JP2019052232A - Polyurethane adhesive composition, and hollow fiber membrane module manufacture by using the same - Google Patents

Polyurethane adhesive composition, and hollow fiber membrane module manufacture by using the same Download PDF

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JP2019052232A
JP2019052232A JP2017176607A JP2017176607A JP2019052232A JP 2019052232 A JP2019052232 A JP 2019052232A JP 2017176607 A JP2017176607 A JP 2017176607A JP 2017176607 A JP2017176607 A JP 2017176607A JP 2019052232 A JP2019052232 A JP 2019052232A
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hollow fiber
fiber membrane
polyurethane adhesive
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JP6965069B2 (en
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中塚　修志
Nobuyuki Nakatsuka
修志 中塚
洋司 井上
Yoji Inoue
洋司 井上
智一 綿部
Tomokazu Watabe
智一 綿部
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Daicen Membrane Systems Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

To provide a polyurethane adhesive composition excellent in durability to hydrolysis, and sufficiently long in flow possible time (time at low viscosity state) of an adhesive composition during a curing reaction, and a medical hollow fiber membrane module manufactured by using the same.SOLUTION: There is provided a polyurethane adhesive composition containing (A) one or more kinds selected from aromatic polyisocyanate and a modified body thereof (hereafter, (A) component), and (B) a curing agent (hereafter, (B) component), (B1) a polyol compound having one or more secondary or tertiary hydroxyl groups and eight or more carbon atoms (hereafter, (B1) component) of 50 mass% or more in the (B) component, and having a ratio of transmittance of absorption peak at 1720 to 1730 cm(Te) to transmittance of absorption peak at 1708 to 1712 cm(Tu) in a microscopic Fourier transformation type infrared spectrophotometer (microscopic FT-IR) measurement of a polyurethane adhesive cured article obtained by a reaction of the (A) component and the (B) component, (Te/Tu) of less than 0.9.SELECTED DRAWING: None

Description

本発明は、蒸気滅菌や熱水殺菌洗浄を実施される医療用中空糸膜モジュールに好適に用いられるポリウレタン接着剤組成物、及びこれを用いて製作される中空糸膜モジュールに関する。   The present invention relates to a polyurethane adhesive composition suitably used for a medical hollow fiber membrane module that is subjected to steam sterilization or hot water sterilization washing, and a hollow fiber membrane module manufactured using the polyurethane adhesive composition.

近年、中空糸を分離膜とした中空糸膜モジュールは、水処理膜などの産業分野、血液処
理などの医療分野などに多岐にわたって用いられている。特に家庭用浄水器、工業用浄水
器、人工腎臓、人工肺などの用途にあっては、その需要が極めて増大している。その中で
も、中空糸膜を集束した端部を接着固定する膜シール材として、常温での可撓性、接着性
、及び耐薬品性に優れているポリウレタン接着剤を用いることが、広く知られている。 In recent years, hollow fiber membrane modules using hollow fibers as separation membranes are widely used in industrial fields such as water treatment membranes and medical fields such as blood treatment. Especially in applications such as household water purifiers, industrial water purifiers, artificial kidneys, and artificial lungs, the demand is extremely increasing. Among them, it is widely known that a polyurethane adhesive having excellent flexibility, adhesiveness, and chemical resistance at room temperature is used as a membrane sealing material for bonding and fixing the end portions where the hollow fiber membranes are converged. Yes.

非特許文献１には、医療用中空糸膜モジュールに用いられるポリウレタン接着剤の要求性能として、（１）基本的なシール性能を有すること、（２）最終硬化物の毒性が低いこと、（３）滅菌が可能なこと、（４）血栓形成を誘起しないこと、（５）溶出物質が無いこと、及び（６）中空糸膜モジュール製作加工性に優れていることであると記載されている。
非特許文献２には、医療分野において、透析液清浄化のために、エンドトキシン捕捉フィルター（ＥＴＲＦ）が設置されること、生菌やエンドトキシンなどの微生物学的汚染物質に関する透析用水や透析液の水質基準が定められていること、透析用水装置の保守管理のため定期的に装置やラインの熱水消毒が実施される場合があることが記載されている。 Non-Patent Document 1 discloses that the required performance of a polyurethane adhesive used in a medical hollow fiber membrane module is (1) basic sealing performance, (2) low toxicity of the final cured product, (3 It is described that it can be sterilized, (4) it does not induce thrombus formation, (5) it has no eluting substance, and (6) it is excellent in processability for producing a hollow fiber membrane module.
Non-Patent Document 2 discloses that in the medical field, an endotoxin capture filter (ETRF) is installed for dialysis fluid purification, and dialysis water and dialysis fluid quality regarding microbiological contaminants such as live bacteria and endotoxin. It is stated that standards are established and that hot water disinfection of equipment and lines may be carried out regularly for maintenance of dialysis water equipment.

特許文献１には、ポリオール成分として、分子量が２００以上、かつ、水酸基を含まないカルボン酸（ｂ１）と、ヒマシ油及び／又はヒマシ油系変性ポリオール（ｂ２）が含有されている硬化剤を用い、イソシアネート成分としてジフェニルメタンジイソシアネート及び／又はカルボジイミド変性体含有ジフェニルメタンジイソシアネートからなる主剤を使用することによって成型加工性を維持したまま、生産性を向上することが可能なポリウレタン系結束材組成物と、これを医療用中空糸膜モジュールのシール材に用いることが記載されている。   Patent Document 1 uses a curing agent containing, as a polyol component, a carboxylic acid (b1) having a molecular weight of 200 or more and no hydroxyl group, and castor oil and / or castor oil-based modified polyol (b2). A polyurethane-based binder composition capable of improving productivity while maintaining molding processability by using a main agent comprising diphenylmethane diisocyanate and / or carbodiimide-modified diphenylmethane diisocyanate as an isocyanate component, and It is described that it is used as a sealing material for a medical hollow fiber membrane module.

特許第５２８８３２４号公報Japanese Patent No. 5288324

ポリウレタン応用技術（1993年11月30日初版発行）222頁（株式会社シーエムシー）Polyurethane applied technology (issued on November 30, 1993, first edition), page 222 (CMC Corporation) 透析用水ガイドブック（2014年3月15日初版発行）（一般社団法人 膜分離技術振興協会）Dialysis Water Guidebook (issued on March 15, 2014, first edition) (General Association for Membrane Separation Technology Promotion)

本発明は、加水分解への耐久性に優れ、硬化反応時における接着剤組成物の流動可能時間（低粘度状態の時間）が十分に長い、ポリウレタン接着剤組成物、及びこれを用いて製作される中空糸膜モジュールを提供することを課題とする。   INDUSTRIAL APPLICABILITY The present invention is a polyurethane adhesive composition having excellent durability to hydrolysis and having a sufficiently long flowable time (low viscosity state time) of the adhesive composition during the curing reaction, and is produced using the polyurethane adhesive composition. It is an object of the present invention to provide a hollow fiber membrane module.

