JP2018095875A - Allophanate group-containing polyisocyanate prepolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an allophanate group-containing polyisocyanate prepolymer with low viscosity and good defoaming properties, and a polyurethane resin-formable composition, a sealant and a film module prepared with the prepolymer.SOLUTION: The problem is solved by an allophanate group-containing polyisocyanate prepolymer (F) that is a reaction product of diphenyl methane diisocyanate (A) and an esterified product (B), the esterified product (B) being an esterified product of ricinoleic acid (B-1) and alcohol (B-2).SELECTED DRAWING: None

Description

  The present invention relates to an allophanate group-containing polyisocyanate prepolymer, a polyurethane resin-forming composition using the same, a sealing material using the forming composition, and a membrane module.

  Polyisocyanate prepolymers containing allophanate groups derived from diphenylmethane diisocyanate (hereinafter referred to as MDI) and an alcohol component are low in viscosity and have low MDI monomer precipitation at low temperatures, and are easy to handle. It is useful and widely applied in the field of agents and sealants.

  As alcohol components to be reacted with MDI, aliphatic monoalcohols and polypropylene glycol monoalkyl ethers are known (see, for example, Patent Document 1). However, the obtained allophanate group-containing polyisocyanate prepolymer has poor defoaming properties, and even if the polyol component is blended and the pressure cannot be reduced even after decompression, many bubbles remain in the cured product, and the original performance of the urethane resin is reduced. There was a problem that it could not be obtained.

JP 2009-30059 A

  Embodiments of the present invention have been made in view of the above-described background art, and the purpose thereof is to use an MDI-based allophanate group-containing polyisocyanate prepolymer having a low viscosity and good defoaming properties, and the prepolymer. A polyurethane resin-forming composition, a sealing material, and a membrane module are provided.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a ricinoleic acid ester as a monool component, and have completed the present invention.

That is, the present invention includes the following embodiments [1] to [11].
[1] A reaction product of diphenylmethane diisocyanate (A), esterified product (B), and polyol (E), wherein the esterified product (B) comprises ricinoleic acid (B-1), alcohol ( An allophanate group-containing polyisocyanate prepolymer (F) which is an esterified product of B-2).
[2] The allophanate group-containing polyisocyanate prepolymer (F) according to the above [1], wherein the esterified product (B) has an average functional group number of less than 2.
[3] The allophanate group-containing polyisocyanate prepolymer (F) according to the above [1] or [2], wherein the alcohol (B-2) is a monool having a molecular weight of greater than 32.
[4] The allophanate group-containing poly (1) according to any one of [1] to [3], wherein the alcohol (B-2) is a polypropylene glycol monoalkyl ether having a molecular weight of 200 or more and 2000 or less. Isocyanate prepolymer (F).
[5] The allophanate group-containing polyisocyanate prepolymer (F) according to any one of [1] to [4] above, wherein the viscosity at 25 ° C. is 2,000 mPa · s or less.
[6] The above [1] to [5], wherein the reaction product is a reaction product of the diphenylmethane diisocyanate (A), the esterified product (B), and the polyol (E). Allophanate group containing polyisocyanate prepolymer (F) of any one of these.
[7] The allophanate group-containing polyisocyanate prepolymer according to the above [6], wherein the polyol (E) has an average number of functional groups of 2 or more.
[8] The allophanate group-containing polyisocyanate prepolymer (F) according to the above [6] or [7], wherein the polyol (E) has a molecular weight of 500 or more and 3000 or less.
[9] A polyurethane resin-forming composition comprising the allophanate group-containing isocyanate prepolymer (F) according to any one of [1] to [8] above and a polyol (G).
[10] A sealing material comprising a cured product of the polyurethane resin-forming composition according to [9].
[11] A membrane module sealed with the sealing material according to [10].

  The allophanate group-containing polyisocyanate prepolymer according to one embodiment of the present invention provides a urethane resin cured product having a low viscosity, good defoaming properties, and excellent appearance. According to another embodiment of the present invention, a polyurethane resin-forming composition that contributes to the formation of a urethane resin cured product having an excellent appearance can be obtained. According to another embodiment of the present invention, a sealing material and a membrane module excellent in appearance can be obtained.

It is a conceptual diagram which shows an example of a structure of the membrane module concerning one Embodiment of this invention.

