Polyurethane resin-forming composition, and film sealing material and film module using same

Abstract

Disclosed is a polyurethane resin-forming composition comprising a polyisocyanate prepolymer (A) and a polyol (B). The polyisocyanate prepolymer (A) contains a reaction product of diphenylmethane diisocyanate (a1-1) and / or a modified diphenylmethane diisocyanate (a1-2) and an active hydrogen-containing compound (a2); the polyol (B) contains a transesterification product (b1) of a castor oil-based polyol and a hydroxyl group-containing amine compound, a hydroxyl group-containing amine compound (b2), and a castor oil-based polyol (b3), and the content of the transesterification product (b1) is 0.1-10 mass% with respect to the total mass of the polyisocyanate prepolymer (A) and the polyol (B).

Description

Technical Field

[0001] The present disclosure relates to a polyurethane resin-forming composition, and a film sealing material and a film module using the polyurethane resin-forming composition. Background Art

[0002] A polyurethane resin-forming composition obtained from an isocyanate component and a polyol component can react at room temperature and has excellent moldability, adhesion, chemical resistance, and mechanical properties. Therefore, it is widely used as a sealing material and the like in various fields.

[0003] Among them, when the main agent uses a modified diphenylmethane diisocyanate and uses castor oil-based polyols and amine-initiated polyalkylene polyols (hydroxyl-containing amine compounds), there is a problem of whitening the appearance of the cured product of the polyurethane resin-forming composition due to compounding. When a sealing material with white appearance is used, it is impossible to visually confirm the inside from the outside of the sealing material, and for example, when used in a dialyzer, it is difficult to find leakage of dialysate and blood.

[0004] To address this problem, Patent Document 1 discloses a polyurethane resin-forming composition containing castor oil-based polyol, polyoxyethylene polypropylene aliphatic polyamine, and polyoxypropylene aliphatic polyamine in a specific content ratio in a polyol component.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2017 / 006650 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] However, the composition of Patent Document 1 has a problem that the cured product becomes cloudy when the amount of ethylene oxide in the aliphatic polyamine increases.

[0010] Therefore, one aspect of the present disclosure is to provide a polyurethane resin-forming composition having good rapid curing properties and being useful for producing a cured product with suppressed whitening in appearance. In addition, another aspect of the present disclosure is to provide a film sealing material and a film module having good appearance.

[0011] Solutions for solving problems

[0012] According to each aspect of the present disclosure, the following embodiments [1] to [8] are provided.

[0013] [1]: A polyurethane resin-forming composition comprising a polyisocyanate prepolymer (A) and a polyol (B),

[0014] The polyisocyanate prepolymer (A) comprises a reaction product of diphenylmethane diisocyanate (a1-1) and / or a modified diphenylmethane diisocyanate (a1-2) and an active hydrogen-containing compound (a2).

[0015] The aforementioned polyol (B) comprises:

[0016] Transesterification product (b1) of castor oil polyol and hydroxyl-containing amine compound, hydroxyl-containing amine compound (b2), and

[0017] Castor oil-based polyol (b3),

[0018] The content of the transesterification product (b1) is 0.1% by mass or more and 10% by mass or less relative to the total mass of the polyisocyanate prepolymer (A) and the polyol (B).

[0019] [2]: The polyurethane resin-forming composition according to [1], wherein the polyisocyanate prepolymer (A) has a urethane group concentration of 0.1 mmol / g or more.

[0020] [3]: A polyurethane resin-forming composition according to [1] or [2], wherein the reaction product comprises at least a reaction site between a modified diphenylmethane diisocyanate (a1-2) and an active hydrogen-containing compound (a2), and the modified diphenylmethane diisocyanate (a1-2) comprises a carbodiimide-modified diphenylmethane diisocyanate and a uretonimine-modified diphenylmethane diisocyanate.

[0021] [4]: The polyurethane resin-forming composition according to any one of [1] to [3], which is for use in a film sealing material.

[0022] [5]: A film sealing material comprising a cured product of the polyurethane resin-forming composition according to [4].

[0023] [6]: A membrane module comprising:

[0024] Main body;

[0025] membrane; and

[0026] a membrane sealing material for sealing a gap between the main body and the membrane,

[0027] The aforementioned film sealing material is the film sealing material described in [5].

[0028] [7]: The membrane module according to [6], wherein

[0029] The aforementioned membrane is a plurality of hollow fiber membranes,

[0030] The aforementioned film sealing material seals the following gaps:

[0031] a gap between the main body and at least a portion of the plurality of hollow fiber membranes, and

[0032] At least a portion of the gaps between the plurality of hollow fiber membranes.

[0033] Effects of the Invention

[0034] One aspect of the present disclosure is to provide a polyurethane resin-forming composition having good rapid curing properties and contributing to the formation of a cured product with suppressed whitening in appearance. In addition, another aspect of the present disclosure is to provide a film sealing material and a film module having good appearance. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a schematic diagram showing an example of the configuration of a membrane module according to one embodiment of the present disclosure. DETAILED DESCRIPTION

[0036] Hereinafter, exemplary embodiments for implementing each mode of the present disclosure are described in further detail. However, the present disclosure is not limited to the following embodiments. In this specification, the numerical range shown by "~" indicates a range that includes the numerical values ​​recorded before and after "~" as the minimum value and the maximum value, respectively. Within the numerical range recorded in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment. The upper limit and lower limit recorded separately can be combined arbitrarily.

[0037] [Polyurethane resin forming composition]

[0038] The polyurethane resin-forming composition according to one embodiment of the present disclosure contains a polyisocyanate prepolymer (A) and a polyol (B).

