JPS633869A - Potting material and separation apparatus - 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 Field of Application) The present invention relates to a polyurethane-based two-component potting material for use in medical fluid separation devices using hollow fa and fibers, and a material for making friends using the same. This invention relates to a medical fluid separation device using hollow bond fibers.

(Prior art and problems to be solved by the invention) Conventionally, in polyurethane potting materials used for medical fluid separation devices using medium-sized fibers, castor oil-based polyols and polyether-based potting materials have been used as OH components. Polyols, polyester polyols, polyamino polyols, etc. are used, and as NGO components, for example, JP-A-53-61695, JP-A-54-102
No. 293, JP-A-54-132698, JP-A-57-
As seen in publications such as No. 155225 and JP-A-58-93716, tolylene diisocyanate (TDI),
4.4'-diphenylmethane diincyanate (MDI)
Aromatic polyisocyanates such as ) have been mainly used.

However, from polyurethane materials using these aromatic polyisocyanates, aromatic diamines are produced by hydrolysis, such as tolylene diamine (TDA) from 5TDI and 4,4'-diphenylmethanediamine (MDA) from MDI. These aromatic diamino compounds are strongly suspected to have carcinogenic properties. However, the use of polyurethane materials derived from aromatic polyisocyanates in medical fluid separation devices that come into direct contact with biological components such as blood is extremely problematic in terms of human health and hygiene, and is currently subject to regulatory requirements. The movement is increasing.

On the other hand, for example, JP-A-60-58156 proposes using a prepolymer obtained by reacting hexamethylene diisocyanate (HMDI) with a polyol as at least a part of the NCO component. However, the prepolymer obtained by reacting the compound with 1,4-butanediol, trimethylolbromine, castor oil, etc. generally contains a relatively large amount of unreacted free HMDI monomer. .This HMD I monomer has a high vapor pressure at room temperature, and has strong skin and mucous membrane irritation and the potential to cause lung damage.A prepolymer containing a large amount of HMDI monomer is used as a raw material for potting material. Doing so is not at all desirable in terms of worker safety and health.

Regarding this point, the present inventors have proposed patent application No. 60-27659.
4, HMD I and a biuret forming agent (HMDI
)/(biuret forming agent) at a molar ratio of 6 to 30, and after the reaction, excess HMD I is removed and purified, and the viscosity at 25C is 8000 cps or less and free HMD I. A method using MD I biuret polyincyanate (substantially free of monomers) was proposed.

In this way, the presence of aliphatic polyisocyanates such as biuret or incyanurate throughout HMDI eliminates the generation of carcinogenic aromatic amines.
Moreover, it is also possible to avoid the adverse effects of HMDI monomers.

However, when such aliphatic polyincyanate is combined with a polyfunctional active hydrogen compound that has a proven track record in 2-deep polyurethane hollow fiber end botting materials, the cured product becomes too hard, resulting in However, in the assembly and assembling process, the conventional product also has the disadvantage that the cut surface is not smooth when cut. Another problem is that the adhesion to the container is poor, resulting in peeling between the container and the potting material.

By the way, from the viewpoint of cuttability in the assembly process,
The hardness of the cured product is Shore D45-65, the breaking strength and elongation are 100 to 300 ky/crl, and 50 to 10.
It is said that a range of 0% is appropriate.

Therefore, we used an aliphatic polyisocyanate that does not generate carcinogenic aromatic amines, and used a highly irritating free HML.
) There has been a long-awaited development of a potting material which does not substantially contain I monomer and which has excellent cuttability and container adhesion of the cured product.

(Means for Solving the Problem) In view of the above points, the present inventors have conducted extensive research, and as a result,
We have discovered that this problem can be solved by using a specific HMD I prepolymer, and have thus completed the present invention.

That is, the present invention provides a polyurethane-based two-component hollow fiber end potting material comprising a polyisocyanate component and a polyfunctional active hydrogen compound component, which is used in a medical fluid separation device using hollow fibers. As at least a part of the NAT component, HMD I and a polycaprolactone diol and/or triol having a number average molecular weight of 500 to 1500 are combined at an N CO/OH equivalent ratio of 5.
A polyurethane-based two-component hollow fiber end botting material characterized by using a prepolymer (hereinafter referred to as PCL prepolymer) obtained by removing unreacted HMD I after reacting at ~40°C. The present invention also relates to a medical fluid separation device using hollow fibers, which is characterized by using this potting material.

