Polyurethane resin-forming composition for membrane sealing materials, membrane sealing material and membrane module

Abstract

To provide a polyurethane resin formative composition which enables formation of a cured product where elution of a low molecular reactant is suppressed, and suppresses reaction heat in molding.SOLUTION: A polyurethane resin formative composition for a film seal material contains a polyisocyanate prepolymer (A), and a polyol component (B), wherein the polyisocyanate prepolymer (A) contains a reaction product of a modified body (a1-1) of hexamethylene diisocyanate, at least one (a1-2) selected from the group consisting of aromatic diisocyanate and its modified body, and an active hydrogen-containing compound (a2), and the polyol component (B) contains polymerized castor oil (b1) and a hydroxyl group-containing amine compound (b2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyurethane resin-forming composition for a film sealing material, a film sealing material, and a film module.

Background Art

[0002] A polyurethane resin-forming composition containing an aromatic diisocyanate such as diphenylmethane diisocyanate and a polyol can be used for a film sealing material for fixing and sealing a film such as a hollow fiber membrane. Examples of the polyol in the polyurethane resin-forming composition include castor oil polymers (see Patent Document 1, etc.).

[0003] When a cured product formed from an aromatic diisocyanate and a polyol is used in a sealing material for a film containing glycerin, the aromatic diisocyanate present in the cured product may react with glycerin, and low molecular weight reaction products among the reaction products may elute into the liquid contacting the film. From the viewpoint of suppressing the elution of low molecular weight reaction products formed by the reaction between an aromatic diisocyanate and glycerin, various proposals have been made so far. Patent Document 2 discloses a polyurethane resin-forming composition for a film sealing material containing a polyisocyanate prepolymer (A) and a polyol (B), wherein the polyol (B) contains a predetermined amount of a castor oil polymer having a number average molecular weight of 1500 or more.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the polyurethane resin-forming composition described in Patent Document 2 had room for improvement in that it had high initial reaction heat during molding, which could cause molding shrinkage and thermal degradation of other components (such as hollow fibers).

[0006] One aspect of this disclosure is directed to provide a polyurethane resin-forming composition that can form a cured product with suppressed elution of low molecular weight reactants and suppressed reaction heat during molding. Another aspect of this disclosure is directed to provide a film sealing material and a film module using the above polyurethane resin-forming composition. [Means for solving the problem]

[0007] Each aspect of this disclosure provides the following embodiments [1] to [9]. [1] A polyurethane resin-forming composition for film sealing materials, comprising a polyisocyanate prepolymer (A) and a polyol component (B), wherein the polyisocyanate prepolymer (A) contains a reaction product of a modified hexamethylene diisocyanate (a1-1), at least one selected from the group consisting of aromatic diisocyanates and their modified forms (a1-2), and an active hydrogen-containing compound (a2), and the polyol component (B) comprises polymerized castor oil (b1) and a hydroxyl group-containing amine compound (b2). [2] The polyurethane resin-forming composition for film sealing materials according to [1], wherein the number average molecular weight of the polymerized castor oil (b1) is 1500 or more. [3] The polyurethane resin-forming composition for film sealing materials according to [1] or [2], wherein the aromatic diisocyanate is diphenylmethane diisocyanate. [4] The polyurethane resin-forming composition for film sealing materials according to any one of [1] to [3], wherein the content of the polymerized castor oil (b1) is 1.0% by mass or more and 30.0% by mass or less with respect to the total amount of the polyisocyanate prepolymer (A) and the polyol component (B). [5] The polyurethane resin-forming composition for film sealing materials according to any one of [1] to [4], wherein the polyol component (B) further comprises a castor oil-based polyol (b3) other than the polymerized castor oil (b1). [6] The polyurethane resin-forming composition for film sealing material according to any one of [1] to [5], wherein the content of the hydroxyl group-containing amine compound (b2) is 1 part by mass or more and 40 parts by mass or less per 100 parts by mass of the total amount of the polyol component (B). [7] A film sealing material comprising a cured product of a polyurethane resin-forming composition for film sealing materials described in any of [1] to [6]. [8] A membrane module comprising a main body, a membrane, and a membrane sealing material described in [7] for sealing the gap between the main body and the membrane. [9] The membrane module according to [8], wherein the membrane is a plurality of hollow fiber membranes, and the membrane sealing material seals the gap between the main body and at least a portion of the plurality of hollow fiber membranes, and at least a portion of the gaps between the plurality of hollow fiber membranes. [Effects of the Invention]

[0008] According to one aspect of this disclosure, it is possible to provide a polyurethane resin-forming composition that enables the formation of a cured product in which the elution of low molecular weight reactants is suppressed, and in which the reaction heat during molding is suppressed. According to one aspect of this disclosure, it is possible to provide a film sealing material and a film module using the above polyurethane resin-forming composition. [Brief explanation of the drawing]

[0009] [Figure 1] This is a conceptual diagram showing an example of the configuration of a membrane module according to one embodiment of the present disclosure. [Modes for carrying out the invention]

[0010] Several embodiments of the present invention will be described below. However, the present invention is not limited in any way to the embodiments described below.

[0011] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. Unless otherwise specified, the units of the numbers before and after "~" are the same. In numerical ranges described in stages within this specification, the upper or lower limit of one stage may be replaced with the upper or lower limit of another stage. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. Also, individually stated upper and lower limits can be combined in any way. The materials exemplified below may be used individually or in combination of two or more, unless otherwise specified. The content of each component in a composition, if multiple substances corresponding to each component exist in the composition, means the total amount of those multiple substances present in the composition, unless otherwise specified.

[0012] [Polyurethane resin-forming composition] A polyurethane resin-forming composition according to one embodiment of the present disclosure comprises a polyisocyanate prepolymer (A) and a polyol component (B). The polyisocyanate prepolymer (A) contains a reaction product of a modified hexamethylene diisocyanate (a1-1), at least one selected from the group consisting of aromatic diisocyanates and their modified forms (a1-2), and an active hydrogen-containing compound (a2). The polyol component (B) comprises polymerized castor oil (b1) and a hydroxyl-containing amine compound (b2).

[0013] The polyurethane resin-forming composition may be a one-component composition in which a polyisocyanate prepolymer (A) and a polyol component (B) are mixed in one liquid, or it may be a two-component composition comprising a first liquid containing the polyisocyanate prepolymer (A) and a second liquid containing the polyol component (B).

[0014] <Polyisocyanate prepolymer (A)> The polyisocyanate prepolymer (A) contains a reaction product of a modified product (a1-1) of hexamethylene diisocyanate (HDI), at least one (a1-2) selected from the group consisting of an aromatic diisocyanate and its modified product, and an active hydrogen-containing compound (a2).

