Polyurethane resin-forming composition, sealing material, membrane module, and hollow fiber-type blood processor or water purifier

Abstract

The present invention relates to a polyurethane resin-forming composition for a sealing material of a membrane module, the polyurethane resin-forming composition containing a polyol component (A) and a polyisocyanate component (B). The polyol component (A) contains an ethylene oxide and / or propylene oxide adduct (A52) of a trivalent to hexavalent alcohol, and a hydroxide (s1) of an alkali metal and / or an alkali metal salt (s2) of a carboxylic acid, and the total of the alkali value derived from the hydroxide (s1) of an alkali metal and the alkali value derived from the alkali metal salt (s2) of a carboxylic acid in the polyol component (A) is 0.10-2.0 mgKOH / g.

Description

Polyurethane resin-forming composition, sealing material, membrane module, and hollow fiber blood treatment device or water purifier

[0001] The present invention relates to a polyurethane resin-forming composition for a sealing material of a membrane module, a sealing material, a membrane module, and a hollow fiber blood treatment device or water purifier.

[0002] Conventionally, as a polyurethane resin-forming composition used as a sealing material for membrane modules, for example, a composition containing a polyol component including a castor oil-based polyol and a polyisocyanate component has been proposed (for example, Patent Document 1).

[0003] Japanese Patent Application Publication No. 53-61695

[0004] However, the hardness of the cured product of the polyurethane resin-forming composition described in Patent Document 1 was not sufficient. Therefore, there has been a demand for a polyurethane resin-forming composition that has excellent hardness of the cured product and is suitable for use as a sealing material for membrane modules. An object of the present invention is to provide a polyurethane resin-forming composition that has an appropriate pot life and excellent hardness of the cured product and is suitable for use as a sealing material for membrane modules.

[0005] The present inventors have conducted extensive research to achieve the above object and have arrived at the present invention. Specifically, the present invention relates to a polyurethane resin-forming composition for a sealing material of a membrane module, comprising a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) comprises an ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol, and an alkali metal hydroxide (s1) and / or an alkali metal salt of a carboxylic acid (s2), and the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali value derived from the alkali metal salt of a carboxylic acid (s2) in the polyol component (A) is 0.10 to 2.0 mgKOH / g.

[0006] The polyurethane resin-forming composition for a membrane module seal of the present invention has the following effects: (1) A moderate pot life. (2) Excellent hardness of the cured product. The polyurethane resin-forming composition for a membrane module seal of the present invention has a moderate pot life, resulting in excellent membrane module productivity. Furthermore, the polyurethane resin-forming composition for a membrane module seal of the present invention has excellent hardness of the cured product, so that when used as a membrane module seal, a membrane module with excellent hardness can be obtained. Therefore, the polyurethane resin-forming composition for a membrane module seal of the present invention is suitably used as a membrane module seal. Furthermore, the membrane module seal of the present invention is made of the polyurethane resin-forming composition for a membrane module seal of the present invention, resulting in a moderate pot life and excellent hardness of the cured product. Furthermore, the membrane module of the present invention is made of a cured product of the membrane module seal of the present invention, resulting in excellent hardness and durability. Furthermore, the hollow fiber blood treatment device or water purifier of the present invention is equipped with the membrane module of the present invention, resulting in excellent hardness and durability.

[0007] <Polyurethane resin-forming composition for membrane module sealing material> The polyurethane resin-forming composition for a membrane module sealing material of the present invention (hereinafter also referred to as the polyurethane resin-forming composition of the present invention) is a polyurethane resin-forming composition containing a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) contains an ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol, and an alkali metal hydroxide (s1) and / or an alkali metal salt of a carboxylic acid (s2), and the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali value derived from the alkali metal salt of a carboxylic acid (s2) in the polyol component (A) is 0.10 to 2.0 mgKOH / g.

[0008] <Polyol Component (A)> The polyol component (A) in the present invention contains an ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol, and an alkali metal hydroxide (s1) and / or an alkali metal salt of a carboxylic acid (s2).

[0009] Examples of the ethylene oxide and / or propylene oxide adducts (A52) of trihydric to hexahydric alcohols include those obtained by adding ethylene oxide (EO) and / or propylene oxide (PO) to trihydric to hexahydric alcohols.

[0010] Examples of trihydric to hexahydric alcohols include trihydric alcohols [glycerin (hereinafter abbreviated as GR), trimethylolpropane (hereinafter abbreviated as TMP), hexanetriol, etc.], tetrahydric alcohols [pentaerythritol, etc.], pentahydric alcohols [xylitol, etc.], and hexahydric alcohols [dipentaerythritol, etc.]. One type of trihydric to hexahydric alcohol may be used alone, or two or more types may be used in combination.

[0011] From the viewpoints of pot life and hardness of the cured product, the ethylene oxide and / or propylene oxide adduct of a trihydric to hexahydric alcohol (A52) is preferably an ethylene oxide and / or propylene oxide adduct of a trihydric or tetrahydric alcohol, and more preferably a propylene oxide adduct of a trihydric alcohol.

[0012] In the polyol component (A), the content of the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol is not particularly limited, but is preferably 70% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more. The upper limit of the content of the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol in the polyol component (A) can be, for example, 99.98% by weight, 99.95% by weight, or 99.9% by weight. In the polyol component (A), the content of the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol in the polyol component (A) is not particularly limited, but is preferably 70 to 99.98% by weight, more preferably 80 to 99.95% by weight, and even more preferably 90 to 99.9% by weight.

