JP3081202B2 - Active hydrogen component and composition for forming cast polyurethane resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active hydrogen component for forming a cast polyurethane resin and a composition comprising the same, and particularly to a cast polyurethane suitable for use as a sealing material for a hollow fiber type blood processor or water purifier. It relates to a resin-forming composition.

[0002]

2. Description of the Related Art Conventionally, a composition for forming a cast polyurethane resin used as a sealing material for a blood processor or a water purifier using hollow fibers or the like includes, for example, castor oil-based polyol and N, N as active hydrogen components. , N ′, N′-tetrakis (2-hydroxypropyl) -ethylenediamine is known (for example, Japanese Patent Application Laid-Open No.
-61695).

[0003]

However, in the conventional composition for forming a cast polyurethane resin, when it is used for a hollow fiber having a high water content, a reaction between an isocyanate group (NCO group) in a polyisocyanate component and water is caused. Generates carbon dioxide gas and causes foaming of the polyurethane resin,
In some cases, this could cause serious troubles such as leakage of liquid from the seal portion. On the other hand, if the NCO group content in the composition is reduced to eliminate the foaming, there are problems such as an increase in the viscosity of the mixture before casting and a decrease in the hardness of the cured resin. In addition, there is an increasing demand for speeding up hardness development in order to improve productivity.

[0004]

Means for Solving the Problems In view of the above problems, the inventors of the present invention have low viscosity even if the NCO group content in the castable polyurethane resin-forming composition is reduced, and quickly reach an appropriate hardness. As a result of diligent studies to obtain a composition having the following characteristics, it has been found that these characteristics can be obtained by using a specific polyfunctional active hydrogen compound as an active hydrogen component, and the present invention has been achieved.

[0005] That is, the present invention comprises a method wherein an alkylene oxide is added to a polyhydric alcohol having a valency of 4 or more selected from the group consisting of dipentaerythritol, diglycerin, polyglycerin and polyvinyl alcohol. At least one polyoxyalkylene compound (a11) having a hydroxyl equivalent of 160 or more.
Active hydrogen component (A) for forming a cast polyurethane resin comprising 0% by weight and at least 1% by weight of an amine-based polyol (a2) having a hydroxyl value of 400 or more; active hydrogen selected from mercapto groups and primary amino groups 1 containing group
Contains at least 10% by weight of a polyoxyalkylene compound (a12) having 4 or more active hydrogen-containing group equivalents in a molecule and having an equivalent weight of 160 or more, and at least 1% by weight of an amine-based polyol (a2) having a hydroxyl value of 400 or more. Active hydrogen component (A) for forming a cast polyurethane resin, comprising: active hydrogen component (A) and polyisocyanate component (B)
A cast polyurethane resin-forming composition comprising: (a)
11) or a cast polyurethane resin-forming composition comprising an active hydrogen component (A) containing at least 10% by weight of (a12), a polyisocyanate component (B), and a metal-based catalyst (C); And a hollow fiber type blood processor and a water purifier sealed with the binding agent. In the present invention, the term "active hydrogen-containing group equivalent" is, as generally used,
It is used to indicate the molecular weight per active hydrogen-containing group selected from a hydroxyl group, a mercapto group and a primary amino group. In addition, the term "casting" refers to, as is generally used, injecting a liquid resin or a resin compound into a mold with no or almost no pressure and curing the resin to obtain a molded product. Is used to mean

[0006]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the number of active hydrogen-containing groups (hereinafter referred to as valence) in one molecule of the active hydrogen-containing polyoxyalkylene compound (a1) constituting the active hydrogen component (A) is usually 4 Above, preferably 5 to 30 or more, more preferably 6 to 25. When the valence is less than 4, the hardness of the cured resin is low. The active hydrogen-containing group equivalent of (a1) is usually 160 or more, preferably 180 or more.
~ 1200, more preferably 220 ~ 850. When the active hydrogen-containing group equivalent is smaller than 160, the viscosity of a mixed solution (mixed solution before casting) with the polyisocyanate component (B) described later increases.