[0015] The content of isocyanate groups in the polyisocyanate prepolymer (A) may be 5.0% by mass or more, 7.0% by mass or more, 8.0% by mass or more, 9.0% by mass or more, 10.0% by mass or more, 13.0% by mass or more, 13.5% by mass or more, 14.0% by mass or more, 15.0% by mass or more, 16.0% by mass or more, 17.0% by mass or more, or 18.0% by mass or more based on the total mass of the polyisocyanate prepolymer (A). The content of isocyanate groups in the polyisocyanate prepolymer (A) may be 35.0% by mass or less, 30.0% by mass or less, 28.0% by mass or less, 26.0% by mass or less, 24.0% by mass or less, 22.0% by mass or less, 21.0% by mass or less, 20.5% by mass or less, or 20.0% by mass or less based on the total mass of the polyisocyanate prepolymer (A). Preferably, the content of isocyanate groups in the polyisocyanate prepolymer (A) is 13.0% by mass or more and 21.0% by mass or less, more preferably 13.5% by mass or more and 20.5% by mass or less, and particularly preferably 14.0% by mass or more and 20.0% by mass or less. When the content of isocyanate groups in the polyisocyanate prepolymer (A) is within the above-mentioned range, the molding processability and adhesion strength of the polyurethane resin are further excellent.

[0016] The content of isocyanate groups in the polyisocyanate prepolymer (A) is measured in accordance with JIS K1603-1:2007.

[0017] The viscosity of the polyisocyanate prepolymer (A) at 25°C may be, for example, 800 mPa·s or more, 900 mPa·s or more, 1000 mPa·s or more, 1100 mPa·s or more, or 1200 mPa·s or more, and may be 2500 mPa·s or less, 2000 mPa·s or less, 1800 mPa·s or less, or 1500 mPa·s or less. The viscosity of the polyisocyanate prepolymer (A) at 25°C is the viscosity measured by a B-type rotational viscometer under a 25°C atmosphere.

[0018] The crosslinking group density of the polyisocyanate prepolymer (A) may be 0.30 mmol / g or more, 0.35 mmol / g or more, 0.40 mmol / g or more, or 0.45 mmol / g or more, and may be 1.50 mmol / g or less, 1.25 mmol / g or less, or 1.00 mmol / g or less, based on the total mass of the polyisocyanate prepolymer (A). The crosslinking group density of the polyisocyanate prepolymer (A) is measured by the method described in the examples below.

[0019] <<Modified product (a1-1) of hexamethylene diisocyanate>> The modified product (a1-1) of hexamethylene diisocyanate is not particularly limited, and examples include urethane-modified products, urea-modified products, allophanate-modified products, biuret-modified products, carbodiimide-modified products, uretonimine-modified products, uretdione-modified products, and isocyanurate-modified products of HDI. The modified product (a1-1) of hexamethylene diisocyanate may be used alone or in combination of two or more. The modified product (a1-1) of hexamethylene diisocyanate may be an isocyanurate-modified product of HDI.

[0020] The content of isocyanate groups in the modified product (a1-1) of hexamethylene diisocyanate may be 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, and may be 35% by mass or less, 30% by mass or less, or 25% by mass or less, based on the total mass of the modified product (a1-1) of hexamethylene diisocyanate.

[0021] The content of the modified hexamethylene diisocyanate (a1-1) relative to 100 parts by mass of the total amount of polyisocyanate prepolymer (A) may be 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more, and may be 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, or 55 parts by mass or less, since this further improves the effect of suppressing the initial reaction heat during molding.

[0022] The content of the modified hexamethylene diisocyanate (a1-1) may be 5% by mass or more, 8% by mass or more, 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, or 20% by mass or more, and may be 35% by mass or less, 30% by mass or less, or 25% by mass or less, based on the total mass of the polyurethane resin-forming composition, in order to further improve the effect of suppressing the initial reaction heat during molding. The content of the modified hexamethylene diisocyanate (a1-1) is preferably 5% by mass or more and 35% by mass or less, more preferably 8% by mass or more and 30% by mass or less, and particularly preferably 10% by mass or more and 25% by mass or less, based on the total mass of the polyurethane resin-forming composition. When the content of the modified hexamethylene diisocyanate (a1-1) is within the above range, the initial reaction heat during molding of the polyurethane resin can be suppressed.

[0023] <<Aromatic diisocyanates and their modified forms (a1-2)>> Aromatic diisocyanates are compounds that contain an aromatic ring and two isocyanate groups directly bonded to the aromatic ring within their molecule. Examples of aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, a mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and 4,4'-diphenyl ethyl Examples include diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropanediisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0024] Modified aromatic diisocyanates are not particularly limited, but examples include urethane modified compounds, carbodiimide modified compounds, polymeric compounds, urea modified compounds, allophanate modified compounds, biuret modified compounds, uretonimine modified compounds, and uretdione modified compounds. Modified aromatic diisocyanates may be used individually or in mixtures of two or more.

[0025] At least one (a1-2) selected from the group consisting of aromatic diisocyanates and their modified forms may be included in the composition, as this further suppresses solvent elution from the cured product. The content of the aromatic diisocyanate modified form may be 1% by mass or 2% by mass or more, based on the total mass of the polyurethane resin-forming composition, and may be 30% by mass or less, or 25% by mass or less, as this further suppresses the increase in liquid viscosity and further improves fillability (moldability). Within the above range, the low molecular weight elution value and solvent extraction value are further improved.

[0026] At least one (a1-2) selected from the group consisting of aromatic diisocyanates and their modified forms may include at least one selected from the group consisting of diphenylmethane diisocyanate (MDI) and its modified forms. MDI may be any MDI monomer that is generally available. The MDI monomer may include at least one selected from the group consisting of 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI. In the MDI monomer, the content of 2,2'-MDI may be 0% to 5% by mass, the content of 2,4'-MDI may be 0% to 95% by mass, and the content of 4,4'-MDI may be 5% to 100% by mass, based on the total mass of the MDI monomer. MDI is defined with 4,4'-MDI as the main component and 2,2'-MDI and 2,4'-MDI as isomer components.

[0027] The content of at least one (a1-2) selected from the group consisting of aromatic diisocyanates and their modified forms may be 20 parts by mass or more, 25 parts by mass or more, or 30 parts by mass or more, and may be 60 parts by mass or less, 55 parts by mass or less, or 50 parts by mass or less, based on 100 parts by mass of the total amount of polyisocyanate prepolymer (A).

[0028] The content of aromatic diisocyanate monomers in the polyisocyanate prepolymer (A) may be 10.0% by mass or more, 15.0% by mass or more, or 20.0% by mass or more, and may be 45.0% by mass or less, 40.0% by mass or less, 35.0% by mass or less, or 31.0% by mass or less, based on the total mass of the polyisocyanate prepolymer (A). The monomer content of aromatic diisocyanate in the polyisocyanate prepolymer (A) is measured by the method described in the examples below.