[0013] In the polyurethane resin-forming composition of the present invention, the number average molecular weight (Mn) of the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol is not particularly limited, but from the viewpoint of hardness, it is preferably 800 to 2,000, more preferably 900 to 1,600. In the present invention, the number average molecular weight (Mn) of the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol is measured, for example, by gel permeation chromatography using THF (tetrahydrofuran) as a solvent and polyoxypropylene glycol as a standard substance. The sample concentration is 0.25 wt %, and the column stationary phase is a combination of one TSKgel Super H2000, one TSKgel Super H3000, and one TSKgel Super H4000 (all manufactured by Tosoh Corporation), and the column temperature is 40°C.

[0014] In the polyurethane resin-forming composition of the present invention, when the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol is an adduct of ethylene oxide and propylene oxide to a trihydric to hexahydric alcohol, the molar ratio of ethylene oxide to propylene oxide (ethylene oxide:propylene oxide) is not particularly limited, but is preferably 10:90 to 1:99.

[0015] Examples of the alkali metal hydroxide (s1) include lithium hydroxide, sodium hydroxide, and potassium hydroxide. The alkali metal hydroxide (s1) may be used alone or in combination of two or more. Among the alkali metal hydroxides (s1), sodium hydroxide and potassium hydroxide are preferred from the viewpoints of pot life and hardness of the cured product.

[0016] As the alkali metal salt of carboxylic acid (s2), for example, an alkali metal salt of a carboxylic acid having 1 to 3 carbon atoms can be used, and more specific examples include sodium formate, potassium formate, lithium acetate, sodium acetate, potassium acetate, sodium propionate, and potassium propionate. The alkali metal salt of carboxylic acid (s2) may be used alone or in combination of two or more. Among the alkali metal salts of carboxylic acid (s2), sodium acetate and potassium acetate are preferred from the viewpoints of pot life and hardness of the cured product. Furthermore, the alkali metal hydroxide (s1) and / or alkali metal salt of carboxylic acid (s2) is preferably an alkali metal salt of carboxylic acid (s2) from the viewpoints of pot life and hardness of the cured product.

[0017] In the polyol component (A), the content of the alkali metal hydroxide (s1) is not particularly limited, but is preferably 200 ppm or more, more preferably 300 ppm or more, and even more preferably 400 ppm or more. In the polyol component (A), the upper limit of the content of the alkali metal hydroxide (s1) is, for example, 2000 ppm. In the polyol component (A), the content of the alkali metal hydroxide (s1) is not particularly limited, but is preferably 200 to 2000 ppm, more preferably 300 to 1500 ppm, and even more preferably 400 to 1000 ppm. In addition, in the polyol component (A), the content of the alkali metal salt of carboxylic acid (s2) is not particularly limited, but is preferably 200 ppm or more, more preferably 300 ppm or more, and even more preferably 400 ppm or more. In the polyol component (A), the upper limit of the content of the alkali metal salt of carboxylic acid (s2) is, for example, 2000 ppm. In the polyol component (A), the content of the alkali metal salt of carboxylic acid (s2) is not particularly limited, but is preferably 200 to 2000 ppm, more preferably 300 to 1500 ppm, and even more preferably 400 to 1000 ppm. －４ It is expressed in weight percent, i.e., 1 ppm = 0.0001 weight percent.

[0018] The sum of the alkali value derived from the alkali metal hydroxide (s1) in the polyol component (A) and the alkali value derived from the alkali metal salt of carboxylic acid (s2) is 0.10 to 2.0 mgKOH / g, preferably 0.20 to 1.50 mgKOH / g, and more preferably 0.30 to 1.0 mgKOH / g. If the sum of the alkali value derived from the alkali metal hydroxide (s1) in the polyol component (A) and the alkali metal salt of carboxylic acid (s2) is less than 0.10 mgKOH / g, the hardness may be insufficient, while if it exceeds 2.0 mgKOH / g, the pot life may be shortened and workability may be poor. In the present invention, the alkali value refers to the number of milligrams of potassium hydroxide equivalent to the amount of perchloric acid required to neutralize all basic components in 1 g of sample, and represents the content of basic components in the sample. In the present invention, the type and content of the alkali metal hydroxide (s1) and alkali metal salt of carboxylic acid (s2) contained in the polyol component (A) can be measured in accordance with JIS K0127 (General Rules for Ion Chromatography). From the obtained measured values, the contents of the alkali metal hydroxide (s1) and the alkali metal salt of carboxylic acid (s2) are converted to potassium hydroxide contents, respectively, to calculate the alkali value derived from the alkali metal hydroxide (s1) contained in the polyol component (A) and the alkali value derived from the alkali metal salt of carboxylic acid (s2) (both units are mgKOH / g). By summing these alkali values, the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali metal salt of carboxylic acid (s2) in the polyol component (A) can be calculated.

[0019] In the polyurethane resin-forming composition of the present invention, the hydroxyl value of the polyol component (A) is not particularly limited, but from the viewpoints of pot life and hardness of the cured product, it is preferably 100 to 500 mgKOH / g, more preferably 120 to 400 mgKOH / g, and even more preferably 140 to 200 mgKOH / g. In the present invention, the hydroxyl value of the polyol component (A) can be measured by the method described in JIS K1157-1.

[0020] In the polyurethane resin-forming composition of the present invention, the polyol component (A) may contain, in addition to the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol and the alkali metal hydroxide (s1) and / or alkali metal salt of a carboxylic acid (s2) described above, another polyol component (A'). Examples of the other polyol component (A') include those other than the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol, such as castor oil polyol (A'1), ethylene oxide and / or propylene oxide adduct (A'2) of a polyamine, ethylene oxide and / or propylene oxide adduct (A'3) of an alkanolamine, polyester polyol (A'4), and polyether polyol (A'5). The other polyol component (A') may be used alone or in combination of two or more.

