマトグラフィ用カラムを得ることができる。(Example 2) A PEEK resin was mixed with a fluorine resin PFA paint (500CL) in place of propylene glycol at a ratio of 8/2 to make an enamel paint, and a porous glass support (Mitsui DuPont Chlorochemical Co., Ltd.) Dip coating to form a uniform film of 100 μm or more at once on the peripheral surface of
m and a strong film was formed. However, when used as a column for liquid chromatography, it took one hour for the foreign substances to flow out at the beginning of the liquid outflow and to be stabilized. A liquid chromatography column satisfying the conditions for effective use in HPLC can be obtained.

【００２３】なお、上記液体クロマトグラフィ用カラム
及びその製造方法において、膜強化剤としてウィスカー
を使用した場合について説明したが、これに限定される
ものではなく、ＰＥＥＫ樹脂の機械的強度の向上と焼成
後の冷却の際に生じる収縮応力の緩和を果たすもの、例
えば、フッソ樹脂、黒鉛、炭化珪素、アルミナ、セラミ
ックファイバー、アルミナシリケート、アルミナ、SI-T
i-C-O 繊維、参加チタン等の一種又は二種以上の適宜量
を添加混合して使用することができる。In the above-described liquid chromatography column and the method for producing the same, the case where whiskers are used as the membrane strengthening agent has been described. However, the present invention is not limited to this. That reduce the shrinkage stress generated during cooling, for example, fluorine resin, graphite, silicon carbide, alumina, ceramic fiber, alumina silicate, alumina, SI-T
One or more appropriate amounts of iCO fiber, participating titanium and the like can be added and mixed for use.

【００２４】なお、本発明を完成するために、公知の、
シリカゲルまたは多孔質ガラス支持体からなる担体及び
該担体に対して化学結合を有するポリ〔Ｎ−（ベンジル
−２−ヒドロキシエトキシカルボニルメチル）アクリル
アミド〕、及びエチル２−アクリルアミド−３−フェニ
ルブロバナートと２−ヒドロキシエチルアクリレートと
の共重合体からなる群より選ばれた高分子物質からなる
多孔質ガラス支持体と、ＰＥＥＫ樹脂を用いて行った、
各種の実験例とその結果を以下説明する。It should be noted that, in order to complete the present invention,
A carrier comprising silica gel or a porous glass support and poly [N- (benzyl-2-hydroxyethoxycarbonylmethyl) acrylamide] having a chemical bond to the carrier, and ethyl 2-acrylamido-3-phenylbrobanate Performed using a porous glass support made of a polymer substance selected from the group consisting of copolymers with 2-hydroxyethyl acrylate and PEEK resin,
Various experimental examples and their results will be described below.

【００２５】（実験例１）多孔質ガラス支持体には導電
性がないために水を塗布して導電性を与え、ＰＥＥＫ樹
脂粉体を用いて静電粉体塗装を行うことにより、多孔質
ガラス支持体の周面に塗装膜を形成した結果、約30〜約
100 μm の塗装膜厚が形成されたが、膜厚は不均一であ
り、焼成後の熱収縮もあって、冷却途中に皮膜が破壊さ
れ多孔質ガラス支持体にクラックを生じることが多く、
また追加塗装しても、溶融時にはじきが発生して熱劣化
がすすむなどの不都合があり、静電粉体塗装手段による
ＰＥＥＫ樹脂皮膜形成手段では、液体クロマトグラフィ
用カラムとしての分解能が得られなかった。(Experimental Example 1) Since the porous glass support is not conductive, water is applied to impart conductivity, and the porous glass support is subjected to electrostatic powder coating using PEEK resin powder, thereby obtaining a porous glass support. As a result of forming a coating film on the peripheral surface of the glass support, about 30 to about
Although a coating film thickness of 100 μm was formed, the film thickness was not uniform, and due to heat shrinkage after firing, the film was broken during cooling and cracks often occurred on the porous glass support,
In addition, even if the additional coating is performed, there is a disadvantage such as the occurrence of cracks during melting and the thermal degradation proceeds, and the resolution as a column for liquid chromatography could not be obtained by the PEEK resin film forming means by the electrostatic powder coating means. .

