JP3002876B2 - Polyol and composition for forming cast polyurethane - 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-forming composition, and more particularly to a castable polyurethane-resin-forming composition suitable for use as a sealing material for a blood processor or a water purifier.

[0002]

2. Description of the Related Art Conventionally, a castable polyurethane resin-forming composition used as a sealing material for a blood treatment device or a water purifier includes, for example,
One using N, N, N ', N'-tetrakis- (2-hydroxypropyl) -ethylenediamine is known (for example, JP-A-53-61695).

[0003]

In recent years, in order to improve the productivity of a blood processing apparatus or a water purifier, a polyurethane resin-forming composition having a rapid curing property has been demanded.
However, the conventional N, N, N ', N'-tetrakis- (2
When -hydroxypropyl) -ethylenediamine is used as a part of the polyol component, its content must be increased in order to make the composition rapidly curable, and the viscosity of the mixture before casting becomes high, and the casting operation becomes difficult. There is a problem such as difficulty in performing. on the other hand,
There is also a method of using a metal catalyst such as dibutyltin dilaurate for quick curing, but when used for applications such as blood processing equipment, the metal may be eluted into the blood and there is a problem with safety. is there.

[0004]

DISCLOSURE OF THE INVENTION In view of the above problems, the present inventors have found that a composition for forming a cast polyurethane which is fast-curing, has a low viscosity, has excellent castability, and does not contain substances eluted in blood. As a result of intensive studies to obtain a product, they have found that these characteristics can be obtained by using a specific amine-based polyol as a polyol component, and have reached the present invention.

That is, the present invention provides the following general formula (1)

[0006]

Embedded image

[Wherein, Z is a 1-imidazolyl group, R is an alkylene group having 1 to 6 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, m and n are 0 or a positive number satisfying m + n = 1 to 200. Wherein (m + n) A's may be the same or different, and when (m + n) oxyalkylene groups (AO) are composed of two or more oxyalkylene groups, the bonding form is block or Any of random may be used. A polyol component for forming a cast polyurethane comprising the compound (a1) and / or its castor oil fatty acid ester (a2); a cast polyurethane comprising the polyol component (A) and a polyisocyanate component (B) A composition for formation; and a hollow fiber type blood processing apparatus using the composition as a sealing material.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The polyol component of the present invention [hereinafter, referred to as "polyol component"]
The polyol component (A)], the alkylene group represented by R generally has 1 to 6, preferably 2 carbon atoms.
~ 3. If the number of carbon atoms exceeds 6, the rapid curability becomes insufficient. The alkylene group is linear or branched,
For example, ethylene group, 1,2- or 1,3-propylene group, 1,2-, 1,3-, 2,3- or 1,4-
Examples thereof include a butylene group, a 3-methylpentylene group, and a hexylene group, and preferred are an ethylene group and a 1,3-propylene group. The number of carbon atoms of the alkylene group represented by A is usually 2 to 4, preferably 2 to 3. 4 carbon atoms
If it exceeds 3, the rapid curability becomes insufficient, and if it is less than 2, the thermal stability of the compound (a1) becomes poor. As the alkylene group, a linear or branched one such as an ethylene group, 1,2
-Or 1,3-propylene group, 1,2-, 1,3
Examples thereof include-, 2,3- or 1,4-butylene groups, and preferred are an ethylene group and a 1,2-propylene group. Further, m and n are such that m + n is usually 1 to 20.
0 or a positive integer satisfying 0, preferably 2 to 100, and more preferably 2 to 10. When m + n exceeds 200, the quick-curing property becomes insufficient, and when m + n is 0, the irritating odor is strong and there is a problem in the working environment.

[0009] The (a1) are, for example, N- aminoalkyl imidazole [i.e. 1- imidazolylalkyl amine _{(Z-R-NH 2)} ] in the alkylene oxide 1
It can be produced by adding ~ 200 mol.

As a preferred specific example of the above (a1),
N-aminoalkylimidazole such as N- (3-aminoethyl) imidazole, N- (3-aminopropyl) imidazole, N- (3-aminohexyl) imidazole, ethylene oxide 2 to 10 mol adduct, propylene oxide 2 10 mol adduct, ethylene oxide 1-5
And a co-adduct (block or random addition) of 1 to 5 moles of propylene oxide and a mixture of two or more thereof. Particularly preferred among these are N
2 to 10 moles of an ethylene oxide adduct of-(3-aminopropyl) imidazole and 2 to 10 moles of a propylene oxide adduct of N- (3-aminopropyl) imidazole.

