Polyurethane resin-formable composition for sealant of membrane module

Abstract

To provide a polyurethane resin-formable composition for a sealant of a membrane module, which is excellent in resin strength of a cured product.SOLUTION: A polyurethane resin-formable composition (P) for a sealant of a membrane module, comprises a polyol component (A) and a polyisocyanate component (B), wherein the polyisocyanate component (B) comprises an isocyanate-terminated urethane prepolymer (U) comprising, as constituent monomers, an alkylene oxide adduct (A52) of a trihydric to pentahydric alcohol (the alkylene having 2-3 carbon atoms) and a polyisocyanate (b).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyurethane resin-forming composition for use as a sealing material in a membrane module. [Background technology]

[0002] Conventionally, as a polyurethane resin-forming composition used as a sealing material, 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). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 53-61695 Summary of the Invention [Problem to be solved by the invention]

[0004] However, even with the technology of Patent Document 1, the resin strength of the cured product cannot be said to be fully satisfactory, and a solution to this problem has been sought. An object of the present invention is to provide a polyurethane resin-forming composition for use as a sealing material for membrane modules, which has excellent resin strength when cured. [Means for solving the problem]

[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 (P) for a sealing material of a membrane module, which comprises a polyol component (A) and a polyisocyanate component (B), wherein the polyisocyanate component (B) contains an isocyanate-terminated urethane prepolymer (U) containing, as constituent monomers, an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (A52) of a trihydric to pentahydric alcohol and a polyisocyanate (b). [Effects of the Invention]

[0006] The polyurethane resin-forming composition (P) for a sealing material of a membrane module of the present invention has the following effects. (1) Excellent resin strength after curing. (2) The elution rate of the cured product is low. DETAILED DESCRIPTION OF THE INVENTION

[0007] <Polyol component (A)> Examples of the polyol component (A) in the present invention include castor oil polyol (A1), alkylene oxide (having 2 to 3 carbon atoms) adduct of polyamine (A2), alkylene oxide (having 2 to 3 carbon atoms) adduct of alkanolamine (A3), polyester polyol (A4), polyether polyol (A5), and mixtures of two or more of these.

[0008] Castor oil polyol (A1): Examples of (A1) 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.

[0009] Polyamine alkylene oxide (carbon number 2-3) adduct (A2): Examples of the polyamine (am) constituting (A2) include the following (am1) to (am4), and mixtures of two or more of these. Examples of (A2) include polyamines (a) above to which alkylene oxides such as ethylene oxide (EO) and / or propylene oxide (PO) are added.

[0010] Aliphatic poly(di- to heptavalent)amine (am1): those having 2 or more carbon atoms (hereinafter sometimes abbreviated as C) and Mn of 500 or less, for example, C2-10 alkylenediamines (ethylenediamine, propylenediamine, etc.), polyalkylene (C2-10) poly(trivalent to hexavalent or higher) amines (diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.), and their alkyl (C1-4) or hydroxyalkyl (C2-4) substituted derivatives, for example, dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine;

[0011] Alicyclic poly(di- to trivalent)amine (am2): C4-15, for example, 1,3-diaminocyclohexane, isophoronediamine;

[0012] Heterocycle-containing poly(di- to trivalent)amine (am3): C4-15, for example, piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine;

[0013] Aromatic ring-containing polyamine (am4): C8-15, for example, xylylenediamine, tetrachloro-p-xylylenediamine, diaminodiphenylmethane.

[0014] Alkanolamine alkylene oxide (carbon number 2-3) adduct (A3): The alkanolamine (am5) constituting (A3) is one having 4 to 12 carbon atoms, such as diethanolamine and triethanolamine. Examples of (A3) include those obtained by adding alkylene oxides such as ethylene oxide (EO) and / or propylene oxide (PO) to the above alkanolamines (am5).

[0015] Polyester polyol (A4): Examples of (A4) include condensation type polyester polyols (polyethylene adipate diol, polybutylene adipate diol, etc.), and polylactone polyols (polyhexamethylene carbonate diol, polypentamethylene carbonate diol, etc.).

[0016] Polyether polyol (A5): Examples of (A5) include those other than the above (A1) to (A4), such as alkylene oxide (alkylene having 2 to 3 carbon atoms) adducts of dihydric alcohols (A51) and alkylene oxide (alkylene having 2 to 3 carbon atoms) adducts of trihydric to pentahydric alcohols (A52).