本発明は、（Ａ）芳香族ポリイソシアネート及びその変性体から選ばれる１種以上（以下、（Ａ）成分という）、及び（Ｂ）硬化剤（以下、（Ｂ）成分という）を含むポリウレタン接着剤組成物であって、
（Ｂ）成分中、（Ｂ１）２級又は３級水酸基を１つ以上有する炭素数８以上のポリオール化合物（以下、（Ｂ１）成分という）を５０質量％以上含有し、
（Ａ）成分と（Ｂ）成分との反応によって得られるポリウレタン接着剤硬化物の顕微フーリエ変換型赤外分光光度計（顕微ＦＴ−ＩＲ）測定において、１７０８〜１７１２ｃｍ−１の吸収ピークの透過率（Ｔｕ）に対する、１７２０〜１７３０ｃｍ−１の吸収ピークの透過率（Ｔｅ）の比（Ｔｅ／Ｔｕ）が０．９未満である、ポリウレタン接着剤組成物に関する。 The present invention provides a polyurethane adhesive comprising (A) one or more selected from aromatic polyisocyanates and modified products thereof (hereinafter referred to as (A) component), and (B) a curing agent (hereinafter referred to as (B) component). An agent composition comprising:
In the component (B), (B1) containing 50% by mass or more of a polyol compound having 8 or more carbon atoms (hereinafter referred to as the component (B1)) having one or more secondary or tertiary hydroxyl groups,
In the micro Fourier transform infrared spectrophotometer (micro FT-IR) measurement of the cured polyurethane adhesive obtained by the reaction between the component (A) and the component (B), the transmittance of the absorption peak of 1708 to 1712 cm −1. It is related with the polyurethane adhesive composition whose ratio (Te / Tu) of the transmittance | permeability (Te) of the absorption peak of 1720-1730cm < -1 > with respect to (Tu) is less than 0.9.

また本発明は、ケースハウジング内に中空糸膜束が収容された中空糸膜モジュールであって、
前記中空糸膜束の少なくとも一端部側と前記ケースハウジングの内壁面が、前記ポリウレタン接着剤組成物の硬化物で一体化されている中空糸膜モジュールに関する。 Further, the present invention is a hollow fiber membrane module in which a hollow fiber membrane bundle is accommodated in a case housing,
The present invention relates to a hollow fiber membrane module in which at least one end side of the hollow fiber membrane bundle and an inner wall surface of the case housing are integrated with a cured product of the polyurethane adhesive composition.

また本発明は、ケースハウジング内に中空糸膜束が収容された中空糸膜モジュールの製造方法であって、
前記中空糸膜束の少なくとも一端部側と前記ケースハウジングの内壁面を、前記ポリウレタン接着剤組成物を使用して、接着して一体化する、中空糸膜モジュールの製造方法に関する。 Further, the present invention is a method for manufacturing a hollow fiber membrane module in which a hollow fiber membrane bundle is accommodated in a case housing,
The present invention relates to a method for producing a hollow fiber membrane module, in which at least one end side of the hollow fiber membrane bundle and an inner wall surface of the case housing are bonded and integrated using the polyurethane adhesive composition.

本発明によれば、加水分解への耐久性に優れ、硬化反応時における接着剤組成物の流動可能時間（低粘度状態の時間）が十分に長い、ポリウレタン接着剤組成物、及びこれを用いて製作される医療用中空糸膜モジュールが提供できる。   According to the present invention, a polyurethane adhesive composition having excellent durability to hydrolysis and having a sufficiently long flowable time (low viscosity state time) of the adhesive composition at the time of the curing reaction, and using the same A manufactured medical hollow fiber membrane module can be provided.

本発明のポリウレタン接着剤組成物は、（Ｂ）成分中、２級又は３級水酸基を１つ以上有する炭素数８以上のポリオール化合物である（Ｂ１）成分の割合が高いため、（Ａ）成分との反応速度を抑制でき、（Ａ）成分と（Ｂ）成分との硬化反応時おける接着剤組成物の流動可能時間（低粘度状態の時間）が十分に長く、中空糸膜を集束した膜モジュール接着硬化部において、全ての中空糸膜の接着部の厚みが均一でシール性が高く接着固定でき、中空糸膜の隅々まで接着剤組成物が行き渡らせることができるため、中空糸膜モジュールの蒸気滅菌や熱水殺菌洗浄におけるリーク頻度を大幅に低減できる。
また（Ｂ）成分中、２級又は３級水酸基を１つ以上有する炭素数８以上のポリオール化合物である（Ｂ１）成分の割合が高いことから疎水性が高く、またポリウレタン接着剤組成物中のエステル基（−Ｃ（＝Ｏ）−Ｏ−）を有する化合物の含有量が少ないため、これを用いて製作された中空糸膜モジュールの接着硬化部の加水分解への耐久性が優れており、中空糸膜モジュール接着部のシール性を保持できるため、蒸気滅菌や熱水殺菌洗浄を長期間にわたり繰返し実施する、エンドトキシン捕捉フィルター（ＥＴＲＦ）などの医療用中空糸膜モジュール用として好適である。 Since the polyurethane adhesive composition of the present invention has a high proportion of the component (B1) which is a polyol compound having 8 or more carbon atoms having one or more secondary or tertiary hydroxyl groups in the component (B), the component (A) The flow rate of the adhesive composition during the curing reaction between the component (A) and the component (B) is sufficiently long (low viscosity state time), and the membrane is obtained by focusing the hollow fiber membranes. Since the thickness of the bonded part of all the hollow fiber membranes is uniform, the sealing property is high and can be bonded and fixed in the module adhesive hardened part, and the adhesive composition can be spread to every corner of the hollow fiber membrane, the hollow fiber membrane module The leak frequency in steam sterilization and hot water sterilization cleaning can be greatly reduced.
In addition, in the component (B), since the ratio of the component (B1) which is a polyol compound having 8 or more carbon atoms having one or more secondary or tertiary hydroxyl groups is high, the hydrophobicity is high, and in the polyurethane adhesive composition Since the content of the compound having an ester group (—C (═O) —O—) is small, the durability to hydrolysis of the adhesion-cured portion of the hollow fiber membrane module produced using this is excellent, Since the sealing property of the bonded portion of the hollow fiber membrane module can be maintained, it is suitable for a medical hollow fiber membrane module such as an endotoxin capture filter (ETRF) that repeatedly performs steam sterilization and hot water sterilization cleaning over a long period of time.