Among the above (a1), those having a hydroxyl group include, for example, low-molecular-weight polyhydric alcohols having 4 or more [alkane polyols having 4 to 6 or more carbon atoms, for example, pentaerythritol, sorbitol, mannitol;
And saccharides (monosaccharides, disaccharides, such as glucose, sucrose, etc.), condensates of tri- or higher-valent low-molecular-weight polyhydric alcohols (alkane polyols described above) (dipentaerythritol, diglycerin, polyglycerin, etc.),
Polyamines having 4 or more active hydrogens [aliphatic polyamines such as alkylene (2 to 2 carbon atoms)] such as polymers or oligomers containing at least two active hydrogens (polyvinyl alcohol (polymerization degree 50 to 100 or more, saponification degree 60% or more), etc.). 6 or more) diamines (ethylenediamine, propylenediamine, etc.); polyalkylenepolyamines (diethylenetriamine, triethylenetetramine, etc.), aromatic polyamines (phenylenediamine, tolylenediamine, diphenylmethanediamine, xylylenediamine, etc.), alicyclic polyamines (Cyclohexylenediamine, isophoronediamine, etc.), heterocyclic polyamines (N, N'-diaminoethylpiperazine, etc.), and polymers or oligomers having two or more amino groups (polyethyleneimine, etc.)] Alkylene oxides (eg, ethylene oxide, propylene oxide, 1,2
-, 1,3-, 2,3- or 1,4-butylene oxide (or two or more thereof) by (co) addition (in the case of co-addition, either block addition or random addition) can do. The addition mole number of the alkylene oxide is usually 3 to 50 mol or more, preferably 4 to 30 mol per active hydrogen.

Among the above (a1), those having a mercapto group include those known as those having a hydroxyl group, which are reacted with mercaptopropionic acid, mercaptoglycolic acid or the like to esterify a part or all of the hydroxyl groups. The method can be used.

Among the above (a1), those having a primary amino group include those exemplified as having a hydroxyl group, and a method in which a part or all of the hydroxyl group is reacted with acrylonitrile to be cyanoethylated and then hydrogenated. It can be manufactured by a known method.

Preferred as (a1) are polyoxyalkylene ethers (especially propylene oxide adducts) of polyhydric alcohols selected from sorbitol, sucrose and polyglycerin (degree of polymerization: 6 to 20) and the above-mentioned methods. With a mercapto group or 1
A tertiary amino group is introduced, and particularly preferred is a propylene oxide adduct of polyglycerin.

In the present invention, the content of (a1) in the active hydrogen component (A) is usually 10 based on the weight of (A).
% By weight or more, preferably 20% by weight or more, more preferably 30% by weight or more. If the content is less than 10% by weight, it is difficult to obtain the desired effects (low viscosity, fast curability) of the present invention.

When the metal catalyst (C) is not used (a1)
The hydroxyl value of the amine polyol (a2) used in combination with the above is usually 400 or more, preferably 400 to 1500, and more preferably 450 to 1200. If the hydroxyl value is less than 400, it is difficult to obtain the effect (rapid curability) aimed at by the present invention.

The (a2) includes N, N, N ', N'
-Tetrakis (2-hydroxypropyl) -ethylenediamine, N, N, N ', N', N "-pentakis (2-
(Hydroxypropyl) -diethylenetriamine, diethanolamine, triethanolamine, oxyalkylated N, N-dimethylpropylenediamine, N, N-
Oxyalkylated dimethyldipropylenetriamine (described in Japanese Patent Application No. 10-158577),
Oxyalkylated N-aminoalkylimidazole (described in Japanese Patent Application No. 10-156664) and the like. Preferred of these are N, N,
N ', N'-tetrakis (2-hydroxypropyl)-
Ethylenediamine, N, N, N ′, N ′, N ″ -pentakis (2-hydroxypropyl) -diethylenetriamine, oxyalkylated N, N-dimethylpropylenediamine and oxyalkylated N-aminoalkylimidazole.