Further, the castor oil fatty acid ester (a2) of (a1) may be obtained by converting a part or all of the hydroxyl groups of (a1) to a castor oil fatty acid or an ester-forming derivative thereof (for example, a lower alkyl ester having 1 to 4 carbon atoms). ) Can be produced by esterification according to a conventional method.

The (a) in the polyol component (A) of the present invention
The content of 1) and / or (a2) is usually 0.1% by weight or more, preferably 1 to 100% by weight, more preferably 3 to 100% by weight. If it is less than 0.1% by weight, sufficient fast-curing properties cannot be obtained. The content of N (based on the imidazole ring) in (A) is usually 0.01 or more, preferably 0.1 to 13% by weight, more preferably 0.3 to 13% by weight.
１３13% by weight.

As the polyol component (A), other polyols can be used in combination with the above (a1) and / or (a2) if necessary. Examples of the other polyol include a low molecular polyol, a polyether polyol, a castor oil fatty acid ester-based polyol, a polyester polyol, and a mixture of two or more thereof.

Examples of the low molecular polyol include tertiary amino group-containing polyols other than (a1) and (a2) and non-amine polyols. Examples of the tertiary amino group-containing polyol include N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine,
N, N ′, N ′, N ″ -pentakis (2-hydroxypropyl) diethylenetriamine, diethanolamine,
Triethanolamine and the like.

As the non-amine-based polyol, divalent ones (ethylene glycol, diethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
6-hexanediol, neopentyl glycol, hydrogenated bisphenol A and the like; trivalent to octavalent (glycerin,
Trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, sucrose, and the like).

Examples of the polyether polyol include adducts of one or more alkylene oxides (for example, ethylene oxide, propylene oxide, butylene oxide, and mixtures of two or more thereof) of the low-molecular polyols and ring-opened polymers of the alkylene oxides. Specific examples include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and the like. The number average molecular weight of the polyether polyol is usually from 200 to 2,000.

Examples of the castor oil fatty acid ester-based polyols include castor oil, castor oil fatty acid esters obtained by transesterification of the above low molecular weight polyol or polyether polyol with castor oil, or esterification reaction of castor oil fatty acid. Is mentioned. The number average molecular weight of the castor oil fatty acid ester-based polyol is usually 200 to 2,000 or more.

Examples of the polyester polyol include polycarboxylic acids [aliphatic saturated or unsaturated polycarboxylic acids (adipic acid, azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid, dimerized linoleic acid, etc.) and / or Linear or branched polyester polyols from aromatic polycarboxylic acids (phthalic acid, isophthalic acid, etc.)] and polyols (the aforementioned low molecular weight polyols and / or polyether polyols); polylactone polyols {eg initiator [glycol] (Ethylene glycol, etc.), triols, etc.]
Caprolactone (ε-caprolactone, α-methyl-ε
-Caprolactone, ε-methyl-ε-caprolactone, etc.) in the presence of a catalyst (organic metal compound, metal chelate compound, fatty acid metal acylate, etc.) in the presence of a polyol (eg, polycaprolactone polyol)｝; Polyetherester polyols obtained by addition-polymerizing an alkylene oxide (such as ethylene oxide and propylene oxide) to a polyester having a carboxyl group and / or a hydroxyl group; and polycarbonate polyols. The number average molecular weight of the polyester polyol is usually from 200 to 2,000 or more.

Preferred among these are castor oil fatty acid ester-based polyols, and particularly preferred is castor oil. When the other polyol is used in combination, the amount of the polyol used is such that the N content based on the imidazole ring in (A) falls within the above range.

In the present invention, the polyisocyanate component (B) constituting the cast polyurethane-forming composition has 2 to 2 carbon atoms (excluding carbon in the NCO group, hereinafter the same).
18 aliphatic polyisocyanates, alicyclic polyisocyanates having 4 to 15 carbon atoms, aromatic polyisocyanates having 6 to 20 carbon atoms, araliphatic polyisocyanates having 8 to 15 carbon atoms, modified products of these polyisocyanates and One or more compounds selected from the group consisting of urethane prepolymers having isocyanate groups are included.

The aliphatic polyisocyanate includes:
For example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (H
DI), dodecamethylene diisocyanate, 1,6,1
1-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate And 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Examples of the alicyclic polyisocyanate include, for example, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). And 4-cyclohexene-1,2-dicarboxylate.

As the aromatic polyisocyanate, for example, tolylene diisocyanate (2,4-TDI, 2,2
6-TDI, crude TDI and mixtures thereof), diphenylmethane diisocyanate (4,4'-MDI,
2,4'-MDI and mixtures thereof), naphthylene diisocyanate (NDI), polymethylene polyphenyl polyisocyanate, and the like.