＜ポリウレタン接着剤組成物＞
本発明の（Ａ）成分は、芳香族ポリイソシアネート及びその変性体から選ばれる１種以上である。（Ａ）成分は、特許３２０５９７７号公報などに記載されている公知の室温で液状である芳香族ポリイソシアネート変性体を用いることができる。芳香族ポリイソシアネートの変性体としては、カルボジイミド変性体、ウレトンイミン変性体などが挙げられる。
（Ａ）成分は、成分全体として室温で液状であるように、ジフェニルメタンジイソシアネート（ＭＤＩ）、トルエンジイソシアネート（ＴＤＩ）、及びこれらの変性体から選ばれる１種以上が好ましい。 <Polyurethane adhesive composition>
(A) component of this invention is 1 or more types chosen from aromatic polyisocyanate and its modified body. As the component (A), known aromatic polyisocyanate-modified products that are liquid at room temperature described in Japanese Patent No. 3205977 can be used. Examples of modified aromatic polyisocyanates include carbodiimide modified products and uretonimine modified products.
The component (A) is preferably at least one selected from diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), and modified products thereof so that the entire component is liquid at room temperature.

本発明の（Ｂ）成分は、硬化剤である。（Ｂ）成分は、（Ｂ）成分中、（Ｂ１）２級又は３級水酸基を１つ以上有する炭素数８以上のポリオール化合物（以下、（Ｂ１）成分という）を５０質量％以上含有する。
（Ｂ１）成分は、加水分解への耐久性の観点から、エステル基（−Ｃ（＝Ｏ）−Ｏ−）を有せず、且つ２級又は３級水酸基を１つ以上有する炭素数８以上のポリオール化合物が好ましい。
本発明において、２級水酸基とは、水酸基が結合している炭素原子に２個の炭素原子が結合しているものをいう。また３級水酸基とは、水酸基が結合している炭素原子に３個の炭素原子が結合しているものをいう。 The component (B) of the present invention is a curing agent. The component (B) contains 50% by mass or more of a polyol compound having 8 or more carbon atoms (hereinafter referred to as the component (B1)) having one or more secondary or tertiary hydroxyl groups in the component (B).
Component (B1) has 8 or more carbon atoms having no ester group (—C (═O) —O—) and having one or more secondary or tertiary hydroxyl groups from the viewpoint of durability to hydrolysis. The polyol compound is preferred.
In the present invention, the secondary hydroxyl group means a group in which two carbon atoms are bonded to the carbon atom to which the hydroxyl group is bonded. A tertiary hydroxyl group means a group in which three carbon atoms are bonded to a carbon atom to which a hydroxyl group is bonded.

（Ｂ１）成分は、加水分解への耐久性の観点から、２級又は３級水酸基を１つ以上有する炭素数８〜２２の脂肪族ポリオール化合物、及び２級又は３級水酸基を１つ以上有する炭素数１２〜２２の脂肪酸と多官能アミン化合物の縮合反応物から選択される１種以上が好ましい。   The component (B1) has an aliphatic polyol compound having 8 to 22 carbon atoms having one or more secondary or tertiary hydroxyl groups and one or more secondary or tertiary hydroxyl groups from the viewpoint of durability to hydrolysis. 1 or more types selected from the condensation reaction material of a C12-C22 fatty acid and a polyfunctional amine compound are preferable.

２級又は３級水酸基を１つ以上有する炭素数８〜２２の脂肪族ポリオール化合物としては、１２−ヒドロキシステアリルアルコール（１，１２−オクタデカンジオール）、２，２，４−トリメチル−１，３−ペンタンジオール、２−エチル−１，３−ヘキサンジオール、２，５−ジメチル−２，５−ヘキサンジオール、及び２，６−ジメチル−３，５−ヘプタンジオールから選ばれる１種以上が挙げられる。
２級又は３級水酸基を１つ以上有する炭素数１２〜２２の脂肪酸と多官能アミン化合物の縮合反応物としては、リシノール酸と多官能アミン化合物との多官能アミド縮合反応物が挙げられる。 Examples of the aliphatic polyol compound having 8 to 22 carbon atoms having one or more secondary or tertiary hydroxyl groups include 12-hydroxystearyl alcohol (1,12-octadecanediol), 2,2,4-trimethyl-1,3- Examples thereof include one or more selected from pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, and 2,6-dimethyl-3,5-heptanediol.
Examples of the condensation reaction product of a C12-22 fatty acid having one or more secondary or tertiary hydroxyl groups and a polyfunctional amine compound include a polyfunctional amide condensation reaction product of ricinoleic acid and a polyfunctional amine compound.

（Ｂ１）成分は、１２−ヒドロキシステアリルアルコール、２，２，４−トリメチル−１，３−ペンタンジオール、２−エチル−１，３−ヘキサンジオール、２，５−ジメチル−２，５−ヘキサンジオール、２，６−ジメチル−３，５−ヘプタンジオール、及びリシノール酸と多官能アミン化合物との多官能アミド縮合反応物から選択される１種以上が好ましい。
また（Ｂ１）成分は、疎水性の観点から、１２−ヒドロキシステアリルアルコールを含むことが好ましいが、Ｂ成分全体が室温で液状であるには、１２−ヒドロキシステアリルアルコールへ２，２，４−トリメチル−１，３−ペンタンジオールなどの他の（Ｂ１）成分を併用することがより好ましい。 (B1) component is 12-hydroxystearyl alcohol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol , 2,6-dimethyl-3,5-heptanediol, and one or more selected from polyfunctional amide condensation reaction products of ricinoleic acid and a polyfunctional amine compound are preferable.
In addition, the component (B1) preferably contains 12-hydroxystearyl alcohol from the viewpoint of hydrophobicity, but in order for the entire B component to be liquid at room temperature, the 2,2,4-trimethyl is added to 12-hydroxystearyl alcohol. More preferably, another component (B1) such as -1,3-pentanediol is used in combination.

本発明における（Ｂ）成分中の（Ｂ１）成分の割合は５０質量％以上であり、７０質量％以上がより好ましく、８０質量％以上が更に好ましく、９０質量％以上がより更に好ましい。また（Ｂ）成分中の（Ｂ１）成分の割合は、１００質量％であってもよい。
（Ｂ）成分中の（Ｂ１）成分の割合が５０質量％を下回る場合は、本発明のポリウレタン接着剤組成物を使用して中空糸膜モジュールの接着硬化する際の流動可能時間が短くなったり、さらに接着硬化部の加水分解への耐久性が低下したりするなどの不具合が生じる。 The proportion of the component (B1) in the component (B) in the present invention is 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more. Moreover, 100 mass% may be sufficient as the ratio of (B1) component in (B) component.
When the ratio of the component (B1) in the component (B) is less than 50% by mass, the flowable time when the hollow fiber membrane module is adhesively cured using the polyurethane adhesive composition of the present invention is shortened. In addition, there is a problem that the durability to hydrolysis of the bonded and hardened portion is lowered.

（Ｂ）成分は、本発明の効果を損なわない範囲内において、（Ｂ２）成分として、（Ｂ１）成分以外の硬化剤を含有してもよい。   The component (B) may contain a curing agent other than the component (B1) as the component (B2) as long as the effects of the present invention are not impaired.