[0021] Examples of the castor oil polyol (A'1) include those having an Mn (number average molecular weight) of 300 to 4,000, such as castor oil, partially dehydrated castor oil, castor oil fatty acid esters obtained by transesterification of polyether polyol and castor oil, castor oil fatty acid esters obtained by esterification of polyether polyol and castor oil fatty acid, and castor oil AO adducts obtained by adding alkylene oxides (hereinafter sometimes abbreviated as AO) having 2 to 8 carbon atoms, preferably 2 to 3 carbon atoms (e.g., ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and mixtures of two or more thereof) to castor oil.

[0022] Examples of the ethylene oxide and / or propylene oxide adduct of polyamine (A'2) include polyamines (am) to which alkylene oxides such as ethylene oxide (EO) and / or propylene oxide (PO) are added. Examples of the polyamine (am) include aliphatic poly(di- to heptavalent)amines (am1), alicyclic-containing poly(di- to tri-valent)amines (am2), heterocyclic-containing poly(di- to tri-valent)amines (am3), and aromatic ring-containing polyamines (am4). One type of polyamine (am) may be used alone, or two or more types may be used in combination.

[0023] Examples of the aliphatic poly(di- to heptavalent)amine (am1) include those having 2 or more carbon atoms (hereinafter sometimes abbreviated as C) and an Mn of 500 or less, such as C2-10 alkylenediamines (ethylenediamine, propylenediamine, etc.), polyalkylene (C2-10) poly(tri- to heptavalent)amines (diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.), and alkyl (C1-4) or hydroxyalkyl (C2-4) substituted products thereof, such as dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, and aminoethylethanolamine.

[0024] Examples of the alicyclic ring-containing poly(di- or trivalent)amine (am2) include those having 4 to 15 carbon atoms, such as 1,3-diaminocyclohexane and isophoronediamine.

[0025] Examples of the heterocycle-containing poly(divalent to trivalent)amine (am3) include those having 4 to 15 carbon atoms, such as piperazine, N-aminoethylpiperazine, and 1,4-diaminoethylpiperazine.

[0026] Examples of the aromatic ring-containing polyamine (am4) include those having 8 to 15 carbon atoms, such as xylylenediamine, tetrachloro-p-xylylenediamine, and diaminodiphenylmethane.

[0027] Examples of the ethylene oxide and / or propylene oxide adduct of alkanolamine (A'3) include those obtained by adding an alkylene oxide such as ethylene oxide (EO) and / or propylene oxide (PO) to alkanolamine (am5). Examples of the alkanolamine (am5) include those with 4 to 12 carbon atoms, such as diethanolamine and triethanolamine. One type of alkanolamine (am5) may be used alone, or two or more types may be used in combination.

[0028] Examples of the polyester polyol (A'4) include condensation type polyester polyols (polyethylene adipate diol, polybutylene adipate diol, etc.), polylactone polyols (polyhexamethylene carbonate diol, polypentamethylene carbonate diol, etc.), and the like.

[0029] The polyether polyol (A'5) may be any other than the above (A'1) to (A'4), such as an ethylene oxide and / or propylene oxide adduct (A'51) of a dihydric alcohol.

[0030] The ethylene oxide and / or propylene oxide adduct of dihydric alcohol (A'51) may be an adduct of a dihydric alcohol with an alkylene oxide such as ethylene oxide (EO) and / or propylene oxide (PO).

[0031] Examples of dihydric alcohols include aliphatic dihydric alcohols [ethylene glycol (EG), propylene glycol (PG), 1,4-butanediol (1,4-BD), neopentyl glycol (NPG), 1,6-hexanediol (1,6-HD), etc.], aromatic ring-containing dihydric alcohols [bisphenol A, etc.], alicyclic ring-containing dihydric alcohols [1,4-cyclohexanediol, cyclohexanedimethanol, etc.], etc. One type of dihydric alcohol may be used alone, or two or more types may be used in combination.

[0032] In the polyurethane resin-forming composition of the present invention, when the polyol component (A) contains another polyol component (A'), the other polyol component (A') is preferably a castor oil polyol (A'1) or an ethylene oxide and / or propylene oxide adduct of a dihydric alcohol (A'51).

[0033] <Polyisocyanate Component (B)> The polyisocyanate component (B) in the present invention is not particularly limited, but preferably contains, for example, an isocyanate-terminated urethane prepolymer (U), which is a reaction product of a polyol and a polyisocyanate (b). The polyisocyanate component (B) may contain a polyol and a polyisocyanate (b) in addition to the isocyanate-terminated urethane prepolymer (U). Examples of the polyol include the ethylene oxide and / or propylene oxide adducts of the above-mentioned trihydric to hexahydric alcohols (A52), castor oil polyols (A'1), ethylene oxide and / or propylene oxide adducts of polyamines (A'2), ethylene oxide and / or propylene oxide adducts of alkanolamines (A'3), polyester polyols (A'4), and polyether polyols (A'5). These polyols may be used alone or in combination of two or more. More preferably, the polyisocyanate component (B) contains an isocyanate-terminated urethane prepolymer (U) which is a reaction product of an ethylene oxide and / or propylene oxide adduct of a dihydric alcohol (A'51) and / or an ethylene oxide and / or propylene oxide adduct of a trihydric to hexahydric alcohol (A52) with the polyisocyanate (b). The polyisocyanate component (B) preferably contains an isocyanate-terminated urethane prepolymer (U), and more preferably is an isocyanate-terminated urethane prepolymer (U).

[0034] In this specification, the isocyanate group-terminated urethane prepolymer (U) refers to a compound having a urethane bond and an isocyanate group.

[0035] The polyisocyanate (b) may be any compound other than the polyisocyanate component (B) described above, having two to three or more isocyanate groups. Examples of such compounds include aromatic polyisocyanates (b1) having 6 to 20 carbon atoms (excluding carbon atoms in isocyanate groups, the same applies below), aliphatic polyisocyanates (b2) having 2 to 18 carbon atoms, alicyclic polyisocyanates (b3) having 4 to 15 carbon atoms, araliphatic polyisocyanates (b4) having 8 to 15 carbon atoms, and modified products (b5) of the above (b1) to (b4). One type of polyisocyanate (b) may be used alone, or two or more types may be used in combination.