The polyisocyanate prepolymer (F) containing an allophanate group according to an embodiment of the present invention is:
Diphenylmethane diisocyanate (hereinafter referred to as MDI) (A),
Esterified product (B) of ricinoleic acid (B-1) and alcohol (B-2);
The reaction product is characterized by having a low viscosity and an excellent defoaming property.

  As a result of further studies on the polyurethane resin-forming composition containing the polyisocyanate prepolymer (F) by the present inventors, it may be eluted into a solvent when cured to obtain a cured product. I found out. If the cured product is eluted in the solvent, it may lead to a decrease in performance, a shortened life, etc., so it is desirable to reduce the amount of extract extracted by the solvent.

As a result of intensive studies by the present inventors, the polyisocyanate prepolymer (F) is further made into a reaction product of a system to which a polyol (E) is added, thereby forming a polyurethane resin containing the reaction product. The cured product obtained by curing the composition was found to reduce the amount of extract extracted by the solvent.
Therefore, the polyisocyanate prepolymer (F) containing an allophanate group according to another embodiment of the present invention is:
MDI (A),
Esterified product (B) of ricinoleic acid (B-1) and alcohol (B-2);
It is a reaction product of polyol (E).

  For MDI (A), a commonly available MDI monomer or polymeric MDI can be used. As specific examples of the MDI monomer, usually 2,2′-MDI is 0% by mass to 5% by mass, 2,4′-MDI is 0% by mass to 95% by mass, and 4,4′-MDI is 5% by mass. It is a simple substance or an isomer mixture of MDI monomers containing from 100% to 100% by mass. Moreover, polymethylene polyphenylene polyisocyanate can be used as polymeric MDI. It is also possible to use a mixture of MDI monomer and polymeric MDI, and the content of polymeric MDI in that case is preferably 0% by mass or more and 50% by mass or less in the isocyanate component to be used. When it exceeds 50% by mass, the viscosity becomes too high, and insoluble matter is easily generated.

  The esterified product (B) is an esterified product of ricinoleic acid (B-1) and alcohol (B-2). Especially, it is preferable that the average number of functional groups of the esterified product (B) of ricinoleic acid is less than 2 from the viewpoint of obtaining an allophanate group-containing polyisocyanate prepolymer having low viscosity and excellent fluidity.

  Here, the ricinoleic acid (B-1) used is ricinoleic acid alone or a fatty acid mixture having a ricinoleic acid content of 50% by mass or more. Among them, ricinoleic acid obtained by saponifying and decomposing castor oil is 85% by mass to 95% by mass, and other fatty acids such as oleic acid, linoleic acid, palmitic acid, stearic acid, hydroxystearic acid, etc. It is preferable to use castor oil fatty acid containing.

  On the other hand, there is no restriction | limiting in particular as alcohol (B-2), For example, methanol, ethanol, 1- and 2-propanol, 1- and 2-butanol, 1-pentanol, 1-hexanol, 2-methyl-1- Pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethylhexanol, 3,5-dimethyl-1-hexanol, 2,2 , 4-trimethyl-1-pentanol, 1-nonanol, 2,6-dimethyl-4-heptanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecane 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol 1-eicosanol, 1-hexacosanol, 1-hepta Tricon pentanol, 1-oleyl alcohol, 2-aliphatic monoalcohols, such as octyldodecanol, and mixtures thereof. In addition to these aliphatic alcohols, for example, polyalkylene glycol monoalkyl / aryl ethers, which are oxyalkylene adducts using compounds containing phenolic hydroxyl groups such as phenol, cresol, xylenol, and nonylphenol as initiators, and mixtures thereof Is mentioned. Moreover, the monocarboxylic acid ester of polyalkylene glycol, a mixture thereof, etc. are mentioned.

  Among these alcohols (B-2), monools having a molecular weight of more than 32 are preferably used in order to exhibit excellent defoaming properties, and in particular, 1-butanol, 1-hexanol, 2-ethylhexanol, 1- It is preferable to use alcohol having 4 or more carbon atoms such as oleyl alcohol, polypropylene glycol monoalkyl ether having a molecular weight of 200 or more and 2000 or less.

  The esterified product (B) can be synthesized by a known method. For example, there are a method of dehydrating and condensing castor oil fatty acid and alcohol (B-2) and a method of removing glycerin while transesterifying castor oil and alcohol (B-2), and the reaction includes known esterification and transesterification catalysts. Can be used.

