JP2623226B2 - Polyurethane resin-forming composition for sealing material of membrane module - Google Patents

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 As a polyurethane resin-forming composition comprising a main component comprising a polyisocyanate component and a curing agent comprising a polyol component for the purpose of sealing a membrane module, diphenylmethane diisocyanate (hereinafter abbreviated as MDI) is used as a polyisocyanate component. ) And castor oil (for example, JP-A-49-65386), carbodiimide-modified M
Those using a prepolymer of DI and castor oil (for example, JP-B-59-33605) and those using a prepolymer of hexamethylene diisocyanate (for example, JP-A-64-2653) are known. ing.

[0003]

However, those using a prepolymer composed of MDI or carbodiimide-modified MDI and castor oil as the polyisocyanate component have a high viscosity and poor fluidity, so that they are not hollow during centrifugal casting. There is a problem that prompt penetration into the end of the yarn bundle is hindered. When the content of the MDI monomer in the polyisocyanate component is increased to lower the viscosity, when used as a sealing material for the hollow fiber, the amount of the substance eluted from the bonded portion of the hollow fiber increases, and there is a problem in safety. Further, those using a prepolymer of hexamethylene diisocyanate have a problem that the eluate from the hollow fiber bonding portion is small, but the curing speed is slow and the workability is reduced.

[0004]

The present inventors have found that the above problems can be solved by using a polyisocyanate component comprising a specific prepolymer, and have reached the present invention.

That is, the present invention relates to a polyurethane resin-forming composition comprising a main component comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B), wherein (A) is a partially dehydrated castor oil and / or A polyurethane resin-forming composition for a sealing material of a membrane module, comprising a prepolymer of partially acylated castor oil and an organic polyisocyanate.

The partially dehydrated castor oil used in the present invention is:
It is obtained by heating castor oil in the presence of an acidic catalyst such as sulfuric acid, phosphoric acid or p-toluenesulfonic acid.

[0007] Partially acylated castor oil is obtained by partially acylating castor oil. As the acylation method, acetylation is generally used, and examples thereof include a method of reacting ketene with a hydroxyl group of castor oil and a method of reacting glacial acetic acid.

The partially dehydrated castor oil or partially acylated castor oil has a hydroxyl value (mgKOH / g) of 100 to 13
0, preferably 115 to 125. In this case, the average number of hydroxyl groups in one molecule is 1.8 to 2.2, which is substantially a diol. If the hydroxyl value is less than 100, the monool content will increase, and the resin properties as a sealing material will decrease. If it exceeds 130, the viscosity of the prepolymer and thus (A) will increase, and workability will not be improved.

In the polyisocyanate component (A),
Examples of the organic polyisocyanate used for the prepolymer of partially dehydrated castor oil and / or partially acylated castor oil and an organic polyisocyanate include polyisocyanate compounds described in JP-A-60-58156. Of these, preferred are aromatic polyisocyanates, and particularly preferred are 4,4'-diphenylmethane diisocyanate (MD
I).

If necessary, other known isocyanate-terminated prepolymers and / or organic polyisocyanates (monomers or multimers) can be used together with (A) these prepolymers. Other isocyanate-terminated prepolymers include polyisocyanate compounds (for example, MDI, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and modified products thereof) and polyol compounds (castor oil, castor oil monoester of fatty acid and diol or triol, polypropylene) Glycol, polyethylene glycol, etc.). Examples of other organic polyisocyanates include aliphatic, alicyclic, and aromatic isocyanate compounds and modified products thereof (such as modified buret, modified isocyanurate, and modified carbodiimide).

In the present invention, the content of the prepolymer from the partially dehydrated castor oil and / or the partially acylated castor oil and the organic polyisocyanate in the polyisocyanate component (A) is usually at least 30% by weight, preferably at least 50% by weight.
% By weight or more, particularly preferably 70% by weight or more. 3
If the amount is less than 0% by weight, it is difficult to achieve the object of the present invention of low viscosity and low elution amount.