[0036] Examples of the aromatic polyisocyanate (b1) having 6 to 20 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'- or 2,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, and crude MDI.

[0037] Examples of the aliphatic polyisocyanate (b2) having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

[0038] Examples of the alicyclic polyisocyanate (b3) having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

[0039] Examples of the aralkyl polyisocyanate (b4) having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI).

[0040] Examples of the modified compounds (b5) of the above (b1) to (b4) include compounds obtained by adding a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group, or an oxazolidone group to the compounds listed in the above (b1) to (b4).

[0041] From the viewpoints of pot life and hardness of the cured product, the polyisocyanate (b) is preferably an aromatic polyisocyanate (b1) having 6 to 20 carbon atoms, more preferably diphenylmethane diisocyanate (MDI), and even more preferably 4,4'-MDI and / or 2,4'-MDI.

[0042] The isocyanate-terminated urethane prepolymer (U) can be obtained, for example, by subjecting an excess of polyisocyanate (b) and the polyol to a urethane reaction by a known method.

[0043] The total weight of the ethylene oxide and / or propylene oxide adduct (A'51) of a dihydric alcohol and the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol, based on the weight of the polyol, is preferably 70% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more. The upper limit of the total weight of the ethylene oxide and / or propylene oxide adduct (A'51) of a dihydric alcohol and the ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol, based on the weight of the polyol, is, for example, 100% by weight.

[0044] The hydroxyl value of the polyol is not particularly limited, but is preferably 50 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g. The hydroxyl value of the polyol can be measured by the method described in JIS K1157-1.

[0045] The isocyanate group content (NCO content) of the polyisocyanate component (B) is preferably 10 to 30% by weight, more preferably 15 to 25% by weight, from the viewpoints of elution rate and hardness. The isocyanate group content (NCO content) of the polyisocyanate component (B) can be measured according to JIS K1603-1 (Method A).

[0046] In the polyurethane resin-forming composition of the present invention, the weight ratio of the content of the polyol component (A) to the content of the polyisocyanate component (B) (polyol component (A):polyisocyanate component (B)) is not particularly limited, but is preferably 35:65 to 70:30, more preferably 40:60 to 65:35, and even more preferably 45:55 to 60:40.

[0047] In the polyurethane resin-forming composition of the present invention, the equivalent ratio (molar ratio) of the isocyanate groups in the polyisocyanate component (B) to the hydroxyl groups in the polyol component (A) (isocyanate groups in the polyisocyanate component (B) / hydroxyl groups in the polyol component (A)) (NCO / OH) is not particularly limited, but is preferably 0.5 to 2.0, more preferably 0.7 to 1.5, and even more preferably 0.8 to 1.2.

[0048] The polyurethane resin-forming composition of the present invention may contain, in addition to the polyol component (A) and polyisocyanate component (B) described above, a known urethanization catalyst (D) depending on the desired curability, as long as the effects of the present invention are not impaired.

[0049] When the polyurethane resin-forming composition of the present invention contains the urethanization catalyst (D), the polyol component (A), the polyisocyanate component (B), and the urethanization catalyst (D) may be mixed simultaneously, or a predetermined amount of the urethanization catalyst (D) may be mixed in advance with the polyol component (A), and the resulting mixture may then be mixed with the polyisocyanate component (B), or a predetermined amount of the urethanization catalyst (D) may be mixed in advance with the polyisocyanate component (B), and the resulting mixture may then be mixed with the polyol component (A).

[0050] The polyurethane resin-forming composition of the present invention can be obtained by weighing out predetermined amounts of polyol component (A), polyisocyanate component (B), and, if necessary, urethane-forming catalyst (D), and then mixing them using a static mixer, mechanical mixer, or the like. The polyol component (A) and polyisocyanate component (B) react to cure and form a polyurethane resin (a cured product of the polyurethane resin-forming composition of the present invention). The polyurethane resin-forming composition of the present invention requires, for example, 3 to 60 minutes from the start of mixing of polyol component (A) and polyisocyanate component (B) to gelation, and requires, for example, 12 to 240 hours to fully cure. Gelling is defined as the loss of fluidity of the polyurethane resin-forming composition of the present invention, and full cure (the end point of the reaction) is defined as the point at which the hardness of the cured product no longer changes. The time required for full cure can be shortened by increasing the curing temperature (e.g., 30 to 60°C).

[0051] In this specification, the polyurethane resin refers to a polymer having a urethane group and having substantially no isocyanate group at the terminal.

[0052] The polyurethane resin-forming composition of the present invention preferably has a hardness of 70 to 100, and more preferably 80 to 95, 2 hours after the start of mixing the polyol component (A) and the polyisocyanate component (B). In this specification, the hardness refers to the hardness measured in accordance with JIS K6253-3.

[0053] The polyurethane resin-forming composition of the present invention is particularly suitable for use as a sealing material for membrane modules. Examples of membrane modules include those used in blood treatment devices, water purifiers, etc. Examples of blood treatment devices include hollow fiber, membrane, and coil type blood treatment devices. Hollow fiber type blood treatment devices are preferred. Blood treatment devices can also be used as artificial organs such as artificial kidneys and artificial lungs. They can also be used for plasma separation.