【００２６】（実験例２）ＰＥＥＫ樹脂にフッソ樹脂Ｐ
ＦＡ塗料（500 CL）を８／２の比率で混合することによ
りエナメル塗料化して、多孔質ガラス支持体（三井デュ
ポンクロロケミカル製）の周面にスプレー塗装すること
により、約30〜約100 μm の塗装膜厚が形成されたが、
その結果は実験例１と同様、膜厚は不均一であり、焼成
後の熱収縮もあって、冷却途中に多孔質ガラス支持体に
クラックが生じ、液体クロマトグラフィ用カラムとして
の分解能が得られなかった。なお、本発明と同じ組成の
塗料を用いて行ったスプレー塗装では、エアーによる霧
化によって高粘度となり、多孔質ガラス支持体と皮膜と
の境界部に、FRP 状の傾斜組織部は形成されず熱変形に
よって隙間が形成されるため、採用することができな
い。(Experimental Example 2) Fluoro resin P was added to PEEK resin.
FA paint (500 CL) is mixed at a ratio of 8/2 to make an enamel paint, and then spray-coated on the peripheral surface of a porous glass support (manufactured by Mitsui Dupont Chlorochemical) to obtain a coating of about 30 to about 100 μm. Although the coating film thickness of was formed,
As a result, as in Experimental Example 1, the film thickness was non-uniform, and there was thermal shrinkage after firing, cracks occurred in the porous glass support during cooling, and the resolution as a liquid chromatography column could not be obtained. Was. In the case of spray coating using a paint having the same composition as that of the present invention, the viscosity becomes high due to atomization by air, and no FRP-like inclined texture is formed at the boundary between the porous glass support and the coating. Since a gap is formed by thermal deformation, it cannot be adopted.

【００２７】なお、コーティング手段として知られる他
の塗装手段（回転塗装、流動浸漬塗装、低温溶射塗装）
についても、種々条件のもとに実験をしたが、結果は実
験例１又は２において説明したのと同様の不都合があっ
た。In addition, other coating means known as coating means (rotational coating, fluidized immersion coating, low-temperature spray coating)
Was also conducted under various conditions, and the result was the same inconvenience as described in Experimental Example 1 or 2.

【００２８】[0028]

【発明の効果】第１発明の液体クロマトグラフィ用カラ
ムは、ＰＥＥＫ樹脂をプロピレングリコールに分散さ
せ、これに膜強化剤としてウィスカー等を添加混合した
組成であって、多孔質ガラス支持体に形成されている孔
径よりも僅かに大きい粒径の粒子が分布された粒子群か
ら構成される皮膜、例えば粒径約3.17〜61.00 μm の粒
子群から構成される皮膜を、例えば平均孔径2 μm の多
孔質ガラス支持体の周囲に、ディッピング手段により 1
00μm 以上500 μm 以下であり且つ多孔質ガラス支持体
（棒状）の表面に前記組成皮膜の一部が浸透状に均質に
形成した構成としたから、液体クロマトグラフィ用カラ
ムとして要求される、200gf/cm2 の加圧下において破損
せず、分析液の漏れ、隙間の発生もなくてリークしない
こと、分析液が溶出イオン・パーティクルで汚染されな
いこと、分析液によって侵されない耐薬品性を具備する
ことの条件を備えた液体クロマトグラフィ用カラムが得
られ、これのＨＰＬＣへの有効利用を可能とすることが
できる。The liquid chromatography column of the first invention has a composition in which PEEK resin is dispersed in propylene glycol, and whiskers and the like are added and mixed as a film strengthening agent, and the column is formed on a porous glass support. A film composed of a group of particles having a particle size slightly larger than the pore size, for example, a film composed of a group of particles having a particle size of about 3.17 to 61.00 μm, for example, a porous glass having an average pore size of 2 μm. Around the support, by means of dipping 1
Since the composition was formed to have a thickness of not less than 00 μm and not more than 500 μm and a part of the composition film formed uniformly on the surface of the porous glass support (rod shape) in a permeable manner, 200 gf / cm required as a column for liquid chromatography. 2. Conditions that are not damaged under pressurization, do not leak due to no leakage of the analytical solution, no gaps are generated, that the analytical solution is not contaminated with eluted ions and particles, and that it has chemical resistance that is not attacked by the analytical solution Thus, a column for liquid chromatography provided with is obtained, which can be effectively used for HPLC.

【００２９】第２発明の液体クロマトグラフィ用カラム
は、ＰＥＥＫ樹脂にフッソ樹脂ＰＦＡ塗料（500 CL）を
混合することによりエナメル塗料化した組成であって、
後記多孔質ガラス支持体に形成されている孔径よりも僅
かに大きい粒径の粒子が分布された粒子群から構成され
る皮膜を、前記第１の発明と同様、ディッピング手段で
多孔質ガラス支持体の周囲に形成した構成としたもの
も、液体流出の始めに異物が流出し、安定するまでに１
時間を必要としたが、前記第１発明と同様の効果を達成
することができる。The liquid chromatography column of the second invention is a composition obtained by mixing a PEEK resin with a fluorine resin PFA paint (500 CL) to form an enamel paint,
A coating film composed of particles in which particles having a particle size slightly larger than the pore size formed in the porous glass support described later are distributed to the porous glass support by dipping means as in the first invention. Is formed around the periphery of the liquid, the foreign matter flows out at the beginning of liquid outflow,
Although time was required, the same effect as in the first invention can be achieved.

