JPH1036474A - Polyurethane-resin-forming composition for sealing material for membrane module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane-resin-forming composition used for a sealing material for membrane module and can give a cured product having a good heat resistance and releasing eluates little by using an isocyanate-terminated urethane prepolymer having a specified structure as the polyisocyanate component. SOLUTION: In a polyurethane-resin-forming composition comprising a base agent comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B), at least part of component A is an isocyanate- terminated urethane prepolymer (A1 ) formed from an organic polyisocyanate (a1 ) and a compound (a2 ) represented by formula I [wherein X is -CH2 -, -CHCH3 -, -C(CH3 )2 -, -(CH3 )C(C2 H5 )-, -C(CF3 )2 -, -(CH3 )C(C6 H5 )- or SO2 -; A is a 2-4C alkylene; and m and n are each 0-10] and/or a castor oil fatty acid ester (a3 ) of component (a2 ). It is desirable that the content of bisphenol residues represented by formula II is 1-60wt.% based on component A.

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 as a sealing material for a membrane module used in a blood processor, a water purifier, or the like. Composition.

[0002]

2. Description of the Related Art Conventionally, a polyurethane resin-forming composition intended for use as a sealing material for a membrane module includes a main component comprising a polyisocyanate component comprising an aromatic polyisocyanate and a castor oil-based polyol, a castor oil-based polyol and a tertiary resin. A curing agent comprising an amino group-containing polyol is known (JP-A-5-2471).
No. 65, etc.).

[0003]

However, there is a problem that the resin obtained by curing these compositions has insufficient heat resistance. An object of the present invention is to provide a polyurethane resin-forming composition for a sealing material of a membrane module, in which the heat resistance of the cured product is good and the amount of eluted material from the cured product is small and the safety is high.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention. That is, the present invention relates to a polyurethane resin-forming composition comprising a main agent comprising a polyisocyanate component (A) and a curing agent comprising a polyol component (B), wherein at least a part of the (A) comprises an organic polyisocyanate (a1 ) And the following general formula (1)

[0005]

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In the formula, X represents —CH ₂ —, —CHCH ₃ —,
_{-C (CH 3) 2 -,} - (CH 3) C (C 2 H 5) -, - C
_{(CF 3) 2 -, -} (CH 3) C (C 6 H 5) - or -S
O ₂ — represents an alkylene group having 2 to 4 carbon atoms [provided that m (AO) and n (AO) may be the same or different, and (AO) m or (AO) When n is composed of two or more different oxyalkylene groups, the bonding form may be either block or random. And m and n each independently represent 0 or an integer of 1 to 10. A polyurethane resin for a sealing material of a membrane module, which is a urethane prepolymer (A1) having terminal isocyanate groups from the compound (a2) represented by｝ and / or the castor oil fatty acid ester (a3) of the compound (a2). The present invention relates to an acidic composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyisocyanate component (A) in the present invention comprises a urethane prepolymer having terminal isocyanate groups from an organic polyisocyanate (a1) and a polyol, or a mixture of the urethane prepolymer and an organic polyisocyanate.

Examples of the organic polyisocyanate (a1) include aromatic diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and naphthalene diisocyanate; hexamethylene diisocyanate (HDI), 1-isocyanato-3-isocyanate. Aliphatic and / or alicyclic diisocyanates such as methyl-3,5,5-trimethylcyclohexane (IPDI) and bis (4-isocyanatocyclohexyl) methane (hydrogenated MDI); modified products of these diisocyanates (modified carbodiimide) , Isocyanurate-modified, uretdione-modified, uretoimine-modified, buret-modified, urea-modified, etc.); polymeric isocyanates (polymeric MDI, polymeric TDI, etc.) And mixtures of two or more thereof. Of these, preferred are aromatic diisocyanates, aliphatic diisocyanates and modified products thereof, and particularly preferred are MDI, HDI and modified products thereof.

In the present invention, the polyol which reacts with the organic polyisocyanate (a1) to form a urethane prepolymer having terminal isocyanate groups (A1) includes:
The compound (a2) represented by the general formula (1) and / or the castor oil fatty acid ester (a3) of the compound (a2) is used.