[0017] Examples of the alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (A51) of dihydric alcohol include those obtained by adding alkylene oxide such as ethylene oxide (EO) and / or propylene oxide (PO) to a dihydric alcohol.

[0018] Examples of the dihydric alcohol 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.], and alicyclic ring-containing dihydric alcohols [1,4-cyclohexanediol, cyclohexanedimethanol, etc.].

[0019] Examples of the alkylene oxide (alkylene having 2 to 3 carbon atoms) adducts (A52) of trihydric to pentahydric alcohols include those obtained by adding alkylene oxides such as ethylene oxide (EO) and / or propylene oxide (PO) to trihydric to pentahydric alcohols.

[0020] Examples of the trihydric to pentahydric alcohols include trihydric alcohols [glycerin (hereinafter abbreviated as GR), trimethylolpropane (hereinafter abbreviated as TMP), hexanetriol, etc.], tetrahydric alcohols [pentaerythritol, etc.], and pentahydric alcohols [xylitol, etc.].

[0021] Of the polyol components (A), from the viewpoints of resin strength and elution rate, (A2), (A3), and combinations of these are preferred, (A3) is more preferred, and an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct of ethylenediamine is particularly preferred. Furthermore, based on the weight of the polyol component (A), the total weight of (A2) and (A3) is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

[0022] The hydroxyl value (unit: KOH mg / g) of the polyol component (A) is preferably 150 to 500, more preferably 180 to 400, and particularly preferably 210 to 300, from the viewpoint of resin strength and elution rate. The hydroxyl value (unit: KOH mg / g) in the present invention can be measured by the method described in JIS K1157-1. The number average molecular weight (Mn) of each polyol component (A) is calculated from the above hydroxyl value.

[0023] The amine value (unit: KOHmg / g) of the polyol component (A) is preferably 30-300, and more preferably 60-250. The amine value (unit: KOH mg / g) in the present invention can be measured as a total amine value by the method described in JIS K7237-1995.

[0024] <Polyisocyanate component (B)> The polyisocyanate component (B) in the present invention contains an isocyanate-terminated urethane prepolymer (U) containing, as constituent monomers, an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (A52) of a trihydric to pentahydric alcohol and a polyisocyanate (b). The polyisocyanate component (B) preferably contains (U), and more preferably is (U).

[0025] Examples of the polyisocyanate (b) include aromatic polyisocyanates (b1) having 6 to 20 carbon atoms (excluding carbon atoms in the isocyanate groups, the same applies hereinafter) and having 2 to 3 or more isocyanate groups, aliphatic polyisocyanates (b2) having 2 to 18 carbon atoms, alicyclic polyisocyanates (b3) having 4 to 15 carbon atoms, aromatic aliphatic polyisocyanates (b4) having 8 to 15 carbon atoms, and modified products (b5) of (b1) to (b4). One type of polyisocyanate (b) may be used alone, or two or more types may be used in combination.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] Examples of the aromatic aliphatic polyisocyanate (b4) having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI).

[0030] Examples of the modified products (b5) of (b1) to (b4) include modified products of (b1) to (b4) having 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.

[0031] Among the polyisocyanates (b), (b1) is preferred from the viewpoint of resin strength, and MDI is more preferred.

[0032] Examples of the isocyanate-terminated prepolymer (U) include those obtained by subjecting an excess of polyisocyanate (b) to a urethane reaction with a polyol containing an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (A52) of a trihydric to pentahydric alcohol by a known method.

[0033] The polyol raw material for (U) may contain, in addition to the alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (A52) of a trihydric to pentahydric alcohol, other polyols such as (A1), (A2), (A3), (A4), and (A51). The weight of (A52) is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more, based on the weight of the raw material polyol.

[0034] Among the alkylene oxide (alkylene having 2 to 3 carbon atoms) adducts (A52) of trihydric to pentahydric alcohols, preferred are alkylene oxide (alkylene having 2 to 3 carbon atoms) adducts of trihydric alcohols, and more preferred are propylene oxide adducts of glycerin. The number average molecular weight (Mn) of the above (A52) is preferably 300 to 3,000, more preferably 500 to 1,500, and particularly preferably 700 to 1,200. The number average molecular weight (Mn) of (A52) is a value calculated based on the hydroxyl value of (A52).

[0035] 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 resin strength.