  As the polyol (E), any polyol having an average functional group number of 2 or more can be used. In view of moldability of polyurethane resin and reduction of eluate, the average number of functional groups is preferably 2 or more and 3 or less.

  Examples of the polyol (E) include polyether polyols, polyester polyols, polylactone polyols, castor oil polyols, and polyolefin polyols. These can be used alone or in combination of two or more. Among these, castor oil-based polyol is preferable because it is excellent in chemical resistance and elution resistance.

  The molecular weight of the polyol (E) is preferably 500 or more and 3000 or less. From the viewpoint of excellent molding processability and adhesive strength of the polyurethane resin, the molecular weight of the polyol (E) is more preferably 600 or more and 2500 or less.

  Further, the viscosity at 25 ° C. of the allophanate group-containing polyisocyanate prepolymer (F) is preferably 2,000 mPa · s or less from the viewpoint of processability.

  The allophanate group-containing polyisocyanate prepolymer (F) comprises an MDI (A), an esterified product (B) of ricinoleic acid (B-1) and an alcohol (B-2), and a polyol (E). After reacting in the presence of (C), the catalyst can be produced by adding the catalyst poison (D) to stop the reaction. At this time, in addition to the esterified product (B), a compound containing a hydroxyl group having an average functional group number of 1 or more and 2 or less, that is, a monool or a diol can be used in combination. However, the compound containing a phenolic hydroxyl group is preferably a compound containing a hydroxyl group other than the phenolic hydroxyl group because the generation ratio of isocyanurate groups is increased and the viscosity may be increased. Moreover, the viscosity of triol or higher polyol may also increase.

  As the allophanate-forming catalyst (C), a known catalyst can be used. For example, zinc acetylacetone, zinc 2-ethylhexanoate, cobalt 2-ethylhexanoate, cobalt naphthenate, etc., metal carboxylates such as lead, tin, copper, cobalt, and hydrates thereof are used. Can do.

  Further, tertiary amines, tertiary amino alcohols, quaternary ammonium salts and mixtures thereof can also be used.

  Examples of the tertiary amine include N, N, N-benzyldimethylamine, N, N, N-dibenzylmethylamine, N, N, N-cyclohexyldimethylamine, N-methylmorpholine, N, N, N- Trialkylamines such as tribenzylamine, N, N, N-tripropylamine, N, N, N-tributylamine, N, N, N-tripentylamine, N, N, N-trihexylamine; N, And polymethyl polyalkylene polyamines such as N, N ′, N′-tetramethylethylenediamine and N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine.

  Examples of the tertiary amino alcohol include 2- (dimethylamino) ethanol, 3- (dimethylamino) propanol, 2- (dimethylamino) -1-methylpropanol, 2- {2- (dimethylamino) ethoxy} ethanol, 2 -{2- (diethylamino) ethoxy} ethanol, 2-[{2- (dimethylamino) ethyl} methylamino] ethanol and the like.

  Examples of the quaternary ammonium salt include tetraalkylammonium such as N, N, N, N, -tetramethylammonium, N, N, N-trimethyl-N-octylammonium, N- (2-hydroxyethyl) -N, A compound obtained by combining a counter ion with a hydroxyalkyltrialkylammonium such as N, N-trimethylammonium or N- (2-hydroxypropyl) -N, N, N, -trimethylammonium can be used.

  The addition amount of the allophanate-forming catalyst (C) is preferably from 1 ppm to 1000 ppm, more preferably from 10 ppm to 500 ppm, based on the total amount of the polyisocyanate prepolymer (F). If it is 1 ppm or more, the reaction is carried out more rapidly, and if it is 1000 ppm or less, coloring of the prepolymer is more highly suppressed, which is preferable.

  The reaction temperature for carrying out allophanatization is not particularly limited, but is preferably 20 ° C or higher and 200 ° C or lower. Especially, in order to suppress the ratio of by-produced isocyanurate to 20 mol% or less and obtain a low viscosity allophanate group-containing prepolymer, the temperature is preferably 60 ° C. or higher and 160 ° C. or lower.