【００３０】また第１、第２発明によって、多孔質ガラ
ス支持体（非粉末）の支持体が具備する、安定して均一
な孔を利用することによる優れた分解能（目標理論段数
6000段）と、分析液を200kgf/cm2の圧力下において短時
間で通すことができる等の利点を有効に生かすことがで
きることから、遺伝子組替えを含むバイオテクノロジー
や、医療の診断を含む生体情報把握のために、大きく貢
献することが可能となる。According to the first and second aspects of the present invention, excellent resolution (target theoretical plate number) can be obtained by utilizing the stable and uniform pores of the porous glass support (non-powder).
6000 steps), and the advantage that the analysis solution can be passed in a short time under a pressure of 200 kgf / cm 2 , etc., can be used effectively, so that biotechnology including genetic modification and biological information including medical diagnosis It is possible to make a significant contribution to understanding.

【００３１】さらに、本発明の液体クロマトグラフィ用
カラムを、ポリエーテルエーテルケトン樹脂をグリコー
ル系有機溶剤に分散し又はフッソ樹脂ＰＦＡ塗料（500
CL）を混合することによりエナメル塗料化して分散さ
せ、これに前者の場合は膜強化剤を添加混合し、後者の
場合は添加しない組成であって、粒径分布が3.17〜61.0
μm の粒子群から構成される塗料を、上端開口の塗料槽
に収容し、該塗料槽を、棒状に成形された孔径 2μm 程
度の多孔質ガラス支持体が気密状態で上下移動でき且つ
真空圧から常圧に戻すことができるようにした真空形成
室内に配設し、該真空形成室内を真空状態とした状態
で、前記多孔質ガラス支持体を塗料槽内の塗料にディッ
ピングした後、真空形成室内を常圧に戻して塗料槽から
前記多孔質ガラス支持体を引き上げて真空形成室内から
取り出し、これに焼成処理を加える方法により製造する
ことにより、従来のように多孔質ガラス支持体粉末のき
わめて厄介な充填作業や、高価な充填装置を必要とする
ことなく、液体クロマトグラフィ用カラムとして要求さ
れるすべての条件を充足した品質の高い液体クロマトグ
ラフィ用カラムを、安価に製作し提供することができ
る。Further, the column for liquid chromatography of the present invention is prepared by dispersing a polyetheretherketone resin in a glycol-based organic solvent or using a fluororesin PFA paint (500
CL) to form an enamel paint and disperse it. In the former case, a film strengthening agent is added and mixed. In the latter case, the composition is not added, and the particle size distribution is 3.17 to 61.0.
The paint composed of particles of μm is accommodated in a paint tank having an opening at the upper end, and a porous glass support having a pore diameter of about 2 μm, which is formed in a rod shape, can be moved up and down in an airtight state and the pressure is reduced from the vacuum pressure. After the porous glass support is dipped in the paint in the paint tank, the vacuum glass is placed in a vacuum forming chamber capable of returning to normal pressure, and the vacuum forming chamber is evacuated. Is returned to normal pressure, the porous glass support is pulled up from the coating tank, taken out of the vacuum forming chamber, and manufactured by a method of adding a baking treatment to the porous glass support. A high-quality liquid chromatography column that meets all the conditions required for a liquid chromatography column is inexpensive without the need for complicated packing operations and expensive packing equipment. Can be manufactured and provided.