（Ｂ２）成分としては、エチレングリコール、プロパンジオール、ブタンジオール、１，１０−デカンジオール、１，１８−オクタデカンジオールなどの２官能アルコール、グリセリン、トリメチロールプロパンなどの３官能アルコール、ペンタエリスリトールなどの４官能アルコール、ダイマー酸ジオール、ひまし油系ポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、液状ゴム系ポリオール、ポリブタジエン系ポリオール、エチレンジアミン、ヘキサメチレンジアミンなどのジアミン化合物、アミノプロパノールなどのヒドロキシアミン化合物などが例示できる。   As the component (B2), bifunctional alcohols such as ethylene glycol, propanediol, butanediol, 1,10-decanediol, 1,18-octadecanediol, trifunctional alcohols such as glycerin and trimethylolpropane, pentaerythritol, etc. Examples include tetrafunctional alcohols, dimer acid diols, castor oil polyols, polyether polyols, polycarbonate polyols, liquid rubber polyols, polybutadiene polyols, diamine compounds such as ethylenediamine and hexamethylenediamine, and hydroxyamine compounds such as aminopropanol.

本発明のポリウレタン接着剤組成物中、（Ａ）成分と（Ｂ）成分の合計含有量は、９０〜１００質量％が好ましく、９５〜１００質量％がより好ましく、また１００質量％であってもよい。   In the polyurethane adhesive composition of the present invention, the total content of the component (A) and the component (B) is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and even 100% by mass. Good.

本発明のポリウレタン接着剤組成物中、（Ａ）成分の含有量と（Ｂ）成分の含有量とのモル比（Ａ／Ｂ）は、０．９５〜１．１０が好ましく、１．０〜１．０５がより好ましい。   In the polyurethane adhesive composition of the present invention, the molar ratio (A / B) between the content of the component (A) and the content of the component (B) is preferably 0.95 to 1.10, 1.0 to 1.05 is more preferable.

本発明のポリウレタン接着剤組成物は、優れた加水分解への耐久性を発現するために、以下の３点を留意して設計されたものである。
（１）該組成物に含まれる化合物の疎水性が高く、ポリウレタン接着剤組成物を硬化した際の硬化部物中に水分を浸透させない。
（２）該組成物中、エステル基（−Ｃ（＝Ｏ）−Ｏ−）を有する化合物を含まない、もしくはその含有量が少ない。
（３）該組成物中、加水分解反応を促進する触媒成分を含まない、もしくはその含有量が少ない。 The polyurethane adhesive composition of the present invention is designed in consideration of the following three points in order to develop excellent durability to hydrolysis.
(1) The compound contained in the composition is highly hydrophobic and does not allow moisture to penetrate into the cured part when the polyurethane adhesive composition is cured.
(2) The composition does not contain a compound having an ester group (—C (═O) —O—) or its content is small.
(3) The composition does not contain a catalyst component that accelerates the hydrolysis reaction or has a low content.

本発明のポリウレタン接着剤組成物を構成する、（Ｂ）成分は疎水性を高めることが好ましい。
（Ｂ）成分の主構成成分は、（Ｂ１）成分であり、炭素数が大きく疎水性が高いため、（Ｂ１）成分の配合割合を高めることが好ましい。
（Ｂ）成分の構成成分として、ポリエーテルポリオールなどの（Ｂ２）成分を含む場合は、（Ｂ）成分の疎水性が低下するため、使用する場合は、含有量を少なくすることが好ましい。 The component (B) constituting the polyurethane adhesive composition of the present invention preferably has increased hydrophobicity.
The main component of the component (B) is the component (B1), and has a large carbon number and high hydrophobicity. Therefore, it is preferable to increase the blending ratio of the component (B1).
When (B) component, such as polyether polyol, is included as a component of (B) component, since the hydrophobicity of (B) component falls, when using, it is preferable to reduce content.

本発明のポリウレタン接着剤組成物において、エステル基（−Ｃ（＝Ｏ）−Ｏ−）を有する化合物の含有率が小さいことが好ましい。
（Ａ）成分の変性に用いる（Ｂ）成分に、ひまし油のようなエステル基（−Ｃ（＝Ｏ）−Ｏ−）を含む化合物を余り多く用いないことが好ましい。 In the polyurethane adhesive composition of the present invention, the content of a compound having an ester group (—C (═O) —O—) is preferably small.
It is preferable not to use too much a compound containing an ester group (—C (═O) —O—) such as castor oil in the component (B) used for modifying the component (A).

本発明のポリウレタン接着剤組成物は、チタン、錫、亜鉛、クロム、ニッケル、ジルコニウム、アルカリ金属などから選択される金属化合物を含んでいない方が好ましい。加水分解の触媒能があるためである。
本発明のポリウレタン接着剤組成物中、前記金属化合物の含有量は２００ｐｐｍ未満が好ましく、１０ｐｐｍ未満がより好ましい。
前記金属化合物の含有量は、ポリウレタン接着剤組成物を反応により硬化して得られるポリウレタン接着剤硬化物を分析する場合は、蛍光Ｘ線元素分析法や走査型電子顕微鏡によるエネルギー分散型Ｘ線分光法（SEM-EDX）によって測定できる。またポリウレタン接着剤組成物中の金属化合物の含有量を分析する場合、適正な精製溶媒を用い高周波誘導結合プラズマ発光分光分析法（ICP-AES）、高周波誘導結合プラズマ質量分析法（ICP-MS）によっても測定できる。 The polyurethane adhesive composition of the present invention preferably does not contain a metal compound selected from titanium, tin, zinc, chromium, nickel, zirconium, alkali metal and the like. This is because of the catalytic ability of hydrolysis.
In the polyurethane adhesive composition of the present invention, the content of the metal compound is preferably less than 200 ppm, more preferably less than 10 ppm.
When analyzing a polyurethane adhesive cured product obtained by curing a polyurethane adhesive composition by reaction, the content of the metal compound is determined by energy dispersive X-ray spectroscopy using a fluorescent X-ray elemental analysis method or a scanning electron microscope. It can be measured by the method (SEM-EDX). In addition, when analyzing the content of metal compounds in polyurethane adhesive compositions, high-frequency inductively coupled plasma optical emission spectrometry (ICP-AES), high-frequency inductively coupled plasma mass spectrometry (ICP-MS) using an appropriate purified solvent Can also be measured.