  The catalyst poison (D) is not particularly limited as long as it is an acidic substance. For example, anhydrous hydrogen chloride, sulfuric acid, phosphoric acid, monoalkylsulfuric acid ester, alkylsulfonic acid, alkylbenzenesulfonic acid, mono- or dialkylphosphoric acid ester, benzoyl chloride, Lewis acids and the like are also included. The addition amount is preferably added in an equivalent amount or more with respect to the number of moles of the allophanate-forming catalyst (C), and more preferably in the range of 1.0 to 1.5 times the molar equivalent.

  The polyol (G) is not particularly limited as long as it can react with the allophanate group-containing polyisocyanate prepolymer (F) to form a urethane resin-forming composition, and may be an active hydrogen group-containing compound. Any of them can be used.

  Examples of the polyol (G) include a low molecular polyol, a polyether polyol, a polyester polyol, a polylactone polyol, a castor oil polyol, a polyolefin polyol, and a hydroxyl group-containing amine compound. These can be used alone or in combination of two or more. Among these, castor oil-based polyol is preferable because it is excellent in chemical resistance and elution resistance.

  Examples of the low molecular polyol include a divalent low molecular polyol and a trivalent or higher low molecular polyol. Specific examples of the divalent low molecular polyol include ethylene glycol, diethylene glycol, propylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 3-methyl- Examples include 1,5-pentanediol, 1,6-hexane glycol, 1,8-octanediol, 1,10-decandiol, neopentyl glycol, hydrogenated bisphenol A, and the like. Specific examples of the trivalent or higher molecular weight polyol include glycerin, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, and the like. The molecular weight of the low-molecular polyol is preferably 50 or more and 200 or less from the viewpoint of excellent moldability during the production of the sealing material.

  Examples of the polyether-based polyol include adducts of the above low-molecular-weight polyols with alkylene oxides (C2-C4 alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc.) and ring-opening polymers of alkylene oxides. It is done. Specific examples of the polyether polyol include polypropylene glycol, polyethylene glycol, polytetramethylene ether glycol, and chipped ether that is a copolymer of ethylene oxide and propylene oxide. The number average molecular weight of the polyether polyol is preferably 200 or more and 7000 or less. From the viewpoint of excellent moldability at the time of producing the sealing material, the polyether polyol preferably has a number average molecular weight of 500 or more and 5000 or less.

  Examples of the polyester polyol include a polyester polyol obtained by condensation polymerization of a polycarboxylic acid and a polyol. More specifically, the polycarboxylic acid is an aliphatic saturated or unsaturated polycarboxylic acid such as azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid, ricinoleic acid, dimerized linoleic acid; aromatic polycarboxylic acid Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and the like. More specifically, examples of the polyol include at least one selected from the group consisting of the low molecular polyol and the polyether polyol. The number average molecular weight of the polyester polyol is preferably from 200 to 5,000. From the viewpoint of excellent moldability during the production of the sealing material, the number average molecular weight of the polyester polyol is more preferably 500 or more and 3000 or less.

  Examples of polylactone polyols include polymerization initiators such as glycols and triols, ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, and β-methyl-σ-valerolactone. Examples include polyols obtained by addition polymerization of at least one selected from the group consisting of organic metal compounds, metal chelate compounds, fatty acid metal acyl compounds and the like in the presence of a catalyst. The number average molecular weight of the polylactone-based polyol is preferably 200 or more and 5000 or less. From the viewpoint of excellent moldability during production of the sealing material, the number average molecular weight of the polylactone-based polyol is more preferably 500 or more and 3000 or less.

  Castor oil-based polyols include linear or branched polyesters obtained by the reaction of castor oil fatty acid and polyol, such as castor oil fatty acid diglyceride, monoglyceride; castor oil fatty acid and trimethylol alkane mono, di or triester; And mono-, di-, or triesters of castor oil fatty acid and polypropylene glycol. More specifically, examples of the polyol include at least one selected from the group consisting of the low molecular polyol and the polyether polyol. The number average molecular weight of the castor oil-based polyol is preferably from 300 to 4,000. From the viewpoint of excellent moldability at the time of producing the sealing material, the number average molecular weight of the castor oil-based polyol is more preferably 500 or more and 3000 or less.

  Examples of the polyolefin-based polyol include polybutadiene-based polyol in which a hydroxyl group is introduced at the terminal of a copolymer of polybutadiene or butadiene and styrene or acrylonitrile.

  Other examples include polyether ester-based polyols obtained by subjecting a polyester having at least one selected from the group consisting of a carboxyl group and a hydroxyl group to an alkylene oxide such as ethylene oxide and propylene oxide.