[0029] The content of aromatic diisocyanate monomers in the polyurethane resin-forming composition is preferably 30.0% by mass or less, 25.0% by mass or less, 23% by mass or less, 21% by mass or less, 20.0% by mass or less, 19% by mass or less, or 18.0% by mass or less, based on the total amount of the polyurethane resin-forming composition, in order to further improve the effect of suppressing the elution of low molecular weight reactants. The content of isocyanate monomers in the polyurethane resin-forming composition may be 5.0% by mass or more, 7.0% by mass or more, 9.0% by mass or more, or 11.0% by mass or more, based on the total amount of the polyurethane resin-forming composition. The content of MDI monomers in the polyurethane resin-forming composition may be within the above-mentioned numerical range as the content of aromatic diisocyanate monomers, based on the total amount of the polyurethane resin-forming composition. The content of isocyanate monomers in the polyurethane resin-forming composition is measured by GPC. Details of the measurement conditions may be as shown in the examples.

[0030] <<Active hydrogen-containing compound (a2)>> The active hydrogen-containing compound (a2) may be a compound having two or more active hydrogen groups. Examples of active hydrogen groups include hydroxyl groups, amino groups, carboxyl groups, and thiol groups.

[0031] The number of active hydrogen groups in the active hydrogen-containing compound (a2) may be two or more per molecule, and may be 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0032] The active hydrogen-containing compound (a2) may be, for example, a polyol. A polyol is a compound having two or more hydroxyl groups. Examples of polyols include castor oil-based polyols, low molecular weight polyols, polyether-based polyols, polyester-based polyols, polylactone-based polyols, and polyolefin-based polyols.

[0033] Examples of castor oil-based polyols include castor oil, partially dehydrated castor oil, polymerized castor oil, diglycerides and monoglycerides of castor oil fatty acids, and reaction products of castor oil or castor oil fatty acids with other polyols. The castor oil may be, for example, refined castor oil. Partially dehydrated castor oil is castor oil from which some of the hydroxyl groups have been removed by a dehydration reaction (intramolecular dehydration reaction). Polymerized castor oil is a polymer obtained by polymerizing castor oil alone.

[0034] Castor oil-based polyols may have a linear or branched structure. The main component of castor oil is ricinoleic acid triglyceride. Castor oil includes hydrogenated castor oil. The main component of castor oil fatty acids is ricinoleic acid, and castor oil fatty acids include hydrogenated castor oil fatty acids. Other polyols may be at least one selected from the group consisting of, for example, low molecular weight polyols and polyether polyols.

[0035] Examples of reaction products between castor oil or castor oil fatty acids and other polyols include mono, di, and triesters of castor oil fatty acids and trimethylol alkanes; mono, di, and triesters of castor oil fatty acids and polypropylene glycol; and the like.

[0036] Examples of trimethylol alkanes include trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, trimethylolpentane, trimethylolhexane, trimethylolheptane, trimethyloloctane, trimethylolnonane, and trimethyloldecane.

[0037] The number-average molecular weight of the castor oil-based polyol may be 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, or 900 or more, and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, or 1000 or less. Preferably, the number-average molecular weight of the castor oil-based polyol is 400 or more and 3000 or less, and more preferably 500 or more and 2500 or less. When the number-average molecular weight of the castor oil-based polyol is 400 or more and 3000 or less, a cured resin with even better physical properties, particularly mechanical properties, required for film sealing materials can be formed. The number-average molecular weights used herein are those measured by the method described in the examples later.

[0038] The hydroxyl value of castor oil-based polyols may be 20 mg KOH / g or more, 40 mg KOH / g or more, 60 mg KOH / g or more, 80 mg KOH / g or more, 100 mg KOH / g or more, or 110 mg KOH / g or more, and may be 300 mg KOH / g or less, 250 mg KOH / g or less, 200 mg KOH / g or less, 150 mg KOH / g or less, or 130 mg KOH / g or less. Preferably, the hydroxyl value of castor oil-based polyols is 20 mg KOH / g or more and 300 mg KOH / g or less, and more preferably 40 mg KOH / g or more and 250 mg KOH / g or less. When the hydroxyl value is 20 mg KOH / g or more and 300 mg KOH / g or less, a cured resin with even better physical properties, particularly mechanical properties, required for film sealing materials can be formed. Furthermore, this can improve the productivity of membrane sealing materials, and consequently, the productivity of hollow fiber membrane modules.

[0039] In this specification, "hydroxyl value" refers to the number of hydroxyl groups and equivalent amounts of potassium hydroxide in milligrams (mg) per gram of sample, and is measured in accordance with JIS K1557-1.

[0040] Examples of low molecular weight polyols include divalent polyols such as ethylene glycol, diethylene glycol, propylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, neopentyl glycol, and hydrogenated bisphenol A, as well as trivalent to octavalent polyols such as glycerin, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, and sucrose. The molecular weight or number-average molecular weight of the low molecular weight polyol is preferably 50 or more and 200 or less.

[0041] Examples of polyether-based polyols include adducts of the above-mentioned low-molecular-weight polyols with alkylene oxides (alkylene oxides with 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, and butylene oxide), and ring-opening polymers of alkylene oxides. Specifically, examples include polypropylene glycol, polyethylene glycol, polytetramethylene ether glycol, or copolymers of ethylene oxide and propylene oxide.

[0042] The number-average molecular weight of the polyether-based polyol is preferably 200 to 7000, and more preferably 500 to 5000, from the viewpoint of further improving moldability during the manufacture of the film sealing material.

[0043] Examples of polyester polyols include those obtained by condensation polymerization of polycarboxylic acids and polyols. Examples of polycarboxylic acids used in polyester polyols include adipic acid, azelaic acid, dodecanediic acid, maleic acid, fumaric acid, itaconic acid, dimerized linoleic acid, phthalic acid, isophthalic acid, terephthalic acid, and other aliphatic saturated and unsaturated polycarboxylic acids, as well as aromatic polycarboxylic acids. Examples of polyols used in polyester polyols include the low molecular weight polyols and polyether polyols mentioned above.

[0044] The number-average molecular weight of the polyester polyol is preferably between 200 and 5000, and more preferably between 500 and 3000. When the number-average molecular weight of the polyester polyol is between 200 and 5000, the moldability when forming the film sealing material is particularly excellent.

[0045] Examples of polylactone-based polyols include polyols obtained by addition polymerization of ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, and β-methyl-δ-valerolactone, etc., in the presence of a catalyst such as an organometallic compound, a metal chelate compound, or a fatty acid metal acyl compound, with glycols or triols as polymerization initiators. The number average molecular weight of the polylactone-based polyol is preferably 200 to 5000, and more preferably 500 to 3000. When the number average molecular weight of the polylactone-based polyol is 200 to 5000, it exhibits particularly excellent moldability when forming film sealing materials.

[0046] Examples of polyolefin-based polyols include polybutadiene, or polybutadiene-based polyols obtained by introducing hydroxyl groups to the terminals of a copolymer of butadiene and styrene or acrylonitrile. Other examples include polyether ester polyols obtained by adding alkylene oxides, such as ethylene oxide or propylene oxide, to polyesters having carboxyl groups and hydroxyl groups at their terminals.

[0047] The active hydrogen-containing compound (a2) is preferably a castor oil-based polyol, considering its compatibility with the polyol component (B), and is even more preferably a partially dehydrated castor oil, as this further improves the effect of suppressing the elution of low molecular weight reactants.