Examples of the polyol component (B) include amine polyols and non-amine polyols (castor oil, castor oil fatty acid esters, polyether polyols, polyester polyols and the like) described in, for example, JP-A-53-61695. ) Can be used. As the non-amine polyol, partially dehydrated castor oil and / or partially acylated castor oil used for the prepolymer in the present invention can also be used.

In the composition of the present invention, the NCO / OH equivalent ratio at the time of mixing the main agent and the curing agent is usually 0.5 to 2.0, preferably 0.8 to 1.5. If the equivalent ratio is less than 0.5, the hardness of the cured product becomes insufficient, and if it exceeds 2.0, the amount of eluted material is undesirably increased.

The gelation time of the composition of the present invention at the time of casting is usually 2 to 60 minutes.
It takes 72 hours, but the curing temperature is high (30-60 ° C)
By doing so, the time until complete curing can be shortened.

The composition of the present invention has good flowability when used in combination with a curing agent due to the low viscosity of the main ingredient,
Excellent workability, such as no casting defects such as porosity. In addition, since the amount of eluted material from the cured product after casting and curing is extremely small, blood processing equipment (hollow fiber type, membrane type or coil type artificial kidney, plasma separation module, etc.), artificial organs (artificial lung, etc.) It is suitable as a sealing material for membrane modules such as water purifiers, 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 use in the case of using it for a blood processor is shown below. First, a main agent and a curing agent are individually prepared in advance, and defoamed 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. Using this mixture, a hollow fiber is formed into a container by a centrifugal casting (molding) method (consisting of a polycarbonate resin, an acrylonitrile-styrene resin, an acrylonitrile-styrene-butadiene resin, etc.).
Embed in. An example of the centrifugal casting (molding) method is Japanese Patent Publication No. 57-5
No. 8963, and the like. As the hollow fiber to be embedded, a hollow fiber generally containing 5 to 80% by weight of glycerin, such as a cellulose, acrylic, polyvinyl alcohol, polyamide, or polysulfone, is used. The mixture gels 2 to 60 minutes after injection and the module can be removed from the casting machine. Cure at 45 ° C for 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 performed by a method other than steam, for example, ethylene oxide gas treatment or γ-ray irradiation.

Since the polyurethane resin obtained by curing the composition of the present invention has a small degree of shrinkage upon curing, there is no fear that the hollow fiber at the hollow fiber bonding portion is crushed. Also, the adhesion to the hollow fiber is very good. The amount of eluted material from the polyurethane resin and the hollow fiber bonding portion is also small. In addition, when used for a water purifier due to high hardness, hot water resistance is improved.

[0018]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the following, "%" indicates% by weight.

Example 1 A 2-L volume 4 equipped with a stirrer, thermometer and nitrogen inlet tube was used.
In a one-necked flask, 599.7 g of MDI (“Millionate MT” manufactured by Nippon Polyurethane) and partially dehydrated castor oil (“HS2G-120” manufactured by Toyokuni Oil, hydroxyl value 120 mg KO)
H / g) (400.3 g) was charged and heated to 70 to 80 ° C. with stirring under a nitrogen stream to react for 4 hours. N of this thing
The CO content is 16.4% and the viscosity is 1,400 cps / 25
° C. This is designated as Main Agent-1.

In a reaction vessel similar to the reaction vessel in which the main agent-1 was prepared, 190.0 g of tetrakis [2-hydroxypropyl] ethylenediamine and 810.0 g of castor oil were charged, and the mixture was stirred at 40 to 50 ° C. for about 30 minutes and uniformly mixed. did.
This had a hydroxyl value of 276 mgKOH / g and a viscosity of 1,100 cps / 25 ° C. This is designated as curing agent-1.

A main fiber-1 and a curing agent-1 are weighed such that the NCO / OH equivalent ratio becomes 1.05 / 1.0 in a hollow fiber containing 60% glycerin inserted in a polycarbonate container. Was stirred and mixed for 10 seconds, followed by centrifugal casting (molding). After curing at 45 ° C. for 2 days, blood circuit connecting parts were attached to prepare an artificial kidney module. Thereafter, the module was autoclaved at 121 ° C. for 30 minutes.
Sterilization was performed by steam heating for one minute. Table 1 shows the test results such as the elution amount of the hollow fiber adhesion portion.