The compound (a) represented by the general formula (1)
2) is bisphenol A, bisphenol F, bisphenol E, bisphenol AF, bisphenol A
One or more bisphenols selected from P, bisphenol S and the like may be added to alkylene oxides having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, 1,2
-, 2,3-, 1,3- or 1,4-butylene oxide) or the like (co). When two or more alkylene oxides are co-added, the addition form may be either block or random, but the terminal hydroxyl group is preferably a primary hydroxyl group from the viewpoint of obtaining a high curing rate. In the general formula (1), m and n are each independently usually 0 or 1 to 10, preferably 1 to 5,
More preferably, it is an integer of 1 to 4. m or n is 1
If it exceeds 0, the heat resistance of the cured product will be insufficient.

As a preferred specific example of the above (a2),
For example, the following formulas (3) to (7) can be mentioned.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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(A2) Castor oil fatty acid ester (a)
3) is a compound obtained by subjecting 1 mol of the above (a2) to a condensation reaction of 1 to 2 mol, preferably 1 mol, of castor oil fatty acid by a known method. By using (a3) as part or all of the polyol constituting (A1), the compatibility with the curing agent comprising the polyol component (B) described below is further improved.

The urethane prepolymer having terminal isocyanate group (A1) in the present invention is obtained by converting (a1) and (a2) and / or (a3) into an NCO / OH ratio (equivalent ratio).
Is usually obtained by reacting at 1.5 to 20, preferably 2 to 10. The reaction temperature is usually 30 to 150 ° C, and the reaction time is usually 3 to 10 hours. The reaction method for obtaining the urethane prepolymer may be either a one-shot method or a multi-step method.

As the polyisocyanate component (A) in the present invention, together with the urethane prepolymer having terminal isocyanate group (A1), if necessary, a urethane prepolymer having terminal isocyanate group from another polyol and at least one kind of organic polyisocyanate (a1) is used. Polymers can be used in combination. Examples of the other polyol include a castor oil-based polyol, a polyether polyol, a polyester polyol, a polycarbonate polyol, a low-molecular-weight polyhydric alcohol, and a mixture of two or more thereof. Castor oil-based polyols include castor oil, partially dehydrated castor oil, partially acylated castor oil, castor oil fatty acid esters [castor oil fatty acids and polyols (ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, triglyceride) Low-molecular-weight polyhydric alcohols such as methylolpropane; polyether polyols such as polyethylene glycol, polypropylene glycol and polyoxytetramethylene glycol; and esterified products with polycaprolactone polyol). Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and the like. Polyester polyols include polycarboxylic acids (adipic acid, azelaic acid, maleic acid, phthalic acid, isophthalic acid, etc.) and low molecular weight polyhydric alcohols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexane) Diols (ε-caprolactone, δ) with a low molecular weight polyhydric alcohol (ethylene glycol, trimethylolpropane, etc.) as an initiator.
-Caprolactone) obtained by ring-opening polymerization of polylactone-based polyester polyols. Polycarbonate polyols include low molecular weight diols (such as 1,6-hexanediol) and dialkyl and / or
Or diallyl carbonate (diethyl carbonate,
Diphenyl carbonate and the like). Examples of the low molecular weight polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, and trimethylolpropane. Preferred among these polyols are castor oil-based polyols and polyether polyols, and particularly preferred are castor oil-based polyols.

The urethane prepolymer having terminal isocyanate groups from the organic polyisocyanate (a1) and the other polyol is obtained by converting (a1) and the other polyol into NCO
/ OH ratio (equivalent ratio) is usually 1.5 to 20, preferably 2
It is obtained by reacting with. The reaction temperature is usually 30 to 150 ° C, and the reaction time is usually 3 to 10 hours. The reaction method for obtaining the urethane prepolymer may be either a one-shot method or a multi-step method.

The following general formula (2) derived from (a2) and / or (a3) in the polyisocyanate component (A) in the present invention.

[0022]

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The content of the bisphenol residue represented by is usually 1 to 60% by weight, preferably 2 to 50% by weight,
Particularly preferably, it is 3 to 40% by weight. If the content of the bisphenol residue is less than 1% by weight, the heat resistance of the cured product becomes insufficient, and if it exceeds 60% by weight, the polyisocyanate component (A) as the main component becomes high in viscosity, and the casting workability decreases.

The free isocyanate group content of the polyisocyanate component (A) in the present invention is usually from 5 to 30.
% By weight, preferably 10 to 25% by weight.