[0048] The content of the active hydrogen-containing compound (a2) may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, and may be 40 parts by mass or less, 35 parts by mass or less, or 30 parts by mass or less, based on 100 parts by mass of the total amount of polyisocyanate prepolymer (A).

[0049] <<Method for producing polyisocyanate prepolymer (A)>> The polyisocyanate prepolymer (A) can be obtained by a method comprising the step of reacting a modified hexamethylene diisocyanate (a1-1), at least one compound (a1-2) selected from the group consisting of aromatic diisocyanates and their modified forms, and an active hydrogen-containing compound (a2). The reaction conditions may be those used in the reaction to form a typical polyisocyanate prepolymer. The polyisocyanate prepolymer (A) can be obtained, for example, by heating a reaction mixture containing the above components (a1-1), (a1-2), and (a2). The heating temperature may be, for example, 50 to 90°C or 60 to 80°C, and the heating time may be 1 to 8 hours or 3 to 5 hours. The reaction may proceed with stirring.

[0050] <Polyol component (B)> Polyol component (B) includes polymerized castor oil (b1) (hereinafter also referred to as "component (b1)") and a hydroxyl group-containing amine compound (b2) (hereinafter also referred to as "component (b2)"). Polyol component (B) may further contain castor oil-based polyols other than polymerized castor oil (b1) (b3) (hereinafter also referred to as "component (b3)"), and may further contain active hydrogen-containing compounds (b4) (hereinafter also referred to as "component (b4)") that do not fall under any of components (b1), (b2), or (b3).

[0051] The hydroxyl value of polyol component (B) may be 50 mg KOH / g or more, 75 mg KOH / g or more, 100 mg KOH / g or more, 150 mg KOH / g or more, 200 mg KOH / g or more, 250 mg KOH / g or more, 280 mg KOH / g or more, 300 mg KOH / g or more, 310 mg KOH / g or more, or 320 mg KOH / g or more, and may be 1000 mg KOH / g or less, 750 mg KOH / g or less, 500 mg KOH / g or less, 450 mg KOH / g or less, 400 mg KOH / g or less, 380 mg KOH / g or less, 360 mg KOH / g or less, or 350 mg KOH / g or less. The hydroxyl value of polyol component (B) is preferably 50 mg KOH / g or more and 1000 mg KOH / g or less, and more preferably 75 mg KOH / g or more and 750 mg KOH / g or less from the viewpoint of ease of handling of polyol component (B). From the viewpoint of excellent moldability and adhesive strength of the polyurethane resin, the hydroxyl value of polyol component (B) is most preferably 100 mg KOH / g or more and 500 mg KOH / g or less.

[0052] The crosslinking group density of polyol component (B) may be 1.50 mmol / g or more, 1.75 mmol / g or more, 2.00 mmol / g or more, or 2.20 mmol / g or more, based on the total mass of polyol component (B), and may be 4.00 mmol / g or less, 3.75 mmol / g or less, 3.50 mmol / g or less, or 3.30 mmol / g or less.

[0053] The viscosity of polyol component (B) at 25°C may be 10,000 mPa·s or less, 9,000 mPa·s or less, or 8,000 mPa·s or less, and may be 800 mPa·s or more, 1,000 mPa·s or more, or 1,200 mPa·s or more. The viscosity of polyol component (B) at 25°C refers to the value measured by a type B rotational viscometer in a 25°C atmosphere.

[0054] The ratio of the total number of moles of isocyanate groups in the polyisocyanate prepolymer (A) to the total number of moles of active hydrogen groups in the polyol component (B) (isocyanate groups / active hydrogen groups) may be 0.95 or more, or 1.00 or more, and may be 1.10 or less, or 1.05 or less.

[0055] <<Polymerized castor oil (b1)>> (b1) Component is a polymerization reaction product obtained by polymerizing castor oil alone. Component (b1) can be obtained, for example, by polymerizing castor oil in a reaction mixture containing castor oil and an organic peroxide. Including component (b1) provides superior effects in improving processability during molding and suppressing leaching.

[0056] (b1) The number-average molecular weight of the component may be 1500 or more, 1600 or more, 1700 or more, 1800 or more, 1900 or more, or 2000 or more, and may be 3000 or less, 2800 or less, 2600 or less, 2400 or less, or 2200 or less.

[0057] (b1) The proportion of components in which the number average molecular weight is 1500 or more may be 40% by mass or more, 45% by mass or more, 50% by mass or more, or 52% by mass or more, and may be 70% by mass or less, 65% by mass or less, 60% by mass or less, or 56% by mass or less, based on the total mass of components (b1).

[0058] (b1) The hydroxyl value of component (b1) may be 100 mg KOH / g or more, 110 mg KOH / g or more, 120 mg KOH / g or more, 130 mg KOH / g or more, 140 mg KOH / g or more, or 150 mg KOH / g or more, and may be 180 mg KOH / g or less, 170 mg KOH / g or less, or 160 mg KOH / g or less.

[0059] The viscosity of component (b1) at 25°C may be 6000 mPa·s or less, 5500 mPa·s or less, or 5000 mPa·s or less, and may be 3000 mPa·s or more, 3500 mPa·s or more, 4000 mPa·s or more, or 4500 mPa·s or more. The viscosity of component (b1) at 25°C refers to the value measured by a Type B rotational viscometer in a 25°C atmosphere.

[0060] The content of component (b1) may be 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, and may be 85 parts by mass or less, or 75 parts by mass or less, based on 100 parts by mass of the total amount of polyol component (B).

[0061] The content of component (b1) may be 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 5.0% by mass or more, or 8.0% by mass or more, based on the total mass of the polyisocyanate prepolymer (A) and polyol component (B), and may be 30.0% by mass or less, 25.0% by mass or less, 20.0% by mass or less, or 18.0% by mass or less. The content of component (b1) is preferably 1.0% by mass or more and 30.0% by mass or less, more preferably 2.0% by mass or more and 30.0% by mass or less, and particularly preferably 3.0% by mass or more and 25.0% by mass or less, based on the total mass of the polyisocyanate prepolymer (A) and polyol component (B). The proportion of components in component (b1) with a number average molecular weight of 1500 or more may be within the numerical range stated as the content of component (b1), based on the total mass of the polyisocyanate prepolymer (A) and polyol component (B). (b1) When the content of component is within the range described above, the moldability of the polyurethane resin and the suppression of elution are further improved.

[0062] <<Hydroxyl group-containing amine compound (b2)>> (b2) The component is a compound containing a hydroxyl group (-OH) and a substituted or unsubstituted amino group. The substituted amino group is, for example, a monosubstituted amino group or a disubstituted amino group.

[0063] The number of hydroxyl groups per molecule of a hydroxyl-containing amine compound may be, for example, 1 or more, 2 or more, or 3 or more, and may be 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less. The total number of substituted amino groups and unsubstituted amino groups per molecule of a hydroxyl-containing amine compound may be, for example, 1 or more, or 2 or more, and may be 8 or less, 6 or less, 4 or less, or 3 or less.