[0036] <Polyurethane resin-forming composition (P) for membrane module sealing material> The polyurethane resin-forming composition (P) for a sealing material of a membrane module of the present invention is a polyurethane resin-forming composition containing the polyol component (A) and the polyisocyanate component (B), and the polyisocyanate component (B) contains an isocyanate-terminated urethane prepolymer (U) containing, as constituent monomers, an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (A52) of a trihydric to pentahydric alcohol and a polyisocyanate (b). A urethanization catalyst (D) can be used in the polyurethane resin-forming composition for sealing materials (P) depending on the intended use and the degree of requirement for rapid curing.

[0037] Examples of (D) include metal catalysts, amine catalysts, etc. Examples of metal catalysts include tin-based catalysts (trimethyltin laurate, trimethyltin hydroxide, etc.), lead-based catalysts (lead oleate, lead 2-ethylhexanoate, etc.), bismuth-based catalysts (bismuth carboxylate, bismuth alkoxide, etc.), titanium-based catalysts (titanium isopropoxytri-N-ethylaminoethyl aminate, 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 naphthenates such as cobalt naphthenate, phenylmercury propionate, etc.).

[0038] The amount of urethanization catalyst (D) used varies depending on the application, but when high speed curing is required, it is preferably 1,000 ppm or less, and particularly preferably 10 to 100 ppm, based on the weight of the composition.

[0039] The equivalent ratio [(B) / (A)] (NCO / OH) of the polyol component (A) to the polyisocyanate component (B) constituting the polyurethane resin-forming composition (P) for a sealing material of a membrane module is preferably 0.5 to 2.0, more preferably 0.7 to 1.5, and particularly preferably 0.8 to 1.2.

[0040] The polyurethane resin-forming composition is composed of, for example, a combination of two components: a polyol component (A) and a polyisocyanate component (B). When a urethanization catalyst (D) is used, a combination of three components (A), (B), and (D) may be used, but for example, a combination of two components is used in which a predetermined amount of (D) is mixed in advance with (A) or (B).

[0041] At the time of use, the components of the polyurethane resin-forming composition are weighed out in predetermined amounts and mixed using a static mixer, mechanical mixer, or the like to react and form a polyurethane resin (a cured product of the forming composition). The gelation time is, for example, 3 to 60 minutes, and complete curing takes, for example, 12 to 240 hours. Complete curing (end point of reaction) is determined when the hardness no longer changes. The time until complete curing can be shortened by increasing the curing temperature (for example, 30 to 60°C).

[0042] The polyurethane resin-forming composition for a membrane module sealant of the present invention is particularly suitable for use as a sealant in blood treatment devices and water purifiers. Examples of blood treatment devices that can be used include hollow fiber, membrane, or coil-type artificial kidneys and plasma separation modules. It can also be used in artificial organs such as artificial lungs.

[0043] When the composition of the present invention is used as a sealing material for a hollow fiber blood treatment device, the following method of use is exemplified. The polyol component (A) and the polyisocyanate component (B) are separately degassed under reduced pressure (0.1 mmHg for 2 hours). These two components are weighed out in predetermined amounts and mixed, and the hollow fibers are embedded in a container by centrifugal molding. An example of the centrifugal molding method is described, for example, in Japanese Patent Publication No. 57-58963. The hollow fibers to be embedded are generally cellulose-based, acrylic-based, polyvinyl alcohol-based, polyamide-based, or polysulfone-based hollow fibers. The container is generally made of polycarbonate, ABS, or polystyrene. The mixture of (A) and (B) gels within 3 to 60 minutes after injection, allowing the module to be removed from the molding machine. The mixture is then cured at room temperature to 60°C to complete hardening. The mixture is then sterilized using steam heating at 121°C for 1 hour in an autoclave, resulting in a finished product. Sterilization can also be carried out by methods other than steam heating, such as ethylene oxide gas or gamma ray irradiation. [Example]

[0044] 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 by weight and % are by weight.

[0045] <Production Example 1> A four-neck flask equipped with a stirrer, thermometer, and nitrogen inlet tube was charged with 60 parts of polyisocyanate (b-1) [a mixture of 4,4'-MDI and 2,4'-MDI, "Lupranate MI" manufactured by BASF Japan Ltd.] and 40 parts of a propylene oxide adduct of glycerin (Mn: 1,500) (A52-1), and the mixture was reacted for 4 hours at 70-80°C under a nitrogen stream to obtain a polyisocyanate component (B-1) containing an isocyanate-terminated urethane prepolymer (U-1). The isocyanate content (NCO%) of (B-1) was 16.8%.