The polyol component (B) in the present invention includes castor oil-based polyols, polyether polyols, polyester polyols, and mixtures of two or more thereof. As castor oil-based polyols,
Castor oil, partially dehydrated castor oil, partially acylated castor oil,
Castor oil fatty acid esters [castor oil fatty acids and polyols (ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, low molecular weight polyhydric alcohols such as glycerin, trimethylolpropane, etc .; polyethylene glycol, polypropylene glycol, poly) Polyether polyols such as oxytetramethylene glycol; polycaprolactone diol, etc.)
With ester]. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and the like. Polyester polyols include polycarboxylic acids (adipic acid, azelaic acid,
Condensed polyester polyols from maleic acid, phthalic acid, isophthalic acid, etc.) and low molecular weight polyhydric alcohols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), and low molecular weight polyvalent Polylactone polyester polyols obtained by ring-opening polymerization of lactones (ε-caprolactone, δ-caprolactone, etc.) using alcohols (ethylene glycol, trimethylolpropane, etc.) as initiators, and the like. Preferred among these polyols are castor oil-based polyols and polyether polyols, and particularly preferred are castor oil-based polyols.

Further, in order to increase the curing speed, a tertiary amino group-containing polyol can be used in combination, if necessary. Examples of the tertiary amino group-containing polyol include triethanolamine, alkylene oxide adducts (such as ethylene oxide and propylene oxide) of alkylenediamine, and alkylene oxide adducts of polyalkylene polyamine. Among these, preferred are alkylene diamines and alkylene oxide adducts of polyalkylene polyamines, and particularly preferred are N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and N, N, N',
N ', N "-pentakis (2-hydroxypropyl) diethylenetriamine.

The average hydroxyl value of the polyol component (B) in the present invention is usually from 80 to 400, preferably from 150 to 400.
300.

In the composition of the present invention, the NCO / OH equivalent ratio when the main component (A) and the curing agent (B) are mixed and cast is usually 0.5 to 2.0, Preferably it is 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 eluted material from the cured product increases, which is not preferable.

The gelation time when the composition of the present invention is cast at room temperature is usually 5 to 60 minutes, and the time until the hardness reaches 90% of the ultimate hardness reached is usually 24 hours to room temperature.
It takes 120 hours, but the curing temperature is high (40-70
C), the time can be further reduced.

The method of using the composition of the present invention is not particularly limited. An example of use of the composition for a blood processor is shown below. First, the main agent consisting of (A) and (B)
Are separately prepared, 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 (polycarbonate resin, acrylonitrile-styrene resin, acrylonitrile-styrene) by centrifugal casting (molding).
(Made of butadiene resin etc.). An example of the centrifugal casting (molding) method is described in JP-B-57-58963. 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 in 5 to 60 minutes after injection, and the module can be removed from the casting machine. Curing is performed at 45 ° C. for about 2 days to complete the curing. Thereafter, the product is sterilized by steam heating usually at 121 ° C. for 30 minutes using an autoclave to produce a product. Sterilization can also be performed by a method other than steam, such as ethylene oxide gas treatment or γ-ray irradiation.

The composition of the present invention is characterized in that a cured product after casting and curing maintains high hardness even at high temperatures and has excellent heat resistance, and is subjected to a blood treatment device (hollow fiber type, membrane type) sterilized by a high pressure steam method. Or coil type, artificial kidney, plasma separation module, etc.), various industrial water purifier, bath water circulation purification device, ultrafiltration membrane (hollow fiber type, spiral type, etc.) It is suitable. The cured product obtained by curing the composition of the present invention has very good adhesion to the hollow fiber, and the amount of the eluted material from the cured product and the bonded portion of the hollow fiber is small. Further, since the resin strength is excellent, a smooth cut surface can be easily obtained when cutting is performed.

[0032]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this. In the following, "%" indicates% by weight.

Example 1 A 2 liter volume 4 equipped with a stirrer, thermometer and nitrogen inlet tube
In a one-necked flask, 676.8 g of MDI (“Lupranate MI” manufactured by BASF Japan) and the following chemical formula

[0034]

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323.2 g of castor oil fatty acid monoester (a3-1) of the compound shown in the above was charged and heated to 70 to 80 ° C. with stirring under a nitrogen stream to react for 4 hours.
The obtained product has an NCO content of 19.0% and a viscosity of 2,3.
00 mPa · s / 25 ° C., the bisphenol residue content was 10.1%. This is designated as the main agent (A-1).