[0064] (b2) Examples of components include alkyldiethanolamines such as linear or branched butyldiethanolamine, hexyldiethanolamine, octyldiethanolamine, lauryldiethanolamine, myristyldiethanolamine, cetyldiethanolamine, and stearyldiethanolamine; low molecular weight polyamines having hydroxyl groups; and low molecular weight amino alcohols.

[0065] (b2) Component may be, for example, an oxyalkylated derivative of an amine compound, or an amino alcohol or a derivative thereof. An oxyalkylated derivative of an amine compound may be, for example, an adduct of alkylene oxide of alkylenediamine. Examples of alkylene oxide adducts of alkylenediamine include N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine and N,N,N',N'-tetrakis[2-hydroxyethyl]ethylenediamine, which are adducts of propylene oxide or ethylene oxide of ethylenediamine. Examples of amino alcohols or derivatives thereof include monoethanolamine, diethanolamine, triethanolamine, and N-methyl-N,N'-diethanolamine.

[0066] (b2) Component is preferably a propylene oxide or ethylene oxide adduct of an amino compound such as ethylenediamine, and more preferably N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine. Using N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine provides further benefits such as improved processability during molding and reduced elution.

[0067] The content of component (b2) may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, or 25 parts by mass or more, and may be 45 parts by mass or less, 40 parts by mass or less, or 35 parts by mass or less, per 100 parts by mass of the total amount of polyol component (B). Preferably, the content of component (b2) is 1 part by mass or more and 40 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, and particularly preferably 10 parts by mass or more and 35 parts by mass or less, per 100 parts by mass of the total amount of polyol component (B). When the content of component (b2) is 5 parts by mass or more per 100 parts by mass of the total amount of polyol component (B), component (b2) exhibits its function more effectively and produces an even greater effect. When the content of component (b2) is 40 parts by mass or less per 100 parts by mass of the total amount of polyol component (B), the initial reaction heat during molding of the polyurethane resin is suppressed, workability is further improved and filling properties are ensured, and the hardness of the resulting film sealant is further suppressed.

[0068] <<Castor oil-based polyols other than polymerized castor oil (b1) (b3)>> As for castor oil-based polyols (b3) other than polymerized castor oil (b1), it is preferable that they be castor oil-based polyols listed in the active hydrogen-containing compound (a2).

[0069] (b3) The component may include at least one selected from the group consisting of castor oil and partially dehydrated castor oil, and may include partially dehydrated castor oil.

[0070] (b3) The content of component (b3) may be 10% by mass or more, 20% by mass or more, or 30% by mass or more, and may be 50% by mass or less, 45% by mass or less, or 40% by mass or less, based on the total mass of polyisocyanate prepolymer (A) and polyol component (B).

[0071] <<Other active hydrogen-containing compounds (b4)>> Component (b4) is a component that does not fall under any of components (b1), (b2), or (b3). Various polyols other than the castor oil-based polyol exemplified as the active hydrogen-containing compound (a2) can be used. Examples of component (b4) include low molecular weight polyols, polyether-based polyols, polyester-based polyols, polylactone-based polyols, polyolefin-based polyols, etc.

[0072] (b4) The content of component (b4) may be 15 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, or 1 part by mass or more, or 3 parts by mass or more, per 100 parts by mass of the total amount of polyol component (B).

[0073] The mass ratio (Mb3 / Mb4) of the content of component (b3) to the content of component (b4) Mb4 is preferably 50 / 50 or more and 100 / 0 or less, and 100 / 0 is particularly preferred.

[0074] The mass ratio of the content of component (b2) Mb2 to the total content of component (b1) and component (b3) (Mb1+Mb3) (Mb2) / {(Mb1)+(Mb3)} is preferably 5 / 95 or more and 30 / 70 or less, preferably 5 / 95 or more and 40 / 60 or less from the viewpoint of curability and filling properties, and more preferably 10 / 90 or more and 35 / 65 or less from the viewpoint of curability and filling properties.

[0075] The polyurethane resin-forming composition may further contain a catalyst. When a catalyst is included, the curing time is further shortened, the reaction temperature is lowered, and the molding shrinkage of the film sealant can be further suppressed.

[0076] The polyurethane resin-forming composition can form a cured product in which the elution of low-molecular-weight reactants is suppressed. Specific examples of low-molecular-weight reactants include the low-molecular-weight components among the reaction products between glycerin and aromatic diisocyanate monomers (e.g., MDI monomers) in the cured product. The elution of low-molecular-weight reactants is evaluated by the low-molecular-weight elution value measured by the method described in the examples below. The low-molecular-weight elution value of the cured product of the polyurethane resin-forming composition may be, for example, 0.050 or less.

[0077] The polyurethane resin-forming composition has suppressed reaction heat during molding. The reaction heat during molding is evaluated by the maximum temperature reached, which is measured by the method described in the examples below. The maximum temperature reached in the polyurethane resin-forming composition may be 95°C or lower, or 90°C or lower.

[0078] Polyurethane resin-forming compositions can form cured products with suppressed solvent elution. A specific example of a solvent is methanol. Solvent elution is evaluated by the methanol extraction rate measured by the method described in the examples below. The methanol extraction rate of the cured product of the polyurethane resin-forming composition may be less than 1.0%.

[0079] The polyurethane resin-forming composition exhibits excellent curability. The curability of the polyurethane resin-forming composition is evaluated by the pot life, which is measured by the method described in the examples below. The pot life of the polyurethane resin-forming composition may be 1700 seconds or less, 1000 seconds or less, 600 seconds or less, or 450 seconds or less.

[0080] The polyurethane resin-forming composition exhibits excellent filling properties. The filling properties of the polyurethane resin-forming composition are evaluated by the mixed viscosity of the polyurethane resin-forming composition, which is measured by the method described in the examples below. The mixed viscosity of the polyurethane resin-forming composition refers to the viscosity 60 seconds after mixing begins, after the polyisocyanate prepolymer (A) and polyol component (B) have been mixed at a temperature of 25°C. The mixed viscosity of the polyurethane resin-forming composition may be 2000 mPa·s or less, 1900 mPa·s or less, 1800 mPa·s or less, 1700 mPa·s or less, 1600 mPa·s or less, or 1500 mPa·s or less, and may be 400 mPa·s or more, 600 mPa·s or more, 800 mPa·s or more, or 1000 mPa·s or more. The mixed viscosity of the polyurethane resin-forming composition is preferably 400 mPa·s to 2000 mPa·s, and more preferably 600 mPa·s to 2000 mPa·s from the viewpoint of excellent moldability of the polyurethane resin.

[0081] The polyurethane resin-forming composition can form a cured product with appropriate hardness. Because the cured product of the polyurethane resin-forming composition has appropriate hardness, it is easy to cut and other processes when used as a film sealing material. The hardness of the cured product of the polyurethane resin-forming composition is measured by the method described in the examples below. The hardness of the cured product of the polyurethane resin-forming composition may be, for example, 50 to 85 or 55 to 75.