The PCL prepolymer used in the present invention is
-28518, obtained as follows.

HMD I and polycaprolactone polyol at 20-2
00C1 Preferably 1-2 at a reaction temperature of 80-140C
Allow time to react. At this time, no solvent may be used, or any solvent inert to incyanato groups may be used. After completion of the reaction, unreacted IMD I in the reaction mixture is recovered using, for example, a thin film evaporator or solvent extraction, and the amount of HMD I monomer contained in the PCL prepolymer is reduced to 0.
It is desirable to keep it below 7%.

Here, it is necessary to use a polycaprolactone polyol having a number average molecular weight within a specific molecular weight range of 500 to 1,500. PCL prepolymers using polycaprolactone polyols with a number average molecular weight of less than 500 are poor in improving cuttability and adhesion; It is waxy and has a low NGO content, making it less practical. Furthermore, H
The equivalent ratio of MDI and polycaprolactone polyol is also important, and it is necessary to select a NCO/OH equivalent ratio of 5 to 40.

If this proportion ratio is less than 5, sequential addition polymerization occurs between HMD I and the polycaprolactone polyol, producing a polymer, which is undesirable because the viscosity of the prepolymer increases.

Moreover, if the NC010R equivalent ratio is larger than 40, productivity will deteriorate, which is not preferable.

The polyincyanate used in combination with the above PCL prepolymer is an aliphatic polyincyanate that does not generate carcinogenic aromatic amines, such as HMDI.
buret polyisocyanate), HMDI incyanurate polyincyanate, and the like. Their blending ratio may be appropriately determined depending on the other component, the polyfunctional active hydrogen compound component, but usually, 31% by weight of the PCL prepolymer in the polyisocyanate component is 10 to 8% by weight.
0, preferably 20-60. Increasing the proportion of the PCL prepolymer more than necessary is undesirable because it leads to a decrease in the strength of the cured product.

The other polyfunctional active hydrogen compound fraction to be combined with the polyisocyanate component to form the two-component hollow fiber end potting material includes various conventionally known polyol components and polyamines. It is possible to use other active hydrogen compounds such as.

These polyol components include, for example, castor oil-based polyols such as castor oil fatty acids and low molecular weight polyols, such as all-polyester polyols; polyether-based polyols such as polyethylene glycol, holiflopylene glycol, and polytetramethylene glycol. ; Polyester polyols produced by the condensation reaction of polycarboxylic acid and low molecular weight polyols or polyether polyols; Polycaprolactone polyols produced by ring-opening polymerization of (substituted) caprolactone: Terminated hydroxyl-terminated polybutadiene and hydrogenated polybutadiene Polyolefin polyols such as N, N, N', N'-tetrakis (
2-hydroxypropyl) ethylene oxide adducts to amino compounds such as ethylene diamine, amine-based polyols such as triethanolamine; 2-7'lopanediol, 1,
Examples include low molecular weight polyols such as 4-butanediol, 1.5-butanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, trimethylolpropane, and glycerin.

Furthermore, for example, the above polyols and HMD I
Aliphatic diincyanates such as 1-incyanato-
Alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexane + IPDI), pis(4-isocyanatocyclohexyl)methane (hydrogenated MDI), and aromatic fats such as xylylene diinocyanate. Polyurethane polyols obtained by reacting a diincyanate selected from group diisocyanates at an NGO10H equivalent ratio of 1 or less can also be suitably used.

Examples of polyamines include ethylenediamine, diethylenetriamine, monoethanolamine, jetanolamine, inphorondiamine, and xylylenediamine.

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

The polyincyanate component and the polyfunctional active hydrogen compound component have an NGO/active hydrogen functional group equivalent ratio of 0.8 to 1.6,
Preferably, it is blended in a range of 0.9 to 1.2, and the hollow fibers km are cured and used as a fiber end botting material for medical fluid separation devices.

At this time, it is also possible to use, for example, a tertiary amino compound, an organometallic compound, or the like as a catalyst for the purpose of increasing the curing speed.