[0039] <Polyisocyanate prepolymer (A)>

[0040] The polyisocyanate prepolymer (A) contains a reaction product of diphenylmethane diisocyanate (a1-1) and / or a modified diphenylmethane diisocyanate (a1-2) and an active hydrogen-containing compound (a2).

[0041] <<Diphenylmethane diisocyanate (a1-1)>>

[0042] As diphenylmethane diisocyanate (a1-1), any monomer of diphenylmethane diisocyanate (hereinafter also referred to as MDI) that is commonly available may also be used. MDI monomers are generally: 2,2'-MDI is 0% to 5% by mass, 2,4'-MDI is 0% to 95% by mass, and 4,4'-MDI is 5% to 100% by mass. Among them, for MDI, 4,4'-MDI is defined as the main component, and 2,2'-MDI and 2,4'-MDI are defined as isomeric components.

[0043] The amount of diphenylmethane diisocyanate (a1-1) used may be 1.0 parts by mass or more, 2.0 parts by mass or more, 3.0 parts by mass or more, or 40.0 parts by mass or less, 30.0 parts by mass or less, 10.0 parts by mass or less, 8.0 parts by mass or less, or 6.0 parts by mass or less, relative to 100 parts by mass of the total of the mass of diphenylmethane diisocyanate (a1-1), the mass of the modified diphenylmethane diisocyanate (a1-2), and the mass of the active hydrogen-containing compound (a2).

[0044] <<Modified diphenylmethane diisocyanate (a1-2)>>

[0045] The diphenylmethane diisocyanate modified body (a1-2) is not particularly limited, and examples thereof include: urethane modified body, carbodiimide modified body, polymer, urea modified body, allophanate modified body, biuret modified body, uretonimine modified body, uretdione modified body, etc. The diphenylmethane diisocyanate modified body (a1-2) can be used alone or in combination of two or more modified bodies.

[0046] The modified diphenylmethane diisocyanate (a1-2) may contain at least one modified product selected from the group consisting of carbodiimide-modified diphenylmethane diisocyanate and uretonimine-modified diphenylmethane diisocyanate.

[0047] The amount of the modified diphenylmethane diisocyanate (a1-2) used may be 25.0 parts by mass or more, 35.0 parts by mass or more, 45.0 parts by mass or more, 55.0 parts by mass or more, 65.0 parts by mass or more, or 75.0 parts by mass or more, or 95.0 parts by mass or less, or 90.0 parts by mass or less, relative to 100 parts by mass of the total of the mass of the diphenylmethane diisocyanate (a1-1), the mass of the modified diphenylmethane diisocyanate (a1-2), and the mass of the active hydrogen-containing compound (a2).

[0048] <<Reaction Products>>

[0049] The reaction product preferably contains at least a reaction site of a modified diphenylmethane diisocyanate (a1-2) containing carbodiimide-modified diphenylmethane diisocyanate and a uretonimine-modified diphenylmethane diisocyanate and an active hydrogen-containing compound (a2).

[0050] <<Active hydrogen-containing compound (a2)>>

[0051] The active hydrogen-containing compound (a2) is not particularly limited as long as it is a compound containing active hydrogen. Examples of the active hydrogen-containing compound (a2) include castor oil-based polyols (castor oil, partially dehydrated castor oil, castor oil-modified polyols), low molecular weight polyols, polyether polyols, polyester polyols, polylactone polyols, polyolefin polyols and the like.

[0052] Examples of castor oil-based polyols include castor oil, partially dehydrated castor oil, and castor oil-based modified polyols. Partially dehydrated castor oil is a dehydration reaction product of castor oil, obtained by removing at least a portion of the hydroxyl groups in castor oil. Examples of castor oil-based modified polyols include linear or branched castor oil-based polyols obtained by reacting castor oil or castor oil fatty acids with at least one polyol selected from the group consisting of low molecular weight polyols and polyether polyols. Specific examples include diglycerides and monoglycerides of castor oil fatty acids; monoesters, diesters, and triesters of castor oil fatty acids and trihydroxymethylalkanes; monoesters, diesters, and triesters of castor oil fatty acids and polypropylene glycol, etc.

[0053] The main component of castor oil is triglyceride of ricinoleic acid, and castor oil includes hydrogenated castor oil. The main component of castor oil fatty acid is ricinoleic acid, and castor oil fatty acid includes hydrogenated castor oil fatty acid.

[0054] Examples of the trimethylolalkane include trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, trimethylolpentane, trimethylolhexane, trimethylolheptane, trimethyloloctane, trimethylolnonane, and trimethyloldecane.

[0055] The number average molecular weight of the castor oil polyol is preferably 400 to 3000, more preferably 500 to 2500. When the number average molecular weight of the castor oil polyol is 400 to 3000, a cured resin having more excellent physical properties, particularly mechanical properties, required for a film sealing material can be formed.

[0056] The "number average molecular weight" in this specification is a value converted to trifunctional polypropylene polyol measured by GPC (gel permeation chromatography). The details of the measurement conditions are as follows.

[0057] (Measurement conditions of number average molecular weight)

[0058] (1) Measurement device: "HLC-8120 (trade name)" (manufactured by Tosoh Corporation)

[0059] (2) Column: Four columns each filled with two TSKgel G2000HXL and two TSKgel G3000HXL (both trade names, manufactured by Tosoh Corporation) as a filler were connected in series.

[0060] (3) Column temperature: 40°C

[0061] (4) Detector: RI (refractive index) meter

[0062] (5) Eluent: tetrahydrofuran (THF) (flow rate: 1 mL / min., 40°C)

[0063] (6) Calibration curve: A calibration curve was obtained using the following trade names of trifunctional polypropylene polyols (all manufactured by Sanyo Chemical Industries, Ltd.).

