JPH0714466B2 - Bundling material and separation device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention uses a polyurethane-based two-component hollow fiber binding material used in a medical fluid separation device using hollow fibers, and a hollow fiber using the same. The present invention relates to a medical fluid separation device.

[Conventional technology]

Conventionally, in polyurethane-based binders used in medical fluid separation devices using hollow fibers, castor oil-based polyols, polyether-based polyols, polyester-based polyols, polyamino-based polyols, and the like are used as OH components. As the NCO component, for example, JP-A-53-61695, JP-A-54-102293, and JP-A-54-13269.
No. 8, JP-A-57-155225, JP-A-58-93716 and the like, tolylene diisocyanate (TDI),
Aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI) have been mainly used.

However, from polyurethane materials using these aromatic polyisocyanates, tolylenediamine (TDA) was obtained from TDI and 4,4'-diphenylmethanediamine (MDA) was obtained from MDI by hydrolysis. It is known to produce diamines, or these aromatic diamino compounds are strongly suspected to be carcinogenic. Therefore, the use of polyurethane materials derived from aromatic polyisocyanates in medical fluid separators that directly contact biological components such as blood is extremely problematic for the health and hygiene of the subjects, and there are currently many regulatory movements. I'm waiting.

On the other hand, for example, JP-A-60-58156 proposes to use a prepolymer obtained by reacting hexamethylene diisocyanate (HMDI) with a polyol as at least a part of the NCO component. However, HMDI
The prepolymer obtained by reacting 1,4-butanediol, trimethylolpropane, castor oil and the like generally contains a relatively large amount of unreacted free HMDI monomer.
This HMDI monomer has a high vapor pressure at room temperature and has strong skin and mucous membrane irritation and lung injury inducing properties.
The use of a prepolymer containing a large amount of monomers as a raw material for a binding material is never preferable in terms of worker safety and health. Also, for example, in the production of prepolymer
When the NCO / OH equivalent ratio approaches 1.0, free H in the prepolymer
It is possible to reduce the amount of MDI monomer, but in this case, the viscosity of the prepolymer itself is remarkably increased, and it cannot be used as the NCO component of the solvent-free two-component hollow fiber binding material.

[Problems to be solved by the invention]

Therefore, in the industry, it is possible to use a conventional product with a proven track record as the polyfunctional active hydrogen compound component in the two-component polyurethane hollow fiber binding material, and the polyisocyanate component having the following characteristics can be used. Development was awaited.

(1) Aromatic polyisocyanate is not used, and therefore, there is no possibility of generation of carcinogenic aromatic polyamino compound due to hydrolysis.

(2) It does not substantially contain a free aliphatic diisocyanate monomer, and therefore there is no problem in terms of worker safety and hygiene during binding work.

(3) It has viscosity characteristics suitable for bundling work.

[Means for solving problems]

The present inventors have conducted extensive studies in view of the above points, and as a result, HM
We have found that this problem can be solved by using a specific biuret polyisocyanate using DI, and completed the present invention.

That is, the present invention relates to a polyurethane-based two-component hollow fiber tying material comprising a polyisocyanate component and a polyfunctional active hydrogen compound component, which is used in a medical fluid separation device using a hollow fiber. It is obtained by reacting hexamethylene diisocyanate as a main component with a biuretizing agent at a ratio of (hexamethylene diisocyanate) / (biuretizing agent) in a molar ratio of 6 to 30, and removing and purifying excess hexamethylene diisocyanate after the reaction. A two-component polyurethane-based hollow fiber binder having a viscosity at 25 ° C. of 8000 cps or less and using hexamethylene diisocyanate biuret polyisocyanate substantially free of free hexamethylene diisocyanate monomer, and Special use of this tying material It relates a fluid separation device for medical use with a hollow fiber to be.

The HMDI biuret polyisocyanate used in the present invention is obtained by reacting an excess HMDI monomer with a biuretizing agent. As the biuretizing agent, a known compound capable of reacting with an isocyanate group to form a biuret structure,
Examples thereof include water, aliphatic tertiary alcohols, aliphatic primary amines, and N, N'-disubstituted ureas. Among these, particularly preferred biuretizing agents include water, tertiary butyl alcohol, and a mixture of both.

In the biuretization reaction, it is preferable to react the HMDI component in a ratio of 6 to 30 moles per mole of biuretizing agent. If the amount of this HMDI is less than 6 mol with respect to the brewing agent / mol, the viscosity of the reaction product will remarkably increase, or the tendency of resinification will increase.
It is unsuitable as a raw material for a hollow fiber binding material. Also, this amount
If it exceeds 30 mol, the amount of HMDI recovered in the reaction mixture unnecessarily increases, which is economically disadvantageous.