  Examples of the hydroxyl group-containing amine compound include amino alcohols as oxyalkylated derivatives of amino compounds.

  Examples of the amino alcohol include N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine, N, N, N ′, N, which are propylene oxide or ethylene oxide adducts of amino compounds such as ethylenediamine. Examples include '-tetrakis [2-hydroxyethyl] ethylenediamine and the like; mono-, di- and triethanolamine, N-methyl-N, N'-diethanolamine and the like. Among these, propylene oxide or ethylene oxide adducts of amino compounds such as ethylenediamine are preferable, and N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine is more preferable. By using N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine, it is possible to obtain more excellent effects for improving processability at the time of molding, suppressing elution, and the like.

  Moreover, when using a hydroxyl-containing amine type compound, the range of 1 to 30 mass% is preferable in a polyol (G), and the range of 5 to 25 mass% is especially preferable. When the proportion of the hydroxyl group-containing amine compound in the polyol (G) is 1% by mass or more, the hydroxyl group-containing amine compound exhibits its function more effectively and exhibits further effects. When the ratio of the hydroxyl group-containing amine compound in the polyol (G) is 30% by mass or less, the reactivity is further suppressed from becoming too high, the workability is further improved, and the filling property is ensured. It is further suppressed that the hardness of the obtained sealing material becomes too high.

  The hydroxyl value of the polyol (G) is preferably 50 mgKOH / g or more and 1000 mgKOH / g or less, and more preferably 75 mgKOH / g or more and 750 mgKOH / g or less from the viewpoint of easy handling of the polyol (G). From the viewpoint of excellent molding processability and adhesive strength of the polyurethane resin, the hydroxyl value of the polyol (G) is most preferably from 100 mgKOH / g to 500 mgKOH / g.

  The viscosity of the polyol (G) at 25 ° C. is preferably from 100 mPa · s to 6000 mPa · s, and more preferably from 200 mPa · s to 4000 mPa · s from the viewpoint of easy handling of the polyol (G). From the viewpoint of the excellent moldability of the polyurethane resin, the viscosity of the polyol (G) at 25 ° C. is most preferably from 400 mPa · s to 2000 mPa · s.

  The polyurethane resin-forming composition of this embodiment can be obtained by reacting the allophanate group-containing polyisocyanate prepolymer (F) with the polyol (G). The obtained polyurethane resin-forming composition can be used as a sealing material for membranes of various forms such as a sealing material for hollow fiber membrane modules, a sealing material for flat membrane modules, and a sealing material for spiral membranes.

  As the polyurethane resin-forming composition, the molar ratio (isocyanate group / active hydrogen group) of the isocyanate group of the allophanate group-containing polyisocyanate composition (F) to the active hydrogen group of the polyol (G) is 0.8 or more. It is preferably within the range of 6 or less. The molar ratio is more preferably in the range of 0.9 or more and 1.2 or less, and more preferably in the range of 1.0 or more and 1.1 or less, from the viewpoint of excellent molding processability and adhesive strength of the polyurethane resin. Particularly preferred. According to the composition obtained at such a mixing ratio, a composition having further excellent durability can be obtained.

  The solvent extraction rate of the polyurethane resin-forming composition (measurement method will be described later) is preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less.

  In this embodiment, a metal compound system such as an organotin compound that accelerates the reaction between the isocyanate group of the allophanate group-containing polyisocyanate prepolymer (F) and the active hydrogen group of the polyol (G) as necessary. Known urethanes such as catalysts and tertiary amine catalysts such as triethylenediamine (TEDA), tetramethylhexamethylenediamine (TMHMDA), pentamethyldiethylenetriamine (PMDETA), dimethylcyclohexylamine (DMCHA) and bisdimethylaminoethyl ether (BDMAEA) A catalyst can be used.

  In addition, the polyurethane resin-forming composition according to this embodiment may contain additives such as an antioxidant, an ultraviolet absorber, and an antifoaming agent as long as the purpose is not impaired.

