JPH0812740A - Polyurethane-resin-forming composition for sealing material of membrane module - Google Patents

Abstract

PURPOSE:To obtain a castable polyurethane-resin-forming composition which can give a cured product having an excellent low-temperature storage stability and a reduced amount of eluate and usable as a sealing material of a membrane module used in a blood processor, a water cleaner or the like. CONSTITUTION:The polyurethane-resin-forming composition comprising a base comprising a polyisocyanate component and a curing agent comprising a polyol, wherein the polyisocyanate component comprises a polyfunctional-isocyanurate- modified hexamethylene diisocyanate having an average isocyanate functionality of 4 or above. The composition shows a high rise of hardness after casting, excellent workability, and good storage stability of the base.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a castable polyurethane resin-forming composition, and more particularly, to a castable polyurethane resin-forming composition suitable for use as a sealing material for membrane modules used in blood treatment devices, water purifiers and the like. Composition.

[0002]

2. Description of the Related Art Polyurethane resin-forming compositions composed of a main component composed of a polyisocyanate component and a curing agent composed of a polyol component for the purpose of a sealing material for a membrane module have hitherto been known as aromatic polyisocyanates and castor oil-based polyols and A sealing material composed of an amine-based polyol is known (for example, JP-A-53-98398). However, when these sealing materials are used, there is a problem that the amount of elution from the sealing portion is large. In order to improve this, one using a prepolymer of hexamethylene diisocyanate (hereinafter abbreviated as HDI) as a polyisocyanate component (for example, JP-A-60-
58156), using a modified burette of HDI (for example, JP-A-62-136208), H
Those using a modified trifunctional isocyanurate of DI (for example, JP-A-2-215822) have been proposed.

[0003]

However, in the case of using a prepolymer or a modified form of HDI as the polyisocyanate component (burette modified product, trifunctional isocyanurate modified product), the rise of hardness is slow, and after casting There is a problem that the assembly work takes time and the productivity is reduced.

[0004]

The present inventors have found that a specific H
They have found that the above problems can be solved by using a DI-based polyisocyanate compound, and have reached the present invention.

That is, the present invention provides a polyurethane resin-forming composition comprising a main agent comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B), wherein (A) has an average number of isocyanate groups of 4 or more. Which is a polyfunctional isocyanurate modified product of hexamethylene diisocyanate (a1), which is a polyurethane resin-forming composition for a sealing material of a membrane module.

The polyfunctional isocyanurate modified product (a1) of HDI constituting the polyisocyanate component (A) is obtained by reacting HDI in the presence of an isocyanurate-forming catalyst, or HDI and an alcohol as an isocyanurate-forming catalyst. And the average number of isocyanate groups is usually 4 or more, preferably 5 or more. When the average number of isocyanate groups is less than 4, the effect of improving the hardness rise is insufficient. Specific examples of (a1) include "Duranate X-1379" manufactured by Asahi Kasei.

The content of (a1) in the polyisocyanate component (A) is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more. If the content of (a1) is less than 10% by weight, the effect of improving the rising of hardness becomes insufficient. In the (A),
In addition to (a1), other publicly known isocyanate compounds [for example, other isocyanate compounds as described in JP-A-63-246175 (aliphatic, alicyclic or aromatic polyisocyanate compounds, modification thereof) And a urethane prepolymer having an isocyanate group)]. Preferred among these are aromatic polyisocyanate compounds, and particularly preferred are 4,4'-diphenylmethane diisocyanate (MDI), liquefied MDI (carbodiimide-modified MDI), and prepolymers of these and polyols. Examples of the polyol include JP-A-6
The thing described in the 3-246175 publication is mentioned.

The content of isocyanate groups (NCO groups) in the polyisocyanate component (A) is usually 10 to 25% by weight, preferably 12 to 23% by weight.

As the polyol component (B), JP-A-60 is used.
Examples include polyether polyols, castor oil-based polyols (castor oil, etc.), polyester polyols and the like, and mixtures of tertiary amino group-containing polyols as described in the specification of JP-A-58156.