The hardness and breaking strength and elongation of the potting material after curing are Shore D4, respectively, due to the requirements of the potting material cutting process.
5 to 65.100 to 300 ky/ad.

50 to 100% is appropriate.

Curing is usually carried out at room temperature or under heating at Fi40 to 80c. At this time, methods for potting the ends of the hollow m fibers include, for example, Japanese Patent Publication No. 57-58965, Japanese Patent Publication No. 57-58964, etc. It is common to use the centrifugal molding method described in .

As a hollow fiber, for example, as a semi-permeable membrane, 'Et'
Products manufactured from semi-cellulose, cellulose acetate, cellulose ether, polyethylene, polypropylene, polyamide, polysulfone, polyacrylamide, polyacrylonitrile, polyester, polycarbonate, polyvinyl chloride, polyurethane, casein, collagen, etc. Can be mentioned.

For example, the bottom of a tank other than the potting material of a medical fluid separation device using hollow fibers sealed with the potting material of the present invention is disclosed in Japanese Patent Application Laid-Open No. 56-15757, % Publication No. 58-7.
5556, JP 58-92423, % JP 58-206757, % JP 59-22506
Products similar to those described in the drawings of Publication No. 6 can be mentioned, and specific examples of applications include, for example, artificial kidneys, artificial lungs, plasma separation devices, and the like.

(Effect of the invention) Medium SF used in the medical fluid separation device thus obtained:
The end botting material of Ii fiber does not contain aromatic incyanate components as a polyisocyanate fraction, so it has the characteristic of aliphatic isocyanate that there is no concern about carcinogenicity caused by aromatic diamines that are hydrolyzed. It also avoids the adverse effects of free HMD I7, and has excellent cuttability and container adhesion, making it extremely useful for bulk production.

Example 1 889.4 parts (10.6 equivalents) of HMD I and polycaprolactone polyol "Plaxel 30B" (Daicel Chemical Industry Co., Ltd., trade name, number average molecular weight 850, hydroxyl value 1)
95) 200 parts (0.7 equivalents) were reacted at 100C for 1 hour. This reaction solution was heated at 16 n C, f'1.2 m
ml was subjected to thin film distillation to remove unreacted HMDI. NCO content 9.4% as can bottom liquid, viscosity is 700c
ps/2 sC, free, ilHMDIo, 2% pale yellow transparent polyisocyanate fraction. This is hereinafter referred to as PCL prepolymer (I).

HMDI biuret polyisocyanate (contains NGO)
23.2%, viscosity 1800 cps/25C) 50
A mixture of 50 parts of polyether polyol "BM-344 (manufactured by Asahi Denka Kogyo, trade name, hydroxyl value 831)" and castor oil-based polyol " Neelik H-62J (manufactured by Ito Sakiyu, trade name, hydroxyl value 270)
50 parts of the mixture as the polyol component, N COlo
They were blended so that the H equivalent ratio was 1.05 and cured at 40C.

The hardness of the cured product is Shore D50, JIS K-6301
The breaking strength and elongation in the tensile test are 129, respectively.
kg/ad, 68%.

When this polyincyanate component and polyol component were mixed and molded using an actual machine and cut, a good cut surface was obtained, and no peeling occurred at the adhesive surface between the potting material and the container.

Example 2 A mixture of 60 parts of HM D I biuret polyincyanate (NGO content 25.2 mm, viscosity 1800 cps/25C) and 40 parts of PCL prepolymer (I) was used as the polyisocyanate component, and polyether polyol l'- B.M.
-34j (manufactured by Jiryu Kakogyo, trade name, hydroxyl value 851)
60i and castor oil-based polyol “Neelik 1 (-62
A mixture of 40 parts of J (manufactured by 9 Fuji Oil Co., Ltd., trade name, hydroxyl value 270) was used as the polyol component, and 75 p of iron 2-ethylhexanoate (1) was added to the total resin to accelerate curing. A friend who will take the test in the same way as 1.

The hardness of the cured product is Shore D65, and the breaking strength and elongation are 252 kg/c! ! ! , 53%. The cutting performance and adhesion on the actual machine were as good as in Example 1.