[0054] The polyurethane resin-forming composition of the present invention can be used as a sealing material for a membrane module used in a hollow fiber blood treatment device, for example, by the following method. First, hollow fibers are embedded in a container by centrifugal molding. An example of the centrifugal molding method is described, for example, in Japanese Patent Application Laid-Open No. 57-58963. Cellulose-based, acrylic, polyvinyl alcohol-based, polyamide-based, or polysulfone-based hollow fibers are generally used as the embedded hollow fibers. The container is generally made of polycarbonate, ABS, or polystyrene. Next, the polyol component (A) and the polyisocyanate component (B) are individually degassed under reduced pressure (0.1 mmHg x 2 hours), and then the respective components are weighed out in predetermined amounts and mixed to obtain the polyurethane resin-forming composition of the present invention. The polyurethane resin-forming composition of the present invention is then injected into the container with the embedded hollow fibers as a sealing material for the membrane module. The polyurethane resin-forming composition of the present invention gels, for example, 3 to 60 minutes after injection and can be removed from the container. The membrane module is then cured at room temperature (25°C to 60°C) until it is completely cured, yielding a membrane module. The membrane module is then sterilized using an autoclave, for example, by steam heating at 121°C for 1 hour, to produce a finished product. Sterilization can also be performed by methods other than steam heating, such as ethylene oxide gas or gamma-ray irradiation.

[0055] The sealing material for a membrane module of the present invention comprises the polyurethane resin-forming composition for a sealing material for a membrane module of the present invention.The membrane module of the present invention comprises a cured product of the sealing material for a membrane module of the present invention.The hollow fiber blood treatment device or water purifier of the present invention comprises the membrane module of the present invention.

[0056] In the sealing material for the membrane module of the present invention, the membrane module of the present invention, and the hollow fiber blood treatment device or water purifier of the present invention, the components contained in the polyurethane resin-forming composition of the present invention, the method for obtaining the polyurethane resin-forming composition of the present invention, the method for curing the polyurethane resin-forming composition of the present invention, the sealing material for the membrane module, the membrane module, the hollow fiber blood treatment device, the water purifier, etc. are the same as those for the polyurethane resin-forming composition of the present invention described above.

[0057] The present specification discloses the following: <1> A polyurethane resin-forming composition for a sealing material of a membrane module, comprising a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) comprises an ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol, and an alkali metal hydroxide (s1) and / or an alkali metal salt of a carboxylic acid (s2), and the sum of the alkali value derived from the alkali metal hydroxide (s1) in the polyol component (A) and the alkali value derived from the alkali metal salt of a carboxylic acid (s2) is 0.10 to 2.0 mgKOH / g. <2> The polyurethane resin-forming composition for a sealant for a membrane module according to the above <1>, wherein the polyisocyanate component (B) contains an isocyanate-terminated urethane prepolymer (U) that is a reaction product of an ethylene oxide and / or propylene oxide adduct of a dihydric alcohol (A'51) and / or an ethylene oxide and / or propylene oxide adduct of a trihydric to hexahydric alcohol (A52) with the polyisocyanate (b). <3> The polyurethane resin-forming composition for a sealant for a membrane module according to the above <1> or <2>, wherein the equivalent ratio of the isocyanate groups in the polyisocyanate component (B) to the hydroxyl groups in the polyol component (A) (isocyanate groups in the polyisocyanate component (B) / hydroxyl groups in the polyol component (A)) is 0.5 to 2.0. <4> A sealant for a membrane module comprising the polyurethane resin-forming composition for a sealant for a membrane module according to any one of the above <1> to <3>. <5> A membrane module comprising a cured product of the sealing material for the membrane module according to <4> above. <6> A hollow fiber blood treatment device or water purifier comprising the membrane module according to <5> above.

[0058] The present invention will be further explained below with reference to examples, but the present invention is not limited thereto. In the following, parts are parts by weight.

[0059] <Production Example 1> A four-neck flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube was charged with 63 parts of polyisocyanate (b-1) [a mixture of 4,4'-MDI and 2,4'-MDI, "Lupranate MI" manufactured by BASF Japan Ltd.] and 37 parts of a propylene glycol propylene oxide (PO) adduct ("Sannyx PP-1000" manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value: 160 mg KOH / g, Mn: 1,000, alkali value: 0 mg KOH / g) (A'51-1), and the mixture was reacted for 4 hours at 70 to 80°C under a nitrogen stream to obtain a polyisocyanate component (B-1) containing an isocyanate group-terminated urethane prepolymer (U-1). The isocyanate group (NCO) content of the polyisocyanate component (B-1) was 18.0 wt%.

[0060] Production Example 2 A four-neck flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube was charged with 42 parts of polyisocyanate (b-1) [a mixture of 4,4'-MDI and 2,4'-MDI, "Lupranate MI" manufactured by BASF Japan Ltd.] and 58 parts of a propylene glycol propylene oxide (PO) adduct ("Sannyx PP-1000" manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value: 160 mg KOH / g, Mn: 1,000, alkali value: 0 mg KOH / g) (A'51-1), and the mixture was reacted for 4 hours at 70 to 80°C under a nitrogen stream to obtain a polyisocyanate component (B-2) containing an isocyanate group-terminated urethane prepolymer (U-2). The isocyanate group content of the polyisocyanate component (B-2) was 15.8% by weight.

[0061] <Production Example 3> Into a four-neck flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, 53 parts of polyisocyanate (b-2) [4,4'-MDI, manufactured by Tosoh Corporation, "Millionate MT"] and 4 parts of a propylene glycol propylene oxide (PO) adduct (manufactured by Sanyo Chemical Industries, Ltd., "Sannyx PP-1000", hydroxyl value: 160 mgKOH / g, Mn: 1,000, alkali value: 0 mgKOH / g) (A'51-1) 0 parts of propylene oxide (PO) adduct of glycerin (manufactured by Sanyo Chemical Industries, Ltd., "SANNICS GP-1500", hydroxyl value: 160 mgKOH / g, Mn: 1,500, alkali value: 0 mgKOH / g) (A52-1) were charged and reacted for 4 hours at 70 to 80°C under a nitrogen stream to obtain a polyisocyanate component (B-3) containing an isocyanate group-terminated urethane prepolymer (U-3). The isocyanate group content of the polyisocyanate component (B-3) was 13.7% by weight.