In the present invention, the content of (a2) in the active hydrogen component (A) is usually 1% by weight or more, preferably 3% by weight or more based on the weight of (A). If it is less than 1% by weight, it is difficult to obtain the effect (rapid curability) aimed at by the present invention.

In addition, the active hydrogen component (A) is composed of the above (a)
Preferred are those consisting of 1) and (a2), but if necessary, other polyols other than those exemplified as having a hydroxyl group in (a1) can be used in combination. Examples of the other polyols include low molecular polyols, polyether polyols, castor oil fatty acid ester-based polyols, polyester polyols, and mixtures of two or more of these.

As the low molecular polyol, divalent ones (ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-
Hexanediol, neopentyl glycol, hydrogenated bisphenol A, etc.); trivalent (glycerin, trimethylolpropane, hexanetriol, etc.); tetravalent or higher (pentaerythritol, sorbitol, etc.); trivalent or higher low molecular weight polyol (Dipentaerythritol, sucrose, polyglycerin, etc.).

As the polyether polyol, one or more alkylene oxides (eg, ethylene oxide, propylene oxide,
1,2-, 1,3-, 2,3- or 1,4-butylene oxide and two or more thereof) (co) adducts and ring-opening polymers of alkylene oxides, and specifically 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 polyol include castor oil, castor oil fatty acid ester obtained by transesterification of the above low molecular weight polyol or polyether polyol with castor oil or esterification of castor oil fatty acid. Is mentioned.

Examples of the polyester polyol include polycarboxylic acids [aliphatic saturated or unsaturated polycarboxylic acids having 4 to 40 carbon atoms (adipic acid, azelaic acid, dodecane diacid, maleic acid, fumaric acid, itaconic acid, dimerized acid) Linear or branched from a linoleic acid or the like and / or an aromatic polycarboxylic acid having 8 to 12 carbon atoms (phthalic acid, isophthalic acid or the like)] and a polyol (the low-molecular polyol and / or polyether polyol described above). Polyester lactone; polylactone polyol {for example, based on an initiator [glycol (eg, ethylene glycol), triol, etc.] and (substituted) caprolactone (ε
-Caprolactone, α-methyl-ε-caprolactone,
a polyol (eg, polycaprolactone polyol) obtained by ring-opening addition polymerization of ε-methyl-ε-caprolactone in the presence of a catalyst (organic metal compound, metal chelate compound, fatty acid metal acylate, etc.); And / or polyetherester polyols obtained by addition-polymerizing an alkylene oxide (ethylene oxide, propylene oxide, etc.) to a polyester having a hydroxyl group; polycarbonate polyols (polyhexamethylene carbonate diol, etc.). The number average molecular weight of the polyester polyol is usually 2
00 to 2,000.

Of these, preferred are castor oil fatty acid ester-based polyols, and particularly preferred is castor oil. When these other polyols are used in combination, the amount thereof is usually at most 80% by weight, preferably at most 50% by weight, more preferably at most 30% by weight, based on the weight of the active hydrogen component (A).

In the present invention, as the polyisocyanate component (B) constituting the castable polyurethane resin-forming composition, the number of carbon atoms (excluding carbon in NCO groups, the same applies hereinafter)
2-18 aliphatic polyisocyanate, 4-15 carbon atoms
Alicyclic polyisocyanate, an aromatic polyisocyanate having 6 to 20 carbon atoms, an araliphatic polyisocyanate having 8 to 15 carbon atoms, a modified product of these polyisocyanates, and a urethane prepolymer having an isocyanate group. One or more compounds.

As the aliphatic polyisocyanate, for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HD
I), dodecamethylene diisocyanate, 1,6,11
-Undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

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

As the aromatic polyisocyanate, for example, tolylene diisocyanate (2,4-TDI, 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.