Example 3 A mixture of 79 parts of HMD I biuret polyisocyanate (NCO content 23.2%, viscosity 1800 (ps/25C)) and PCL prepolymer (I) 21 MS was used as the polyincyanate component, and polyether polyol l
'-CM-43' (manufactured by Asahi Nemuka Kogyo Co., Ltd., trade name, hydroxyl value 279) and 19.4 parts of the above HMD I bullet polyisocyaner) were reacted for 4 hours at 1100C to synthesize the urethane polyol ( Hydroxyl value 183) 54
The polyol component was a mixture of 46 parts of polyether polyol "BM-34" (trade name, hydroxyl value 831, manufactured by Jiryu Kakogyo Rip), and a mixture of iron 2-ethylhexanoate (HI)' Wffl1gi & A test was carried out in the same manner as in Example 1, using 200 calories.

The hardness of the cured product is Shore D52, and the breaking strength and elongation are 226 kg/crt! , 50%. The cutting performance and adhesion on the actual machine were as good as in Example 1.

Example 4 A mixture of 80 parts of HM D I biuret polyisocyanate (tNco content 23.2%, viscosity 1800 cps/25C) and 20 parts of PCL prepolymer (I) was used as the polyincyanate component, and polyether polyol "BM-
34j (manufactured by Jiryuka Kogyo, trade name, hydroxyl value 831) 3
7i and polyester polyol “Plaxel 308J (
A mixture of 63 parts of Daicel Chemical Industries, trade name, hydroxyl value 195) was used as a polyol component, and iron (In) 2-ethylhexanoate was added to the total resin to accelerate curing.
The entire test was carried out in the same manner as in Example 1.

The hardness of the cured product was Shore D50, and the breaking strength and elongation were 217 ky/crl and 57%, respectively. The cutting performance and adhesion in the actual machine were as good as in Example 1.Example 5
Content 21.6%, viscosity 2100 cps/25C) 50
The test was conducted in the same manner as in Example 1, using a mixture of PCL prepolymer (I) and PCL prepolymer (I) 50 as the polyincyanate component, and using the same polyol component as in Example 1.

The hardness of the cured product is Shore D55, and the breaking strength and elongation are 150 kjL/ct! , 60%. The cutting performance and adhesion on the actual machine were as good as in Example 1.

Comparative example 1 HMD I billet polyincyanate t Ne.

The test was conducted in the same manner as in Example 1, using the same polyol component as in Example 1 and using the same polyisocyanate component as in Example 1.

The hardness of the cured product was Shore D73, and the breaking strength and elongation were 356 ky/cI and 20%, respectively. The cutting performance with the actual machine was poor, and peeling occurred at the adhesive surface between the botting material and the container.

Comparative Example 2 HMD I in cyanurate polyisocyanate (Ne
o content 21.6%, viscosity $2100 cps/25c)
All tests were conducted in the same manner as in Example 1, using the same polyol component as in Example 1 and using the same polyincyanate component as in Example 1.

The hardness of the cured product is Shore D75, and the breaking strength and elongation are Soh-'
f: h 560 kv layer, 20%. Cutting performance with the actual machine was poor, and peeling occurred at the adhesive surface between the potting material and the container.

The above results are summarized in Table 1.

Table 1 Par'-'g.

Lou 1. ′ Procedural amendment September 16, 1986

Claims (2)

[Claims] (1) In a polyurethane-based two-component hollow fiber end potting material consisting of a polyisocyanate component and a polyfunctional active hydrogen compound component, which is used in a medical fluid separation device using hollow fibers, the polyisocyanate component is At least in part, after reacting hexamethylene diisocyanate with a polycaprolactone diol and/or triol having a number average molecular weight of 500 to 1500 at an NCO/OH equivalent ratio of 5 to 40, unreacted hexamethylene diisocyanate is A two-component polyurethane-based hollow fiber end potting material characterized by using a prepolymer obtained by removing. (2) As at least a part of the polyisocyanate component, hexamethylene diisocyanate and a number average molecular weight of 50
A prepolymer obtained by reacting polycaprolactone diol and/or triol of 0 to 1500 at an NCO/OH equivalent ratio of 5 to 40 and then removing unreacted hexamethylene diisocyanate was used. A medical fluid separation device using hollow fibers, characterized in that a polyurethane-based two-component hollow fiber end potting material is used.