Examples of the tertiary amino group-containing polyol include triethanolamine, alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts of alkylene diamine, and alkylene oxide adducts of polyalkylene polyamine. Of these, preferred are alkylenediamines and alkyleneoxide adducts of polyalkylenepolyamines, and particularly preferred are tetrakishydroxypropylethylenediamine and pentakishydroxypropyldiethylenetriamine.

A reaction product obtained by a partial transesterification reaction between a castor oil-based polyol and a tertiary amino group-containing polyol can be preferably used.

The partial transesterification reaction between the tertiary amino group-containing polyol and the castor oil fatty acid ester is usually carried out under a nitrogen atmosphere in the presence of a catalyst at a temperature of 150 to 200 ° C. for 4 to 4 times.
It is carried out by reacting for 6 hours. The hydroxyl value of the reaction product obtained by these partial transesterification reactions is usually 130
˜1200, preferably 200 to 900.

Particularly preferred as the polyol component (B) in the present invention are a mixture of castor oil and a tertiary amino group-containing polyol, and a reaction product obtained by a partial transesterification reaction of castor oil and a tertiary amino group-containing polyol. And mixtures thereof.

The hydroxyl value of the polyol component (B) is usually 1
It is 50 to 800, preferably 200 to 600.

In the composition of the present invention, the NCO / OH equivalent ratio is usually 0.5 to 2.0 when the main agent of (A) and the curing agent of (B) are mixed and cast. It is preferably 0.8 to 1.5. If the corresponding amount ratio is less than 0.5, the hardness of the cured product becomes insufficient, and if it exceeds 2.0, the amount of eluate in the cured product increases, which is not preferable.

The gelling time when cast at room temperature using the composition of the present invention is usually 5 to 60 minutes, and the time until the hardness reaches 90% of the final hardness is 24 hours at room temperature. It takes ~ 72 hours, but the curing temperature is high (30-60
C.) can further shorten the time.

The component (A) in the present invention is stable even when stored at a low temperature of 10 ° C. or lower, and is stable without changing its properties even after repeated heat cycles of 45 ° C./0° C. Can be stored for a period. In addition, since the amount of eluate after casting and curing is extremely small, blood treatment devices (hollow fiber type, membrane type or coil type artificial kidneys, blood separation modules, etc.), artificial organs (artificial lungs, etc.), water purifiers, It is suitable as a sealing material for membrane modules such as ultrafiltration membranes (hollow fiber type, spiral type, etc.).

The method of using the composition of the present invention is not particularly limited, but an example of using the composition for a blood processing device is shown below. First, a main agent composed of the component (A) and a curing agent composed of the component (B) are separately prepared in advance,
Each is degassed under reduced pressure (for example, 20 mmHg × 2 hours). Next, the main agent and the curing agent are weighed and mixed so as to have a predetermined NCO / OH equivalent ratio. The hollow fiber is embedded in a container (consisting of a polycarbonate resin, an acrylonitrile-styrene resin, an acrylonitrile-styrene-butadiene resin, etc.) by a centrifugal casting (molding) method using this mixed solution. An example of the centrifugal casting method is Japanese Patent Publication No. 57-58963.
It is described in the specification of the gazette and the like. As the hollow fiber to be embedded, generally, a hollow fiber such as a cellulose-based, acrylic-based, polyvinyl alcohol-based, polyamide-based, polysulfone-based hollow fiber containing 5 to 80% by weight of glycerin is used. The mixture gels 5 to 60 minutes after injection,
The module can be removed from the casting machine. Curing is performed at 40 ° C. for about 2 days to complete curing.
Then, it is usually 30 ° C. at 121 ° C. using an autoclave.
The product is sterilized by steam heating for a minute. The sterilization treatment can also be carried out by a method other than steam, for example, ethylene oxide gas treatment or γ-ray irradiation.

The polyurethane resin obtained by curing the composition of the present invention has very good adhesion to the hollow fiber, and the amount of the eluate of the polyurethane resin and the hollow fiber bonded portion is small. In addition, because of its high hardness, when used for a water purifier, a product having excellent hot water resistance can be obtained.