[0064] "Sannix GP-250" (number average molecular weight = 250)

[0065] "Sannix GP-400" (number average molecular weight = 400)

[0066] "Sannix GP-600" (number average molecular weight = 600)

[0067] "Sannix GP-1000" (number average molecular weight = 1000)

[0068] "Sannix GP-3000" (number average molecular weight = 3000)

[0069] "Sannix GP-4000" (number average molecular weight = 4000)

[0070] "Sannix GP-5000" (number average molecular weight = 5000)

[0071] (7) Sample solution: 0.05 g sample in 10 mL THF

[0072] The average hydroxyl value of castor oil-based polyols can be 20 mgKOH / g or more and 350 mgKOH / g or less, preferably 20 mgKOH / g or more and 300 mgKOH / g or less, more preferably 40 mgKOH / g or more and 250 mgKOH / g or less. When the average hydroxyl value is 20 mgKOH / g or more and 300 mgKOH / g or less, a cured resin having excellent physical properties, especially mechanical properties, required by a membrane sealing material can be formed. Furthermore, when the average hydroxyl value is 20 mgKOH / g or more and 300 mgKOH / g or less, the productivity of the membrane sealing material and the productivity of the hollow fiber membrane assembly can also be improved.

[0073] The average hydroxyl value of the castor oil-based polyol may be 50 mgKOH / g or more, 70 mgKOH / g or more, 90 mgKOH / g or more, 110 mgKOH / g or more, 130 mgKOH / g or more, or 140 mgKOH / g or less, or 350 mgKOH / g or less, or 330 mgKOH / g or less, or 310 mgKOH / g or less, or 290 mgKOH / g or less, or 270 mgKOH / g or less.

[0074] The average hydroxyl value is a value measured by a method using an acetylating agent in accordance with JIS K 1557-1:2007.

[0075] Examples of low molecular weight polyols include divalent polyols such as ethylene glycol, diethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol 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; trivalent to octavalent polyols such as glycerol, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, and sucrose. The number average molecular weight of the low molecular weight polyol is preferably 50 or more and 200 or less.

[0076] Examples of polyether polyols include: alkylene oxide (alkylene oxides having 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above-mentioned low molecular weight polyols, and ring-opening polymers of alkylene oxides, etc. Specifically, examples include: polypropylene glycol, polyethylene glycol, polytetramethylene ether glycol, or copolymers of ethylene oxide and propylene oxide, etc. From the viewpoint of further excellent molding processability when manufacturing film sealing materials, the number average molecular weight of the polyether polyol is preferably 200 or more and 7000 or less, and more preferably 500 or more and 5000 or less.

[0077] Examples of the polyester polyol include polyester polyols obtained by polycondensation of polycarboxylic acids and polyols.

[0078] Examples of the polycarboxylic acid used for the polyester polyol include aliphatic saturated polycarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, maleic acid, fumaric acid, itaconic acid, dimerized linoleic acid, phthalic acid, isophthalic acid, and terephthalic acid, aliphatic unsaturated polycarboxylic acids, and aromatic polycarboxylic acids.

[0079] Examples of the polyol used for the polyester polyol include the above-mentioned low molecular weight polyols and polyether polyols.

[0080] The number average molecular weight of the polyester polyol is preferably 200 to 5000, more preferably 500 to 3000. When the number average molecular weight of the polyester polyol is 200 to 5000, the molding processability when formed into a film sealing material is particularly excellent.

[0081] As polylactone polyols, for example, polyols obtained by addition polymerization of ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, β-methyl-δ-valerolactone, etc. with a polymerization initiator of a diol or triol in the presence of a catalyst such as an organic metal compound, a metal chelate compound, or a fatty acid metal acyl compound can be cited. The number average molecular weight of the polylactone polyol is preferably 200 to 5000, and more preferably 500 to 3000. When the number average molecular weight of the polylactone polyol is 200 to 5000, the molding processability when forming a film sealing material is particularly excellent.

[0082] Examples of polyolefin polyols include polybutadiene polyols having hydroxyl groups introduced into the ends of polybutadiene or copolymers of butadiene and styrene or acrylonitrile, and polyetherester polyols obtained by addition reaction of polyesters having carboxyl groups and hydroxyl groups at the ends with alkylene oxides such as ethylene oxide and propylene oxide.

[0083] Among them, as the active hydrogen-containing compound (a2), castor oil-based polyols are preferred, and partially dehydrated castor oil is more preferred in view of compatibility with the polyol (B). When the isocyanate component is used as a film sealing material for a glycerol-containing film, the isocyanate component sometimes reacts with the glycerol, and low molecular weight reactants in the reactants are eluted into the liquid in contact with the film. When the active hydrogen-containing compound (a2) contains partially dehydrated castor oil, when used as such a film sealing material, the elution of low molecular weight reactants can be further suppressed.

[0084] The amount of the active hydrogen-containing compound (a2) used may be 3.0 parts by mass or more, 5.0 parts by mass or more, or 7.0 parts by mass or more, or 45.0 parts by mass or less, 40.0 parts by mass or less, 35.0 parts by mass or less, 30.0 parts by mass or less, 25.0 parts by mass or less, 20.0 parts by mass or less, or 15.0 parts by mass or less, relative to 100 parts by mass of the total of the mass of the diphenylmethane diisocyanate (a1-1), the mass of the modified diphenylmethane diisocyanate (a1-2), and the mass of the active hydrogen-containing compound (a2).

[0085] <<Isocyanate content>>

[0086] The content of the isocyanate group of the polyisocyanate prepolymer (A) is preferably 13.0% by mass or more and 27.0% by mass or less, more preferably 13.5% by mass or more and 26.5% by mass or less, particularly preferably 14.0% by mass or more and 26.0% by mass or less. When the content of the isocyanate group of the polyisocyanate prepolymer (A) is within these ranges, the molding processability and bonding strength of the polyurethane resin are further excellent. The content of the isocyanate group of the polyisocyanate prepolymer (A) can be, for example, 13.0% by mass or more, 15.0% by mass or more, 17.0% by mass or more, 19.0% by mass or more, 21.0% by mass or more, 22.0% by mass or more, 23.0% by mass or more, or 24.0% by mass or more.