[0062] Production Example 4 A four-neck flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube was charged with 64 parts of polyisocyanate (b-1) [a mixture of 4,4'-MDI and 2,4'-MDI, "Lupranate MI" manufactured by BASF Japan Ltd.], 32 parts of a propylene oxide (PO) adduct of glycerin ("SANNICS GP-1500" manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value: 160 mg KOH / g, Mn: 1,500, alkali value: 0 mg KOH / g) (A52-1), and 4 parts of castor oil [ELA-DR manufactured by Toyokuni Oil Mills Co., Ltd., hydroxyl value 161 mg KOH / g] (A'1-1), and the mixture was reacted at 70 to 80°C for 4 hours under a nitrogen stream to obtain a polyisocyanate component (B-4) containing an isocyanate group-terminated urethane prepolymer (U-4). The isocyanate group content of the polyisocyanate component (B-4) was 18.3% by weight.

[0063] In Production Examples 1 to 4, the isocyanate group (NCO) content of the polyisocyanate components (B-1) to (B-4) was measured in accordance with JIS K1603-1 (Method A).

[0064] The raw materials used in Production Examples 1 to 4 and their compositions (unit: parts by weight) are shown in Table 1. Table 1 also shows the isocyanate group (NCO) contents (unit: % by weight) of the polyisocyanate components (B-1) to (B-4) obtained in Production Examples 1 to 4.

[0065]

[0066] <Production Example 5> An autoclave was charged with 153.3 parts of glycerin and 1.4 parts of an aqueous potassium hydroxide solution (concentration: 48% by weight). After nitrogen substitution (oxygen concentration in the gas phase: 450 ppm), the mixture was vacuum dehydrated at 120°C for 60 minutes. Next, 845.3 parts of propylene oxide was injected at 100 to 130°C over approximately 10 hours, and the reaction was continued at 130°C for 3 hours, followed by cooling to 30°C. This was designated polyol component (A-1). Polyol component (A-1) contained a propylene oxide (PO) adduct of glycerin (Mn: 1,000) and potassium hydroxide. The polyol component (A-1) had a potassium hydroxide content of 700 ppm, a hydroxyl value of 160 mgKOH / g, and a total of the alkali value derived from the alkali metal hydroxide (s1) and the alkali metal salt of carboxylic acid (s2) of 0.70 mgKOH / g.

[0067] <Production Example 6> An autoclave was charged with 153.3 parts of glycerin and 1.4 parts of an aqueous potassium hydroxide solution (concentration 48% by weight). After nitrogen substitution (oxygen concentration in the gas phase: 450 ppm), the mixture was vacuum dehydrated at 120°C for 60 minutes. Next, 845.3 parts of propylene oxide was injected at 100 to 130°C over approximately 10 hours, and the reaction was continued at 130°C for 3 hours, followed by cooling to 30°C. Next, 0.72 parts of acetic acid was added, and the mixture was stirred and subjected to a vacuum dehydration step at 100°C for 2 hours. This was designated polyol component (A-2). Polyol component (A-2) contained a glycerin PO adduct (Mn: 1,000) and potassium acetate. The polyol component (A-2) had a potassium acetate content of 1,225 ppm, a hydroxyl value of 160 mg KOH / g, and a total of the alkali value derived from the alkali metal hydroxide (s1) and the alkali metal salt of carboxylic acid (s2) of 0.70 mg KOH / g.

[0068] <Production Example 7> An autoclave was charged with 153.3 parts of glycerin and 1.0 part of an aqueous potassium hydroxide solution (concentration 48% by weight). After nitrogen substitution (oxygen concentration in the gas phase: 450 ppm), the mixture was vacuum dehydrated for 60 minutes at 120°C. Next, 845.3 parts of propylene oxide was injected at 100 to 130°C over approximately 10 hours, and the reaction was continued at 130°C for 3 hours, followed by cooling to 30°C. Next, 0.51 parts of acetic acid was added, and the mixture was stirred and subjected to a vacuum dehydration step at 100°C for 2 hours. This was designated polyol component (A-3). Polyol component (A-3) contains a glycerin PO adduct (Mn: 1,000) and potassium acetate. The polyol component (A-3) had a potassium acetate content of 875 ppm, a hydroxyl value of 160 mgKOH / g, and a total of the alkali value derived from the alkali metal hydroxide (s1) and the alkali metal salt of carboxylic acid (s2) of 0.50 mgKOH / g.

[0069] <Production Example 8> An autoclave was charged with 153.3 parts of glycerin and 2.0 parts of an aqueous potassium hydroxide solution (concentration 48% by weight). After nitrogen substitution (oxygen concentration in the gas phase: 450 ppm), the mixture was vacuum dehydrated at 120°C for 60 minutes. Next, 845.3 parts of propylene oxide was injected at 100 to 130°C over approximately 10 hours, and the reaction was continued at 130°C for 3 hours, followed by cooling to 30°C. This was designated polyol component (A-4). Polyol component (A-4) contains a glycerin PO adduct (Mn: 1,000) and potassium hydroxide. The potassium hydroxide content of polyol component (A-4) was 1,000 ppm, the hydroxyl value was 160 mgKOH / g, and the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali value derived from the alkali metal salt of carboxylic acid (s2) was 1.00 mgKOH / g.

[0070] <Production Example 9> An autoclave was charged with 136 parts of pentaerythritol and 1.6 parts of an aqueous potassium hydroxide solution (concentration: 48 wt%). After nitrogen substitution (oxygen concentration in the gas phase: 450 ppm), the mixture was vacuum dehydrated at 120°C for 60 minutes. Next, 1,364 parts of propylene oxide was injected at 100 to 130°C over approximately 10 hours, and the reaction was continued at 130°C for 3 hours, followed by cooling to 30°C. This was designated polyol component (A-5). Polyol component (A-5) contains a pentaerythritol PO adduct (Mn: 1,500) and potassium hydroxide. The potassium hydroxide content of polyol component (A-5) was 500 ppm, the hydroxyl value was 160 mgKOH / g, and the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali value derived from the alkali metal salt of carboxylic acid (s2) was 0.50 mgKOH / g.