  When obtaining a sealing material for a module using a hollow fiber separation membrane using the polyurethane resin-forming composition according to this embodiment, the composition is allowed to react at room temperature (20 ° C. or higher and 30 ° C. or lower), or In order to shorten the gelation time and decrease the mixing viscosity, the allophanate group-containing polyisocyanate composition (F) and the polyol (G) may be heated to 30 ° C. or more and 60 ° C. or less for reaction. In order to shorten the gelation time, the molding temperature may be set to 0 ° C. or higher and 100 ° C. or lower, preferably 20 ° C. or higher and 80 ° C. or lower, more preferably 30 ° C. or higher and 60 ° C. or lower, as necessary.

<Sealing material, membrane module>
The sealing material concerning one Embodiment of this invention consists of hardened | cured material of the polyurethane resin forming composition mentioned above. That is, the polyurethane resin-forming composition described above can be cured and used as a sealing material. At this time, the sealing material is preferably transparent to such an extent that the other side can be visually observed from one side of the sealing material. In particular, a sealing material for a membrane module that constitutes a medical or industrial separation apparatus is required to have no turbidity visually in order to confirm the inclusion of foreign matter.

  Moreover, the membrane module according to one embodiment of the present invention fills the gap between the membrane and a part of the module (particularly, the gap between the end of the membrane and the inner wall of the housing) with the above-described polyurethane resin-forming composition. The gap is sealed by curing to form a sealing material. That is, the membrane module according to one embodiment of the present invention is sealed with the sealing material described above.

A membrane module according to an embodiment of the present invention will be described in more detail with reference to the drawings.
FIG. 1 is a conceptual diagram showing an example of the configuration of a membrane module according to an embodiment of the present invention.
A membrane module (hollow fiber membrane module) 100 shown in FIG. 1 includes a housing 11 in which a plurality of hollow fiber membranes 13 are filled. For example, in the case of a hollow fiber membrane module used as a dialyzer, thousands to tens of thousands of hollow fiber membranes are filled.

  The housing 11 has a cylindrical shape. Sealing materials 19 are respectively provided at both ends (left and right ends in FIG. 1) inside the housing 11. The sealing material fills and seals the gap between the hollow fiber membranes 13 and the gap between the hollow fiber membrane 13 and the inner wall of the housing 11, and binds the plurality of hollow fiber membranes 13 together.

  Further, a first fluid inlet 15 and a first fluid outlet 17 are provided on the side surface of the housing 11, and the first fluid (gas or liquid) flows in and out from the outside. The first fluid flowing in from the first fluid inlet 15 passes through the gap (outside of the hollow fiber membrane) while contacting with the plurality of hollow fiber membranes 13 filled in the housing 11, and the first fluid outlet 17. Discharged from. In addition, since the sealing material 19 does not exist inside the hollow fiber membrane 13, the hollow fiber membrane 13 includes a second inlet (one end side) and a second outlet (provided with a cap member (not shown)). The second fluid (gas or liquid) flows in and out from the outside through the other end side. Then, when the first fluid and the second fluid come into contact with each other through the hollow fiber membrane 13, mass transfer from one fluid to the other fluid occurs. For example, in the case of a hollow fiber membrane type dialyzer, when the dialysate comes into contact with blood, waste products and excess water in the blood move to the dialysate.

  The membrane module 100 shown in FIG. 1 includes a plurality of hollow fiber membranes 13 and the sealing material 19 seals the gaps at both ends thereof, but the membrane module according to the present embodiment is not limited to this. Is not to be done. For example, it may be a film having various shapes such as a plurality or a single flat film, a spiral film, or the like. Further, the sealing material is not limited to the configuration provided at both ends of the membrane, and may be provided only on a part of the membrane (one end in the case of a hollow fiber shape). It may be provided in all the outer edge parts. Further, the sealing material may be provided and sealed at a part other than the end of the film.

  The membrane module according to one embodiment of the present invention is excellent in defoaming properties and the extract is favorably suppressed, and therefore can be suitably used as a medical module or a water treatment module. Specific examples of the membrane module include a plasma separator, an artificial lung, an artificial kidney, an artificial liver, and a household / industrial water treatment device.

  The present invention will be described below, but the present invention is not construed as being limited to these examples. In the following, “%” means “mass%” unless otherwise specified.