[0087] The content of the isocyanate group is the total content of the isocyanate group based on the total mass of the polyisocyanate prepolymer (A). The content of the isocyanate group is measured according to the method of JIS K1603-1:2007.

[0088] <<Carbamate group concentration>>

[0089] The polyisocyanate prepolymer (A) preferably has a carbamate group concentration of 0.1 mmol / g or more. The carbamate group concentration refers to the concentration of carbamate groups in the polyisocyanate prepolymer (A) based on the total mass of the polyisocyanate prepolymer (A) (unit: mmol / g). The carbamate group concentration in the polyisocyanate prepolymer (A) can be calculated based on the content of the active hydrogen-containing compound and the isocyanate group-containing compound used to form the polyisocyanate prepolymer (A).

[0090] The urethane group concentration of the polyisocyanate prepolymer (A) may be 0.10 mmol / g or more, 0.15 mmol / g or more, or 0.20 mmol / g or more, from the viewpoint of less heat generation during molding and less molding shrinkage, and further improving the yield rate. From the viewpoint of controlling the viscosity of the prepolymer within a range suitable for molding and achieving better handling and filling properties, the urethane group concentration may be 1.3 mmol / g or less, 1.1 mmol / g or less, 0.90 mmol / g or less, 0.70 mmol / g or less, 0.50 mmol / g or less, 0.40 mmol / g or less, or 0.30 mmol / g or less.

[0091] <<MDI monomer content>>

[0092] Based on the total mass of the polyisocyanate prepolymer (A), the MDI monomer content of the polyisocyanate prepolymer (A) may be 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 55% by mass or more, or 70% by mass or less, or 65% by mass or less. The MDI monomer content is measured by GPC (gel permeation chromatography). The details of the measurement conditions are described in the examples described below.

[0093] <<Viscosity of polyisocyanate prepolymer (A)>>

[0094] The viscosity of the polyisocyanate prepolymer (A) at 25° C. may be 7000 mPa·s or less, 5000 mPa·s or less, 3000 mPa·s or less, 1000 mPa·s or less, 800 mPa·s or less, 700 mPa·s or less, or 650 mPa·s or less, or 100 mPa·s or more, 200 mPa·s or more, 300 mPa·s or more, or 400 mPa·s or more.

[0095] <<Urethane reaction>>

[0096] The polyisocyanate prepolymer (A) can be obtained by a conventional urethanization reaction. The urethanization reaction is preferably carried out in a temperature range of 40°C to 80°C until the target NCO content is reached. When the reaction temperature is 40°C or higher, the crystal precipitation of the MDI monomer can be better suppressed, and when the reaction temperature is 80°C or lower, the generation of side reactions can be further suppressed.

[0097] <Polyol (B)>

[0098] The polyol (B) includes an ester exchange product (b1) of a castor oil-based polyol and a hydroxyl-containing amine compound, a hydroxyl-containing amine compound (b2), and a castor oil-based polyol (b3).

[0099] <<Transesterification product (b1)>>

[0100] The transesterification product (b1) of castor oil-based polyol and hydroxyl-containing amine compound is a reaction product obtained by a transesterification reaction of castor oil-based polyol and hydroxyl-containing amine compound.

[0101] The castor oil polyol used in the transesterified product (b1) is a castor oil polyol containing an ester bond, and specific examples thereof include the same castor oil polyol as in the active hydrogen-containing compound (a2). From the viewpoint of better transparency of the cured product, the castor oil polyol used in the transesterified product (b1) is preferably castor oil.

[0102] The hydroxyl-containing amine compound used in the transesterification product (b1) may be the same as the hydroxyl-containing amine compound (b2) described later. The hydroxyl-containing amine compound used in the transesterification product (b1) may be the same type as the hydroxyl-containing amine compound (b2) or a different type from the hydroxyl-containing amine compound (b2).

[0103] From the viewpoint of promoting curing and forming a cured product with a high cross-linking density and having better dissolution resistance, the hydroxyl-containing amine compound used in the ester exchange product (b1) is preferably an alkylene oxide adduct (for example, propylene oxide or ethylene oxide adduct) of an amino compound (diamino compound) such as ethylenediamine, and more preferably N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine.

[0104] The content of the transesterified product (b1) may be 0.15% by mass or more, 0.5% by mass or more, 0.8% by mass or more, or 1.0% by mass or more relative to the polyol (B), and from the viewpoint of easily obtaining a cured product with further suppressed whitening in appearance, it may be 1.5% by mass or more, 2.0% by mass or more, 3.0% by mass or more, or 4.0% by mass or more. From the viewpoint of excellent curability, the content of the transesterified product (b1) may be 12% by mass or less, 10% by mass or less, 8% by mass or less, or 6% by mass or less relative to the polyol (B).

[0105] Relative to the total mass of polyisocyanate prepolymer (A) and polyol (B), the content of transesterification product (b1) is 0.1% by mass or more and 10.0% by mass or less. From the viewpoint of easily obtaining a cured product whose appearance whitening is further suppressed, the content of transesterification product (b1) is more preferably 0.2% by mass or more and 9.0% by mass or less, particularly preferably 0.3% by mass or more and 8.0% by mass or less relative to the total mass of polyisocyanate prepolymer (A) and polyol (B). When the content of transesterification product (b1) is within these ranges, the molding processability and suppression of elution of polyurethane resin are further excellent. Relative to the total mass of polyisocyanate prepolymer (A) and polyol (B), the upper limit of the content of transesterification product (b1) can be 7.0% by mass or less, 6.0% by mass or less, 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, 2.5% by mass or less, 2.0% by mass or less, or 1.5% by mass or less. The content of the transesterified product (b1) can be measured by liquid chromatography, and the detailed measurement conditions are as described in the examples described below.