[0071] <Production Example 10> 76.1 parts of propylene glycol and 1.0 part of an aqueous potassium hydroxide solution (concentration 48% by weight) were charged into an autoclave, and after nitrogen substitution (oxygen concentration in the gas phase: 450 ppm), the mixture was vacuum dehydrated at 120°C for 60 minutes. Next, 924 parts of propylene oxide were injected at 100 to 130°C over approximately 10 hours, and the reaction was continued at 130°C for 3 hours, followed by cooling to 30°C. Next, 0.53 parts of acetic acid was added, and the mixture was stirred and subjected to a vacuum dehydration step at 100°C for 2 hours. This was designated polyol component (A'5-1). Polyol component (A'5-1) contained a propylene glycol PO adduct (Mn: 1,000) and potassium acetate. The potassium acetate content of polyol component (A'5-1) was 1,225 ppm, the hydroxyl value was 116 mg KOH / g, and the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali value derived from the alkali metal salt of carboxylic acid (s2) was 0.50 mg KOH / g. Polyol component (A-6) was obtained by stirring and mixing 75 parts of polyol component (A-5) and 25 parts of polyol component (A'5-1). Polyol component (A-6) contains the pentaerythritol PO adduct (Mn: 1,500) and potassium hydroxide contained in polyol component (A-5), and the propylene glycol PO adduct (Mn: 1,000) and potassium acetate contained in polyol component (A'5-1). The polyol component (A-6) had a potassium hydroxide content of 375 ppm, a potassium acetate content of 306 ppm, a hydroxyl value of 142 mgKOH / g, and a total of the alkali value derived from the alkali metal hydroxide (s1) and the alkali metal salt of carboxylic acid (s2) of 0.55 mgKOH / g.

[0072] <Production Example 11> An autoclave was charged with 153.3 parts of glycerin and 0.52 parts of an aqueous sodium hydroxide solution (concentration 48% by weight). After nitrogen substitution (oxygen concentration in the gas phase: 450 ppm), the mixture was vacuum dehydrated at 120°C for 60 minutes. Next, 845.3 parts of propylene oxide was injected at 100 to 130°C over approximately 10 hours, and the reaction was continued at 130°C for 3 hours, followed by cooling to 30°C. This was designated polyol component (A-7). Polyol component (A-7) contains a glycerin PO adduct (Mn: 1,000) and sodium hydroxide. The sodium hydroxide content of polyol component (A-7) was 250 ppm, the hydroxyl value was 160 mgKOH / g, and the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali value derived from the alkali metal salt of carboxylic acid (s2) was 0.35 mgKOH / g.

[0073] Production Example 12 90 parts of polyol component (A-7) and 10 parts of castor oil (A'1-1) [manufactured by Toyokuni Oil Mills, Ltd., ELA-DR, hydroxyl value 161 mgKOH / g] were stirred and mixed to obtain polyol component (A-8). Polyol component (A-8) contains the glycerin PO adduct (Mn: 1,000) and sodium hydroxide contained in polyol component (A-7), as well as castor oil. The sodium hydroxide content of polyol component (A-8) was 225 ppm, the hydroxyl value was 160 mgKOH / g, and the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali value derived from the alkali metal salt of carboxylic acid (s2) was 0.31 mgKOH / g.

[0074] Comparative Production Example 1: 100 parts of the polyol component (A-7) obtained in Production Example 11 above, 7 parts of an acid adsorbent [Kyoward #600, manufactured by Kyowa Chemical Industry Co., Ltd.], and 1.5 parts of water were placed in a vessel and stirred at 70°C for 1 hour. The contents were then filtered through a Sparkler filter. The filtrate was then placed in a vessel and vacuum dehydrated at 100°C for 2 hours while stirring to obtain polyol component (A'-1). Polyol component (A'-1) contains a glycerin PO adduct (Mn: 1,000) but does not contain sodium hydroxide. The sodium hydroxide content of polyol component (A'-1) was 0 ppm, the hydroxyl value was 160 mgKOH / g, and the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali value derived from the alkali metal salt of carboxylic acid (s2) was 0.00 mgKOH / g.

[0075] In Production Examples 5 to 12 and Comparative Production Example 1, the number average molecular weight (Mn), the contents of alkali metal hydroxide (s1) and alkali metal salt of carboxylic acid (s2), the hydroxyl value, and the alkali value were measured or calculated by the following methods. (Number Average Molecular Weight (Mn)) Measurement was performed by gel permeation chromatography using THF (tetrahydrofuran) as the solvent and polyoxypropylene glycol as the standard substance. The sample concentration was 0.25 wt %, and the column stationary phase consisted of one TSKgel Super H2000, one TSKgel Super H3000, and one TSKgel Super H4000 (all manufactured by Tosoh Corporation) connected together, and the column temperature was 40°C. (Contents of alkali metal hydroxide (s1) and alkali metal salt of carboxylic acid (s2)) Measurement was performed in accordance with JIS K0127 (General Rules for Ion Chromatography). (Hydroxyl value) Measured by the method described in JIS K 1157-1. (Alkali value) The contents of the alkali metal hydroxide (s1) and the alkali metal salt of carboxylic acid (s2) measured above were each converted into a potassium hydroxide content to calculate the alkali value derived from the alkali metal hydroxide (s1) contained in the polyol component (A) and the alkali value derived from the alkali metal salt of carboxylic acid (s2) (both in mgKOH / g units), and the sum of these was defined as the alkali value of the polyol component (A).