Examples of the araliphatic polyisocyanate include:
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 compound is used. No. Examples of the active hydrogen compound include low molecular polyols, polyether polyols, castor oil fatty acid ester-based polyols, and polyester polyols similar to those exemplified as the other polyols in the active hydrogen component (A).

In the urethane prepolymer having an isocyanate group, the equivalent ratio of the NCO group in the polyisocyanate compound or a modified product thereof to the active hydrogen in the active hydrogen compound (NCO / active hydrogen equivalent ratio) is usually 1.
The ratio is from 1/1 to 100/1, preferably from 2/1 to 80/1, and more preferably from 3/1 to 60/1. The NCO group content in the urethane prepolymer is usually from 3 to 35% by weight.

In the castable polyurethane resin-forming composition of the present invention, a metal catalyst (C) can be used together with the active hydrogen component (A) comprising (a1) and the isocyanate component (B). Examples of (C) include a tin-based catalyst [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannas octoate, dibutyltin maleate, etc.], a lead-based catalyst [olein Lead acid, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], titanium catalyst [isopropoxytri-N-ethylaminoethylaminate titanium, tetrabutyl titanate, tetraisopropoxybisdioctyl phosphite titanium, etc.] , Iron-based catalysts [iron carboxylate compounds (iron lactate, iron ricinoleate, etc.), ferrocene-based compounds (ferrocene, acetylferrocene, etc.), iron phthalocyanine, etc.], and other metal catalysts [metal naphthenate salts such as cobalt naphthenate, etc.] , Phenylmercury propyl Onoate]
Is mentioned. Of these, preferred are tin-based catalysts, and particularly preferred is dibutyltin dilaurate.

The content of (C) is usually at least 10 ppm, preferably 50 to 50, based on the weight of the composition.
00 ppm or more. If it is less than 10 ppm, sufficient fast-curing properties cannot be obtained.

From the active hydrogen component (A) and the polyisocyanate component (B) constituting the cast polyurethane resin-forming composition of the present invention, or from (A) and (B) and the metal catalyst (C). When forming a polyurethane resin, the NCO / active hydrogen-containing group equivalent ratio is usually 1/5 to 5 /
1, preferably 1/4 to 4/1, more preferably 1 /
3 to 3/1.

The composition usually comprises a combination of two components, an active hydrogen component (A) and a polyisocyanate component (B). When a metal-based catalyst (C) is used, (A) and (B) And a combination of the three liquids of (C),
Usually, it consists of a combination of two liquids in which a predetermined amount of (C) is previously mixed with (A) or (B).

At the time of use, each of the compositions is weighed in a predetermined amount and then reacted by mixing with a static mixer or a mechanical mixer to form a polyurethane resin. The gelation time is usually 3 to 60 minutes, and complete curing requires 12 to 240 hours at room temperature. The point at which the hardness no longer changes is regarded as complete curing (reaction end point). In addition,
By increasing the curing temperature (for example, 30 to 60 ° C.), the time until complete curing can be shortened. The hardness of the cured resin obtained by reacting the composition (JIS-
A; 10 seconds value) is usually 50 to 100, preferably 60 to 100.
95.

Viscosity of a mixture comprising (A) and (B) or (A) and (B) and (C) (viscosity before casting, 25 ° C.)
Is usually 50 to 10,000 mPa · s, preferably 1
00 to 5,000 mPa · s, more preferably 200 to 5,000 mPa · s
3,000 mPa · s.

The NCO group content in the mixture immediately after mixing (A) and (B) or (A) with (B) and (C) is usually 2 to 13% by weight, preferably 3 to 10% by weight. %
It is.

The castable polyurethane resin-forming composition of the present invention is particularly preferably used as a sealant for blood treatment devices and water purifiers. Examples of the target blood processing apparatus include hollow fiber type, membrane type or coil type artificial kidneys, plasma separation modules, and the like. 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 active hydrogen component (A) or a premix of the predetermined amount of the metal-based catalyst (C) and the polyisocyanate component (B) are separately defoamed under reduced pressure (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,
-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. The sterilization treatment can also be performed by a method other than steam heating, for example, irradiation with ethylene oxide gas or γ-ray.