The following components were used in the examples and comparative examples.
(1) MDI
Iso A1; 4,4′-MDI (Millionate MT, 99% purity, manufactured by Tosoh Corporation)
Iso A2; 4,4′-MDI / (2,4′-MDI + 2,2′-MDI) = 45/55% by mass of MDI (Millionate NM, manufactured by Tosoh Corporation)
(2) Polyol compound Poly B1; esterified product of castor oil fatty acid and methanol (COFA methyl ester-D hydroxyl value 163 KOHmg / g average functional group number 1 manufactured by Ito Oil Co., Ltd.)
Poly B2: esterified product of castor oil fatty acid and 1-butanol (COFA butyl ester-D hydroxyl value 148 KOHmg / g average functional group number 1 manufactured by Ito Oil Co., Ltd.)
Poly B3: esterified product of castor oil fatty acid and polypropylene glycol monobutyl ether (molecular weight 340) (compound obtained in Monol Synthesis Example 1 below, average functional group number 1)
Poly B4; 2-octyldodecanol (calcol 200GD, hydroxyl value 185 KOHmg / g, average functional group number 1 manufactured by Kao Corporation)
Poly B5: Polypropylene glycol mono 2-ethylhexyl ether (Leocon 1015H, hydroxyl value 72 KOHmg / g, average functional group number 1 manufactured by Lion Specialty Chemicals)
Poly E1; castor oil (LAV hydroxyl value 160 KOHmg / g molecular weight 947 average functional group number 2.7 manufactured by Ito Oil Co., Ltd.)
Poly E2; polyoxypropylene glycol (P-1000 hydroxyl value 110 KOH mg / g, molecular weight 1000, average functional group number 2 manufactured by ADEKA)
Poly H1; castor oil (LAV hydroxyl value 160 KOHmg / g, manufactured by Ito Oil Co., Ltd.)
Poly H2; N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine (EDP-300, hydroxyl value 760 KOHmg / g, manufactured by ADEKA)
(3) Catalyst Catalyst C: Acetylacetone zinc (manufactured by Tokyo Chemical Industry Co., Ltd.)
(4) Catalyst poison Catalyst poison D: Benzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.).

<Defoaming evaluation method>
1) Weigh 100 g of the prepolymer obtained in a 200 ml polypropylene (PP) cup.
2) Stir at 500 rpm with a clover blade attached to a rotating machine for 10 seconds.
3) Transfer 20 ml of sample to a 100 ml PP cup.
4) Set 3) in a filter bell equipped with a vacuum pump and start depressurization.
5) The pressure is reduced to an absolute pressure of 70 mmHg in 20 seconds from the start of pressure reduction.
6) The height of the foam 60 seconds after the start of decompression is read with a capacity of 100 ml PP cup.

  Those with good defoaming swell once, but break up and return to the original volume (20 ml) around 20-30 seconds after defoaming starts. Those with poor defoaming properties remain inflated without breaking. In the above test, a prepolymer having a capacity of 20 ml or more and 50 ml or less after 60 seconds from the start of decompression was immediately judged to be defoamed because it could be immediately subjected to molding.

<Solvent extraction rate evaluation procedure>
(Solvent extraction rate measurement sample molding method)
Each polyurethane resin-forming composition having a combination shown in Table 2 was degassed under reduced pressure at 10 to 20 kPa for 3 minutes, and then poured into release paper (220 mm × 170 mm × 10 mm). This was left to cure at 45 ° C. for 2 days to obtain a cured resin.

(Extraction test method)
The obtained resin cured product was cut into 1 cm square, 20 g of this was weighed, 10 times the amount of methanol was added to the resin mass, and shaken at 25 ° C. for 24 hours. After filtration and drying, the extraction rate was calculated from the resin mass before and after extraction.

<Resin defoaming property>
Each of the polyurethane resin-forming compositions having the combinations shown in Table 2 was degassed under reduced pressure at 10 to 20 kPa for 3 minutes, and then poured into a stainless steel mold (100 mm × 100 mm × 8 mm). This was left to cure at 45 ° C. for 2 days and then demolded to obtain a cured product. About the obtained hardened | cured material, the external appearance was evaluated visually, the thing without a bubble was set to A, and the thing in which even a bubble is recognized is set to B.