[0082] <Cured product of polyurethane resin-forming composition> Cured polyurethane resin-forming compositions can be obtained by a method that includes a step of reacting a polyisocyanate prepolymer (A) and a polyol component (B) (urethane reaction). It is preferable to react the polyisocyanate prepolymer (A) and polyol component (B) until the target NCO content is reached. The reaction temperature may be 0°C to 100°C, preferably 20°C to 95°C, more preferably 30°C to 90°C, or 40°C to 80°C. When the reaction temperature is 40°C or higher, the crystal precipitation of compounds that may be contained in each component (e.g., MDI monomer) can be suppressed more effectively. When the reaction temperature is 80°C or lower, the generation of by-reactants can be suppressed more effectively.

[0083] <Membrane sealing material> A film sealing material according to one embodiment of the present disclosure includes a cured product (polyurethane resin) of the polyurethane resin-forming composition described above.

[0084] The membrane sealing material can be manufactured by a method that includes a curing step in which a polyurethane resin-forming composition is cured in a mold. The polyurethane resin-forming composition described above suppresses the reaction heat during molding, thereby suppressing the occurrence of molding shrinkage and also suppressing the thermal degradation of other components such as hollow fibers. The cured product of the polyurethane resin-forming composition described above has a suitable hardness, making it easy to perform processes such as cutting after removing the cured product from the mold. In addition, the membrane sealing material containing the cured product of the polyurethane resin-forming composition described above suppresses the elution of low molecular weight reactants as well as the elution of solvents, making it suitable for use as a medical membrane sealing material (potting agent) in plasma separators, artificial lungs, artificial kidneys, artificial livers, etc.

[0085] <Membrane Module> A membrane module according to one embodiment of the present disclosure comprises a main body, a membrane, and the above-described membrane sealing material. The membrane may be a plurality of hollow fiber membranes. The membrane sealing material seals the gap between the main body and the membrane. Preferably, the membrane sealing material seals the gap between the main body and at least a portion of the plurality of hollow fiber membranes, and at least a portion of the gaps between the plurality of hollow fiber membranes.

[0086] Next, a membrane module according to one embodiment of the present disclosure will be described in more detail with reference to the drawings. Figure 1 is a conceptual diagram showing an example of the configuration of a membrane module according to one embodiment of the present disclosure. The membrane module (hollow fiber membrane module) 100 shown in Figure 1 comprises a housing (main body) 11, and a plurality of hollow fiber membranes (membranes) 13 are filled inside it. For example, in the case of a hollow fiber membrane module used as a dialyzer, several thousand to tens of thousands of hollow fiber membranes are filled inside.

[0087] The housing 11 has a cylindrical shape. Membrane sealing material 19 is provided at both ends inside the housing 11 (the left and right ends in Figure 1). The membrane sealing material fills and seals the gaps between the hollow fiber membranes 13 and the gaps between the hollow fiber membranes 13 and the inner wall of the housing 11, and also binds together multiple hollow fiber membranes 13.

[0088] A first fluid inlet 15 and a first fluid outlet 17 are provided on the side of the housing 11. A first fluid (gas or liquid) flows in and out of the housing 11 through the first fluid inlet 15 and the first fluid outlet 17. The first fluid that flows in from the first fluid inlet 15 passes through the gap (outside the hollow fiber membranes) while in contact with a plurality of hollow fiber membranes 13 filled inside the housing 11, and is discharged from the first fluid outlet 17. Since there is no membrane sealing material 19 inside the hollow fiber membranes 13, a second fluid (gas or liquid) flows in and out of the hollow fiber membranes 13 through a second inlet (one end) and a second outlet (the other end) provided on a cap member (not shown). Then, as the first fluid and the second fluid come into contact through the hollow fiber membranes 13, mass transfer occurs from one fluid to the other (or from one fluid to the other). For example, in the case of a hollow fiber membrane type dialyzer, when the dialysate comes into contact with the blood, waste products and excess water in the blood move into the dialysate.

[0089] The membrane module 100 shown in Figure 1 comprises a plurality of hollow fiber membranes 13, with membrane sealing material 19 sealing the gaps at both ends. However, the membrane module according to this embodiment is not limited to this configuration. For example, the membrane may be a single or multiple membrane having various shapes such as a flat membrane or a spiral membrane. The membrane sealing material is not limited to being provided at both ends of the membrane; it may be provided only at a part of the membrane (one end if it is hollow fiber), or at all ends of the membrane, for example, at all outer edges of a flat membrane. The sealing material may also be provided at a part of the membrane other than the ends to seal it. The housing 11 of the membrane module 100 shown in Figure 1 has a cylindrical shape, but it may have any shape other than cylindrical.

[0090] The membrane module 100 can be manufactured by sealing the gaps between the hollow fiber membranes 13 at the ends of a bundle of multiple hollow fiber membranes 13 with the polyurethane resin-forming composition for membrane sealing material described above, and curing the composition to form the membrane sealing material described above (the gaps between the hollow fiber membranes are sealed by the membrane sealing material).

[0091] A membrane module according to one embodiment of this disclosure can be suitably used as a medical or water treatment module because the elution of low molecular weight reactants is suppressed. Specific examples of membrane modules include plasma separators, artificial lungs, artificial kidneys, artificial livers, and household and industrial water treatment equipment. [Examples]

[0092] The present invention will be described below based on examples, but the present invention is not limited to these examples. In the following, "%" means "mass%" unless otherwise specified.

[0093] The following components were used in the examples and comparative examples.

[0094] [Polyisocyanate prepolymer (A)] a1-1; HDI isocyanurate (manufactured by Tosoh Corporation, product name Coronate HXLV) Isocyanate group content = 23.0% a1-2; a mixture of 2,4'-MDI and 4,4'-MDI (manufactured by Tosoh Corporation) Product name: Myrionate NM, Isocyanate group content = 33.6% Isomer = approximately 55%) • Carbodiimide modified form of a1-3;4,4'-MDI (manufactured by Tosoh Corporation) Product name: Myrionate MTL-C, Isocyanate group content = 28.6% Carbodiimide / uretonimine modified compound content = 30%, isomer = approximately 1% a2; Partially dehydrated castor oil (manufactured by Ito Oil Co., Ltd., molecular weight 950, OHV=119mgKOH / g, viscosity (25℃)=420mPa·s)

[0095] [Polyol (B)] • b1; Castor oil polymerized polyol (manufactured by Ito Oil Co., Ltd., product name Polycaster #30) Hydroxyl value (OHV) = 155 mg KOH / g, viscosity (25℃) = 4800 mPa·s. Content of polymerized castor oil with a number-average molecular weight of 1500 or more = approximately 54% ·b2;N,N,N',N'-Tetrakis[2-hydroxypropyl]ethylenediamine (Manufactured by ADEKA Corporation, product name EDP-300, OHV = 760 mg KOH / g) Viscosity (25℃)=50000mPa s) • b3-1; Castor oil (manufactured by Ito Oil Co., Ltd., product name URIC H-30) Hydroxyl value (OHV) = 160 mg KOH / g, viscosity (25℃) = 690 mPa·s) ) b3-2; Partially dehydrated castor oil (manufactured by Ito Oil Co., Ltd., number average molecular weight 950) Hydroxyl value (OHV) = 119 mg KOH / g, viscosity (25℃) = 420 mPa·s)

[0096] [Examples of polymerized castor oil synthesis] 1000 parts by mass of castor oil (manufactured by Ito Oil Co., Ltd., product name URIC H-30) was added to a 2-liter four-necked flask equipped with a stirrer, thermometer, heating device, and dropping funnel, and the temperature was raised to 140°C under a nitrogen stream. 70 parts by mass of di-t-butyl peroxide were added dropwise over 30 minutes while blowing in nitrogen gas, and the temperature was raised to 150°C and the reaction was allowed to proceed for 4 hours. Subsequently, the decomposition products were collected under reduced pressure for 1 hour, and the mixture was filtered and purified with clay at 120°C to obtain polymerized castor oil. The hydroxyl value of the obtained polymerized castor oil was 155 mgKOH / g.