The reaction temperature in the method of the present invention needs to be selected in the range of 70 to 200 ° C. If the temperature is less than 70 ° C, the reaction rate is too low
Substantially no reaction of the urea compound to the biuret compound proceeds, and if it is higher than 200 ° C., the polyisocyanate is polymerized and the coloring becomes remarkable.

In the method of the present invention, the reaction can be carried out without a solvent, but a solvent can be used if desired. As such a solvent, for example, a hydrophilic solvent such as ethylene glycol monoalkyl acetate or phosphoric acid trialkyl ester is preferable. Particularly suitable solvents are ethylene glycol monomethyl ether acetate and trimethyl phosphate. These may be used alone or in combination of two or more.

When the reaction is completed, excess diisocyanate and solvent in the reaction mixture are recovered using, for example, a falling film evaporator or a solvent extraction method. This excess diisocyanate is recovered as completely as possible, and the amount of diisocyanate monomer contained in the prepolymer is preferably 0.7% by weight or less based on the prepolymer. If more diisocyanate monomer is contained, toxicity and irritation due to the high vapor pressure of the diisocyanate monomer contained in the prepolymer become problems.

The HMDI biuret polyisocyanate obtained in this way is 8000 cps / 25 which is suitable for curing and molding as a binding material.
Since it has a viscosity of ℃ or less and does not substantially contain HMDI monomer, it has no toxicity or irritation.

The present invention, as a polyisocyanate component of a binding material used in a medical fluid separation device using a hollow fiber, the above-mentioned HM
Although it is not excluded to mix and use DI biuret polyisocyanate and other polyisocyanates (excluding HMDI monomer) in combination, in order to achieve the object of the present invention, other polyisocyanate components The use is 50% by weight or less of the total polyisocyanate component, preferably
It should be kept below 30% by weight.

Also, non-aromatic diisocyanates other than HMDI, for example,
/ -Isocyanatomethyl-3,5,5-trimethylcyclohexane (IPDI), bis (4-isocyanatocyclohexyl) methane (hydrogenated MDI) and xylylene diisocyanate (XDI)
All of the biuret polyisocyanates derived from the above have extremely high viscosity or are in a solid state and cannot be used as a raw material of the binding material which is the object of the present invention.

As the polyfunctional active hydrogen compound component, which is the other component to be combined with the above polyisocyanate component to form the two-component hollow fiber binding material, various polyol components and other active hydrogens such as polyamines which are conventionally known are used. It is possible to use compounds.

Examples of these polyol components include castor oil, castor oil-based polyols such as castor oil fatty acid and low molecular weight polyols, partial or total polyester polyols; polyether-based polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol; Polyester polyols produced by condensation reaction of carboxylic acid and low-molecular weight polyol or polyether polyol; polycaprolactone polyols produced by ring-opening polymerization of (substituted) caprolactone; -Based polyols; propylene oxide or ethylene oxide adducts with amino compounds such as N, N, N'N'-tetrakis (2-hydroxypropyl) ethylenediamine, triethanol Amine polyols such as Min; more ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3
Butanediol, neopentyl glycol, 2-ethyl-
Examples include low molecular weight polyols such as 1,3-hexanediol, trimethylolpropane and glycerin.

Furthermore, for example, with the above polyols, aliphatic diisocyanates such as HMDI, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (IPDI),
Bis (4-isocyanatocyclohexyl) methane (hydrogenated MD
Polyurethane polyols obtained by reacting an alicyclic diisocyanate such as I) and a diisocyanate selected from araliphatic diisocyanates such as xylylene diisocyanate at an NCO / OH equivalent ratio / below can also be suitably used. Is.

Examples of polyamines include ethylenediamine, diethylenetriamine, monoethanolamine, diethanolamine, isophoronediamine, and xylylenediamine.

Generally, these polyfunctional active hydrogen compounds are appropriately mixed and used according to the required performance of the binding material.

The polyisocyanate component and the polyfunctional active hydrogen compound component have an NCO / active hydrogen functional group equivalent ratio of 0.8 to 1.6, preferably
It is used as a fiber end binding material for a medical fluid separation device using hollow fibers, by curing it by blending it in a range of 0.9 to 1.2. At this time, for the purpose of accelerating the curing speed, for example, a tertiary amino compound, an organometallic compound or the like can be used as a catalyst. The hardness of the tying material after hardening depends on the request of the cutting process after tying, and the Shore D hardness of 40-
80 is appropriate.