[0038]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to 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 A glycerin hexamer (valence =
8, hydroxyl value = 974) [manufactured by Daicel Chemical Industries, Ltd .;
"Polyglycerin 06"] 124 parts and potassium hydroxide 2
And 876 parts of propylene oxide were added dropwise at 105 ° C. over 8 hours to react. The reaction mixture was treated with a magnesium oxide-based adsorbent [Kyowad 600, manufactured by Kyowa Chemical Industry Co., Ltd.] to obtain an adduct (a1-1) of about 56 mol of glycerin hexamer propylene oxide. This has a valence of 8, a hydroxyl value of 121 [active hydrogen-containing group (hydroxyl group) equivalent 464], and a viscosity of 0.8 Pa · s.
/ 25 ° C.

Production Example 2 In a stirred autoclave, glycerin decamer (valence =
12, hydroxyl value = 871) [Daicel Chemical Industries, Ltd.
[Polyglycerin 10]] and 95 parts of potassium hydroxide, and 905 parts of propylene oxide were added dropwise at 105 ° C. over 8 hours to react. Thereafter, the same treatment as in Production Example 1 was carried out to obtain an adduct (a1-2) of about 126 mol of propylene oxide of glycerin 10-mer. This has a valence of 12, a hydroxyl value of 83 (hydroxyl equivalent of 67).
6), the viscosity was 0.8 Pa · s / 25 ° C.

Production Example 3 In a stirred autoclave, a propylene oxide adduct of sucrose (valence = 8, hydroxyl value = 416) [manufactured by Sanyo Chemical Industries, Ltd .;
10A "], 407 parts and 2 parts of potassium hydroxide are charged,
To this, 593 parts of propylene oxide was added dropwise at 105 ° C. over 8 hours to cause a reaction. Thereafter, the same treatment as in Production Example 1 was carried out to obtain an adduct (a1-3) of about 40 mol of propylene oxide of sucrose. This has a valence of 8, a hydroxyl value of 168 (hydroxyl equivalent 334), and a viscosity of 1.3 Pa ·
s / 25 ° C.

Production Example 4 A 2 L volume 4 equipped with a stirrer, thermometer and nitrogen inlet tube
In a one-neck flask, 87 parts of (a1-1) obtained in Production Example 1 and 13 parts of N, N, N ', N'-tetrakis (2-hydroxypropyl) -ethylenediamine were charged, and 40 to 50 under a nitrogen stream. At 1 ° C. for 1 hour.
-1) was obtained. (A-1) had a hydroxyl value of 205 and a viscosity of 1.5 Pa · s / 25 ° C.

Production Example 5 In a reaction vessel similar to that of Production Example 4, (a1-
2) 87 parts and 13 parts of N, N, N ', N'-tetrakis (2-hydroxypropyl) -ethylenediamine were charged and stirred and mixed at 40-50 ° C for 1 hour under a nitrogen stream to obtain an active hydrogen component (A- 2) was obtained. The (A-2) had a hydroxyl value of 172 and a viscosity of 1.5 Pa · s / 25 ° C.

Production Example 6 In a reaction vessel similar to that of Production Example 4, (a1-
3) 96 parts and N, N-dimethyl-N ', N'-bis (2
-Hydroxypropyl) propylenediamine (4 parts) was mixed with stirring at 40 to 50 ° C for 1 hour under a nitrogen stream to obtain an active hydrogen component (A-3). The (A-3) had a hydroxyl value of 182 and a viscosity of 1.1 Pa · s / 25 ° C.

Production Example 7 In a reaction vessel similar to that of Production Example 4, (a1-
3) 100 parts and 0.1 part of dibutyltin dilaurate [manufactured by Sankyoki Gosei Co., Ltd .; "STANN BL"] are charged, and the mixture is stirred and mixed at 40 to 50 ° C. for 1 hour in a nitrogen stream to obtain an active hydrogen component (A -4) was obtained. The (A-4) had a hydroxyl value of 168 and a viscosity of 1.3 Pa · s / 25 ° C.