In a reaction vessel similar to the one prepared in (A-1), 160.0 g of N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and castor oil ("ELA-DR" manufactured by Toyokuni Oil Co., Ltd.) )), And stirred at 40-50 ° C. for about 30 minutes to mix uniformly.
The obtained product has a hydroxyl value of 256 and a viscosity of 1,200 m.
Pa · s / 25 ° C. This is used as a curing agent (B-
1).

94 g of (B-1) was blended with 100 g of (A-1), and the cured product was cured at 45 ° C. for 2 days, and the hardness was measured. Table 1 shows the evaluation results. Separately (A-1) 1
94 g of (B-1) was added to 00 g, and the mixture was injected into a polycarbonate fiber containing hollow fiber containing 30% glycerin and centrifugally cast (molded). After curing at 45 ° C. for 2 days, the results of measuring the amount of eluted material at the hollow fiber adhesive portion are shown in Table 1.

Comparative Example 1 An MDI was placed in a reaction vessel similar to that used in Example 1.
(“Lupranate MI” manufactured by BASF Japan) 681.
3 g and castor oil 318.7 g were charged, and the mixture was heated to 70 to 80 ° C. with stirring under a nitrogen stream and reacted for 4 hours. The obtained product has an NCO content of 19.1% and a viscosity of 1,200.
mPa · s / 25 ° C. This is designated as Comparative Main Agent (A-2).

(A-2) 95 g of the curing agent (B-1) of Example 1 was blended with 100 g of the same, and the hardness was measured in the same manner as in Example 1. Table 1 shows the evaluation results. Separately (A-2)
95 g of (B-1) was mixed with 100 g, and centrifugally cast (molded) in the same manner as in Example 1. After curing this at 45 ° C. for 2 days, the results of measuring the amount of eluted material at the hollow fiber bonding portion are shown in Table 1.
Shown in

[0040]

[Table 1]

The test method is as follows. Hardness: J on the surface of cured product cured at 45 ° C for 2 days
An IS-A hardness tester is pressed and the value after 10 seconds is measured. Amount of eluted material: A hollow fiber adhesive portion of one module cured and cured at 45 ° C. for 2 days 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 standing to cool, supernatant liquid 1.0m
Take 1 and add deionized water to make exactly 50 ml.
Using this solution as a test solution, the maximum absorbance at a wavelength of 280 to 240 nm is measured using deionized water as a control.
(Approval criteria for dialysis-type artificial kidney device [Notice 4
No. 94]. )

[0042]

The polyurethane resin-forming composition for a sealing material of a membrane module according to the present invention has the following effects. (1) The cured product after casting and curing maintains high hardness even at high temperatures, and has little deformation under high temperature conditions. (2) The amount of eluted material from the cured product after casting and curing is extremely small. Due to the above effects, the composition of the present invention can be used for a blood processor (hollow fiber type, membrane type or coil type, artificial kidney, module for plasma separation, etc.) which is sterilized by a high pressure steam method, an artificial organ (artificial organ). Lung, etc.), various industrial water purifiers, bath water circulation purification equipment, ultrafiltration membranes (hollow fiber type, spiral type, etc.)
It is extremely useful as a sealing material for membrane modules.

Claims (2)

[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 at least a part of (A) comprises an organic polyisocyanate ( a1)
And the following general formula (1): {In the formula, X _{-CH 2 -, - CHCH 3 -} , - C (C
_{H 3) 2 -, - (} CH 3) C (C 2 H 5) -, - C (C
_{F 3) 2 -, - (} CH 3) C (C 6 H 5) - or -SO ₂ -
A represents an alkylene group having 2 to 4 carbon atoms [provided that m (AO) and n (AO) may be the same or different, and (AO) m or (AO) n is 2 When composed of at least two different oxyalkylene groups, the bonding form may be either block or random. And m and n each independently represent 0 or an integer of 1 to 10. And / or (a2)
2) A polyurethane resin-forming composition for a sealing material of a membrane module, which is a urethane prepolymer having terminal isocyanate groups (A1) from the castor oil fatty acid ester (a3). 2. The compound represented by the following general formula (2) in (A): [Wherein, X is the same as in general formula (1). ] The composition of Claim 1 whose content of the bisphenol residue shown by this is 1-60 weight%.