JPS62231671A - Hollow fiber bundled material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polyurethane-based hollow fiber binding material used in a medical fluid separation device using hollow fibers.

[Conventional technology]

Conventionally, in polyurethane binding materials used in medical fluid separation devices using hollow fibers, castor oil polyols, polyether polyols, polyester polyols, polyamino polyols, etc. are used as the 10H component. As NCO components, for example,
Japanese Patent Publication No. 53-1695, Japanese Patent Publication No. 1695. 93
No., JP-A-11-11-/J-Kotqr, JP-A-57-13
No. 1225, JP-A No. 11-937/4, etc., tolylene diisocyanate (TDI), 4
(, #'-diphenylmethane diisocyaner) (MDI
Aromatic polyisocyanates such as ) have been mainly used.

However, from polyurethane materials using these aromatic polyisocyanates, tolylene diamine (TDA) is produced from TDI by hydrolysis.

From MDI, p, II'-2 phenylmethanediamine (
It is known that aromatic diamines such as MDA) are produced, and these aromatic diamino compounds are strongly suspected to be carcinogenic. Therefore, polyurethanes derived from aromatic polyisocyanates The use of materials in medical fluid separation devices that come into direct contact with biological components such as blood is extremely problematic in terms of the health and hygiene of test subjects, and there is currently an increasing movement toward regulation.

On the other hand, for example, JP-A-60-! In the r/st publication, hexamethylene diisocyaner) (HMD I)
It has been proposed to use a prepolymer obtained by reacting NCO and a polyol as at least a part of the NCO component, and to use an amine polyol as the polyol.

[Problems to be solved by the invention] However, compared to the reactivity of aromatic isocyanates such as MDI, the reactivity of HMDI is very low;
It has the disadvantage that the curing speed after casting is extremely slow, which adversely affects productivity. Although the use of amine polyols somewhat improves this drawback, it is still not satisfactory.

Also, Tokukai Akira! rA-/4 (Ta 9/6, JP-A-57-r
7'lIj issue, Tokukai Shota! -937/No. Otsu's bulletin states:
The application of tin-based compounds to hollow fiber binding materials has been proposed. It is true that Sn compounds have high catalytic activity, and HM
Fast curing speeds can be achieved using aliphatic polyisocyanates such as DI-based polyisocyanates, but 5 nspb SZn,
If heavy metals such as CD were to be eluted into the blood, they would have an adverse effect on living organisms, so they are not desirable as constituents of medical devices, and are currently regulated.

Therefore, the industry has been looking forward to the development of a polyurethane-based hollow fiber binding material in which conventional polyol components can be used, and which have the following properties.

(1) No aromatic polyisocyanate is used, thus reducing the possibility of generation of carcinogenic aromatic polyamino compounds.

(2) It should have high curing properties comparable to those of aromatic polyisocyanate.

(3) Does not contain heavy metals such as 5nXPb, Zn, and Cd as a catalyst.

[Means for solving interlayer points]

The inventors of the present invention have conducted extensive research in view of the above points, and have solved this problem by using a non-aromatic polyisocyanate as the polyisocyanate component and an iron-containing compound as the catalyst. That is, the present invention relates to a polyurethane-based hollow fiber binding material used in a medical fluid separation device using hollow fibers.
The present invention relates to a hollow fiber binding material characterized in that an aliphatic polyisocyanate, an alicyclic polyisocyanate, or an araliphatic polyisocyanate is used as a polyisocyanate component, and an iron-containing compound is used as a catalyst.

Examples of the aliphatic or alicyclic polyisocyanate or araliphatic polyisocyanate used in the present invention include hexamethylene diisocyanate (I (MDI),
+, lI- or co, 2.1-) aliphatic diisocyanate monomers such as lymethylhexamethylene diisocyanate or inphorone diincyanate, hydrogenated MDI,
Alicyclic diincyanate monomers such as diisocyanatomethylcyclohexane and diisocyanatocyclohexane, or araliphatic diisocyanates such as xylylene diisocyanate, or biurets, incyanurates, urethanes, allophanates, etc. derived therefrom. Oligomers having a bond, and further 3 such as lysine ester triisocyanate, ha-l-diinocyanato q-inocyanatomethyloctane, /, t,D-triisocyanatoundecane, triinocyanatomethykX/chlorohexane, etc.
Examples include functional polyisocyanates.