Production Example 8 Refined castor oil (valency =
3, hydroxyl value = 161) [manufactured by Toyokuni Oil Co., Ltd .;
-DR "], 96 parts and N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) propylenediamine (4 parts) are charged, and stirred and mixed at 40 to 50 ° C for 1 hour under a nitrogen stream to obtain active hydrogen. The component (A'-1) was obtained. (A′-1)
Has a hydroxyl value of 175 and a viscosity of 0.56 Pa · s / 25 ° C.
Met.

Production Example 9 In the same reaction vessel as in Production Example 4, 9 mol of propylene oxide adduct of sorbitol (valence = 6, hydroxyl value = 49).
3, hydroxyl equivalent 114) [manufactured by Sanyo Chemical Industries, Ltd .; "Sanix Hexaol SP-750"] 96 parts and N,
N-Dimethyl-N ', N'-bis (2-hydroxypropyl) propylenediamine (4 parts) was charged, and the mixture was stirred and mixed at 40 to 50 ° C. for 1 hour under a nitrogen stream to obtain an active hydrogen component (A ′).
-2) was obtained. The (A′-2) had a hydroxyl value of 494 and a viscosity of 19.3 Pa · s / 25 ° C.

Production Example 10 Purified castor oil (valence =) was placed in the same reaction vessel as in Production Example 4.
3, hydroxyl value = 161) [manufactured by Toyokuni Oil Co., Ltd .;
-DR "], 62 parts and N, N, N ', N'-tetrakis (2-hydroxypropyl) -ethylenediamine (38 parts) are charged and stirred and mixed at 40 to 50 ° C for 1 hour in a nitrogen stream to obtain an active hydrogen component ( A′-3) was obtained. (A'-3)
Had a hydroxyl value of 392 and a viscosity of 4.2 Pa · s / 25 ° C.

Production Example 11 In a reaction vessel similar to that of Production Example 4, (a1-
2) 81 parts and 19 parts of N, N, N ', N'-tetrakis (2-hydroxypropyl) -ethylenediamine were charged, and mixed by stirring at 40 to 50 ° C for 1 hour under a nitrogen stream to obtain an active hydrogen component (A- 5) was obtained. The (A-5) had a hydroxyl value of 213 and a viscosity of 2.0 Pa · s / 25 ° C.

Production Example 12 Purified castor oil (valence =) was placed in the same reaction vessel as in Production Example 4.
3, hydroxyl value = 161) [manufactured by Toyokuni Oil Co., Ltd .;
-DR "] 81 parts and N, N, N ', N'-tetrakis (2-hydroxypropyl) -ethylenediamine 19 parts are charged and stirred and mixed under a nitrogen stream at 40 to 50 ° C for 1 hour to obtain an active hydrogen component ( A'-4) was obtained. (A'-4)
Had a hydroxyl value of 276 and a viscosity of 1.6 Pa · s / 25 ° C.

Production Example 13 In the same reaction vessel as in Production Example 4, carbodiimide-modified 4,
4'-MDI [Dow Polyurethane Japan Ltd .;
SONATE 143LJ ”] castor oil fatty acid monoester of 518 parts and polypropylene glycol (number average molecular weight 950) [manufactured by Ito Oil Co., Ltd .;“ URIC H-5 ”
3 "], and reacted at 70 to 80 ° C. for 4 hours to obtain a polyisocyanate component (B-1) comprising an NCO-terminated urethane prepolymer. N of said (B-1)
The CO group content is 12.2%, and the viscosity is 2.8 Pa · s / 25.
° C.