本発明のポリウレタン接着剤組成物に含まれるエステル基（−Ｃ（＝Ｏ）−Ｏ−）を有する化合物の含有量は、ポリウレタン接着剤組成物を反応により硬化して得られるポリウレタン接着剤硬化物の顕微フーリエ変換型赤外分光光度計（顕微ＦＴ−ＩＲ）測定によって判断することが可能である。
本発明のポリウレタン接着剤硬化物の顕微フーリエ変換型赤外分光光度計（顕微ＦＴ−ＩＲ）測定において、ウレタン基（−Ｏ−Ｃ（＝Ｏ）−ＮＨ−）の吸収ピークは、１７０８〜１７１２ｃｍ−１に、エステル基（−Ｃ（＝Ｏ）−Ｏ−）の吸収ピークは、１７２０〜１７３０ｃｍ−１に現われるものと見なす。
本発明のポリウレタン接着剤組成物を反応により硬化して得られるポリウレタン接着剤硬化物において、前記ウレタン基の吸収ピークの透過率（Ｔｕ）に対するエステル基の吸収ピークの透過率（Ｔｅ）の比（Ｔｅ／Ｔｕ）が０．９未満であり、好ましくは０．８未満、より好ましくは０．７未満である。また１７２０〜１７３０ｃｍ−１のエステル基に由来する吸収ピークが確認できない場合、そのポリウレタン接着剤組成物中のエステル基を有する化合物の含有量が少ないことを示しているため、Ｔｅ／Ｔｕが本発明の範囲内であると見なすことができる。但し、１７０８〜１７１２ｃｍ−１のウレタン基に由来する吸収ピークの透過率が７５〜９０％の範囲内にあり、顕微フーリエ変換型赤外分光光度計（顕微ＦＴ−ＩＲ）測定における適正な測定条件範囲内にあることが必要である。 The content of the compound having an ester group (—C (═O) —O—) contained in the polyurethane adhesive composition of the present invention is a polyurethane adhesive cured product obtained by curing the polyurethane adhesive composition by reaction. It is possible to make a judgment based on a micro Fourier transform infrared spectrophotometer (micro FT-IR).
In the microscopic Fourier transform infrared spectrophotometer (microscopic FT-IR) measurement of the polyurethane adhesive cured product of the present invention, the absorption peak of the urethane group (—O—C (═O) —NH—) is 1708 to 1712 cm. -1 , the absorption peak of the ester group (—C (═O) —O—) is considered to appear at 1720 to 1730 cm −1 .
In the polyurethane adhesive cured product obtained by curing the polyurethane adhesive composition of the present invention by reaction, the ratio of the transmittance (Te) of the absorption peak of the ester group to the transmittance (Tu) of the absorption peak of the urethane group ( Te / Tu) is less than 0.9, preferably less than 0.8, more preferably less than 0.7. Further, when an absorption peak derived from an ester group of 1720 to 1730 cm −1 cannot be confirmed, it indicates that the content of the compound having an ester group in the polyurethane adhesive composition is small, and therefore Te / Tu is the present invention. Can be considered within the range. However, the transmittance of the absorption peak derived from the urethane group of 1708 to 1712 cm −1 is in the range of 75 to 90%, and appropriate measurement conditions in the micro Fourier transform infrared spectrophotometer (micro FT-IR) measurement Must be within range.

本発明のポリウレタン接着剤組成物は、（Ｂ）成分中、（Ｂ１）成分の含有量が多いことから、粘度の低い流動可能時間が十分に長い特徴を有する。
粘度の低い流動可能時間とは、（Ａ）成分と（Ｂ）成分の液温を４５℃に調整し、それらを接着剤組成物として適切な混合割合に均一混合した直後に、室温環境下に設置されたＢ型粘度計（ローターＮＯ．１、回転数６ｒｐｍ）での測定粘度（接着剤組成物の液温は４５℃からは成り行き）が、均一混合後から４分間は２００ｍＰａ・ｓ以下を保ち、且つ均一混合後から８分間は４００ｍＰａ・ｓ以下を保つ状態を示す。 Since the polyurethane adhesive composition of the present invention has a large content of the component (B1) in the component (B), it has a characteristic that the flowable time with a low viscosity is sufficiently long.
The flowable time with low viscosity means that the liquid temperature of the component (A) and the component (B) is adjusted to 45 ° C., and immediately after they are uniformly mixed to an appropriate mixing ratio as an adhesive composition, Viscosity measured with the installed B-type viscometer (rotor No. 1, rotation speed 6 rpm) (liquid temperature of the adhesive composition starts from 45 ° C.) is less than 200 mPa · s for 4 minutes after uniform mixing. The state is maintained at 400 mPa · s or less for 8 minutes after the uniform mixing.

本発明のポリウレタン接着剤組成物を反応により硬化して得られるポリウレタン接着剤硬化物は、具体的には、（Ａ）成分と（Ｂ）成分を混合して、本発明のポリウレタン接着剤組成物を室温化で調製し、好ましくは４０℃〜８０℃、より好ましくは４０℃〜５０℃の温度条件下で、（Ａ）成分と（Ｂ）成分とを反応・硬化させることにより好適に形成することができる。
また硬化反応後は、８０℃〜１２０℃の温度条件下で、０．５〜５時間ポストベイクすることが好適である。 Specifically, the polyurethane adhesive cured product obtained by curing the polyurethane adhesive composition of the present invention by reaction is a mixture of the component (A) and the component (B), and the polyurethane adhesive composition of the present invention. Is preferably formed by reacting and curing the component (A) and the component (B) under a temperature condition of preferably 40 ° C. to 80 ° C., more preferably 40 ° C. to 50 ° C. be able to.
Moreover, after the curing reaction, it is preferable to post-bake for 0.5 to 5 hours under a temperature condition of 80 to 120 ° C.

＜中空糸膜モジュール及びその製造方法＞
本発明の中空糸膜モジュールは、ケースハウジング内に中空糸膜束が収容された中空糸膜モジュールであって、
前記中空糸膜束の少なくとも一端部側と前記ケースハウジングの内壁面が、本発明のポリウレタン接着剤組成物の硬化物で一体化されている中空糸膜モジュールである。
また本発明の中空糸膜モジュールの製造方法は、ケースハウジング内に中空糸膜束が収容された中空糸膜モジュールの製造方法であって、
前記中空糸膜束の少なくとも一端部側と前記ケースハウジングの内壁面を、本発明のポリウレタン接着剤組成物を使用して、接着して一体化する、中空糸膜モジュールの製造方法である。 <Hollow fiber membrane module and manufacturing method thereof>
The hollow fiber membrane module of the present invention is a hollow fiber membrane module in which a hollow fiber membrane bundle is accommodated in a case housing,
In the hollow fiber membrane module, at least one end side of the hollow fiber membrane bundle and an inner wall surface of the case housing are integrated with a cured product of the polyurethane adhesive composition of the present invention.
The method for producing a hollow fiber membrane module of the present invention is a method for producing a hollow fiber membrane module in which a hollow fiber membrane bundle is accommodated in a case housing,
In the method for producing a hollow fiber membrane module, at least one end of the hollow fiber membrane bundle and an inner wall surface of the case housing are bonded and integrated using the polyurethane adhesive composition of the present invention.