Preferred among these are biuret or incyanurate derived from MDI or an oligomer having a urethane bond and containing substantially no free HMDI monomer.

Further, in order to adjust the viscosity of the polyisocyanate component and the hardness of the cured product, these can be mixed as appropriate.

HMDI biuret polyisocyanate is disclosed in, for example, JP-A-Sholl9-/J-Da-Otsu-2q, JP-A-Sho! ;3-IO&7
It can be obtained by the method described in Japanese Patent No. 97.

In addition,) IMDI's incyanurate polyisocyanate is disclosed in, for example, JP-A No. 2003-111012, JP-A No. 1, No. 1, No. 1, No.
No. 3160 and JP-A-Shoj'9-229/4.

HMD I urethane polyisocyanate is HMD I
and a polyfunctional alcohol compound.
A method such as that described in f7-200ψNoro is preferred. Also, JP-A-4/-21! Urethane polyisocyanates such as those described in the lif publication are also preferably used.

As mentioned earlier, these polyisocyanate-based HMDs
It is preferable that it be purified to such an extent that it does not substantially contain I 7-mer and have a viscosity of I 000 cpa or less at room temperature.

Examples of the iron-containing compound used as a catalyst component in the present invention include ferrocene, n-butylferrocene,
1. Ferrocene compounds such as /'-di-n-butylferrocene, hydroxymethylferrocene, acetylferrocene, iron phthalocyanine, and further, for example, iron acetate, iron butyrate,
Iron in aliphatic carboxylic acids such as ferric oxalate, iron dicyclohexylbutyrate, iron coethylhexanoate, iron caprylate, iron naphthenate, ferric stearate, iron oleate, iron citronellaate, iron laurate, etc. salts, such as lactic acid, hydroxystearic acid, ricinoleic acid, malic acid,
Citric acid, tartaric acid, pantothenic acid, glyceric acid, erythronic acid, threonic acid, ribbonic acid, araponic acid, kydyuronic acid, lyxonic acid, aronic acid, altronic acid, gluconic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid,
Iron salts of carboxylic acids with OH groups such as gulonic acid, gluconoheptonic acid, mannoheptonic acid, galaheptonic acid, glutamic acid, or glycylate, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine 1-aspartic acid Iron salts of amino acids such as , glutamic acid, lysine, arginine, phenylaanihetyrosine, histidine, tryptophan, brolyloxyproline, β-alanine, γ-aminobutyric acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid. etc.

These may be hydrated and used dissolved or dispersed in the polyol component or polyisocyanate component, or mixed immediately before casting. 1 These can also be used in advance by making them into a solution in glycerin or the like.

Among these, preferred ones are represented by the general formula (%) (wherein R represents a monovalent organic group, and n represents an integer of 2 or 3). ] Iron carboxylate compounds represented by the above formula, more preferably iron lactate, iron citrate, iron ricinoleate, iron gluconate, iron glutamate, etc., in which R in the above general formula represents at least one functional group having an active hydrogen. Examples include carboxylate compounds of iron, which have an organic group.

When such a compound is used as a reaction catalyst for a binding material, it reacts with polyisocyanate and chemically bonds to the polymer network of the resin, so there is a possibility that iron components contained in the binding material may be eluted into the blood. can be made extremely small.

Among the compounds exemplified above, iron gluconate is the most preferred because of its low toxicity and high solubility in polyols.

The polyfunctional active hydrogen compound component, which is the other component to be combined with the polyisocyanate component and the iron-containing compound as a catalyst to form the hollow fiber binding material, is as follows:
Various conventionally known polyol components and other active hydrogen compounds such as polyamines can be used.