[0106] The transesterification product (b1) can be produced, for example, by subjecting a castor oil polyol and a hydroxyl-containing amine compound to a transesterification reaction in a reaction solution containing a castor oil polyol, a hydroxyl-containing amine compound and a base. As the base, for example, sodium methoxide can be cited. The amount of the base used can be 0.01 to 1.00 parts by mass or 0.05 to 0.50 parts by mass relative to a total of 100 parts by mass of the amount of the castor oil polyol used and the amount of the hydroxyl-containing amine compound used.

[0107] The reaction temperature of the transesterification reaction may be, for example, 100° C. or more, 150° C. or more, or 180° C. or more, for example, 150 to 250° C. or 180 to 220° C. The time for maintaining the above reaction temperature may be, for example, 3 hours or more, 5 hours or more, or 7 hours or more, or 5 to 10 hours. The transesterification reaction may be carried out, for example, under a nitrogen atmosphere.

[0108] <<Hydroxy-containing amine compound (b2)>>

[0109] As hydroxyl-containing amine compounds (b2), for example, there can be mentioned: alkyl diethanolamines such as linear or branched butyl diethanolamine, hexyl diethanolamine, octyl diethanolamine, lauryl diethanolamine, myristyl diethanolamine, hexadecyl diethanolamine, stearyl diethanolamine, etc.; low molecular weight polyamines; low molecular weight amino alcohols and other amine compounds. As amine compounds, more specifically, there can be mentioned: propylene oxide or ethylene oxide adducts of ethylenediamine, i.e., oxyalkylated derivatives of amino compounds such as N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine and N,N,N',N'-tetrakis[2-hydroxyethyl]ethylenediamine; monoethanolamine, diethanolamine, triethanolamine; amino alcohol derivatives such as N-methyl-N,N'-diethanolamine, etc.

[0110] Among them, propylene oxide or ethylene oxide adducts of amino compounds such as ethylenediamine are preferred, and N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine is most preferred. By using N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine, further effects are achieved due to improved processability during molding and reduced elution.

[0111] In addition, in the polyol (B), the content of the hydroxyl-containing amine compound (b2) is preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less. When the content of the hydroxyl-containing amine compound (b2) in the polyol (B) is 5% by mass or more, the hydroxyl-containing amine compound (b2) can better exert its function and play a further effect. When the proportion of the hydroxyl-containing amine compound (b2) in the polyol (B) is 40% by mass or less, the initial reaction heat during the molding of the polyurethane resin is suppressed, the operability is further improved, the filling property is ensured, and the hardness of the obtained film sealing material is further suppressed from becoming too high.

[0112] <<Castor oil-based polyol (b3)>>

[0113] As the castor oil-based polyol (b3), castor oil-based polyols listed above as the active hydrogen-containing compound (a2) are preferably used. Castor oil-based polyol (b3) is preferably castor oil from the viewpoint of achieving a better balance between viscosity and crosslinking density.

[0114] In the polyol (B), from the viewpoint of moldability, the content of the castor oil-based polyol (b3) may be 50.0 mass % or more, 55.0 mass % or more, 60.0 mass % or more, or 65.0 mass % or less, or 98.8 mass % or less, 97.0 mass % or less, or 95.0 mass % or less.

[0115] <<Active hydrogen-containing compound (b4)>>

[0116] The polyol (B) may further contain an active hydrogen-containing compound (hereinafter referred to as "active hydrogen-containing compound (b4)") other than the transesterified product (b1), the hydroxyl-containing amine compound (b2) and the polyol (b3). As the active hydrogen-containing compound (b4), various polyols listed as the active hydrogen-containing compound (a2) can be used (except the transesterified product (b1), the hydroxyl-containing amine compound (b2) and the castor oil-based polyol (b3)).

[0117] In the polyol (B), the mass ratio (Mb3) / (Mb4) of the content Mb3 of the castor oil-based polyol (b3) to the content Mb4 of the active hydrogen-containing compound (b4) is preferably 50 / 50 or more and 100 / 0 or less, and particularly preferably 100 / 0. That is, the polyol (B) particularly preferably contains only the transesterified product (b1), the hydroxyl-containing amine compound (b2) and the castor oil-based polyol (b3).

[0118] The hydroxyl value of the polyol (B) is preferably 50 mgKOH / g or more and 1000 mgKOH / g or less, and is more preferably 75 mgKOH / g or more and 750 mgKOH / g or less from the viewpoint that the polyol (B) is easy to handle. From the viewpoint of excellent molding processability and bonding strength of the polyurethane resin, the hydroxyl value of the polyol (B) is most preferably 100 mgKOH / g or more and 500 mgKOH / g or less. From the viewpoints of ease of handling of the polyol (B), excellent molding processability and bonding strength of the polyurethane resin, the hydroxyl value of the polyol (B) may be, for example, 150 mgKOH / g or more, 200 mgKOH / g or more, 250 mgKOH / g or more, 300 mgKOH / g or more, or 320 mgKOH / g or more, and may also be 450 mgKOH / g or less, 400 mgKOH / g or less, or 350 mgKOH / g or less.

[0119] <<Polyisocyanate prepolymer (A) / polyol (B) (molar ratio)>>

[0120] The ratio of the number of moles of isocyanate groups in the polyisocyanate prepolymer (A) to the number of moles of active hydrogen groups in the polyol (B) (isocyanate groups / active hydrogen groups) may be, for example, 0.95 to 1.10 or 1.00 to 1.05.