[0076] Table 2 shows the compositions (unit: parts by weight) of the polyol components (A-1) to (A-8) and (A'-1) obtained in Production Examples 5 to 12 and Comparative Production Example 1. Table 2 also shows the hydroxyl values ​​(unit: mg KOH / g) and alkali values ​​(unit: mg KOH / g) of the polyol components (A-1) to (A-8) and (A'-1) obtained in Production Examples 5 to 12 and Comparative Production Example 1. The alkali value is the sum of the alkali value derived from the alkali metal hydroxide (s1) in the polyol component (A) and the alkali value derived from the alkali metal salt of carboxylic acid (s2).

[0077]

[0078] Examples 1 to 9, Comparative Example 1 Polyisocyanate component (B) (polyisocyanate components (B-1) to (B-4)) obtained in Production Examples 1 to 4 and polyol component (A) (polyol components (A-1) to (A-8) and (A'-1)) obtained in Production Examples 5 to 12 and Comparative Production Example 1 were adjusted to 25°C, then charged into a container in the weight ratios shown in Table 3 and mixed at 25°C for 30 seconds to obtain polyurethane resin-forming compositions of Examples 1 to 9 and Comparative Example 1 (polyurethane resin-forming compositions (P-1) to (P-9) and (P'-1)). The resulting polyurethane resin-forming compositions (P-1) to (P-9) and (P'-1) were evaluated for pot life and hardness of the cured product according to the following procedures. The results are shown in Table 3. Table 3 also shows the equivalent ratio of the isocyanate groups in the polyisocyanate component (B) to the hydroxyl groups in the polyol component (A) (isocyanate groups in the polyisocyanate component (B) / hydroxyl groups in the polyol component (A)) (NCO / OH).

[0079] (1) Pot life (unit: min) 100 g of each of the polyurethane resin-forming compositions (P-1) to (P-9) and (P'-1) was placed in a container. In accordance with JIS K6870 (Method 5: Determination based on exothermic reaction temperature (determination using a thermocouple thermometer)), a thermocouple was immersed in the polyurethane resin-forming composition, and the time required for the polyol component (A) and the polyisocyanate component (B) to reach the maximum temperature from the start of mixing was recorded as the pot life. A pot life of 5 to 20 minutes was considered to be adequate.

[0080] (2) Hardness of Cured Product 25 g of each of the polyurethane resin-forming compositions (P-1) to (P-9) and (P'-1) was degassed under reduced pressure and molded into a 1 cm thick sheet. The sheet was then allowed to stand at 25°C for 2 hours from the start of mixing the polyol component (A) and the polyisocyanate component (B) to cure. The hardness of the resulting cured product was measured in accordance with JIS K6253-3. Industrially, it is considered preferable that the hardness of the cured product measured by the above method be 70 or higher. Typically, the hardness of the cured product after complete curing is slightly higher than the hardness of the cured product 2 hours after the start of mixing. Therefore, when comparing the hardness of two or more cured products, a cured product with a higher hardness 2 hours after the start of mixing is generally considered to have a higher hardness after complete curing.

[0081]

[0082] The results in Table 3 show that the polyurethane resin-forming compositions for sealing materials in membrane modules of the present invention, which contain an ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol, and an alkali metal hydroxide (s1) and / or an alkali metal salt of carboxylic acid (s2), and which contain a polyol component (A) (polyol components (A-1) to (A-8) obtained in Production Examples 5 to 12) having an alkali value (the sum of the alkali value derived from the alkali metal hydroxide (s1) and the alkali value derived from the alkali metal salt of carboxylic acid (s2)) of 0.10 to 2.0 mg KOH / g, have a moderate pot life and excellent hardness of the cured product, compared to the polyurethane resin-forming composition of Comparative Example 1 which does not contain the polyol component (A).

[0083] The polyurethane resin-forming composition for a sealant for a membrane module of the present invention has a moderate pot life, resulting in excellent productivity for membrane modules. Furthermore, the polyurethane resin-forming composition for a sealant for a membrane module of the present invention has excellent hardness after curing, so that by using it as a sealant for a membrane module, a membrane module with excellent hardness can be obtained. Therefore, the polyurethane resin-forming composition for a sealant for a membrane module of the present invention is suitable for use as a sealant for membrane modules, and is particularly useful as a sealant for membrane modules in artificial organs such as blood treatment devices and water purifiers.

Claims

1. A polyurethane resin-forming composition for a sealing material of a membrane module, comprising a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) comprises an ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol, an alkali metal hydroxide (s1) and / or an alkali metal salt of a carboxylic acid (s2), and the sum of the alkali value derived from the alkali metal hydroxide (s1) in the polyol component (A) and the alkali value derived from the alkali metal salt of a carboxylic acid (s2) is 0.10 to 2.0 mgKOH / g.

2. A polyurethane resin-forming composition for sealing materials of membrane modules according to claim 1, wherein the polyisocyanate component (B) contains an isocyanate-terminated urethane prepolymer (U) which is a reaction product of an ethylene oxide and / or propylene oxide adduct (A'51) of a dihydric alcohol and / or an ethylene oxide and / or propylene oxide adduct (A52) of a trihydric to hexahydric alcohol with polyisocyanate (b).

3. A polyurethane resin-forming composition for a sealing material of a membrane module according to claim 1, wherein the equivalent ratio of the isocyanate groups in the polyisocyanate component (B) to the hydroxyl groups in the polyol component (A) (isocyanate groups in the polyisocyanate component (B) / hydroxyl groups in the polyol component (A)) is 0.5 to 2.

0.

4. A membrane module sealant comprising the polyurethane resin-forming composition for membrane module sealants according to any one of claims 1 to 3.

5. A membrane module comprising the cured sealant of claim 4.

6. A hollow fiber blood treatment device or water purifier equipped with the membrane module according to claim 5.

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