Curing is usually carried out at room temperature or under heating at 40 to 80 ° C. At this time, as a method for binding and sealing the ends of the hollow fibers, for example, JP-B-57-58963 and JP-B-57-58964 are disclosed. It is general to use the centrifugal molding method described in the above. In order for this casting operation to be carried out smoothly, it is desirable that the initial viscosity of the two-pack type compound at the time of mixing is about 8000 cps or less. If the clay of the initial mixture is too high, it becomes difficult to uniformly mix the two-component mixture and perform a smooth casting work, and the performance of the cured molded product varies, which is not preferable. Further, from the viewpoint of uniform mixing of the two-part blend, it is desirable that the viscosities of the polyisocyanate component and the active hydrogen compound component are not different from each other. That is, both the polyisocyanate component and the active hydrogen compound component are 8000.
The cps or less is most preferable for the casting operation.

As the hollow fiber, for example, regenerated cellulose having a property as a semipermeable membrane, cellulose acetate, cellulose ether, polyethylene, polypropylene, polyamide, polysulfone, polyacrylamide, polyacrylonitrile, polyester, polycarbonate, polyvinyl chloride, polyurethane, casein. , Collagen, and the like.

The constitution other than the binding material of the medical fluid separation device using the hollow fiber sealed with the binding material of the present invention is, for example, JP-A-56-
15757, JP-A-58-75556, JP-A-58-9242
3, JP-A-58-206757, JP-A-59-225066
The same thing as what was described in the drawing of the gazette can be mentioned, and an example of a concrete use is an artificial kidney, an artificial lung, a plasma separation device, etc., for example.

〔The invention's effect〕

The end binding material of the hollow fiber used in the medical fluid separation device thus obtained does not contain an aromatic isocyanate component as a polyisocyanate component, so there is no concern about carcinogenicity due to aromatic diamine due to hydrolysis. ,
In addition, since it does not substantially contain free HMDI monomer, which is highly toxic and irritating, it is excellent in terms of stable hygiene for assembly workers, and
It has an excellent feature that it has a viscosity suitable for two-component centrifugal molding, and is extremely useful industrially.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention should not be limited thereto. In the examples, "part" means part by weight and% means% by weight.

Example 1 1680 parts of HMDI and 18 parts of water were mixed with 300 parts of methyl cellosolve acetate.
After reacting 1 part at 160 ° C for 1 hour, a thin film evaporator (about 160 ° C, about 0.2mmHg; hereinafter, this condition is used when a thin film evaporator is used), unreacted HMDI and solvent etc. Removed and collected. Viscosity of HMDI biuret polyisocyanate obtained as bottom liquid is 2000cps at 25 ℃, NCO content
The amount was 23.2% and the amount of free HMDI was 0.2%. Hereinafter this is referred to as polyisocyanate [A].

A mixture of 40 parts of tetrakis (2-hydroxypropyl) ethylenediamine (THPED) and 60 parts of castor oil-based polyol (Ito Oil Co., Ltd. Yuriku H-81 ": hydroxyl value = 340) was used as a polyol component, and this was mixed with the above polyisocyanate [ A] and NCO / OH equivalent ratio = 1.03
Cured at 30 ° C.

The polyol component and the polyisocyanate component were rapidly mixed and homogenized by stirring at the time of mixing to give a mixture having an initial viscosity of 2000 cps, and smooth casting and molding were possible.

In addition, there was no odor or irritation to the eyes due to the HMDI monomer during compounding and molding.

The obtained cured product had a Shore D hardness of 60.

Example 2 1176 parts of HMDI and 18 parts of water were added to 250 parts of methyl cellosolve acetate.
Part and trimethyl phosphate (250 parts) in a mixed solvent at 160 ° C. for 1 hour and then purified using a thin film evaporator. The HMDI biuret polyisocyanate obtained had a viscosity at 25 ° C of 7,000 cps, an NCO content of 21.5%, and a residual HMDI content of 0.4%. This is designated as polyisocyanate [B].

40 parts of THPED and castor oil type polyol (Ito Oil Co., Ltd.)
"Yurik H-102": A mixture of 50 parts of hydroxyl value = 320) and 10 parts of polypropylene glycol (average molecular weight about 1000, hydroxyl value = 170) was used as a polyol component, and this and the above polyisocyanate [B] were mixed with NCO / OH. It was mixed so as to have an equivalent ratio of 1.02 and cured at 30 ° C. Both components were homogeneously compatible (viscosity 3800 cps when mixed), smooth casting and molding were possible, and there was no odor or eye irritation due to the HMDI monomer during the work.