【００３２】特に、ＰＥＥＫ樹脂とプロピレングリコー
ルとの比率を、20/80 〜24/76 とし、これに対する膜強
化剤としてウィスカーを使用しその添加量を１〜５％と
した場合には、その効果は顕著であり、また、製造方法
において、その焼成処理を、150 〜200 ℃まで１時間、
200 〜350 ℃まで30分、350 〜400 ℃まで１時間、400
〜350 ℃まで１時間の焼成条件において実施する場合に
は、多孔質ガラス支持体と皮膜との境界部に、最適のFR
P 状の傾斜組織（ＰＥＥＫ樹脂と多孔質ガラス支持体が
混じった層組織）が形成される結果、ＰＥＥＫ樹脂が多
孔質ガラス支持体の中心部まで浸透せずに分析液の流通
が確保され、優れた分解能が発揮させることができる。In particular, when the ratio of PEEK resin to propylene glycol is set to 20/80 to 24/76, whiskers are used as a film strengthening agent, and the added amount is set to 1 to 5%. Is remarkable, and in the manufacturing method, the baking treatment is performed at 150 to 200 ° C. for 1 hour.
30 minutes from 200 to 350 ° C, 1 hour from 350 to 400 ° C, 400
In the case of firing for 1 hour up to 350 ° C, the optimal FR is applied to the boundary between the porous glass support and the coating.
As a result of the formation of a P-shaped gradient structure (layer structure in which the PEEK resin and the porous glass support are mixed), the flow of the analysis solution is secured without the PEEK resin penetrating to the center of the porous glass support, Excellent resolution can be exhibited.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明に係る液体クロマトグラフィ用カラムの
軸方向の拡大断面図である。FIG. 1 is an enlarged sectional view in the axial direction of a column for liquid chromatography according to the present invention.

【図２】図１の軸直角拡大断面図である。FIG. 2 is an enlarged cross-sectional view perpendicular to the axis of FIG.

【図３】図１のＤ部分の拡大詳細図である。FIG. 3 is an enlarged detailed view of a portion D in FIG. 1;

【図４】粒度体積分布図である。FIG. 4 is a particle size distribution chart.

【図５】全体個数に対する粒度個数分布図である。FIG. 5 is a particle size distribution diagram with respect to the whole number.

【符号の説明】[Explanation of symbols]

１ 多孔質ガラス支持体 ２ 皮膜 ３ 傾斜組織部 Reference Signs List 1 porous glass support 2 coating 3 inclined texture

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 ポリエーテルエーテルケトン樹脂をグリ
コール系有機溶剤に分散させ、これに耐熱性、耐薬品性
等を備えたウィスカー等の膜強化剤を添加混合した組成
であって、後記多孔質ガラス支持体に形成されている孔
径よりも僅かに大きい粒径の粒子が分布された粒子群か
ら構成される皮膜を、棒状に成形された多孔質ガラス支
持体の周囲に、ディッピング手段により薄くとも 100μ
m 以上〜500 μm 以下の膜厚とし且つ多孔質ガラス支持
体の表面に前記組成の皮膜の一部が浸透状に均質に形成
されていることを特徴とする液体クロマトグラフィ用カ
ラム。1. A composition comprising a polyetheretherketone resin dispersed in a glycol-based organic solvent, and a film strengthening agent such as a whisker having heat resistance, chemical resistance and the like added thereto and mixed with the dispersion. A coating composed of particles in which particles having a particle size slightly larger than the pore diameter formed in the support is distributed is coated on a porous glass support formed into a rod shape by a dipping means to a thickness of at least 100 μm.
A liquid chromatography column having a thickness of at least m and not more than 500 μm, and wherein a part of the film having the above composition is uniformly formed in a permeable manner on the surface of the porous glass support. 【請求項２】 ポリエーテルエーテルケトン樹脂とグリ
コール系有機溶剤との比率が20/80 〜24/76 、これに対
する膜強化剤としてのウィスカーの添加量は１〜５％で
ある請求項１記載の液体クロマトグラフィ用カラム。2. The method according to claim 1, wherein the ratio of the polyetheretherketone resin to the glycol-based organic solvent is 20/80 to 24/76, and the addition amount of whiskers as a film strengthening agent is 1 to 5%. Column for liquid chromatography. 【請求項３】 ＰＥＥＫ樹脂に、グリコール系有機溶剤
の一種であるプロピレングリコールに代えてフッソ樹脂
ＰＦＡ塗料（500 CL）を混合することによりエナメル塗
料化した組成であって、後記多孔質ガラス支持体に形成
されている孔径よりも僅かに大きい粒径の粒子が分布さ
れた粒子群から構成される皮膜を、棒状に成形された多
孔質ガラス支持体の周囲に、ディッピング手段により 1
00μm以上〜500 μm 以下の膜厚とし且つ多孔質ガラス
支持体の表面に前記組成の皮膜の一部が浸透状に均質に
形成されていることを特徴とする液体クロマトグラフィ
用カラム。3. A composition in which a PEEK resin is enameled by mixing a fluorine resin PFA paint (500 CL) in place of propylene glycol, which is a kind of a glycol-based organic solvent, to form an enamel paint. A coating composed of particles in which particles having a particle size slightly larger than the pore diameter formed in the porous glass support is distributed around a porous glass support formed into a rod shape by dipping means.
A column for liquid chromatography, having a thickness of not less than 00 μm to not more than 500 μm, and wherein a part of the film having the above composition is formed uniformly on the surface of the porous glass support in a permeable manner. 【請求項４】 ポリエーテルエーテルケトン樹脂をグリ
コール系有機溶剤に分散し又はフッソ樹脂ＰＦＡ塗料
（500 CL）を混合することによりエナメル塗料化して分
散させ、これに前者の場合は膜強化剤を添加混合し、後
者の場合は添加しない組成であって、粒径分布が3.17〜
61.00 μm の粒子群から構成される塗料を、上端開口の
塗料槽に収容し、該塗料槽を、棒状に成形された孔径 2
μm 程度の多孔質ガラス支持体が気密状態で上下移動で
き且つ真空圧から常圧に戻すことができるようにした真
空形成室内に配設し、該真空形成室内を真空状態とした
状態で、前記多孔質ガラス支持体を塗料槽内の塗料にデ
ィッピングした後、真空形成室内を常圧に戻して塗料槽
から前記多孔質ガラス支持体を引き上げて真空形成室内
から取り出し、これに焼成処理を加えることを特徴とす
る液体クロマトグラフィ用カラムの製造方法。4. A polyetheretherketone resin is dispersed in a glycol-based organic solvent or is mixed with a fluorine resin PFA paint (500 CL) to form an enamel paint and dispersed, and in the former case, a film strengthening agent is added. Mixed, the latter is a composition not added in the latter case, the particle size distribution is 3.17 ~
A paint composed of particles of 61.00 μm is accommodated in a paint tank having an opening at an upper end, and the paint tank is filled with a rod-shaped pore having a diameter of 2 μm.
A porous glass support of about μm is disposed in a vacuum forming chamber capable of moving up and down in an airtight state and returning from vacuum pressure to normal pressure. After dipping the porous glass support into the paint in the paint tank, the vacuum forming chamber is returned to normal pressure, the porous glass support is pulled up from the paint tank, taken out of the vacuum forming chamber, and subjected to a baking treatment. A method for producing a column for liquid chromatography, comprising:
JP8027547A 1996-02-15 1996-02-15 Column for liquid chromatography and production thereof Pending JP2000002697A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP8027547A JP2000002697A (en) 1996-02-15 1996-02-15 Column for liquid chromatography and production thereof
PCT/JP1997/000339 WO1997030349A1 (en) 1996-02-15 1997-02-07 Column element for liquid chromatography and process for producing the same