[0121] <<MDI monomer content>>

[0122] Based on the total mass of the polyisocyanate prepolymer (A) and the polyol (B), the MDI monomer content of the polyurethane resin forming composition can be 10% by mass or more, 20% by mass or more, or 45% by mass or less, or 40% by mass or less. The MDI monomer content is measured by GPC (gel permeation chromatography). The details of the measurement conditions are described in the examples described below.

[0123] <Viscosity>

[0124] For the polyurethane resin forming composition, when the viscosity after 60 seconds from the time when the polyisocyanate prepolymer (A) and the polyol (B) are mixed is defined as the mixed viscosity, it is preferably 400 mPa·s or more and 2000 mPa·s or less. From the viewpoint of excellent molding processability of the polyurethane resin, the mixed viscosity is more preferably 600 mPa·s or more and 2000 mPa·s or less.

[0125] <Validity period>

[0126] When the pot life (unit: seconds) is the time from when the polyisocyanate prepolymer (A) and the polyol (B) start to be mixed until the viscosity of the mixture reaches 50000 mPa·s, the pot life of the polyurethane resin forming composition can be 100 seconds to 3000 seconds, or 60 seconds to 9000 seconds.

[0127] The polyurethane resin forming composition shows good rapid curing properties, and the appearance whitening of the cured product is suppressed. Therefore, the polyurethane resin forming composition of one embodiment of the present disclosure is helpful in producing a film sealing material, and the film sealing material is helpful in producing a molded body with suppressed appearance whitening. That is, the polyurethane resin forming composition is a polyurethane resin forming composition for film sealing materials suitable for film sealing material applications.

[0128] <Method for producing polyurethane resin-forming composition>

[0129] The polyurethane resin-forming composition according to one embodiment of the present disclosure can be produced by a method including preparing the polyisocyanate prepolymer (A) and preparing the polyol (B).

[0130] <Cured product>

[0131] The cured product of one embodiment of the present disclosure is a cured product of the polyurethane resin-forming composition. The whiteness of the cured product may be 11.0 or less, or 10.5 or less. The whiteness is measured by the method described below.

[0132] [Membrane sealing material]

[0133] A film sealing material according to one embodiment of the present disclosure includes a cured product of the polyurethane resin-forming composition for a film sealing material.

[0134] The membrane sealing material can be suitably formed by reacting and curing the isocyanate component constituting the aforementioned polyisocyanate prepolymer (A) and the polyol component constituting the aforementioned polyol (B) under a temperature condition of 0°C to 100°C, preferably 20°C to 95°C, more preferably 30°C to 90°C. The temperature condition of the reaction may be 80°C or less, 70°C or less, 60°C or less, or 25°C or more. Although the membrane sealing material can be formed in a high temperature region to shorten the gelation time, there is a problem of easily causing molding shrinkage and thermal degradation of other components such as hollow fibers, so non-high temperature forming is preferred.

[0135] [Membrane module]

[0136] The membrane assembly of one embodiment of the present disclosure comprises: a main body; a membrane; and a membrane sealing material, which seals the gap between the main body and the membrane. The membrane is a plurality of hollow fiber membranes. The membrane sealing material is the above-mentioned membrane sealing material. The membrane sealing material preferably seals the following gaps: 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.

[0137] Next, a membrane module according to an embodiment of the present disclosure will be described in further detail with reference to the accompanying drawings.

[0138] Figure 1 This is a schematic diagram showing an example of the configuration of a membrane module according to one embodiment of the present disclosure. Figure 1 The membrane module (hollow fiber membrane module) 100 shown includes a housing (main body) 11, the interior of which is filled with a plurality of hollow fiber membranes (membranes) 13. For example, in the case of a hollow fiber membrane module used as a dialyzer, several thousand to several tens of thousands of hollow fiber membranes are filled.

[0139] The housing 11 has a cylindrical shape. Figure 1 The membrane sealing material 19 is provided at the left and right ends of the hollow fiber membranes 13. 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 bundles the plurality of hollow fiber membranes 13.

[0140] In addition, a first fluid inlet 15 and a first fluid outlet 17 are provided on the side of the housing 11, and the first fluid (gas or liquid) flows in and out of the housing 11 by means of these. The first fluid flowing in from the first fluid inlet 15 contacts the plurality of hollow fiber membranes 13 filled in the housing 11, passes through the gaps (outside the hollow fiber membranes) and is discharged from the first fluid outlet 17. It should be noted that there is no membrane sealing material 19 inside the hollow fiber membrane 13, so the second fluid (gas or liquid) flows in and out of the hollow fiber membrane 13 by means of the second inlet (one end side) and the second outlet (the other end side) provided on the cover member not shown in the figure. Then, the first fluid is brought into contact with the second fluid by means of the hollow fiber membrane 13, thereby causing the movement of a substance from one fluid to another fluid (or further from another fluid to one fluid). For example, in the case of a hollow fiber membrane type dialyzer, the dialysate contacts the blood, so that waste and excess water in the blood move into the dialysate.

[0141] It should be noted that Figure 1 The membrane assembly 100 shown is a structure having a plurality of hollow fiber membranes 13 and a membrane sealing material 19 for sealing the gaps at both ends thereof, but the membrane assembly of this embodiment is not limited to the above structure at all. For example, it may be a plurality of or a single membrane having various shapes such as a flat membrane or a spiral membrane. In addition, the membrane sealing material is not limited to a structure provided at both ends of the membrane, and may be provided only at a part of the membrane (one end if it is a hollow fiber), or may be provided at all ends of the membrane, such as the entire outer edge of a flat membrane. Furthermore, the sealing material may also be a structure provided at a part of the membrane other than the end and sealed. In addition, Figure 1 The housing 11 of the membrane module 100 shown has a cylindrical shape, but may have any shape other than a cylindrical shape.