As the araliphatic polyisocyanate,
For example, xylylene diisocyanate (XDI), α,
α, α ′, α′-Tetramethylxylidene diisocyanate (TMXDI), diisocyanatoethylbenzene, and the like.

As the modified products of these polyisocyanate compounds, some or all of the isocyanate groups of the polyisocyanates exemplified above are modified into carbodiimide groups, uretdione groups, uretoimine groups, urea groups, burette groups, isocyanurate groups and the like. Compounds which have been mentioned.

As the urethane prepolymer having an isocyanate group, an isocyanate group-terminated urethane prepolymer obtained by reacting at least one selected from the polyisocyanate compounds exemplified above and modified products thereof with an active hydrogen-containing compound is used. Is mentioned. Examples of the active hydrogen-containing compound include the same low molecular weight polyols, polyether polyols, castor oil fatty acid ester-based polyols and polyester polyols as those exemplified as the polyol component (A).

In the urethane prepolymer having an isocyanate group, the equivalent ratio (NCO / OH ratio) between the NCO group in the polyisocyanate compound or a modified product thereof and the hydroxyl group in the active hydrogen-containing compound is usually 1.1 to 1.0.
50, preferably 1.5 to 30, particularly preferably 3 to
20. The NCO group content of the urethane prepolymer is usually 3 to 30% by weight.

The NCO / OH equivalent ratio in the case of forming a polyurethane resin from the polyol component (A) and the polyisocyanate component (B) constituting the composition of the present invention is usually 0.5 to 2, preferably 0.1 to 0.2. It is 7-1.5, more preferably 0.8-1.2.

The composition of the present invention usually comprises a combination of two components, a polyol component (A) and a polyisocyanate component (B), and the two components are mixed and reacted during use to form a polyurethane resin. A predetermined amount of each of (A) and (B) can be measured and then mixed with a static mixer or a mechanical mixer to cause a reaction. The gel time is usually 3 to 60 minutes, and 12 to 4 for complete curing.
It takes 8 hours. The point at which the hardness no longer changes is regarded as complete curing (reaction end point). In addition, it is also possible to shorten the time until complete curing by increasing the curing temperature (for example, 30 to 60 ° C.).

The viscosity (viscosity before casting, 30 ° C.) of the mixture comprising (A) and (B) is usually 50 to 10,000 mPa.
S, preferably 100 to 5,000 mPa · s.

The hardness (Shore D; instantaneous value) of the cured resin obtained by reacting (A) and (B) is usually 20 to 10
0, preferably 30 to 80.

The composition for forming a cast polyurethane of the present invention is particularly preferably used as a sealing material for a blood processor or a water purifier. Examples of the target blood processing apparatus include a hollow fiber type, a membrane type or a coil type artificial kidney, and a plasma separation module. It can also be used for artificial organs such as artificial lungs.

A specific method of using the composition of the present invention as a sealing material for a blood processing apparatus will be described. The polyol component (A) and the polyisocyanate component (B) are individually degassed under reduced pressure (for example, 0.1 mmHg × 2 hours).
After measuring a predetermined amount of these two liquids, they are mixed, and the hollow fiber is embedded in a container by a centrifugal molding method. An example of the centrifugal molding method is, for example,
No. 7-58963. As the hollow fibers to be embedded, generally, hollow fibers of cellulose type, acrylic type, polyvinyl alcohol type, polyamide type, polysulfone type and the like are used. In general, containers made of polycarbonate, ABS, polystyrene and the like are used. The two-part mixture gels after 3 to 60 minutes from the injection, and the module can be removed from the molding machine. Next, curing is performed at room temperature to 60 ° C. to complete the curing. Thereafter, sterilization is performed by steam heating at 121 ° C. for 1 hour using an autoclave to produce a product. Sterilization is performed by a method other than steam heating, such as ethylene oxide gas or γ.
It can also be carried out by irradiation with light.

With the polyurethane resin formed from the composition of the present invention, there is no fear that the hollow fibers in the liquid processor will be crushed. Also, adhesion to the hollow fiber is very good, and the amount of eluted material from the cured resin is small.

[0035]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following, “part” indicates “part by weight” and “%” indicates “% by weight”.

Production Example 1 N- (3-aminopropyl) was added to a stirring type autoclave.
519 parts of imidazole were charged, and 481 parts of propylene oxide was added dropwise thereto at 140 ° C. over 3 hours to cause a reaction, whereby a 2-mol adduct of propylene oxide of N- (3-aminopropyl) imidazole was obtained. This had a hydroxyl value of 466 and a viscosity of 400 mPa · s / 25 ° C.