Production Example 14 4,4′-MDI and 2,4′-MDI were placed in the same reaction vessel as in Production Example 4.
4′-MDI mixture [manufactured by BASF Japan Ltd .;
"Lupranate MI"] 520 parts and partially dehydrated castor oil [manufactured by Toyokuni Oil Co., Ltd .; "HS-2G-120"] 4
80 parts, and reacted at 70 to 80 ° C. for 4 hours.
A polyisocyanate component (B-2) comprising a CO-terminated urethane prepolymer was obtained. The (B-2) had an NCO group content of 12.9% and a viscosity of 4.1 Pa · s / 25 ° C.

Production Example 15 4,4′-MDI and 2,4′-MDI were placed in the same reaction vessel as in Production Example 4.
4′-MDI mixture [manufactured by BASF Japan Ltd .;
“Lupranate MI”] 541 parts and castor oil fatty acid monoester of polypropylene glycol (number average molecular weight 950) [manufactured by Ito Oil Co., Ltd .; “URIC H-5”
3 "] 459 parts and reacted at 70 to 80 ° C. for 4 hours to obtain a polyisocyanate component (B-3) comprising an NCO-terminated urethane prepolymer. NC of the (B-3)
The O group content is 15.5% and the viscosity is 0.78 Pa · s / 25.
° C.

Production Example 16 In the same reaction vessel as in Production Example 4, 4,4′-MDI and 2,4′-MDI were added.
4′-MDI mixture [manufactured by BASF Japan Ltd .;
"Lupranate MI"] 374 parts and castor oil fatty acid monoester of polypropylene glycol (number average molecular weight 950) [manufactured by Ito Oil; "URIC H-5"
3 "] 626 parts, and reacted at 70 to 80 ° C. for 4 hours to obtain a polyisocyanate component (B′-1) composed of an NCO-terminated urethane prepolymer. The (B′-1) has an NCO group content of 9.0% and a viscosity of 3.8 Pa · s / 25.
° C.

Production Example 17 In the same reaction vessel as in Production Example 4, carbodiimide-modified 4,
4'-MDI [Dow Polyurethane Japan Ltd .;
SONATE 143LJ "] and 460 parts of castor oil fatty acid monoester of polypropylene glycol (number average molecular weight 950) [manufactured by Ito Oil Co., Ltd .;
53 "] 335 parts and refined castor oil [Toyokuni Oil Co., Ltd.
"ELA-DR"], and 205 to 70 parts.
The mixture was reacted at 0 ° C. for 4 hours to obtain a polyisocyanate component (B′-2) composed of an NCO-terminated urethane prepolymer. The (B′-2) had an NCO group content of 9.1% and a viscosity of 25.0 Pa · s / 25 ° C.

Production Example 18 4,4′-MDI and 2,4′-MDI were placed in the same reaction vessel as in Production Example 4.
4′-MDI mixture [manufactured by BASF Japan Ltd .;
[Lupranate MI]] 936 parts and partially dehydrated castor oil [produced by Toyokuni Oil Co., Ltd .; "HS-2G-120"] 64 parts, and reacted at 70 to 80 ° C for 4 hours to obtain NCO-terminated urethane prepolymer. A polyisocyanate component (B-4) was obtained. The (B-4) has an NCO group content of 3
0.8% and a viscosity of 0.05 Pa · s / 25 ° C.

Production Example 19 In the same reaction vessel as in Production Example 4, carbodiimide-modified 4,
4'-MDI [Dow Polyurethane Japan Ltd .;
SONATE 143LJ "] 593 parts and castor oil fatty acid monoester of polypropylene glycol (number average molecular weight 950) [manufactured by Ito Oil Co., Ltd .;" URIC H-5 "
3 "], and reacted at 70 to 80 ° C. for 4 hours to obtain a polyisocyanate component (B′-3) comprising an NCO-terminated urethane prepolymer. (B'-3)
Has an NCO group content of 14.5% and a viscosity of 2.0 Pa · s /
25 ° C.