[0097] [Production Examples 1-5 of Polyisocyanate Prepolymer (A)] a1-2, a1-3, and a2 were charged according to the mixing ratios shown in Table 1 and reacted by stirring and mixing at 70°C for 4 hours. After the reaction was complete, a1-1 was blended in to synthesize polyisocyanate prepolymers (A-1) to (A-5).

[0098] [Table 1]

[0099] [Preparation Examples 1 to 6 of Polyol Component (B)] Each raw material was charged in the blending ratios shown in Table 2, and then stirring and uniform mixing were carried out to obtain polyol-containing components (B-1) to (B-6). [Table 2]

[0100] [Preparation and Evaluation of Urethane Resin-Forming Composition] The urethane resin-forming compositions of Examples 1 to 5 and Comparative Examples 1 to 7 were prepared and molded with the compositions shown in Table 3 or 4. The values described in Table 3 or 4 were calculated from the following test results.

[0101] [Measurement of NCO Content] In the polyisocyanate prepolymers (A-1) to (A-5) shown in Table 1, the NCO content was determined according to JIS K1603-1:2007.

[0102] [Measurement of Aromatic Diisocyanate (MDI) Monomer Content] In the polyisocyanate prepolymers (A-1) to (A-5) shown in Table 1, the content (mass %) of the MDI monomer was determined by GPC measurement under the following conditions and methods.

[0103] [Measurement Conditions of Aromatic Diisocyanate Monomer Content] (1) Measuring device: "HLC-8120 (trade name)" (manufactured by Tosoh Corporation) (2) Column temperature: 40 °C (3) Detector: RI (refractive index) meter (4) Column: Columns filled with three types of TSKgel G3000HXL, TSKgel G2000HXL, and TSKgel G1000HXL (all trade names, manufactured by Tosoh Corporation) as fillers were connected in series for measurement. (5) Eluent: Tetrahydrofuran (THF) (flow rate: 1 mL / min, 40 °C) (6) Calibration curve: Calibration curves were obtained using the following grades of polystyrene (TSK standard POLYSTYRENE): F-2 (1.81 × 10⁴), F-1 (1.02 × 10⁴), A-5000 (5.97 × 10³), A-2500 (2.63 × 10³), A-500 (Mw = 6.82 × 10², 5.78 × 10², 4.74 × 10², 3.70 × 10², 2.66 × 10²), Toluene (Mw = 92). (7) Sample: 0.05 g of sample in 10 mL of THF solution

[0104] (Method for measuring the content of aromatic diisocyanate monomers (MDI monomers)) First, using polystyrene as a standard substance, a calibration curve was obtained from a chart resulting from detection based on refractive index differences. Next, for each sample, the mass percentage of the peak around a peak molecular weight (number-average molecular weight) of 230, representing the MDI monomer, was determined from a chart obtained from detection based on refractive index differences using the same calibration curve.

[0105] <Measurement of number-average molecular weight and measurement of polymerized castor oil content with a number-average molecular weight of 1500 or more> For the polyols (B-1) to (B-6) shown in Table 2, the castor oil polymer content (mass%) with a number average molecular weight of 1500 or more was determined by GPC measurement under the following conditions and method.

[0106] (Measurement conditions for number-average molecular weight) (1) Measuring device: "HLC-8120 (product name)" (manufactured by Tosoh Corporation) (2) Columns: Four columns, each packed with two tubes of TSKgel G2000HXL and two tubes of TSKgel G3000HXL (both product names, manufactured by Tosoh Corporation), were connected in series. (3) Column temperature: 40℃ (4) Detector: RI (refractive index) meter (5) Eluent: Tetrahydrofuran (THF) (Flow rate: 1 mL / min, 40°C) (6) Calibration curve: A calibration curve was obtained using the following trifunctional polypropylene polyols (all manufactured by Sanyo Chemical Industries, Ltd.). • "Sannix GP-250" (number-average molecular weight = 250) • "Sannix GP-400" (number-average molecular weight = 400) • "Sannix GP-600" (number-average molecular weight = 600) • "Sannix GP-1000" (number-average molecular weight = 1000) • "Sannix GP-3000" (number-average molecular weight = 3000) • "Sannix GP-4000" (number-average molecular weight = 4000) • "Sannix GP-5000" (number-average molecular weight = 5000) (7) Sample solution: 0.05 g of sample in 10 mL of THF solution

[0107] (Method for measuring the content of polymerized castor oil with a number-average molecular weight of 1500 or more) A calibration curve was obtained from a chart obtained by detecting the refractive index difference using a trifunctional polypropylene polyol as a standard substance. Next, for each sample, the mass percentage of the peak around a peak molecular weight (number average molecular weight) of 1000, which represents refined castor oil, was determined from the chart obtained by detecting the refractive index difference based on the same calibration curve. Peaks other than refined castor oil had a number average molecular weight of 1500 or more, and the mass percentages other than that of refined castor oil were determined as the mass percentages of polymerized castor oil (castor oil polymer).

[0108] The methods for measuring the physical properties of the polyurethane resin-forming compositions or their cured products in Examples 1-5 and Comparative Examples 1-7 are as follows.

[0109] <Maximum temperature reached> Polyisocyanate prepolymers (A-1) to (A-5) and polyol-containing components (B-1) to (B-6) were blended in the combinations shown in Table 3 or Table 4, with a liquid temperature of 45°C, an isocyanate group / active hydrogen group ratio of 1.00 or 1.05 (molar ratio), and a total mass of 50 g to obtain a mixed solution. The temperature change over time was measured using an ondotori (TR-71wf, manufactured by T&D CORPORATION), and the highest observed temperature of the mixed solution was defined as the maximum temperature reached.