Production Example 2 A 2-L volume 4 equipped with a stirrer, thermometer and nitrogen inlet tube
In a one-necked flask, 500 parts of an adduct of 2 mol of propylene oxide of N- (3-aminopropyl) imidazole obtained in Production Example 1 and purified castor oil [manufactured by Toyokuni Oil Co., Ltd .;
-DR "], 500 to 40 to 50 parts under a nitrogen stream.
The mixture was stirred and mixed at a temperature of 1 ° C. for 1 hour to obtain a polyol component (A-1). (A-1) has a hydroxyl value of 313 and a viscosity of 500 m.
Pa · s / 25 ° C.

Comparative Production Example 1 In a reaction vessel similar to that of Production Example 2, 500 parts of N, N, N ', N'-tetrakis- (2-hydroxypropyl) ethylenediamine and purified castor oil [manufactured by Toyokuni Oil Co., Ltd .; "EL
A-DR "], and 500 to 500 parts under a nitrogen stream.
The mixture was stirred and mixed at 0 ° C. for 1 hour, and the comparative polyol component (A ′) was mixed.
-1) was obtained. The (A′-1) had a hydroxyl value of 463 and a viscosity of 7,000 mPa · s / 25 ° C.

Example 1 In a polycarbonate container into which a cellulose hollow fiber was inserted,
Polyol component (A-1) obtained in Production Example 2 and HDI-based bifunctional prepolymer [manufactured by Asahi Kasei Corporation; "Duranate D-1" as a polyisocyanate component (B-1)
01 "] (NCO / OH equivalent ratio = 1.
05/1), casting by centrifugal molding method, curing at 40 ° C,
Created a module. The viscosity of the mixture before casting and the resin hardness of the seal portion of the module were measured by the following test methods. Table 1 shows the results. (Test Method) Viscosity before casting: The polyol component (A) and the polyisocyanate component (B) were uniformly mixed at 30 ° C., and the viscosity (Pa · s) one minute after the start of mixing was measured. Hardness: The hardness (Shore D, instantaneous value) of the cured resin when cured at 40 ° C. after casting (3 hours, 24 hours, and at the time of complete curing) was measured.

Comparative Example 1 In the same manner as in Example 1 except that the polyol component (A'-1) obtained in Comparative Production Example 1 was used in the same amount instead of the polyol component (A-1) of Example 1. The module was created and tested. Table 1 shows the results.

Comparative Example 2 Instead of the polyol component (A-1) of Example 1, N,
A module was prepared and tested in the same manner as in Example 1, except that N, N ', N'-tetrakis- (2-hydroxypropyl) ethylenediamine (A'-2) was used in the same equivalent amount. Table 1 shows the results.

[0042]

[Table 1]

[0043]

The composition for forming a cast polyurethane of the present invention has the following effects. (1) Low viscosity and excellent castability. (2) It is quick-curing and can significantly reduce the time until cutting, so that productivity is remarkably improved. (3) Since the cured resin does not contain substances eluted in blood or water, the safety is excellent. Because of the above-mentioned effects, the cast polyurethane-forming composition of the present invention is particularly useful for artificial organs such as blood processors and sealants for water purifiers. Further, the cured resin obtained from the composition of the present invention is excellent in electric properties and adhesiveness to various substrates, etc., so that it is used for electric insulation such as sealing of electronic circuit boards, and water stoppage for sealing optical fiber cable connection parts. It can be suitably used for building materials such as bonding of heat insulating aluminum sashes and bonding of aluminum honeycomb panels, potting materials for emblems of automobiles and side moldings.

Claims (6)

(57) [Claims] [Claim 1] The following general formula (1) [Wherein, Z is a 1-imidazolyl group, R is an alkylene group having 1 to 6 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and m and n are 0 or a positive integer satisfying m + n = 1 to 200. And (m + n) A may be the same or different, and when (m + n) oxyalkylene groups (AO) are composed of two or more oxyalkylene groups, the bonding form is either block or random. May be. ] And / or a castor oil fatty acid ester thereof (a2). (A1) is represented by the following general formula (2): [In the formula, p and q represent 0 or a positive integer satisfying p + q = 1 to 200. The polyol component according to claim 1, which is a compound represented by the formula: 3. The polyol component according to claim 1, wherein the content of (a1) and / or (a2) in the polyol component is at least 0.1% by weight. 4. The polyol component according to claim 1, wherein the polyol component comprises (a1) and / or (a2) and a castor oil fatty acid ester-based polyol. 5. A cast polyurethane-forming composition comprising the polyol component (A) according to claim 1 and a polyisocyanate component (B). 6. A hollow fiber type blood processor using the composition according to claim 5 as a sealing material.