Example 2 600 parts of castor oil and 80 parts of acetic anhydride were charged into a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser.
The mixture was heated to 0 to 150 ° C. and reacted for about 1.5 hours. Then, these reactants were washed with water to separate and collect by-produced acetic acid and unreacted acetic anhydride.
g and dehydrated under reduced pressure. This gives a hydroxyl value of 117 mg.
A partially acetylated castor oil having a KOH / g and a viscosity of 480 cps / 25 ° C. was obtained.

In a reaction vessel similar to the reaction vessel in which the base agent-1 was prepared, 589.7 g of MDI and 410.3 g of the above partially acetylated castor oil were charged and stirred under a nitrogen stream.
The mixture was heated to ℃ 80 ° C. and reacted for 4 hours. NCO of this thing
The content was 16.0% and the viscosity was 1,540 cps / 25 ° C. This is designated as Main Agent-2. A module was prepared in the same manner as in Example 1, except that the main agent-2 and the curing agent-1 of Example 1 were used. Table 1 shows the test results such as the elution amount of the hollow fiber adhesion portion.

Comparative Example 1 A carbodiimide-modified MDI ("ISONAT" manufactured by Mitsubishi Kasei Dow) was placed in a reaction vessel similar to the reaction vessel in which the base material-1 was prepared.
E 143L ") with 681.5 g of castor oil (having a hydroxyl value of 1).
318.5 g of (61 mg KOH / g) was charged and heated to 70 to 80 ° C. with stirring under a nitrogen stream to react for 4 hours.
It has an NCO content of 16.1% and a viscosity of 3,400.
cps / 25 ° C. This is designated as Main Agent-3.
A module was prepared in the same manner as in Example 1, except that the main agent-3 and the curing agent 1 of Example 1 were used. Table 1 shows the test results such as the elution amount of the hollow fiber adhesion portion.

[0025]

[Table 1] Performance test results as sealing material

The test method is as follows. Initial viscosity after mixing: Indicates the viscosity one minute after the start of mixing of a mixture of the main agent and the curing agent at 25 ° C. Gelation time: Indicates the time until the viscosity of the mixed solution reaches 10,000 cps after mixing. Resin hardness: J on the surface of the resin cured at 25 ° C for 24 hours.
An IS-A hardness tester is pressed and the value after 10 seconds is measured.
(Measurement temperature: 25 ° C.) Amount of elution of hollow fiber adhesive portion: A hollow fiber adhesive portion of one module is cut out and cut into 1 cm square. To this, 200 ml of deionized water is added, and the mixture is extracted with gentle shaking at 40 ° C. for 2 hours. After cooling, take 1.0 ml of the supernatant and add deionized water to make exactly 50 ml. This solution was used as a test solution, and deionized water was used as a control.
The absorbance at 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])

[0027]

The composition of the present invention has the following effects. 1. Low viscosity during casting and good work life. 2. Since the amount of eluted material after casting and curing is extremely small, the amount of eluted material eluted into blood from the sealant when used as a sealing material for a membrane module used for blood treatment or the like is reduced. Because of the above effects, the composition of the present invention can be used for a blood treatment device (hollow fiber type, membrane type or coil type, artificial kidney,
Modules for plasma separation, etc.), artificial organs (artificial lungs, etc.),
It is extremely useful as a sealant for membrane modules such as water purifiers and ultrafiltration membranes (hollow fiber type, spiral type, etc.).

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08G 18/64 NER C08G 18/64 NER (56) References JP-A-64-22914 (JP, A JP-A-62-100513 (JP, A) JP-A-6-145281 (JP, A) JP-A-6-100649 (JP, A) JP-A-51-1596 (JP, A) 247165 (JP, A)

Claims (1)

(57) [Claims] 1. A polyurethane resin-forming composition comprising a main component comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B), wherein said (A)
Comprises a prepolymer of a partially dehydrated castor oil and / or a partially acylated castor oil and an organic polyisocyanate, wherein the composition is a polyurethane resin-forming composition for a sealing material of a membrane module.