[0020]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In addition, "%" shows weight% below.

Example 1 2 L capacity 4 equipped with stirrer, thermometer and nitrogen inlet tube
In a one-necked flask, 351.9 g of MDI (“Millionate MT” manufactured by Nippon Polyurethane Co., Ltd.) and 148.1 g of castor oil (“ELA-DR” manufactured by Toyokuni Oil Co., Ltd.) were charged and heated to 70 to 80 ° C. while stirring under a nitrogen stream. After reacting for a time,
Isocyanurate modified product of HDI having an average number of isocyanate groups of 6 (“Duranate X-1379” manufactured by Asahi Kasei) 50
0.0 g was charged, and the mixture was stirred at 45 ° C. for 30 minutes and uniformly mixed. The obtained product had an NCO content of 19.1%.
This is used as the main agent (A-1).

200.0 g of pentakishydroxypropyldiethylenetriamine and 800.0 g of castor oil were charged in the same reaction vessel as that used for preparing (A-1).
The mixture was stirred at 40 to 50 ° C for about 30 minutes and mixed uniformly. The hydroxyl value of this product was 268. Let this thing be a hardening | curing agent (B-1).

A hollow fiber containing 60% by weight of glycerin was inserted into a polycarbonate container, and (A-1) and (B-1) had an NCO / OH equivalent ratio of 1.05 / 1.0.
The mixture was weighed and mixed with stirring for 10 seconds, and then centrifugally cast (molded). After curing at 40 ° C. for 2 days, a blood circuit connecting part was attached to prepare an artificial kidney module. Then the module is autoclaved 121
Sterilization was performed by steam heating at 30 ° C. for 30 minutes. The performance test results are shown in Tables 1 and 2.

COMPARATIVE EXAMPLE 1 351.9 g of MDI and 148.1 g of castor oil were charged in a reaction vessel similar to the reaction vessel in which (A-1) of Example 1 was prepared, and the mixture was heated to 70 to 80 ° C. with stirring under a nitrogen stream. 4
HDI with an average number of isocyanate groups of 3 after reacting for hours
Modified isocyanurate ("Duranate T" manufactured by Asahi Kasei
PA-100 ") 500.0 g was charged, and 30 at 45 ° C.
The mixture was stirred for a minute and mixed uniformly. The obtained product had an NCO content of 21.5%. This is the main agent for comparison (A-2)
And Using (A-2) and the curing agent (B-1) of Example 1, a module was prepared in the same manner as in Example 1.
The performance test results are shown in Tables 1 and 2.

Comparative Example 2 MDI (351.9 g) and castor oil (148.1 g) were charged in a reaction container similar to the reaction container in which (A-1) of Example 1 was prepared, and the mixture was heated to 70 to 80 ° C. with stirring under a nitrogen stream. After heating and reacting for 4 hours, 500.0 g of a HDI buret modified product (“Duranate 24A-100” manufactured by Asahi Kasei) was charged, and the mixture was stirred at 45 ° C. for 30 minutes and uniformly mixed. The obtained product had an NCO content of 21.6%. This is used as a comparative main agent (A-3). A module was prepared in the same manner as in Example 1 using the (A-3) and the curing agent (B-1) of Example 1. The performance test results are shown in Table 1 and Table 2.
Shown in

Comparative Example 3 In a reaction vessel similar to the reaction vessel in which (A-1) of Example 1 was prepared, 703.8 g of MDI and 296.2 g of castor oil were charged, and the mixture was heated to 70 to 80 ° C. with stirring under a nitrogen stream. It was heated and reacted for 4 hours. The obtained product has an NCO content of 20.1
%Met. This is designated as (A-4-).

In a similar reaction vessel, 325.7 g of HDI and 674.3 g of castor oil were charged and reacted at 100 to 120 ° C. for 6 hours while stirring under a nitrogen stream. The NCO content of the obtained prepolymer was 7.9%. This is designated as (A-4-).