These polyol components include, for example, castor oil-based polyols such as castor oil, a portion of castor oil fatty acid and a low molecular weight polyol, or a whole polyester polyol; polyether-based polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; Polyester polyols produced by the condensation reaction of carboxylic acid and low molecular weight polyols or polyether polyols; Polycaprolactone polyols produced by ring-opening polymerization of (substituted) caprolactone; Terminated hydroxyl-terminated polybutadiene and its hydrogenated products, etc. Polyolefin polyols: Adducts of propylene oxide or ethylene oxide to amino compounds such as N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, amine polyols such as triethanolamine: Further ICd ethylene glycol, l
, 3-propanediol, λ-propanediol, 4+-2tanediol, /, 3-butanediol, neopentyl glycol, 2-ethyl-/, J-hexanediol, trimethylolpropane, glycerin, and other low molecular weight polyols. Examples include.

Furthermore, for example, polyurethane polyols obtained by reacting the above polyols with an incyaner component selected from aliphatic, cycloaliphatic or araliphatic polyisocyanates as described above at an NC010H equivalent ratio of 1 or less are also available. Also, examples of polyamines that can be suitably used include ethylenediamine, diethylenetriamine, monoethanolamine, jetanolamine, isophoronediamine, and xylylenediamine.

These polyfunctional active hydrogen compounds are generally mixed as appropriate depending on the required performance of the binding material.

The polyisocyanate component and the polyfunctional active hydrogen compound component have an NCO/active water active hydrogen functional group equivalent ratio of −0t to 1.
It is preferably blended in a range of 0.9 to 0.2 to be cured and used as a fiber end binding material of a medical fluid separation device using hollow fibers. At this time, the amount of the iron-containing compound used as a catalyst to be added is approximately o, oos to -% with respect to the binding resin gold JilC.

If the amount added is too small, the effect of promoting hardening will be poor, and if it is too large, the resin will be heavily colored, which is not preferable.

The hardness of the binding material after curing is approximately Shore D410-to, which is suitable for the requirements of the cutting process after binding.

Curing is usually carried out at room temperature or under heating at 0-10"C. At this time, the method of binding and sealing the ends of the hollow fibers is described, for example, in Japanese Patent Publication No. 7-41963 and Japanese Patent Publication No. 57-11.
Generally, a centrifugal molding method such as that described in Japanese Patent No. 9611 is used. In order for this casting and molding operation to be carried out smoothly, - The initial viscosity of the wave-shaped compound during mixing is approximately 1000 cps or less, and the resin does not lose fluidity due to a curing reaction after mixing. The cooking time is 75 minutes or less,
More preferably, the time is 10 minutes or less.

If the time until this flow stops is too long, it will not only have a negative effect on the productivity of the medical fluid separation device, but also cause the binding material resin to penetrate into the hollow interior through the holes in the outer wall of the hollow fiber, and eventually This causes the fatal drawback of clogging the hollow fibers.

The hollow fibers to be sealed with the binding material of the present invention include, for example, regenerated cellulose, cellulose acetate, cellulose ether, polyethylene/
, polypropylene/, polyamide, polysulfone, polyacrylamide, polyacrylonitrile, polyester,
Examples include those manufactured from polycarbonate, polyvinyl chloride, polyurethane casein, kudzu collagen, and the like.

The structure of the medical fluid separation device other than the binding material is disclosed in, for example, JP-A No. 7!7, JP-A No. 556, SHOTA R-7,
Tokukai Showa SR-Day 4I Ko No. 3, Tokukai Showa 5! - Products similar to those described in drawings such as KoOb7ta No. 7 and JP-A No. 2Ko5ott, etc. can be mentioned, and examples of specific uses include, for example, artificial kidneys. , artificial lungs, plasma separation devices, etc.

The thus obtained hollow fiber end binding material used in medical fluid separation devices does not contain aromatic isocyanate components as polyisocyanate components, so there is no concern about carcinogenicity caused by aromatic diamines due to hydrolysis. Not, again,
Although it does not contain any permanent metals such as Sn, Pb%Zn%Cd, etc., it has hardening properties that do not struggle, making it extremely useful industrially.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention should not be limited thereto.

In the examples, "parts" indicate parts by weight, and "%" indicates weight %.