本発明の中空糸膜モジュールにおいて、ケースハウジング内に収容された中空糸膜束の一端部側又は両端部側とケースハウジングの内壁面を、本発明のポリウレタン接着剤組成物の硬化物で一体化させる方法としては、遠心接着法を適用できる。
遠心接着法（遠心成形法）は公知であり、特開昭５２−３８７９７号公報の第５図などにも遠心接着法（遠心成形法）の実施形態が図示されており、そのほかにも、特開昭５１−９３７８８号公報、特開昭６１−１７１５０３号公報、特開昭６１−１７１５０４号公報にも記載されている。
さらには、特開２０１１−２００３６号公報に記載の仮キャップを使用して遠心接着する方法、実開平５−５１４３０号公報および特開平４−２５６４２２号公報に記載の方法も適用することができる。
本発明の中空糸膜モジュール（中空糸膜型濾過装置）の具体的構造としては、特開昭６１−０１３９６５号公報や特開２００４−８２０７３号公報に記載の構造を挙げることができるが、これらに限定されるものではない。 In the hollow fiber membrane module of the present invention, one end side or both end sides of the hollow fiber membrane bundle accommodated in the case housing and the inner wall surface of the case housing are integrated with the cured product of the polyurethane adhesive composition of the present invention. As a method of making it, a centrifugal bonding method can be applied.
The centrifugal bonding method (centrifugal molding method) is known, and an embodiment of the centrifugal bonding method (centrifugal molding method) is illustrated in FIG. 5 of JP-A-52-38797. Also described in Japanese Utility Model Laid-Open Nos. 51-93788, 61-171503, and 61-171504.
Furthermore, a method of centrifugal bonding using a temporary cap described in Japanese Patent Application Laid-Open No. 2011-20036 and a method described in Japanese Utility Model Laid-Open No. 5-51430 and Japanese Patent Application Laid-Open No. 4-256422 can be applied.
Specific examples of the structure of the hollow fiber membrane module (hollow fiber membrane filtration device) of the present invention include the structures described in JP-A Nos. 61-013965 and 2004-82073. It is not limited to.

本発明の中空糸膜モジュールは、接着硬化部の加水分解への耐久性が優れており、中空糸膜モジュール接着部のシール性を保持できるため、蒸気滅菌や熱水殺菌洗浄を長期間にわたり繰返し実施する、エンドトキシン捕捉フィルター（ＥＴＲＦ）用の中空糸膜モジュールとして好適である。   The hollow fiber membrane module of the present invention is excellent in durability to hydrolysis of the adhesive-cured part and can maintain the sealing property of the bonded part of the hollow fiber membrane module, so that steam sterilization and hot water sterilization washing are repeated over a long period of time. It is suitable as a hollow fiber membrane module for endotoxin capture filter (ETRF) to be implemented.

（１）ポリウレタン接着剤硬化物の調製
実施例１
（ａ）（Ｂ）成分の調製
ガラス製容器に、１２−ヒドロキシステアリルアルコール（商品名「ソバモール９１２」、コグニスジャパン株式会社製、水酸基価：３４５〜３６５ＫＯＨ ｍｇ／ｇ）２４０ｇと２，２，４，−トリメチル−１，３−ペンタンジオール６０ｇを加え、９０℃で溶融混合後、４５℃まで冷却し、４５℃で保管した。
混合ポリオールの水酸基価は、４３７ ＫＯＨ ｍｇ／ｇであった。 (1) Preparation Example 1 of Cured Polyurethane Adhesive
(A) Preparation of component (B) In a glass container, 12-hydroxystearyl alcohol (trade name “Sobamol 912”, manufactured by Cognis Japan, hydroxyl value: 345 to 365 KOH mg / g) 240 g and 2,2,4 , -Trimethyl-1,3-pentanediol (60 g) was added, melt-mixed at 90 ° C, cooled to 45 ° C, and stored at 45 ° C.
The hydroxyl value of the mixed polyol was 437 KOH mg / g.

（ｂ）ポリウレタン接着剤硬化物の調製
ガラス製容器に、（Ａ）成分として、特許３２０５９７７公報の段落００３７に記載の方法と同様の方法で調製したＭＤＩのウレトンイミン及びカルボジイミド変性体（ＮＣＯ＝２７．８質量％）の４５℃保管品３００ｇと、（ａ）で調製した（Ｂ）成分の４５℃保管品２５０ｇを均一混合（（Ａ）／（Ｂ）（モル比）：１．０２）し、その一部をポリシリコン製型容器に流し込み、４５℃の恒温乾燥機中で３０分反応させ、その後、徐々に９０℃まで昇温させ、１時間ポストベイクした。
室温まで冷却し、直径４ｃｍ、厚み２ｃｍの円柱状接着剤硬化物を５つ取り出した。
（Ａ）成分と（Ｂ）成分を均一混合したものの残部を用いて、室温環境化に設置されているＢ型粘度計で粘度測定を実施し、均一混合後から４分間は２００ｍＰａ・ｓ以下であり、均一混合後から８分間は４００ｍＰａ・ｓ以下であることを確認した。 (B) Preparation of polyurethane adhesive cured product In a glass container, as component (A), a modified uretonimine and carbodiimide modified product of NDI (NCO = 27.M) prepared as a component (A) by the same method as described in paragraph 0037 of Japanese Patent No. 3205977. 8 mass%) of 45 ° C. storage product 300 g and (a) component (B) 45 ° C. storage product 250 g uniformly mixed ((A) / (B) (molar ratio): 1.02), A part of the solution was poured into a polysilicon mold container and reacted in a constant temperature dryer at 45 ° C. for 30 minutes, and then gradually heated to 90 ° C. and post-baked for 1 hour.
After cooling to room temperature, five cylindrical adhesive cured products having a diameter of 4 cm and a thickness of 2 cm were taken out.
Viscosity is measured with a B-type viscometer installed in a room temperature environment using the remainder of the component (A) and component (B) that are uniformly mixed, and for 4 minutes after uniform mixing, the viscosity is 200 mPa · s or less. Yes, it was confirmed that it was 400 mPa · s or less for 8 minutes after uniform mixing.

比較例１
ガラス製容器に、芳香族ポリイソシアネートとして、実施例１で用いたＭＤＩのウレトンイミン及びカルボジイミド変性体（ＮＣＯ＝２７．８質量％）の４５℃保管品１５０ｇと、硬化剤としてひまし油（伊藤製油製、ひまし油カクトクＡ、水酸基価１５６〜１６５ ＫＯＨ ｍｇ／ｇ）の４５℃保管品３４１ｇを均一混合（（芳香族イソシアネート）／（硬化剤）（モル比）：１．０２）し、その一部をポリシリコン製型容器に流し込み、４５℃の恒温乾燥機中で３０分反応させ、その後、徐々に９０℃まで昇温させ、１時間ポストベイクした。
室温まで冷却し、直径４ｃｍ、厚み２ｃｍの円柱状接着剤硬化物を５つ取り出した。
芳香族ポリイソシアネートと硬化剤とを均一混合したものの残部を用いて、室温環境化に設置されているＢ型粘度計で粘度測定を実施し、均一混合後４分以内に２００ｍＰａ・ｓを上回り、均一混合後８分以内に４００ｍＰａ・ｓを上回ったことを確認した。 Comparative Example 1
In a glass container, as aromatic polyisocyanate, MDI uretonimine used in Example 1 and carbodiimide modified product (NCO = 27.8% by mass) of 45 g stored at 45 ° C., castor oil as a curing agent (manufactured by Ito Oil Co., Ltd., 341 g of 45 ° C. stored product of castor oil Kakutoku A and hydroxyl value 156 to 165 KOH mg / g) is uniformly mixed ((aromatic isocyanate) / (curing agent) (molar ratio): 1.02), and a part thereof is poly The mixture was poured into a silicon mold container and reacted in a constant temperature dryer at 45 ° C. for 30 minutes, and then gradually heated to 90 ° C. and post-baked for 1 hour.
After cooling to room temperature, five cylindrical adhesive cured products having a diameter of 4 cm and a thickness of 2 cm were taken out.
Using the remainder of the homogenous mixture of aromatic polyisocyanate and curing agent, the viscosity was measured with a B-type viscometer installed in a room temperature environment, exceeding 200 mPa · s within 4 minutes after uniform mixing, It was confirmed that it exceeded 400 mPa · s within 8 minutes after uniform mixing.