[0110] <Mixing viscosity and pot life test> The mixed viscosity and pot life of the polyurethane resin-forming compositions of Examples 1-5 and the Comparative Example were determined by the following method. Polyisocyanate prepolymers (A-1) to (A-5) and polyol-containing components (B-1) to (B-6) were weighed and mixed in the combinations shown in Table 3 or Table 4, at a liquid temperature of 45°C, with an isocyanate group / active hydrogen group ratio of 1.00 to 1.05 (molar ratio), to obtain a mixture totaling 50g. The viscosity of the mixture was then measured using a rotational viscometer (Type B, rotor No. 4) under a 25°C atmosphere. The viscosity 60 seconds after the start of mixing of the polyisocyanate prepolymers and polyol-containing components was defined as the mixed viscosity, and the time until the viscosity of the mixture reached 50,000 mPa·s was defined as the pot life (seconds). A mixed viscosity of 2,000 mPa·s or less was judged to be good packing properties. A pot life of 1,700 seconds or less was judged to be good curing properties.

[0111] <Hardness (10 seconds value)> Polyisocyanate prepolymers (A-1) to (A-5) and polyol-containing components (B-1) to (B-6) were weighed in the combinations shown in Tables 3 and 4, with a liquid temperature of 45°C and an isocyanate group / active hydrogen group ratio of 1.00 to 1.05 (molar ratio), totaling 50g. The mixture was mixed with a spatula for 30 seconds, and degassed under vacuum at 50 mmHg for 60 seconds. After degassing, 30g was transferred to a 100ml poly cup and cured at 45°C for 48 hours. The cured material was removed from the poly cup and left in an environment of 25°C for 4 hours, and its hardness was measured using a durometer D hardness tester. The reading 10 seconds after pressing the hardness tester was taken as the hardness (10-second value).

[0112] <Measurement of low molecular weight elution levels> (Preparation of samples for low molecular weight dissolution testing) Polyisocyanate prepolymers (A-1) to (A-5) and polyol-containing components (B-1) to (B-6) were blended in the combinations shown in Tables 3 and 4, with a liquid temperature of 45°C, an isocyanate group / active hydrogen group ratio of 1.00 to 1.05 (molar ratio), and a total mass of 30 g to obtain a mixed solution. The resulting mixed solution was then stirred for 15 seconds. Further, 10 g of glycerin was added (assuming the glycerin contained in the hollow fibers) and stirred for 15 seconds to obtain a cured polyurethane resin-forming composition. This cured product was left to stand in a constant temperature bath under primary curing conditions of 50°C for 10 minutes and secondary curing conditions of 45°C for 2 days.

[0113] (Low molecular weight substance extraction test) The low molecular weight elution values ​​of the cured polyurethane resin-forming compositions obtained in Examples 1-5 and Comparative Examples 1-7 were measured by the following method. First, 20g of each sample obtained from each example and comparative example for measuring low molecular weight elutions was weighed out after cutting it into a fan shape. The samples were then immersed in 100ml of purified water preheated to 40°C and left at 40°C for 2 hours to extract the low molecular weight elutions into the purified water. Next, the obtained extract was decanted, 10ml was placed in a 50ml volumetric flask, and the resulting solution was adjusted to 50ml with purified water to be used as the test solution. The UV absorbance of the test solution was then measured (Shimadzu Corporation, product name UV-1500). The low molecular weight elution value was defined as one-tenth of the maximum absorbance value at 240-245nm. If the low molecular weight elution value is 0.050 or less, it can be judged that there are few elutes.

[0114] <Measurement of solvent extraction rate> (Sample preparation for solvent extraction test) Polyisocyanate prepolymers (A-1) to (A-5) and polyol-containing components (B-1) to (B-6) were weighed in combinations shown in Table 3 or Table 4, under conditions of a liquid temperature of 45°C and an isocyanate group / active hydrogen group ratio of 1.00 to 1.05 (molar ratio), so that the total mass of the polyisocyanate prepolymers and polyol-containing components was 100g. The mixture was mixed with a spatula for 30 seconds, and degassed under vacuum at 50 mmHg for 60 seconds. After degassing, the mixture was spread onto release paper to form a 1 mm thick sheet, and left to stand in a constant temperature bath at 45°C for 2 days.

[0115] (Solvent extraction test) The solvent extraction rates of the cured polyurethane resin-forming compositions obtained in Examples 1-5 and Comparative Examples 1-7 were measured by the following method. First, the measurement samples obtained in each example and comparative example were cut into 10 mm squares. Next, 10 g of the cut sample and 100 g of methanol were placed in a 200 ml sample bottle, sealed tightly, and shaken at 25°C for 24 hours. After shaking, the mixture was filtered, and the extract was collected in a 300 ml round-bottom flask and evaporated to dryness. The methanol extraction rate was then determined using the following formula. Methanol extraction rate (%) = {Weight of the round-bottom flask after evaporation to dryness (g) - Weight of the empty round-bottom flask (g)} / Weight of the sample (g) × 100 A methanol extraction rate of less than 1.0% is preferred.

[0116] In Tables 3 and 4, the "aromatic diisocyanate monomer content," "HDI modified product content," and "polymerized castor oil content" are based on the total mass of the polyurethane resin-forming composition.

[0117] [Table 3] [Table 4] [Explanation of Symbols]

[0118] 11…Housing, 13…Hollow fiber membrane, 15…First fluid inlet, 17…First fluid outlet, 19…Membrane sealant, 100…Membrane module (Hollow fiber membrane module)

Claims

1. Polyisocyanate prepolymer (A), A polyurethane resin-forming composition for film sealing materials, comprising a polyol component (B), The polyisocyanate prepolymer (A) Modified form of hexamethylene diisocyanate (a1-1), At least one (a1-2) selected from the group consisting of aromatic diisocyanates and their modified forms, It contains an active hydrogen-containing compound (a2) and the reaction product thereof. The aforementioned polyol component (B) is Polymerized castor oil (b1), A polyurethane resin-forming composition for film sealing materials, comprising a hydroxyl group-containing amine compound (b2).

2. The polyurethane resin-forming composition for film sealing material according to claim 1, wherein the number average molecular weight of the polymerized castor oil (b1) is 1500 or more.

3. The polyurethane resin-forming composition for film sealing materials according to claim 1 or 2, wherein the aromatic diisocyanate is diphenylmethane diisocyanate.

4. The polyurethane resin-forming composition for film sealing material according to claim 1 or 2, wherein the content of the polymerized castor oil (b1) is 1.0% by mass or more and 30.0% by mass or less, based on the total mass of the polyisocyanate prepolymer (A) and the polyol component (B).

5. The polyurethane resin-forming composition for film sealing materials according to claim 1 or 2, wherein the polyol component (B) further comprises a castor oil-based polyol (b3) other than the polymerized castor oil (b1).

6. The polyurethane resin-forming composition for film sealing material according to claim 1 or 2, wherein the content of the hydroxyl group-containing amine compound (b2) is 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the polyol component (B).

7. A film sealing material comprising a cured product of the polyurethane resin-forming composition for film sealing materials described in claim 1 or 2.

8. The main body and membrane and A membrane module comprising a membrane sealing material according to claim 7 for sealing the gap between the main body and the membrane.

9. The aforementioned membrane is a plurality of hollow fiber membranes, The aforementioned film sealing material The gap between the main body and at least a portion of the plurality of hollow fiber membranes, The membrane module according to claim 8, which seals at least a portion of the gaps between the plurality of hollow fiber membranes.

Images