[0142] The membrane assembly 100 uses the above-mentioned membrane sealing material polyurethane resin forming composition to seal the gaps between the hollow fiber membranes 13 at the end of the bundle of multiple hollow fiber membranes 13, and solidifies the composition to form the above-mentioned membrane sealing material (the gaps between the hollow fiber membranes are sealed by this membrane sealing material).

[0143] The membrane module of one embodiment of the present disclosure suppresses the production of extracts well, and thus can be suitably used as a medical module or a water treatment module. Specific examples of the membrane module include: a plasma separation device, an artificial lung, an artificial kidney, an artificial liver, and a domestic / industrial water treatment device.

[0144] Example

[0145] Hereinafter, the present disclosure will be described based on examples, but the present disclosure is not limited to these examples. It should be noted that, unless otherwise specified, "%" means "mass %". "OHV" means hydroxyl value.

[0146] The following components were used in Examples and Comparative Examples.

[0147] [Polyisocyanate prepolymer (A)]

[0148] a1-1; 4,4'-MDI (manufactured by Tosoh Corporation, product name: Millionate MT, isocyanate group content = 33.6%)

[0149] a1-2; carbodiimide-modified 4,4′-MDI (manufactured by Tosoh Corporation, product name Millionate MTL-C, isocyanate group content = 28.6%, carbodiimide / uretonimine-modified body content = 30%, isomers = about 1%)

[0150] a2: castor oil (manufactured by Ito Oil Manufacturing Co., Ltd., product name URIC H-30, OHV = 160 mgKOH / g, viscosity (25°C) = 690 mPa·s)

[0151] [Polyol (B)]

[0152] b1'; a polyol containing an ester exchange product of castor oil and N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine (polyol obtained in Synthesis Example 1 of the following ester exchange product polyol, OHV = 334 mgKOH / g, b1 content = 66 mass %)

[0153] b1; Transesterification of castor oil and N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine

[0154] b2; N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine (manufactured by ADEKA Corporation, product name EDP-300, OHV = 760 mgKOH / g, viscosity (25°C) = 50000 mPa·s)

[0155] b3: castor oil (manufactured by Ito Oil Products Co., Ltd., product name URIC H-30, OHV = 160 mgKOH / g, viscosity (25°C) = 690 mPa·s)

[0156] <Example 1 of Synthesis of Polyol Containing Transesterification Product>

[0157] In a 2-liter four-necked flask equipped with a stirrer, a thermometer, a heating device, and a dropping funnel, 710 parts by mass of castor oil (manufactured by Ito Oil Products Co., Ltd., product name URIC H-30), 290 parts by mass of N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine, and 1 part by mass of sodium methoxide were added, and the temperature was raised to 200° C. under a nitrogen flow, and then reacted for 8 hours to obtain an ester exchange product. The hydroxyl value of the obtained ester exchange product was 334 mgKOH / g, and the ester exchange product content was 66% by mass.

[0158] <Production Examples 1 to 5 of Polyisocyanate Prepolymer (A)>

[0159] a1-1, a1-2 and a2 were added in the blending ratio shown in Table 1, and stirred and mixed at 70°C for 4 hours to react, thereby synthesizing polyisocyanate prepolymers (A-1) to (A-3).

[0160] [Table 1]

[0161]

[0162] <Preparation Examples 1 to 3 of Polyol (B)>

[0163] The raw materials shown in Table 2 were added according to the blending ratios, stirred and uniformly mixed to obtain polyols (B-1) to (B-3).

[0164] [Table 2]

[0165]

[0166] <Examples 1 to 4 and Comparative Examples 1 to 4>

[0167] A polyurethane resin-forming composition was molded by mixing a polyisocyanate prepolymer (main component) and a polyol (curing agent) in the composition shown in Table 3. The values ​​described in Table 3 were calculated based on the following test results.

[0168] [NCO content determination]

[0169] In the polyisocyanate prepolymers (A-1) to (A-3) shown in Table 1, the NCO content was determined based on JIS K1603-1:2007.

[0170] [Determination of MDI monomer content]

[0171] In the polyisocyanate prepolymers (A-1) to (A-3) shown in Table 1, the content (mass %) of the MDI monomer was measured by GPC (Gel Permeation Chromatography) and determined under the following conditions and method.

[0172] <Measurement conditions>

[0173] (1) Measurement device: "HLC-8120 (trade name)" (manufactured by Tosoh Corporation)

[0174] (2) Column temperature: 40°C

[0175] (3) Detector: RI (refractive index) meter

[0176] (4) Column: Columns filled with three types of fillers, namely, TSKgel G3000HXL, TSKgel G2000HXL and TSKgel G1000HXL (all trade names, manufactured by Tosoh Corporation), were connected in series and measured.

[0177] (5) Eluent: tetrahydrofuran (THF) (flow rate: 1 mL / min, 40°C)

[0178] (6) Calibration curve: A calibration curve was obtained using polystyrene of the following grade (TSK standard POLYSTYRENE; manufactured by Tosoh Corporation).

[0179] F-2(1.81×10 4 )F-1(1.02×10 4 )A-5000(5.97×10 3 )A-2500(2.63×10 3 )A-500(Mw=6.82×10 2 , 5.78×10 2 4.74×10 2 3.70×10 2 , 2.66×10 2 )Toluene (Mw = 92)

[0180] (7) Sample: 0.05 g sample in 10 mL THF solution

[0181] <Measurement method>

[0182] First, polystyrene was used as a standard substance, and a calibration curve was obtained based on a graph detected by a refractive index difference. Next, for each sample, based on the same calibration curve, the mass % of the peak near the peak top molecular weight (number average molecular weight) of 230 of the MDI monomer was obtained based on a graph detected by a refractive index difference.