(A-4-) 700.0 g and (A-4-)
) 300.0 g was stirred at 45 ° C. for 30 minutes and mixed uniformly. The obtained product had an NCO content of 16.4%. This is used as a comparative main agent (A-4). The (A-
4) and (B-1) of Example 1 were used to prepare a module in the same manner as in Example 1. The performance test results are shown in Table 1.
And shown in Table 2.

Comparative Example 4 In a reaction container similar to the reaction container in which (A-1) was prepared, M
DI 703.8 g and castor oil 296.2 g were charged and heated to 70 to 80 ° C. with stirring under a nitrogen stream and reacted for 4 hours. The obtained product had an NCO content of 20.0%. This is used as a comparative main agent (A-5). The (A-
Using 5) and (B-1) of Example 1, a module was prepared in the same manner as in Example 1. The performance test results are shown in Table 1.
And shown in Table 2.

[0030]

[Table 1]

The test method is as follows. Initial viscosity of mixing: Indicates the viscosity of the mixture of the main agent and the curing agent mixed at 25 ° C. one minute after the start of mixing. Gelation time: Indicates the time until the viscosity of the mixed solution reaches 10,000 cps after mixing. 90% hardness development time: On the surface of resin cured at 25 ° C,
The JIS-A hardness meter is pressed every 12 hours and the value after 10 seconds is measured. This operation is continued until the hardness becomes parallel. The time when the hardness reaches 90% of the parallel value is defined as the 90% hardness development time. (Measurement temperature 25 ° C) Elution amount: Module 1 cured and cured at 40 ° C for 2 days
The hollow fiber adhesive portion for this is cut off and cut into 1 cm squares.
To this, 200 ml of deionized water is added, and the mixture is gently shaken and extracted at 40 ° C. for 2 hours. After cooling, take 1.0 ml of the supernatant and add deionized water to make exactly 50 ml. Using this solution as a test solution and deionized water as a control, a wavelength of 28
The absorbance at 0-240 nm is measured. (The dissolution test method specified in the dialysis type artificial kidney device approval standard [Notice No. 494 of the Director of Pharmaceutical Affairs Bureau, Ministry of Health and Welfare])

[0032]

[Table 2]

The test method is as follows. Storage stability: The main ingredient is stored in a constant temperature bath at 10 ° C for 1 month, and the change in appearance is observed. Heat cycle test: The main component is stored at 45 ° C for 12 hours, and then stored at 0 ° C for 12 hours to complete one cycle.
After repeating this for 20 cycles, the change in appearance is observed.

[0034]

EFFECT OF THE INVENTION The polyurethane resin-forming composition for a sealant of a membrane module of the present invention has the following effects. (1) Hardness rises quickly after casting, and workability is good. (2) Since the amount of eluate after casting and curing is extremely small, when used as a sealing material for a membrane module used for blood treatment or the like, the amount of elution from the sealing material into blood is small and the safety is high. (3) Since it has excellent stability at low temperatures and heat cycle resistance, it can be stored for a long time even in winter. From the above effects, the composition of the present invention is a blood treatment device (hollow fiber type, membrane type or coil type, artificial kidney, blood and blood separation module, etc.), artificial organ (artificial lung, etc.), water purifier, It is extremely useful as a sealing material for membrane modules such as ultrafiltration membranes (hollow fiber type, spiral type, etc.).

Claims (3)

[Claims] 1. A polyurethane resin-forming composition comprising a main agent comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B), wherein the above (A)
Is a polyfunctional isocyanurate modified product (a1) of hexamethylene diisocyanate having an average number of isocyanate groups of 4 or more, and a polyurethane resin-forming composition for a sealing material of a membrane module. 2. The composition according to claim 1, wherein the content of (a1) in the polyisocyanate component (A) is at least 10% by weight. 3. The polyol component (B) comprises castor oil and 3
The composition according to claim 1 or 2, which comprises a mixture with a primary amino group-containing polyol and / or a reaction product obtained by a partial transesterification reaction of castor oil and a tertiary amino group-containing polyol.