Examples 1-4 and Comparative Examples 1-3 Active hydrogen component (A) obtained in Production Examples 4-10 and polyisocyanate component (B) obtained in Production Examples 13-17
Were mixed in the proportions shown in Table 1, and cast into a polycarbonate container into which a cellulose hollow fiber was inserted by centrifugal molding.
Cured at 25 ° C. to make 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: Active hydrogen component (A) and polyisocyanate component (B) were uniformly mixed at 25 ° C., and the viscosity (Pa · s) was measured one minute after the start of mixing. Hardness: The hardness (JIS-A, 10 second value) of the cured resin when cured at 25 ° C. for a predetermined time after casting is measured.

Example 5 and Comparative Example 4 Active hydrogen component (A) obtained in Production Examples 11 and 12
And the polyisocyanate component (B) obtained in Production Examples 18 and 19 were mixed at the ratio shown in Table 2, and
A module was prepared and tested in the same manner as in No. 4. Table 2 shows the results.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

The cast polyurethane resin-forming composition using the active hydrogen component for forming a cast polyurethane resin of the present invention has the following effects. (1) The mixed liquid before casting has a low viscosity, has excellent casting properties, and forms a cured resin without foaming. (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. Due to the above effects, the cast polyurethane resin-forming composition using the active hydrogen component for forming a cast polyurethane resin of the present invention is particularly useful as a sealant for artificial organs such as blood processors and water purifiers. is there. Further, the cured resin obtained from the composition is excellent in electric insulation, water resistance and adhesion to various substrates, so that it can be used for electric insulation such as sealing of electronic circuit boards, sealing of optical fiber cable connection parts, etc. It can be suitably used for building materials such as water use, bonding of heat insulating aluminum sash and bonding of aluminum honeycomb panel, potting material for automobile emblem and side molding, and laminating and bonding of various films.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C02F 1/44 C02F 1/44 H C08G 18/50 C08G 18/50 A (56) References JP-A-8-165323 (JP, A) JP-A-57-87418 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18/48-18/50 C08G 18/66

Claims (8)

(57) [Claims] An alkylene oxide is added to a polyhydric alcohol having a valency of 4 or more selected from the group consisting of dipentaerythritol, diglycerin, polyglycerin and polyvinyl alcohol.
At least 10% by weight of a polyoxyalkylene compound (a11) having a hydroxyl equivalent of 160 or more, and an amine-based polyol (a2) having a hydroxyl value of 400 or more.
An active hydrogen component (A) for forming a cast polyurethane resin comprising at least 1% by weight of 2. The active hydrogen component (A) according to claim 1, wherein (a11) is a polyoxyalkylene ether of polyglycerin. 3. A polyoxyalkylene compound (a12) having four or more active hydrogen-containing groups selected from a mercapto group and a primary amino group in one molecule and having an active hydrogen-containing group equivalent of 160 or more, at least 10% by weight. %, And an active hydrogen component (A) for forming a cast polyurethane resin, comprising at least 1% by weight of an amine-based polyol (a2) having a hydroxyl value of 400 or more. 4. A cast polyurethane resin-forming composition comprising the active hydrogen component (A) according to claim 1 and a polyisocyanate component (B). 5. An alkylene oxide is added to a polyhydric alcohol having a valency of 4 or more selected from the group consisting of dipentaerythritol, diglycerin, polyglycerin and polyvinyl alcohol.
Polyoxyalkylene compound (a11) having a hydroxyl equivalent of 160 or more or an active hydrogen-containing group selected from a mercapto group and a primary amino group having a hydroxyl equivalent of 160 or more in one molecule, and having an active hydrogen-containing equivalent of one or more. At least 10% by weight of a polyoxyalkylene compound (a12) of 160 or more
A cast polyurethane resin-forming composition comprising an active hydrogen component (A), a polyisocyanate component (B) and a metal catalyst (C). 6. A binding agent comprising the composition according to claim 4. 7. A hollow fiber type blood processor sealed with the binding agent according to claim 6. 8. A hollow fiber type water purifier sealed with the binding agent according to claim 6.