<Monoall synthesis example 1>
In a 1 liter four-necked flask with a stirrer, thermometer, heating device, and distillation tower, 479 parts of ricinoleic acid (CO-FA manufactured by Ito Oil Co., Ltd.), polypropylene glycol monobutyl ether having a number average molecular weight of 340 (Sanyo Chemical Industries) 479 parts), heated to 190 ° C. while raising the temperature at 110 ° C. for 2 hours at a rate of 10 ° C./hour under a nitrogen stream, and further reacted at 190 ° C. for 2 hours. Distilled off. Next, 0.05 parts of tetrabutyl titanate (TBT-100 manufactured by Katayama Chemical Industry Co., Ltd.) was added to stop the nitrogen, and while maintaining the temperature at 190 ° C., the pressure was gradually reduced to 5 kPa, and the water produced by reacting for 4 hours after reaching 5 kPa. Was distilled off. The obtained esterified product had a hydroxyl value of 70 mgKOH / g.

<Example 1>
655.0 g of MDI A1 was added to a 1-liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, 345.0 g of polyol B1 was added with stirring, and the temperature was raised to 90 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 90 ° C., 0.1 g of catalyst C was added, and after reacting at 90 ° C. for 4 hours, 0.14 g of catalyst poison E was added to stop the reaction. The synthesized prepolymer was a pale yellow transparent liquid, and its viscosity at 25 ° C. was 1900 mPa · s. As a result of evaluating the defoaming property, the prepolymer F1 which is the object of one embodiment of the present invention was obtained after defoaming was started. The properties and defoaming evaluation results are shown in Table 1.

<Examples 2 to 6>
MDI and polyol were changed to the compositions shown in Table 1, and a prepolymer was synthesized in the same manner as in Example 1. All were pale yellow transparent liquid prepolymers, and prepolymers having low viscosity and good defoaming properties were obtained. The properties and defoaming evaluation results are shown in Table 1.

<Comparative Examples 1-2>
The components A and B were changed to the compositions shown in Table 1, and a prepolymer was synthesized in the same manner as in Example 1. The obtained prepolymer was a pale yellow transparent liquid, but had poor defoaming properties. The properties and defoaming evaluation results are shown in Table 1.

<Production example of polyol (G1)>
Polyol component G1 was prepared by mixing 180 parts by mass of poly H and 20 parts by mass of poly H2. The viscosity at 25 ° C. was 1150 mPa · s, and the hydroxyl value was 280 mgKOH / g.

<Examples 7 to 12>
The polyurethane resin-forming composition having the combination shown in Table 2 was a polyurethane resin-forming composition having excellent defoaming properties. Moreover, the obtained polyurethane resin was excellent in appearance. Furthermore, in Example 11 and Example 12 using polyol (E), a polyurethane resin with a small extract was obtained.

<Comparative Examples 3-4>
All of the polyurethane resin-forming compositions having the combinations shown in Table 2 were poorly defoaming polyurethane resins. Further, the obtained polyurethane resin was not excellent in appearance.

Claims (11)

A reaction product of diphenylmethane diisocyanate (A), esterified product (B), and polyol (E),
The esterified product (B) is
Ricinoleic acid (B-1);
Allophanate group-containing polyisocyanate prepolymer (F), which is an esterified product of alcohol (B-2).   2. The allophanate group-containing polyisocyanate prepolymer (F) according to claim 1, wherein the esterified product (B) has an average functional group number of less than 2. 3.   The allophanate group-containing polyisocyanate prepolymer (F) according to claim 1 or 2, wherein the alcohol (B-2) is a monool having a molecular weight of greater than 32.   The allophanate group-containing polyisocyanate prepolymer (F) according to any one of claims 1 to 3, wherein the alcohol (B-2) is a polypropylene glycol monoalkyl ether having a molecular weight of 200 or more and 2000 or less. .   The allophanate group-containing polyisocyanate prepolymer (F) according to any one of claims 1 to 4, wherein the viscosity at 25 ° C is 2,000 mPa · s or less.   The allophanate group-containing polyisocyanate prepolymer (F), wherein the reaction product is a reaction product of the diphenylmethane diisocyanate (A), the esterified product (B), and a polyol (E).   The allophanate group-containing polyisocyanate prepolymer according to claim 6, wherein the polyol (E) has an average number of functional groups of 2 or more.   The allophanate group-containing polyisocyanate prepolymer (F) according to claim 6 or 7, wherein the polyol (E) has a molecular weight of 500 or more and 3000 or less.   A polyurethane resin-forming composition comprising the allophanate group-containing isocyanate prepolymer (F) according to any one of claims 1 to 8, and a polyol (G).   A sealing material comprising a cured product of the polyurethane resin-forming composition according to claim 9.   A membrane module sealed with the sealing material according to claim 10.

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