[0183] [Determination of the content of ester exchange products between castor oil and N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine]

[0184] In the polyols (B-1) to (B-2) shown in Table 2, the content (mass %) of the transesterification product between castor oil and N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine was determined by liquid chromatography (LC) under the following conditions and method.

[0185] <Measurement conditions>

[0186] (1) Measurement device: "Agilent 1290 Infinity II series (trade name)" (manufactured by Agilent Technologies)

[0187] (2) Column: As filler, TSKgel ODS-100V (trade name, manufactured by Tosoh Corporation)

[0188] (3) Column temperature: 40°C

[0189] (4) Detector: Evaporative light scattering detector (ELSD) G4260B (manufactured by Agilent Technologies)

[0190] (5) Mobile phase: 10 mM ammonium acetate-methanol

[0191] Ammonium acetate (special grade made by Fujifilm Wako Pure Chemicals)

[0192] Methanol (manufactured by Fujifilm Wako Pure Chemical Industries, for HPLC)

[0193] (6) Flow rate: 0.4 mL / min

[0194] (7) Sample concentration: 1.0 mg / mL

[0195] (8) Injection volume: 10 μL

[0196] <Measurement method>

[0197] First, castor oil and N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine were used as standard substances, and a calibration curve excluding the transesterification products was obtained from a graph obtained by ELSD chromatographic detection. Next, for each sample, based on the same calibration curve, the mass % of castor oil and N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine was obtained from a graph obtained by ELSD chromatographic detection, and the mass % of the peak representing the transesterification products other than the above was obtained.

[0198] In Examples 1 to 4 and Comparative Examples 1 to 4, the methods for measuring the values ​​of the physical properties are as follows.

[0199] <Mixed viscosity / pot life test>

[0200] The mixed viscosity / pot life when the resin cured product is obtained is determined by the following method.

[0201] The main agent (A-1) to (A-3) and the curing agent (B-1) to (B-3) are measured and mixed in a combination shown in Table 3 in such a way that the isocyanate group / active hydrogen group = 1.00 to 1.05 (molar ratio) at a liquid temperature of 45°C and the total amount reaches 50g, thereby obtaining a mixture. Next, the viscosity of the mixture is measured using a rotational viscometer (type B, rotor No. 4) in an atmosphere of 25°C. The viscosity after 60 seconds from the time when the main agent and the curing agent begin to mix is ​​taken as the mixed viscosity, and the time until the viscosity of the mixture reaches 50000mPa·s is taken as the pot life (seconds). If the mixed viscosity is less than 2000mPa·s, it is judged that the filling property is good, and if the pot life is within 1700 seconds, it is judged that the curing property is good.

[0202] <Appearance Evaluation>

[0203] The polyurethane resin forming composition for film sealing material using the combination shown in Table 3 was degassed at 10 to 20 kPa for 3 minutes and then poured into a stainless steel mold (100 mm × 100 mm × 8 mm). It was left to stand at 45°C for 2 days for curing and then demolded to obtain a cured product. The appearance of the obtained cured product was visually evaluated, and the one without turbidity was rated A, the one with slightly turbidity was rated B, and the one with white turbidity was rated C.

[0204] <Whiteness>

[0205] Preparation of samples for whiteness evaluation

[0206] A sample for whiteness evaluation was obtained by the same method as described in the appearance evaluation.

[0207] Evaluation of whiteness

[0208] The whiteness of the obtained whiteness evaluation sample is measured. The whiteness is measured in accordance with JIS-P8123. The whiteness is preferably 10 or less, more preferably 8 or less.

[0209] [Table 3]

[0210]

[0211] Description of Reference Numerals

[0212] 11 ... housing, 13 ... hollow fiber membrane, 15 ... first fluid inlet, 17 ... first fluid outlet, 19 ... membrane sealing material, 100 ... membrane module (hollow fiber membrane module)

Claims

1. A polyurethane resin-forming composition comprising a polyisocyanate prepolymer (A) and a polyol (B), The polyisocyanate prepolymer (A) comprises a reaction product of diphenylmethane diisocyanate (a1-1) and / or a modified diphenylmethane diisocyanate (a1-2) and an active hydrogen-containing compound (a2). The polyol (B) comprises: Transesterification product (b1) of castor oil-based polyol and hydroxyl-containing amine compound, A hydroxyl-containing amine compound (b2), and Castor oil-based polyol (b3), The content of the transesterification product (b1) is 0.1% by mass or more and 10% by mass or less relative to the total mass of the polyisocyanate prepolymer (A) and the polyol (B).

2. The polyurethane resin-forming composition according to claim 1, wherein The polyisocyanate prepolymer (A) has a urethane group concentration of 0.1 mmol / g or more.

3. The polyurethane resin-forming composition according to claim 1, wherein The reaction product contains at least a reaction site of a modified diphenylmethane diisocyanate (a1-2) and an active hydrogen-containing compound (a2), wherein the modified diphenylmethane diisocyanate (a1-2) contains carbodiimide-modified diphenylmethane diisocyanate and uretonimine-modified diphenylmethane diisocyanate. 4 . The polyurethane resin-forming composition according to claim 1 , which is for use in a film sealing material. 5 . A film sealing material comprising a cured product of the polyurethane resin-forming composition according to claim 4 .

6. A membrane module comprising: Main body; membrane; and a membrane sealing material for sealing a gap between the main body and the membrane, The film sealing material is the film sealing material according to claim 5.

7. The membrane module according to claim 6, wherein: The membrane is a plurality of hollow fiber membranes, The film sealing material seals the following gaps: a 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.

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