[0046] <Production Examples 2 to 6, Comparative Production Example 1> In Production Example 1, polyisocyanate components (B) containing each isocyanate group-terminated urethane prepolymer (U) were obtained in the same manner as in Production Example 1, except that the raw materials (parts) in Table 1 were used.

[0047] <Examples 1 to 9, Comparative Examples 1 and 2> The raw materials (parts) shown in Table 1 were charged into a vessel and stirred to prepare each polyol component (A). Next, each polyisocyanate component (B) and each polyol component (A) were charged into a container in the weight ratio [(B) / (A)] shown in Table 1 and mixed at 25°C to obtain each polyurethane resin-forming composition (P), which was then evaluated according to the following procedures. The results are shown in Table 1.

[0048] <Resin strength: tear strength (N / mm)> Each of the obtained polyurethane resin-forming compositions (P) was mixed at 25°C, degassed under reduced pressure, and a 1 mm thick resin sheet was prepared. In accordance with JIS K6251, an angle-shaped test piece was cut out using a punching die for angle-shaped test pieces, and the tear strength was measured at a temperature of 23°C, a relative humidity of 50%, and a tear speed of 500 mm / min.

[0049] <Elution rate (%)> The resin sheet prepared above was cut into 10 mm squares, weighed out at 4.5±0.1 g, placed in a container, and extracted for 24 hours at 50°C with approximately 40 ml of ethanol, an extraction solvent. The resin pieces were then removed, the ethanol was distilled off, the pieces were dried, and the weight was measured. The elution rate (%) was calculated using the following formula. Elution rate (%) = (weight of container after drying - weight of container before use) x 100 / (weight of resin piece)

[0050] [Table 1]

[0051] The raw materials in Table 1 are as follows: Polyisocyanate (b-1): A mixture of 4,4'-MDI and 2,4'-MDI, manufactured by BASF Japan Ltd., "Lupranate MI" (A52-1): Glycerin propylene oxide adduct, Mn: 1,500 (A52-2): Propylene oxide adduct of glycerin, Mn: 400 (A52-3): Glycerin propylene oxide adduct, Mn: 3,000 (A52-4): Propylene oxide adduct of pentaerythritol, Mn: 2,000 (A1-1): Castor oil, Toyokuni Oil Mills, "ELA-DR" (A51-1): Propylene glycol propylene glycol adduct, Mn: 1,000 (A2-1): Propylene oxide adduct of ethylenediamine, Mn: 1,000 (A2-2): Propylene oxide adduct of ethylenediamine, Mn: 500 (A2-1): Propylene oxide adduct of ethylenediamine, Mn: 1,500 (A3-1): Propylene glycol adduct of triethanolamine, Mn: 730

[0052] The results in Table 1 show that the polyurethane resin-forming composition (P) for a sealing material of a membrane module of the present invention is superior in resin strength and elution rate compared to the comparative compositions. [Industrial Applicability]

[0053] The polyurethane resin-forming composition for membrane module sealing materials of the present invention has excellent resin strength and a low elution rate, and therefore little elution from membrane modules using the composition into treatment liquids, making it particularly useful as a sealing material for artificial organs such as blood treatment devices and water purifiers. Furthermore, the cured resin obtained from the composition has excellent electrical insulation properties, water resistance, and adhesion to various substrates, making it suitable for use in electrical insulation applications such as sealing electronic circuit boards, waterproof applications such as sealing optical fiber cable connections, building materials such as bonding insulated aluminum sashes and aluminum honeycomb panels, potting materials for automobile emblems and side moldings, and laminate bonding of various films.

Claims

1. The polyurethane resin-forming composition (P) for use as a sealing material for a membrane module contains a polyol component (A) and a polyisocyanate component (B), wherein the polyisocyanate component (B) contains an isocyanate-terminated urethane prepolymer (U) containing, as constituent monomers, an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (A52) of a trihydric to pentahydric alcohol and a polyisocyanate (b).

2. The polyurethane resin-forming composition for a sealing material of a membrane module according to claim 1, wherein the polyol component (A) contains an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (A2) of a polyamine and / or an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (A3) of an alkanolamine.

3. 2. The polyurethane resin-forming composition according to claim 1, wherein the equivalent ratio of the polyol component (A) to the polyisocyanate component (B) [(A) / (B)] is 0.5 to 2.

0.

4. A sealing material for a membrane module, which is obtained by using the composition according to any one of claims 1 to 3.

5. A membrane module comprising the sealing material according to claim 4.

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

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