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Application Number Priority Date Filing Date Title
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JP2000002697A true JP2000002697A (en) 2000-01-07

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Cited By (4)

* Cited by examiner, † Cited by third party
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JP2002060432A (en) * 2000-06-23 2002-02-26 Ausimont Spa Hot processable tetrafluoroethylene copolymer microsphere
JP2008102077A (en) * 2006-10-20 2008-05-01 Hellermann Tyton Co Ltd Cartridge column and column module
WO2014013368A1 (en) * 2012-07-19 2014-01-23 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for producing a chromatography analysis column
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6385689B1 (en) 1998-02-06 2002-05-07 Analog Devices, Inc. Memory and a data processor including a memory
WO2003005019A1 (en) * 2001-07-06 2003-01-16 Api Corporation Method of determining pyrithione metal salt
US6749749B2 (en) * 2002-06-26 2004-06-15 Isco, Inc. Separation system, components of a separation system and methods of making and using them
JP3957078B1 (en) * 2005-05-24 2007-08-08 ヘラマンタイトン株式会社 Cartridge column

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS549691A (en) * 1977-06-22 1979-01-24 Pilot Precision Column for chromatography
JPH02291963A (en) * 1989-05-02 1990-12-03 Matsunami Glass Kogyo Kk Glass tube wherein porous glass is sealed and sealing method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002060432A (en) * 2000-06-23 2002-02-26 Ausimont Spa Hot processable tetrafluoroethylene copolymer microsphere
JP2008102077A (en) * 2006-10-20 2008-05-01 Hellermann Tyton Co Ltd Cartridge column and column module
WO2014013368A1 (en) * 2012-07-19 2014-01-23 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for producing a chromatography analysis column
FR2993665A1 (en) * 2012-07-19 2014-01-24 Commissariat Energie Atomique PROCESS FOR MANUFACTURING A CHROMATOGRAPHIC ANALYZING COLUMN
US20150219605A1 (en) * 2012-07-19 2015-08-06 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for Producing a Chromatography Analysis Column
US9835599B2 (en) * 2012-07-19 2017-12-05 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for producing a chromatography analysis column
US9885692B2 (en) 2012-07-19 2018-02-06 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for producing a chromatography-enrichment column

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