実施例１のポリウレタン接着剤組成物は、比較例１のポリウレタン接着剤組成物と比較して、均一混合した後の粘度が低い状態を維持しており、本発明のポリウレタン接着剤組成物が、粘度の低い流動可能時間が長いことが分かる。   The polyurethane adhesive composition of Example 1 maintains a low viscosity state after uniform mixing as compared with the polyurethane adhesive composition of Comparative Example 1, and the polyurethane adhesive composition of the present invention is It can be seen that the flowable time with low viscosity is long.

（２）ポリウレタン接着剤硬化物の加水分解への耐久性評価
実施例１および比較例１で得た円柱状接着剤硬化物の各３つを、加水分解への耐久性を評価するために、同じ２％のクエン酸水溶液の入った２つの耐圧金属製容器に分けて沈めて、８０℃に温度制御したオーブンの中にいれ、１０５時間加熱を継続した。残りの円柱状接着剤硬化物の各２つは、実験室に保管した。
室温まで冷却後、円柱状接着剤硬化物を取り出し、水洗いした物を、実験室の中に保管していた残りの物と目視およびニッパで切り裂く際の感触を比較した。実施例１のものは外観、ニッパで切り裂く感触共に２者に大きな違いは無かったが、比較例１の冷却後水洗いした円柱状接着剤硬化物は、部屋の中に保管していた物と比べ明らかに艶がなくなり、表面が粉落ちしそうな状態であった。また、ニッパで切り裂く際、刃によって直ぐに切断するほど脆くなっていた。以上の結果から、実施例１のポリウレタン接着剤硬化物は、比較例１のものに比べて、加水分解への耐久性に優れていることが分かる。 (2) Durability evaluation to hydrolysis of polyurethane adhesive cured product Each of the three columnar adhesive cured products obtained in Example 1 and Comparative Example 1 was evaluated in order to evaluate the durability to hydrolysis. It was submerged in two pressure-resistant metal containers containing the same 2% aqueous citric acid solution, placed in an oven controlled at 80 ° C., and heating was continued for 105 hours. Each two of the remaining cylindrical adhesive cured products were stored in a laboratory.
After cooling to room temperature, the cured columnar adhesive was taken out, and the washed product was compared visually with the remaining material stored in the laboratory and the feel when tearing with nippers. Although the thing of Example 1 did not have a big difference in both the appearance and the feeling of tearing with nippers, the cylindrical adhesive cured product washed with water after cooling in Comparative Example 1 was compared with the one stored in the room. The gloss was clearly lost, and the surface seemed to fall off. Moreover, when cutting with nippers, it was so brittle that it was cut immediately with a blade. From the above results, it can be seen that the cured polyurethane adhesive of Example 1 is superior to that of Comparative Example 1 in durability to hydrolysis.

（３）ＦＴ−ＩＲ測定
実施例１および比較例１で得た円柱状接着剤硬化物の顕微ＦＴ−ＩＲ測定を実施し、また市販されている２社のＥＴＲＦ用の中空糸膜モジュールについて、中空糸膜束の接着硬化部を取り出し、顕微ＦＴ−ＩＲ測定を実施した。各測定において、ウレタン基に由来する１７０８〜１７１２ｃｍ−１の吸収ピークの透過率（Ｔｕ）、及びエステル基に由来する１７２０〜１７３０ｃｍ−１の吸収ピークの透過率（Ｔｅ）を計測した。
測定装置：アジレント社製ＵＭＡ−６００
測定条件：顕微全反射測定法（顕微ＡＴＲ法）
分解能：４ｃｍ−１
測定波数領域：680〜4000ｃｍ−１
積算回数：６４回 (3) FT-IR measurement About the hollow fiber membrane module for ETRF of 2 companies which carried out the microscopic FT-IR measurement of the column-shaped adhesive hardened | cured material obtained in Example 1 and Comparative Example 1, The adhesive cured part of the hollow fiber membrane bundle was taken out and microscopic FT-IR measurement was performed. In each measurement, the transmittance (Tu) of the absorption peak of 1708 to 1712 cm −1 derived from the urethane group and the transmittance (Te) of the absorption peak of 1720 to 1730 cm −1 derived from the ester group were measured.
Measuring apparatus: UMA-600 manufactured by Agilent
Measurement conditions: Microscopic total reflection measurement method (microscopic ATR method)
Resolution: 4cm -1
Measurement wave number range: 680 to 4000 cm −1
Integration count: 64 times

結果、実施例１の円柱状接着硬化物のＦＴ−ＩＲスペクトルで、エステル基に由来する１７２０〜１７３０ｃｍ−１の吸収ピークは確認できなかった。これは、ポリウレタン接着剤硬化物中のエステル基を有する化合物の含有量が少ないことを示しており、Ｔｅ／Ｔｕが本発明の範囲内であると見なすことができる。
比較例１の円柱状接着硬化物のＦＴ−ＩＲスペクトルで、（Ｔｅ／Ｔｕ）は１．０３であり、またＥＴＲＦとして現在市販されている２社の製品のウレタン接着剤を同様に測定した結果、それぞれの（Ｔｅ／Ｔｕ）は、０．９９と０．９８であった。 As a result, in the FT-IR spectrum of the columnar adhesive cured product of Example 1, an absorption peak at 1720 to 1730 cm −1 derived from an ester group could not be confirmed. This indicates that the content of the compound having an ester group in the cured polyurethane adhesive is low, and Te / Tu can be regarded as being within the scope of the present invention.
In the FT-IR spectrum of the cylindrical adhesive cured product of Comparative Example 1, (Te / Tu) was 1.03, and the results of measuring the urethane adhesives of products of two companies currently marketed as ETRF were similarly measured. The respective (Te / Tu) were 0.99 and 0.98.