Manufacturing example 1 HMDI/≦! After reacting 300 parts of methylcerone lube acetate (part Q and part of water with 300 parts of methylcerone lube acetate) as a solvent at /lO"c for 1 hour, using a membrane evaporator (about 1lO"c) and 300 parts of methylceronlube acetate (about 100 parts of water), use a film evaporator (about 1 liter, °C, approx. 0.
21MIHg (hereinafter, this condition was used when using a thin film evaporator), unreacted HMD I, solvent, etc. were removed and recovered. The viscosity of HMD I biuret polyisocyanate obtained as a bottom liquid at 25°C was 2000 cp8, N
CO content 1 to 2j-%, free HMDI amount Q, 2% Thea7'C0 Production Example 2 Hexamethylene diisocyanate 100 parts by weight, /, 3
-2 parts by weight of butanediol and 200 parts by weight of ethylene glycol monomethyl ether acetate as a solvent were mixed, 1 part by weight of sodium methoxide as a catalyst and 3 parts of phenol O were added, and the mixture was heated at qo''C for 7 hours.

After passing the sodium methoxide out of the resulting Y reaction solution, excess hexamethylene diisocyanate and the solvent were removed using a thin film evaporator. Viscosity 2100 cps at 25°C as bottom liquid, NCO content λ/, 3%, free I
(MD I It O, 2% polyisocyanurate of hexamethylene diisocyanate was obtained.

Production example 3 HMDI 21209 Tohe-3-butanediol 909
The mixture was reacted without solvent at 7 io°C for 7 hours. Purification was carried out in the same manner as in Production Example 1, and the viscosity at Coj''C was 700c.
p8, NCO content/9.41%, free T (MD I amount O
, 5% urethane polyisocyanate was obtained.

Examples/~io and Comparative Examples 1 to 3 The polyisocyanate obtained in Production Examples 1 to 3 and da, II'-dicyclohexylmethane diisocyanate (hydrogenated MD I) were used as inocyanate components, and as the active hydrogen compound. is N,N,N',N'-tetrakis(--hydroxypropyl)ethylenediamine (TI
(PED), castor oil polyol rH-1r/J (
Ito Oil ■, hydroxyl value = 3 dao), castor oil-based polyol rlF (-102'' (Ito Oil ■, hydroxyl value: 3)
20), polypropylene glycol (average molecular weight approximately 10
00. Hydroxyl value = /70) was used. Further, as catalysts, iron coethylhexanoate (mineral spirits diluted product, Fe content: about 6%), iron naphthenate (Fe content: about 1%), and diptyltin dilaurate were used.

These were blended in the parts by weight listed in Table 1, stirred and mixed, and then cast and cured at a temperature of 0''C.Evaluation was made by tracking the increase in viscosity of the mixture over time and measuring the time required to reach 10,000 cptr. The quality was judged based on the following criteria.

◎: / 0000 cps arrival time less than io minutes ○
：ノ0N15minute×：〃 Ko! 〜IIo min××=IIO min or more Also, after separately forming a sample with the same composition into a sheet shape with a thickness of about 71111,
about! ■ Cut into squares and soak in water containing 5% ethanol (ratio: 7 g of sample/100 rd solvent).
A dissolution test was conducted by heating for 70 minutes. After concentrating the obtained elution test solution, Sn was quantified by atomic absorption spectrometry, and samples in which Sn elution of /- or more was observed were evaluated as ×, and those in which no Sn was observed were evaluated as ○. .

(Margin below)

Claims (3)

[Claims] (1) In polyurethane-based hollow fiber binding materials used in medical fluid separation devices using hollow fibers, aliphatic polyisocyanate, alicyclic polyisocyanate, or araliphatic polyisocyanate is used as the polyisocyanate component. , and a hollow fiber binding material characterized by using an iron-containing compound as a catalyst. (2) The iron-containing compound has the general formula (RCOO)nFe [wherein R represents a monovalent organic group and n represents an integer of 2 or 3]. ] The binding material according to claim 1, which is an iron carboxylate compound represented by: (3) The binding material according to claim 1, wherein the aliphatic polyisocyanate is a buret polyisocyanate derived from hexamethylene diisocyanate (HMDI).