Example 3 1680 parts of HMDI and 37 parts of tertiary butyl alcohol were reacted in the absence of a solvent at 185 ° C. for 3 hours and then purified using a thin film evaporator. 25 of the obtained pure polyisocyanate
Viscosity at 650 cps, NCO content 24.8%, residual HMDI
The amount was 0.3%. This is polyisocyanate [C]
And The polyol component was the same as in Example 1, and this and polyisocyanate [C] were used in an NCO / OH equivalent ratio = 1.03.
It was compounded so as to be, and cured at 30 ° C.

Both components were uniformly compatible (viscosity 1000 cps when mixed), smooth casting and molding were possible, and there was no odor or eye irritation due to the HMDI monomer during the work.

The obtained cured product had a Shore D hardness of 65.

Comparative Example 1 Polyisocyanate was synthesized in exactly the same manner as in the first stage of Example 1 except that the amount of water was changed to 36 parts. The viscosity of the resulting polyuret polyisocyanate at 25 ° C was 40,000 cps and the NCO content was 19.2%.

This product was used as a polyisocyanate component and blended in the same manner as in the latter part of Example 1. However, since the viscosity of the polyisocyanate component was too high, it was difficult to make it uniform by stirring, and the viscosity after mixing was 10000 cps. It was impossible to cast over.

Comparative Example 2 HMDI 504 parts and trimethylolpropane 134 parts were reacted at 100 ° C. for 8 hours to obtain an HMDI prepolymer. The obtained prepolymer did not show fluidity at room temperature and was unsuitable as a casting raw material.

Comparative Example 3 756 parts of HMDI and 134 parts of trimethylol propane were added at 100 ° C.
Was reacted for 4 hours to obtain an HMDI prepolymer. The viscosity of the obtained prepolymer at 25 ° C. was 1400 cps, the NCO content was 28.2%, and the amount of free HMDI monomer was 22.7%.

This was used as a polyisocyanate component, and was compounded and molded in the same manner as in the latter part of Example 1. At this time, there was a strong odor and irritation to the eyes due to the HMDI monomer in the polyisocyanate component, which was unfavorable for work hygiene.

Comparative Example 4 1680 parts of HMDI and 74 parts of tertiary butyl alcohol were reacted at 185 ° C. for 3 hours in the same manner as in Example 3 in the absence of solvent to obtain a polyisocyanate component as it was without purification with a thin film evaporator.

This product contained 78% free HMDI monomer and could not be handled safely.

Comparative Example 5 IPDI biuret polyisocyanate was obtained by carrying out the reaction and purification in the same manner as in Example 1 except that 2202 parts of IPDI was used instead of HMDI. The polyisocyanate obtained has a softening point of 80-
It was a solid having a temperature of 90 ° C. and could not be used as the polyisocyanate component of the binding material.

Claims (4)

[Claims] 1. A polyurethane-based two-component hollow fiber binding material comprising a polyisocyanate component and a polyfunctional active hydrogen compound component, which is used in a medical fluid separation device using a hollow fiber, comprising: As a main component, hexamethylene diisocyanate is reacted with a biuretizing agent at a ratio of (hexamethylene diisocyanate) / (biuretizing agent) in a molar ratio of 6 to 30, and excess hexamethylene diisocyanate is removed and purified after the reaction. A polyurethane-based two-component hollow fiber tying material having a viscosity at 25 ° C of 8000 cps or less and using hexamethylene diisocyanate biuret polyisocyanate which does not substantially contain free hexamethylene diisocyanate monomer. 2. A biuretizing agent is water, tertiary butyl alcohol, or a mixture of both of them.
Bundling material described in paragraph. 3. The content of free hexamethylene diisocyanate monomer in the biuret polyisocyanate is 0.
The binding material according to claim 1, which is 7% by weight or less. 4. Hexamethylene diisocyanate as a main component in the polyisocyanate component and a buretting agent are reacted at a molar ratio of (hexamethylene diisocyanate) / (bulletizing agent) of 6 to 30, and an excess of hexane is added after the reaction. Polyurethane-based two-component hollow fiber bundle obtained by removing and purifying methylene diisocyanate and having a viscosity at 25 ° C of 8000 cps or less and hexamethylene diisocyanate biuret polyisocyanate containing substantially no free hexamethylene diisocyanate monomer A medical fluid separation device using hollow fibers, characterized by using a material.