Claims (7)

（Ａ）芳香族ポリイソシアネート及びその変性体から選ばれる１種以上（以下、（Ａ）成分という）、及び（Ｂ）硬化剤（以下、（Ｂ）成分という）を含むポリウレタン接着剤組成物であって、
（Ｂ）成分中、（Ｂ１）２級又は３級水酸基を１つ以上有する炭素数８以上のポリオール化合物（以下、（Ｂ１）成分という）を５０質量％以上含有し、
（Ａ）成分と（Ｂ）成分との反応によって得られるポリウレタン接着剤硬化物の顕微フーリエ変換型赤外分光光度計（顕微ＦＴ−ＩＲ）測定において、１７０８〜１７１２ｃｍ−１の吸収ピークの透過率（Ｔｕ）に対する、１７２０〜１７３０ｃｍ−１の吸収ピークの透過率（Ｔｅ）の比（Ｔｅ／Ｔｕ）が０．９未満である、ポリウレタン接着剤組成物。 (A) A polyurethane adhesive composition containing at least one selected from aromatic polyisocyanates and modified products thereof (hereinafter referred to as component (A)) and (B) a curing agent (hereinafter referred to as component (B)). There,
In the component (B), (B1) containing 50% by mass or more of a polyol compound having 8 or more carbon atoms (hereinafter referred to as the component (B1)) having one or more secondary or tertiary hydroxyl groups,
In the micro Fourier transform infrared spectrophotometer (micro FT-IR) measurement of the cured polyurethane adhesive obtained by the reaction between the component (A) and the component (B), the transmittance of the absorption peak of 1708 to 1712 cm −1. A polyurethane adhesive composition having a ratio (Te / Tu) of transmittance (Te) of an absorption peak of 1720 to 1730 cm −1 to (Tu) of less than 0.9. （Ｂ１）成分が、２級又は３級水酸基を１つ以上有する炭素数８〜２２の脂肪族ポリオール化合物、及び２級又は３級水酸基を１つ以上有する炭素数１２〜２２の脂肪酸とジアミン化合物との縮合反応物から選択される１種以上である、請求項１に記載のポリウレタン接着剤組成物。   The component (B1) is an aliphatic polyol compound having 8 to 22 carbon atoms having one or more secondary or tertiary hydroxyl groups, and a fatty acid and diamine compound having 12 to 22 carbon atoms having one or more secondary or tertiary hydroxyl groups. The polyurethane adhesive composition according to claim 1, which is at least one selected from condensation products with （Ｂ１）成分が、１２−ヒドロキシステアリルアルコール、２，２，４−トリメチル−１，３−ペンタンジオール、２−エチル−１，３−ヘキサンジオール、２，５−ジメチル−２，５−ヘキサンジオール、２，６−ジメチル−３，５−ヘプタンジオール、及びリシノール酸と多官能アミン化合物との多官能アミド縮合反応物から選択される１種以上である、請求項１又は２に記載のポリウレタン接着剤組成物。   Component (B1) is 12-hydroxystearyl alcohol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol The polyurethane adhesive according to claim 1 or 2, which is one or more selected from 2,6-dimethyl-3,5-heptanediol and a polyfunctional amide condensation reaction product of ricinoleic acid and a polyfunctional amine compound. Agent composition. ケースハウジング内に中空糸膜束が収容された中空糸膜モジュールであって、
前記中空糸膜束の少なくとも一端部側と前記ケースハウジングの内壁面が、請求項１〜３の何れか１項に記載のポリウレタン接着剤組成物の硬化物で一体化されている中空糸膜モジュール。 A hollow fiber membrane module in which a hollow fiber membrane bundle is accommodated in a case housing,
The hollow fiber membrane module by which the at least one end part side of the said hollow fiber membrane bundle and the inner wall surface of the said case housing are integrated with the hardened | cured material of the polyurethane adhesive composition of any one of Claims 1-3. . 前記中空糸膜モジュールが医療用である、請求項４に記載の中空糸膜モジュール。   The hollow fiber membrane module according to claim 4, wherein the hollow fiber membrane module is for medical use. 前記中空糸膜モジュールがエンドトキシン捕捉フィルター用である、請求項４に記載の中空糸膜モジュール。   The hollow fiber membrane module according to claim 4, wherein the hollow fiber membrane module is for an endotoxin capture filter. ケースハウジング内に中空糸膜束が収容された中空糸膜モジュールの製造方法であって、
前記中空糸膜束の少なくとも一端部側と前記ケースハウジングの内壁面を、請求項１〜３の何れか1項に記載のポリウレタン接着剤組成物を使用して、接着して一体化する、中空糸膜モジュールの製造方法。 A hollow fiber membrane module manufacturing method in which a hollow fiber membrane bundle is accommodated in a case housing,
A hollow, in which at least one end side of the hollow fiber membrane bundle and the inner wall surface of the case housing are bonded and integrated using the polyurethane adhesive composition according to any one of claims 1 to 3. A method for manufacturing a yarn membrane module.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021118289A1 (en) * 2019-12-11 2021-06-17 주식회사 엘지화학 Hot-melt adhesive composition for water treatment element, adhesive film, and water treatment element comprising same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09100264A (en) * 1995-10-04 1997-04-15 Nisshinbo Ind Inc Production of dicyclohexylcarbodiimide
JP3205977B2 (en) * 1994-11-29 2001-09-04 日本ポリウレタン工業株式会社 Polyurethane resin composition and adhesive, sealant and binding agent using the composition
WO2006043386A1 (en) * 2004-10-19 2006-04-27 Nippon Polyurethane Industry Co., Ltd. Polyurethane resin forming composition, process for production of sealant, and process for production of hollow-fiber membrane modules
WO2013146080A1 (en) * 2012-03-30 2013-10-03 東レ株式会社 Hollow fiber membrane module and production method therefor
WO2015133494A1 (en) * 2014-03-04 2015-09-11 三井化学株式会社 Isocyanurate composition
US20160090515A1 (en) * 2013-05-15 2016-03-31 Sika Technology Ag Two component polyurethane composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3205977B2 (en) * 1994-11-29 2001-09-04 日本ポリウレタン工業株式会社 Polyurethane resin composition and adhesive, sealant and binding agent using the composition
JPH09100264A (en) * 1995-10-04 1997-04-15 Nisshinbo Ind Inc Production of dicyclohexylcarbodiimide
WO2006043386A1 (en) * 2004-10-19 2006-04-27 Nippon Polyurethane Industry Co., Ltd. Polyurethane resin forming composition, process for production of sealant, and process for production of hollow-fiber membrane modules
WO2013146080A1 (en) * 2012-03-30 2013-10-03 東レ株式会社 Hollow fiber membrane module and production method therefor
US20160090515A1 (en) * 2013-05-15 2016-03-31 Sika Technology Ag Two component polyurethane composition
WO2015133494A1 (en) * 2014-03-04 2015-09-11 三井化学株式会社 Isocyanurate composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021118289A1 (en) * 2019-12-11 2021-06-17 주식회사 엘지화학 Hot-melt adhesive composition for water treatment element, adhesive film, and water treatment element comprising same

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